JP7238500B2 - Printing device and printing method - Google Patents

Description

The present invention relates to a printing apparatus, a printing method, and a glossiness control method for a printed image.

Non-permeable recording media such as plastic films are used to improve durability such as light resistance, water resistance, and wear resistance in industrial applications such as advertisements and billboards, and packaging materials for food, beverages, and daily necessities. Various inks have been developed for use in such impermeable recording media.

As such ink, for example, solvent-based ink using an organic solvent as a solvent, ultraviolet (UV) curable ink containing a polymerizable monomer as a main component, and the like are widely used. However, the solvent-based ink is concerned about environmental impact due to evaporation of the organic solvent. For the UV curable ink, the choice of polymerizable monomers to be used may be limited in terms of safety.
Therefore, an ink set containing a water-based ink, which has a low environmental load and can be directly recorded on a non-permeable recording medium, has been proposed.

On the other hand, an inkjet recording apparatus having a gloss control function has been developed.
For example, a liquid ejecting head capable of ejecting ink containing thermoplastic resin particles from a nozzle toward an impact target, and heating means for heating ink droplets that have landed on the impact target, wherein the heating means is the ink A liquid ejecting apparatus has been proposed that controls the degree of film formation on the surface of an ink droplet by heating at a film formation control temperature corresponding to the minimum film formation temperature at which film formation on the surface of the ink droplet starts (for example, patent Reference 1).

SUMMARY OF THE INVENTION An object of the present invention is to provide a printing apparatus that can handle both matte and gloss gloss control.

A printing apparatus according to the present invention as a means for solving the above-mentioned problems includes a liquid containing portion for containing liquid, an ejection head for ejecting the liquid to form a print layer, and a heating means for heating an object to be printed. wherein the liquid is clear ink containing resin and water, and the printing device has a matte gloss print mode that imparts matte gloss and a print mode that imparts gloss gloss T _matte (° C.) is the temperature of the substrate in the matte printing area to be printed in the matte gloss printing mode when a certain gloss gloss printing mode is provided, and the heating means attaches the liquid to the substrate, and the liquid When T _gloss (° C.) is the temperature of the substrate in the gloss printing area printed in the gloss printing mode when attaching to the substrate, the following formula, T _matte >T _gloss Let Gm be the glossiness of the printed material, and Gp be the glossiness of the surface of the printing layer after printing. , the following equation is satisfied: Gm≧Gp.

According to the present invention, it is possible to provide a printing apparatus that can handle both matte and gloss gloss control.

FIG. 1 is a diagram showing an example of an image forming apparatus for carrying out the image forming method of the present invention. FIG. 2 is a perspective explanatory view showing an example of a main tank of the image forming apparatus of FIG. 1. FIG.

(Printing device and printing method)
A printing apparatus of the present invention is a printing apparatus having a liquid storage unit that stores a liquid, an ejection head that ejects the liquid to form a print layer, and a heating means that heats an object to be printed, wherein the liquid is It is a clear ink containing resin and water, and the printing device has a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss, and the heating means is , the temperature of the substrate in the matte printing area to be printed in the matte gloss print mode when the liquid is attached to the substrate is T _matte (° C.), and the liquid is attached to the substrate and printed in the gloss gloss print mode. Assuming that the temperature of the substrate in the gloss printing area is T _gloss (° C.), the following formula, T _matte >T _gloss , is heated so that the glossiness of the substrate is Gm, and the surface of the printed layer after printing If Gp is the glossiness of Gp, the following expression Gp≧Gm is satisfied in the case of the gloss gloss print mode, and the following expression Gm≧Gp is satisfied in the case of the matte gloss print mode. and have other means.

A printing apparatus according to the present invention is a printing apparatus having a liquid storage unit that stores a liquid, an ejection head that ejects the liquid to form a print layer, and a heating unit that heats an object to be printed, wherein the liquid is , a resin, and a clear ink containing water; Assuming that the temperature of the heating means in the matte gloss printing mode is HT _matte (°C) and the temperature of the heating means in the gloss gloss printing mode is HT _gloss (°C), the following expression, HT _matte >HT _gloss , is satisfied. Gm is the glossiness of the printed material, and Gp is the glossiness of the surface of the printing layer after printing. In the case of the matte glossy print mode, the following expression Gm≧Gp is satisfied, and other means are provided as necessary.

A printing method of the present invention includes a printing step of ejecting a liquid onto a printed material to form a printing layer, and a heating step of heating the printed printed material, wherein the liquids are resin and water. The printing method has a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss, and in a heating step, the liquid is Let T _matte (°C) be the temperature of the matte print area to be printed in the matte gloss print mode when adhering to the print material, and the gloss print area to be printed in the gloss gloss print mode when the liquid is attached to the print material. When the temperature of the printed material is T _gloss (° C.), the following formula, T _matte >T _gloss , is heated so as to satisfy the glossiness of the printed material, Gm is the glossiness of the surface of the printed layer after printing. When Gp is used, in the case of the glossy print mode, the following formula is satisfied: Gp≧Gm, and other steps are included as necessary.

A printing method of the present invention is a printing method including a printing step of ejecting a liquid onto a printing material to form a printing layer, and a heating step of heating the printed printing material with a heating means, wherein the liquid is It is a clear ink containing a resin and water, and the printing method has a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss, and the matte Assuming that the temperature of the heating means in the gloss print mode is HT _matte (°C) and the temperature of the heating means in the gloss gloss print mode is HT _gloss (°C), the following expression, HT _matte >HT _gloss , is satisfied. Gm is the glossiness of the printed material after heating, and Gp is the glossiness of the surface of the printing layer after printing. In the case of the matte glossy print mode, the following formula, Gm≧Gp, is satisfied, and other steps are included as necessary.

Conventionally, in an inkjet recording apparatus using clear ink (UV clear ink) that is cured by irradiation with ultraviolet rays, there has been proposed a gloss control method capable of controlling the gloss to a matte tone or gloss tone by controlling the amount of irradiation light. .
However, the problem with UV clear ink is that it has a strong odor, and the odor remains on printed matter, so it is not suitable for printed matter for indoor use. For this reason, an environment in which the ink jet printing apparatus can be installed needs to be ventilated, and the installation places are limited. In addition, UV clear ink requires an ultraviolet irradiation device, which poses problems of increasing the size and cost of the device.

In the printing apparatus and printing method of the present invention, in the prior art of Patent Document 1, color ink containing a coloring material is used, and film formation control is performed according to the lowest film formation temperature at which film formation on the surface of the ink droplets is started by the heating means. Glossiness is adjusted by controlling the degree of film formation on the surface of the ink droplets by heating with temperature, but color inks containing colorants have sufficient glossiness compared to clear inks that do not contain colorants. This is based on the knowledge that no difference can be obtained and that both matte and gloss gloss control cannot be achieved.

The printing apparatus and printing method of the present invention use clear ink containing resin and water as the liquid, and perform both gloss control and matte gloss control by controlling the heating temperature. When matte gloss is applied, printing is performed at a higher temperature than in the gloss gloss application mode. Since the temperature during printing is high, the resin-containing clear ink suppresses wetting and spreading of dots, suppresses the coalescence of adjacent dots, and forms dots with a high dot sphere height (pile height). These dots form unevenness on the surface and impart a matte gloss.
On the other hand, when performing gloss glossing, printing is performed at a lower temperature than in the matte glossing mode. Since the printing temperature is low, the resin-containing water-based clear ink promotes wetting and spreading of dots and coalescence of adjacent dots, forming a smooth surface and imparting glossiness.

Therefore, the printing apparatus of the present invention uses a clear ink containing a resin and water as a liquid, and has a matte gloss print mode that is a print mode that imparts a matte gloss and a gloss gloss print mode that is a print mode that imparts a gloss gloss. and when the heating means attaches the liquid to the printing material, the temperature of the printing material in the matte printing area printed in the matte gloss printing mode is T _matte (° C.), and the liquid is attached to the printing material When the temperature of the printed material in the gloss printing area printed in the gloss gloss printing mode is T _gloss (° C.), the following formula: T _matte > T _gloss , or heating means in the matte gloss printing mode Let HT _matte (° _C ) be the _temperature of the heating means in the glossy gloss printing mode, and HT _gloss (°C) be the temperature of the heating means in the gloss gloss printing mode. Supports gloss control.

The heating means in the printing apparatus of the present invention heats the substrate so that the temperature of the substrate satisfies the following formula: T _matte >T _gloss , and the following formula: T _matte −T _gloss ≧10° C. More preferably, the heating is performed so as to satisfy the following formula: T _matte −T _gloss ≧20° C. Further, as the temperature HT (°C) of the heating means, the temperature of the heating means in the matte gloss printing mode is HT _matte (°C), and the temperature of the heating means in the glossy gloss printing mode is HT _gloss (°C). , HT _matte >HT _gloss , preferably HT _matte >HT _gloss ≧10° C., more preferably HT _matte >HT _gloss ≧20° C.
As a result, in the matte glossy print mode, the heating temperature is raised to suppress the wetting and spreading of the dots, forming dots with a high pile height and forming a surface with large unevenness. On the other hand, in the gloss-gloss print mode, the heating temperature can be lowered to promote wetting and spreading of the dots, and the coalescence of adjacent dots can form a smooth surface.
The temperature HT (° C.) of the heating means is not particularly limited and can be appropriately selected according to the purpose. For example, the set temperature of the heating means can be used.

The temperature T _matte (°C) of the printing material in the printing unit in the matte gloss printing mode is preferably 50°C or higher, more preferably 50°C or higher and 80°C or lower.
The temperature T _gloss (°C) of the printing material in the printing unit in the gloss/gloss printing mode is preferably 70°C or less, more preferably 60°C or less.
The temperature of the heating means in the matte gloss printing mode, HT _matte (°C), is preferably 50°C or higher, more preferably 50°C or higher and 80°C or lower.
The temperature of the heating means in the glossy printing mode, HT _gloss (°C), is preferably 70°C or less, more preferably 60°C or less.
By setting such a temperature range, it is possible to achieve a large change in glossiness in each print mode using water-based clear ink.
The temperature of the printed material in the printing unit can be measured, for example, by placing a thermocouple on the recording medium as the printed material and directly measuring the temperature of the recording medium, or by measuring the temperature of the heater that heats the recording medium. and a method in which the temperature around the recording medium is measured in a non-contact manner using a radiation thermometer or the like to obtain the recording medium temperature.

In the present invention, when the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp, in the case of the gloss gloss printing mode, the following expression Gp≧Gm is satisfied, and the matte gloss In the case of the print mode, it is preferable to satisfy the following expression, Gm≧Gp, and in the case of the gloss gloss print mode, it is preferable to satisfy the following expression, Gp−Gm≧20. In the case of the matte gloss print mode, It is preferable to satisfy the following expression, Gm−Gp≧30, and in the case of the gloss gloss print mode, it is more preferable to satisfy the following expression, Gp−Gm≧49, and in the case of the matte gloss print mode, the following expression More preferably, the formula Gm-Gp≧57 is satisfied.
When the difference in glossiness is within the above numerical range, the difference between the gloss gloss area and the matte gloss area and the surroundings can be clearly visually recognized.

<Root-mean-square slope Sdq>
ISO25178 indicates Sdq (root-mean-square slope) as one of the parameters representing the surface roughness of a defined area. A large value of Sdq means that there are many inclined portions or large inclined surfaces in the defined area. This leads to scattering of light on the slanted surface, resulting in a decrease in glossiness. Therefore, when imparting matte gloss, Sdq should be increased, and when imparting gloss gloss, Sdq should be decreased.
As a result of further investigation from this point, in the present invention, when the Sdq of the printed material is Sdqm and the Sdq of the surface of the printing layer after printing is Sdqp, in the case of the gloss/gloss printing mode, the following formula is obtained: Sdqm≧Sdqp, preferably satisfies the following formula: Sdqp≧Sdqm in the matte gloss print mode, and satisfies the following formula: Sdqm−Sdqp≧0.03 in the case of the gloss gloss print mode is more preferable, and in the case of the matte glossy print mode, it is more preferable to satisfy the following equation: Sdqp-Sdqm≧0.05. By setting the difference in Sdq within this range, the difference between the glossy glossy area and matte glossy area and the surroundings can be clearly visually recognized.
The root-mean-square slope Sdq can be obtained, for example, by measuring the ISO25178 surface properties (ISO25178 parameters) using a scanning white light microscope (manufactured by Hitachi High-Technologies Corporation, VS1530).

In the present invention, assuming that the print rate of a matte print image printed in the matte gloss print mode is D _matte , and the print rate of a gloss print image printed in the gloss gloss print mode is D _gloss , the following formula is D _gloss >D _matte. , and more preferably satisfy the following formula: D _gloss −D _matte >10%.
The higher the print rate, the easier it is to form a smooth surface, so an image with a high print rate is used in the gloss/glossy print mode. On the other hand, in the matte/gloss print mode, if the print rate is high, adjacent dots will merge, making it difficult to form surface irregularities, so an image with a low print rate is used.
Here, the print rate means the following: print rate (%) = number of clear ink print dots / (vertical resolution x horizontal resolution) x 100
(However, in the above formula, the "number of dots printed with clear ink" is the number of dots actually printed with clear ink per unit area, and the "vertical resolution" and "horizontal resolution" are the resolutions per unit area, respectively. When clear ink is printed so that the same dot position is printed, the "number of dots printed with clear ink" is the total number of dots actually printed with clear ink per unit area.)
Note that the print rate of 100% means the maximum single-color ink weight for a pixel.

<Ink container>
The ink containing portion contains ink.
The ink container is not particularly limited as long as it is a member capable of containing ink, and examples thereof include an ink container and an ink tank.
The ink storage container stores the ink therein, and further includes other members appropriately selected as necessary.
The container is not particularly limited, and its shape, structure, size, material, etc. can be appropriately selected according to the purpose. Those having at least are included.
Examples of ink tanks include a main tank and a sub-tank.

<Ejection head>
The ejection head ejects ink to form a print layer.
The ejection head has a nozzle plate, a pressure chamber, and a stimulus generator.

－Nozzle plate－
The nozzle plate has a nozzle substrate and an ink-repellent film on the nozzle substrate.

－Pressurized chamber－
The pressurizing chambers are a plurality of individual flow paths that are individually arranged corresponding to the plurality of nozzle holes provided in the nozzle plate and communicate with the nozzle holes. It may also be called a pressure chamber, a discharge chamber, a liquid chamber, or the like.

- Stimulus generating means -
The stimulus generating means is means for generating a stimulus to be applied to ink.
The stimulus in the stimulus generating means is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include heat (temperature), pressure, vibration and light. These may be used individually by 1 type, and may use 2 or more types together. Among these, heat and pressure are preferred.
Examples of the stimulation generating means include a heating device, a pressure device, a piezoelectric element, a vibration generator, an ultrasonic oscillator, and a light. Specifically, the stimulus generating means includes a piezoelectric actuator such as a piezoelectric element, a thermal actuator utilizing a phase change due to film boiling of ink using an electrothermal conversion element such as a heating resistor, and a metal phase change due to temperature change. and a shape memory alloy actuator using an electrostatic force, an electrostatic actuator using an electrostatic force, and the like.

When the stimulus is "heat", thermal energy corresponding to a recording signal is applied to the ink in the ink discharge head using, for example, a thermal head. A method of generating air bubbles in the ink by the thermal energy and ejecting the ink as droplets from the nozzle holes of the nozzle plate by the pressure of the air bubbles may be used.
When the stimulus is "pressure", for example, by applying a voltage to the piezoelectric element adhered to the position called the pressure chamber in the ink flow path in the ink ejection head, the piezoelectric element bends. . As a result, the volume of the pressure chamber shrinks, and the ink is ejected as droplets from the nozzle holes of the ink ejection head.
Among these, the piezo method in which a voltage is applied to a piezo element to cause ink to fly is preferable.

<Heating Means>
The heating means heats the material to be printed.
The heating means includes means for heating and drying the printing surface and the back surface of the recording medium as the printing material, examples of which include infrared heaters, hot air heaters, and heating rollers. These may be used individually by 1 type, and may use 2 or more types together.

The method for drying the recording medium as the material to be printed is not particularly limited and can be appropriately selected according to the purpose. a method of contacting a recording medium to which ink has been applied and a heating member to heat by heat transfer; a method of heating a recording medium to which ink has been applied by irradiating energy rays such as infrared rays and far infrared rays. etc.
Heating can occur before, during, and/or after printing.
Heating before and during printing enables printing on a heated medium, and heating after printing dries the printed material.
The heating time is not particularly limited as long as the surface temperature of the recording medium can be controlled to a desired temperature, and can be appropriately selected according to the purpose.
It is preferable to control the heating time by controlling the conveying speed of the recording medium as the material to be printed.

<Liquid>
A water-based clear ink is used as the liquid.
Clear ink means colorless and transparent ink that does not substantially contain a coloring material.
A water-based clear ink means a clear ink containing water as a solvent, and may contain an organic solvent as necessary.
The water-based clear ink contains water and a resin, preferably contains a surfactant, and further contains other components as necessary.

<<Water>>
The water is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include pure water such as ion-exchanged water, ultrafiltrated water, reverse osmosis water, distilled water, and ultrapure water. . These may be used individually by 1 type, and may use 2 or more types together.
The water content is preferably 15% by mass or more and 60% by mass or less with respect to the total amount of water-based clear ink. When the content is 15% by mass or more, it is possible to prevent the viscosity from becoming high and to improve the ejection stability. On the other hand, when it is 60% by mass or less, the wettability to the impermeable recording medium is favorable, and the image quality can be improved.

<<Resin>>
The resin is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyurethane resin, polyester resin, acrylic resin, vinyl acetate resin, styrene resin, butadiene resin, styrene-butadiene resin, and vinyl chloride resin. , acrylic-styrene resin, acrylic-silicone resin, and the like.
When producing the ink, it is preferable to add these resin particles as resin particles. The resin particles may be added to the ink in the form of a resin emulsion dispersed using water as a dispersion medium. As the resin particles, appropriately synthesized ones may be used, or commercially available products may be used. These may be used singly or in combination of two or more resin particles. Among these, polyurethane resins are preferred. By adding a polyurethane resin, when an ink film is formed using clear ink, the coating film itself becomes tough. As a result, it is preferable from the viewpoint that it is easy to suppress the change in the color of the friction part due to the breakage inside the coating film and the peeling of a part of the coating film, or the change in the surface condition of the coating film.

-Polyurethane Resin-
Examples of polyurethane resins include polyether-based polyurethane resins, polycarbonate-based polyurethane resins, and polyester-based polyurethane resins.

The polyurethane resin is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include polyurethane resins obtained by reacting polyol and polyisocyanate.

-Polyol-
Examples of the polyols include polyether polyols, polycarbonate polyols, and polyester polyols. These may be used individually by 1 type, and may use 2 or more types together.

-Polyether Polyol-
Examples of the polyether polyol include those obtained by addition polymerization of alkylene oxide using at least one compound having two or more active hydrogen atoms as a starting material.

Examples of compounds having two or more active hydrogen atoms include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, and 1,6-hexane. Diol, glycerin, trimethylolethane, trimethylolpropane and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran and the like. These may be used individually by 1 type, and may use 2 or more types together.

The polyether polyol is not particularly limited and can be appropriately selected depending on the intended purpose. Propylene glycol is preferred. These may be used individually by 1 type, and may use 2 or more types together.

-Polycarbonate polyol-
Polycarbonate polyols that can be used in the production of the polyurethane resin include, for example, those obtained by reacting carbonate ester and polyol, and those obtained by reacting phosgene with bisphenol A and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the carbonate include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1, 2-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 - octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydroquinone, resorcinol , bisphenol-A, bisphenol-F, 4,4′-biphenol, etc.; polyether polyols such as polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol; polyhexamethylene adipate, polyhexamethylene Examples include polyester polyols such as succinate and polycaprolactone. These may be used individually by 1 type, and may use 2 or more types together.

-Polyester Polyol-
Examples of the polyester polyol include those obtained by esterifying a low-molecular-weight polyol and polycarboxylic acid, polyesters obtained by ring-opening polymerization of cyclic ester compounds such as ε-caprolactone, and copolymerization thereof. Examples include polyester. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the low-molecular-weight polyols include ethylene glycol and propylene glycol. These may be used individually by 1 type, and may use 2 or more types together.
Examples of the polycarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, and anhydrides or ester-forming derivatives thereof. These may be used individually by 1 type, and may use 2 or more types together.

- Polyisocyanate -
Examples of the polyisocyanate include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate and naphthalene diisocyanate; Aliphatic or alicyclic diisocyanates such as diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate are included. These may be used individually by 1 type, and may use 2 or more types together. Among these, alicyclic diisocyanates are preferred from the viewpoint of weather resistance.

Furthermore, the use of at least one alicyclic diisocyanate makes it easier to obtain the desired coating film strength and abrasion resistance.
Examples of the alicyclic diisocyanate include isophorone diisocyanate and dicyclohexylmethane diisocyanate.
As content of the said alicyclic diisocyanate, 60 mass % or more is preferable with respect to the isocyanate compound whole quantity.

[Method for producing polyurethane resin]
Polyurethane resins are not particularly limited, and can be obtained by conventionally generally used production methods, such as the following methods.
First, in the absence of solvent or in the presence of an organic solvent, the polyol and the polyisocyanate are reacted at an equivalent ratio in which the isocyanate groups are excessive to produce an isocyanate-terminated urethane prepolymer.
Next, the anionic groups in the isocyanate-terminated urethane prepolymer are neutralized with a neutralizing agent if necessary, then reacted with a chain extender, and finally the organic solvent in the system is removed if necessary. can be obtained by

Examples of organic solvents that can be used for producing the polyurethane resin include ketones such as acetone and methyl ethyl ketone; ethers such as tetrahydrofuran and dioxane; acetic esters such as ethyl acetate and butyl acetate; nitriles such as acetonitrile; , N-methylpyrrolidone, and amides such as N-ethylpyrrolidone. These may be used individually by 1 type, and may use 2 or more types together.
Examples of the chain extender include polyamines and other active hydrogen group-containing compounds.

Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4′-dicyclohexylmethanediamine, and 1,4-cyclohexane. Diamines such as diamines; Polyamines such as diethylenetriamine, dipropylenetriamine and triethylenetetramine; Hydrazines such as hydrazine, N,N'-dimethylhydrazine and 1,6-hexamethylenebishydrazine; Dihydrazide succinate and dihydrazide adipic acid , glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of other active hydrogen group-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, Glycols such as saccharose, methylene glycol, glycerin and sorbitol; class; water and the like. These may be used singly or in combination of two or more as long as the storage stability of the ink is not lowered.

As the polyurethane resin, a polycarbonate-based polyurethane resin is preferable from the viewpoint of water resistance, heat resistance, abrasion resistance, weather resistance, and scratch resistance of images due to the high cohesive force of the carbonate group. In the case of the polycarbonate-based polyurethane resin, an ink suitable for recorded matter used in harsh environments such as outdoor applications can be obtained.

Commercially available products may be used as the polyurethane resin. Permaline UA-200 (polyether-based polyurethane resin) (manufactured by Sanyo Chemical Industries, Ltd.) and the like. These may be used individually by 1 type, and may use 2 or more types together.

The content of the resin contained in the clear ink is preferably 8% by mass or more, more preferably 8% by mass or more and 25% by mass or less. When the resin content is 8% by mass or more, matte gloss and gloss gloss can be controlled with a small amount of clear ink. On the other hand, if the resin content exceeds 25% by mass, the ejection stability of the ink may deteriorate.

The matte gloss is achieved by forming isolated dots with a high dot sphere height (pile height) and giving unevenness to the surface.
When the content of the resin in the clear ink is large, dots having a high pile height are likely to be formed, which is preferable because matte gloss is easily imparted.
On the other hand, the glossiness imparts smoothness by filling the unevenness of the surface with clear ink to form a smooth surface. In order to fill the unevenness of the surface with the clear ink, it is preferable that the resin content in the clear ink is high because the unevenness of the surface can be filled with a small amount of the clear ink, and glossiness can be easily imparted.

<Surfactant>
Clear ink preferably contains a surfactant.
By adding a surfactant to the ink, the surface tension is lowered, and the penetration of the ink droplets into the recording medium after landing on the paper or the like becomes faster, so feathering and color bleeding can be reduced. can be done.
Surfactants are classified into nonionic, anionic, and amphoteric according to the polarity of the hydrophilic group.
They are also classified into fluorine-based, silicone-based, acetylene-based, etc., depending on the structure of the hydrophobic group.
In the present invention, fluorine-based surfactants are mainly used, but silicone-based surfactants and acetylene-based surfactants may be used in combination.
The content of the surfactant is preferably 2% by mass or less, more preferably 0.05% by mass or more and 2% by mass or less, and still more preferably 0.1% by mass or more and 2% by mass or less. By setting the surfactant content to 2% by mass or less, a significant reduction in glossiness can be obtained in the matte gloss printing mode.

Any of silicone surfactants, fluorosurfactants, amphoteric surfactants, nonionic surfactants, and anionic surfactants can be used as surfactants.
The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the purpose. Among them, those that do not decompose even at high pH are preferable. Those having an oxyethylene group or a polyoxyethylene polyoxypropylene group are particularly preferred because they exhibit good properties as water-based surfactants. As the silicone-based surfactant, a polyether-modified silicone-based surfactant can also be used, and examples thereof include compounds in which a polyalkylene oxide structure is introduced into the side chain of the Si portion of dimethylsiloxane.
Examples of fluorine-based surfactants include perfluoroalkylsulfonic acid compounds, perfluoroalkylcarboxylic acid compounds, perfluoroalkylphosphoric acid ester compounds, perfluoroalkylethylene oxide adducts, and perfluoroalkyl ether groups in side chains. Polyoxyalkylene ether polymer compounds are particularly preferred due to their low foaming properties. Examples of the perfluoroalkylsulfonic acid compound include perfluoroalkylsulfonic acid and perfluoroalkylsulfonate. Examples of the perfluoroalkylcarboxylic acid compounds include perfluoroalkylcarboxylic acids and perfluoroalkylcarboxylic acid salts. As the polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain, a sulfate ester salt of a polyoxyalkylene ether polymer having a perfluoroalkyl ether group in a side chain, and a perfluoroalkyl ether group in a side chain Examples thereof include salts of polyoxyalkylene ether polymers. Counter ions _of salts _in these fluorosurfactants include Li, Na, _K , _NH4 , _NH3CH2CH2OH , _NH2 ( _CH2CH2OH ) _{2 ,} and NH( _CH2CH2OH ). ₃ and the like.
Amphoteric surfactants include, for example, laurylaminopropionate, lauryldimethylbetaine, stearyldimethylbetaine, lauryldihydroxyethylbetaine and the like.
Nonionic surfactants include, for example, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene alkylamines, polyoxyethylene alkylamides, polyoxyethylene propylene block polymers, sorbitan fatty acid esters, polyoxyethylene sorbitan Examples include fatty acid esters and ethylene oxide adducts of acetylene alcohol.
Examples of anionic surfactants include polyoxyethylene alkyl ether acetates, dodecylbenzene sulfonates, laurates, and salts of polyoxyethylene alkyl ether sulfates.
These may be used individually by 1 type, or may use 2 or more types together.

The silicone-based surfactant is not particularly limited and can be appropriately selected depending on the intended purpose. Examples include polydimethylsiloxane modified at both chain ends, and polyether-modified silicone-based surfactants having polyoxyethylene groups or polyoxyethylene-polyoxypropylene groups as modifying groups exhibit excellent properties as water-based surfactants. preferable.
As such a surfactant, an appropriately synthesized one may be used, or a commercially available product may be used. Commercially available products are available from, for example, BYK Chemie Co., Ltd., Shin-Etsu Chemical Co., Ltd., Dow Corning Toray Silicone Co., Ltd., Nihon Emulsion Co., Ltd., Kyoeisha Chemical Co., Ltd., and the like.
The above polyether-modified silicone-based surfactant is not particularly limited and can be appropriately selected according to the purpose. For example, a polyalkylene oxide structure represented by the following general formula (S-1) Examples include those introduced into the side chain of the Si portion of dimethylpolysiloxane.

（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。） [General formula (S-1)]

(However, in general formula (S-1), m, n, a, and b each independently represent an integer, R represents an alkylene group, and R' represents an alkyl group.)

Commercially available products can be used as the above polyether-modified silicone-based surfactants. -1906EX (manufactured by Nippon Emulsion Co., Ltd.), FZ-2105, FZ-2118, FZ-2154, FZ-2161, FZ-2162, FZ-2163, FZ-2164 (manufactured by Dow Corning Toray Silicone Co., Ltd.), BYK -33, BYK-387 (manufactured by BYK-Chemie Co., Ltd.), TSF4440, TSF4452, TSF4453 (manufactured by Toshiba Silicon Co., Ltd.) and the like.

As the fluorine-based surfactant, a fluorine-substituted compound having 2 to 16 carbon atoms is preferable, and a fluorine-substituted compound having 4 to 16 carbon atoms is more preferable.
Examples of fluorine-based surfactants include perfluoroalkyl phosphate ester compounds, perfluoroalkyl ethylene oxide adducts, and polyoxyalkylene ether polymer compounds having perfluoroalkyl ether groups in side chains. Among these, a polyoxyalkylene ether polymer compound having a perfluoroalkyl ether group in a side chain is preferable because of its low foamability, and in particular fluorine represented by the following general formulas (F-1) and (F-2) system surfactants are preferred.

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。 [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)]
_{CnF2n +1- CH2CH} (OH)CH2 _- O-( _CH2CH2O ) _{a -} Y
In the compound represented by the general formula (F-2), Y is H, or C _m F _2m+1 and m is an integer of 1 to 6, or CH ₂ CH(OH)CH ₂ —C _m F _2m+1 and m is an integer from 4 to 6, or C _p H _2p+1 where p is an integer from 1 to 19; n is an integer of 1-6. a is an integer from 4 to 14;

Commercially available products may be used as the fluorosurfactant.
Examples of commercially available products 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.); Fleurard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (both manufactured by Sumitomo 3M); Megafac F-470, F -1405, F-474 (both manufactured by Dainippon Ink and Chemicals); 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 Omnova), Unidyne DSN-403N (manufactured by Daikin Industries, Ltd.), etc. Among them, FS-3100, FS-34, FS-300 manufactured by Chemours Co., Ltd., from the viewpoint of remarkably improving good print quality, especially color development, penetrability to paper, wettability, and level dyeing. , Neos Co., Ltd. FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW, Omnova Polyfox PF-151N and Daikin Industries Co., Ltd. Unidyne DSN-403N is particularly preferred.

<<Organic solvent>>
The clear ink may contain an organic solvent. The organic solvent is not particularly limited and can be appropriately selected depending on the intended purpose. Examples thereof include water-soluble organic solvents. In addition, water solubility means dissolving 5g or more in 100g of water of 25 degreeC, for example.

Examples of water-soluble organic solvents include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 3 -methyl-1,3-butanediol, 3-methoxy-3-methylbutanol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,6 -Hexanediol, glycerin, 1,2,6-hexanetriol, 2-ethyl-1,3-hexanediol, ethyl 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, etc. Hydric alcohols: Polyhydric alcohols 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, propylene glycol monoethyl ether, and dipropylene glycol monomethyl ether Alkyl 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 nitrogen-containing heterocyclic compounds such as imidazolidinone, ε-caprolactam and γ-butyrolactone; amides such as formamide, N-methylformamide and N,N-dimethylformamide; amines such as monoethanolamine, diethanolamine and triethylamine; sulfur-containing compounds such as sulfoxide, sulfolane and thiodiethanol; propylene carbonate, ethylene carbonate and the like; These may be used individually by 1 type, and may use 2 or more types together.

The content of the organic solvent in the water-based clear ink is not particularly limited and can be appropriately selected according to the purpose. It is preferably 20% by mass or more and 60% by mass or less.

The water-based clear ink may optionally contain other components such as antifoaming agents, antiseptic agents, antirust agents, and pH adjusters.

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

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

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

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

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

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

In the present invention, it is preferable to use a printing material having a high glossiness in the matte gloss printing mode. A substrate having a high glossiness is preferable because the matte gloss effect of the clear ink is easily emphasized.
On the other hand, in the gloss/gloss print mode, it is preferable to use a printing material having a low glossiness. A substrate having a low glossiness is preferable because the glossiness effect of the clear ink is likely to be emphasized.
Therefore, when the glossiness of the printing material used in the matte gloss printing mode is G _matte and the glossiness of the printing material used in the gloss gloss printing mode is G _gloss , the following expression, G _matte > G _gloss , is preferably satisfied, It is more preferable to satisfy the following formula: G _matte −G _gloss ≧100.

(Method for controlling glossiness of printed image)
The printed image glossiness control method of the present invention includes:
A printing step of ejecting a liquid onto a printed material to provide a printing layer;
a heating step of heating the printed substrate;
A printed image glossiness control method comprising:
the liquid is clear ink containing resin and water;
The method for controlling glossiness of a printed image includes a matte gloss print mode that is a print mode for applying matte gloss and a gloss gloss print mode that is a print mode for applying gloss gloss,
When printing in the matte glossy print mode, control is performed to increase the root-mean-square slope Sdq of the print layer surface or to increase the heating temperature,
When printing in the glossiness printing mode, control is performed to reduce the root-mean-square gradient Sdq of the print layer surface or to lower the heating temperature.

(printed matter)
A printed material related to the present invention is a printed material having a printed material and a printed layer on the printed material,
The printed layer is made of a clear ink layer containing a resin,
The printed matter has a matte print image printed in a matte gloss print mode and a gloss print image printed in a gloss gloss print mode,
Let Gm be the glossiness of the printed material and Gp be the glossiness of the surface of the printing layer after printing. satisfies the following equation: Gm≧Gp.
An image can be formed by an inkjet printing device and an inkjet printing method to obtain a printed matter.

<Recording device, recording method>
In the following description of the recording apparatus and recording method, black (K) ink, cyan (C) ink, magenta (M) ink, and yellow (Y) ink are used. In addition to these, a water-based clear ink may be used.
The clear ink used in the present invention can be suitably used for various inkjet recording apparatuses, such as printers, facsimile machines, copiers, printer/fax/copier complex machines, stereolithography machines, and the like.
Unless otherwise specified, the printing apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Further, the printing apparatus includes not only a desk-top type but also a wide-width recording apparatus and, for example, a continuous paper printer capable of using continuous paper wound into a roll as a recording medium.
In the present invention, a recording apparatus and a recording method refer to a device capable of ejecting ink, various treatment liquids, and the like onto a recording medium, and a method of performing recording using the device. A recording medium means a medium to which ink and various treatment liquids can adhere even temporarily.
This recording apparatus can include not only a head portion for ejecting ink, but also means for feeding, conveying, and discharging a recording medium, and other devices called pre-processing devices and post-processing devices. .
Also, the recording apparatus and recording method are not limited to those that visualize significant images such as characters and graphics with ink. For example, it includes those that form patterns such as geometric patterns, and those that form three-dimensional images.
In addition, unless otherwise specified, the recording apparatus includes both a serial type apparatus in which the ejection head is moved and a line type apparatus in which the ejection head is not moved.
Furthermore, this recording device is not only a desktop type, but also a wide recording device that can print on A0 size recording media. A continuous feed printer is also included.
An example of a recording apparatus will be described with reference to FIGS. 1 and 2. FIG. FIG. 1 is a perspective explanatory view of a recording apparatus. FIG. 2 is a perspective explanatory view of the main tank. An image forming apparatus 400 as an example of a recording apparatus is a serial image forming apparatus. A mechanical unit 420 is provided inside the exterior 401 of the image forming apparatus 400 . Each ink container 411 of the main tank 410 (410k, 410c, 410m, 410y) for each color of black (K), cyan (C), magenta (M), and yellow (Y) is made of, for example, an aluminum laminated film. It is formed by a packaging member. The ink containing portion 411 is housed, for example, in a container case 414 made of plastic. Thus, the main tank 410 is used as an ink cartridge for each color.
On the other hand, a cartridge holder 404 is provided on the far side of the opening when the cover 401c of the apparatus main body is opened. A main tank 410 is detachably attached to the cartridge holder 404 . As a result, each ink discharge port 413 of the main tank 410 communicates with the ejection head 434 for each color via the supply tube 436 for each color, and ink can be ejected from the ejection head 434 onto the printing medium.

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

It should be noted that the method of using the ink is not limited to the ink jet recording method, and can be widely used. In addition to the inkjet recording method, for example, 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 can be used.

The use of the ink is not particularly limited and can be appropriately selected according to the purpose. Furthermore, 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 three-dimensional images (three-dimensional objects).
The three-dimensional modeling apparatus for modeling a three-dimensional object can use a known one, and is not particularly limited. be able to. The three-dimensional object includes a three-dimensional object obtained by applying ink repeatedly. It also includes a molded product obtained by processing a structure obtained by applying ink onto a base material such as a recording medium. The molded product is, for example, a sheet-shaped or film-shaped recorded matter or structure that is subjected to molding such as heat stretching or punching.・Suitably used for applications where molding is performed after the surface is decorated, such as electronic equipment, meters for cameras, and operation panels.

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

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

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

(Preparation Example 1)
<Preparation of Polycarbonate Polyurethane Resin Emulsion 1>
1,500 mass of polycarbonate diol (reaction product of 1,6-hexanediol and dimethyl carbonate (number average molecular weight (Mn): 1,200)) was added to a reaction vessel equipped with a stirrer, a reflux condenser, and a thermometer. 2,2-dimethylolpropionic acid (hereinafter sometimes referred to as “DMPA”) 220 parts by mass, and N-methylpyrrolidone (hereinafter sometimes referred to as “NMP”) 1,347 parts by mass of nitrogen The mixture was charged under an air current and heated to 60° C. to dissolve DMPA.
Next, 1,445 parts by mass of 4,4′-dicyclohexylmethane diisocyanate and 2.6 parts by mass of dibutyltin dilaurylate (catalyst) are added and heated to 90° C. for 5 hours to carry out a urethanization reaction to the isocyanate terminal. A urethane prepolymer was obtained. This reaction mixture was cooled to 80° C., 149 parts by mass of triethylamine was added thereto, 4,340 parts by mass of the mixture was extracted, and 5,400 parts by mass of water and 15 parts by mass of triethylamine were stirred under strong stirring. was added into the mixed solution of
Next, 1,500 parts by mass of ice is added, and 626 parts by mass of a 35% by mass 2-methyl-1,5-pentanediamine aqueous solution is added to carry out a chain extension reaction so that the solid content concentration becomes 30% by mass. The solvent was distilled off to obtain a polycarbonate-based polyurethane resin emulsion 1.
The minimum film-forming temperature of the obtained polycarbonate-based polyurethane resin emulsion was 55° C. when measured with a "film-forming temperature tester" (manufactured by Imoto Seisakusho Co., Ltd.).

(Preparation Example 2)
<Preparation of acrylic resin emulsion 1>
A reaction vessel equipped with a stirrer, a reflux condenser, a dropping device, and a thermometer was charged with 900 parts by mass of ion-exchanged water and 1 part by mass of sodium lauryl sulfate, and the temperature was raised to 70°C while stirring and replacing with nitrogen. The internal temperature was kept at 70° C., 4 parts by mass of potassium persulfate was added as a polymerization initiator, and after dissolution, 450 parts by mass of deionized water, 3 parts by mass of sodium lauryl sulfate, 20 parts by mass of acrylamide, 365 parts by mass of styrene, An emulsion prepared by adding 545 parts by mass of butyl acrylate and 10 parts by mass of methacrylic acid while stirring was added dropwise to the reaction solution continuously over 4 hours. After completion of dropping, the mixture was held for 3 hours. After the resulting aqueous emulsion was cooled to room temperature, ion-exchanged water and an aqueous sodium hydroxide solution were added to adjust the pH to 8, thereby obtaining acrylic resin emulsion 1 (solid concentration: 30% by mass).

(Production example 1)
-Production of Clear Ink A-
Polyurethane resin emulsion 1 of Preparation Example 1 (solid content concentration: 30% by mass) 25% by mass, 19% by mass 1,2-propanediol, 11% by mass 1,3-propanediol, 3% by mass 1,2-butanediol , 6% by mass of the product name "FS-300" (manufactured by DuPont, fluorine-based surfactant, solid content concentration 40% by mass) as a surfactant, and 36% by mass of high-purity water are added, mixed and stirred to prepare a mixture. bottom.
Next, the obtained mixture was filtered through a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M) to prepare clear ink A.

(Production Examples 2 to 5)
-Production of clear inks B to E-
Clear inks B to E were prepared in the same manner as in Production Example 1, except that the ink composition was changed to that shown in Table 1.

(Production example 6)
-Manufacture of magenta ink-
<Preparation of self-dispersion type magenta pigment dispersion>
After premixing the following formulation mixture, a disk-type bead mill (manufactured by Shinmaru Enterprises Co., Ltd., KDL type, media: using zirconia balls with a diameter of 0.3 mm) is circulated for 7 hours to obtain a self-dispersing magenta pigment dispersion. (Pigment solid content concentration: 15% by mass) was obtained.
Pigment Red 122 (trade name: Toner Magenta EO02, manufactured by Clariant Japan Co., Ltd.)...15 parts by mass Anionic surfactant (trade name: Pionin A-51-B, manufactured by Takemoto Oil Co., Ltd.)... 2 parts by mass ・Ion-exchanged water ... 83 parts by mass

<Production of magenta ink>
Polyurethane resin emulsion 1 of Preparation Example 1 (solids concentration: 30% by mass) 25% by mass, self-dispersing magenta pigment dispersion (pigment solids concentration: 15% by mass) 20% by mass, 1,2-propanediol 20% by mass %, 11% by mass of 1,3-propanediol, 3% by mass of 1,2-butanediol, and as a surfactant, the trade name "FS-300" (manufactured by DuPont, fluorine-based surfactant, solid content concentration of 40% by mass. ) and 15% by mass of high-purity water were added and mixed and stirred to prepare a mixture.
Then, the resulting mixture was filtered through a polypropylene filter having an average pore size of 0.2 μm (trade name: Betafine polypropylene pleated filter PPG series, manufactured by 3M) to prepare a magenta ink.

( Reference example 1)
<Inkjet printing>
An ink cartridge of a modified inkjet printer GXe5500 (manufactured by Ricoh Co., Ltd.) was filled with the clear ink A of Production Example 1, and the ink cartridge filled with the ink was mounted on the modified inkjet printer GXe5500 to carry out inkjet printing.
The inkjet printer GXe5500 modified machine was provided with a heater (temperature control controller, model MTCD, manufactured by Misumi Co., Ltd.) so that the back surface of the recording medium can be heated before, during, and after printing. As a result, it is possible to print on the recording medium heated by the heater before and during printing, and to heat and dry the printed matter by the heater after printing.
Printing was performed by changing the type of recording medium, the heating conditions, and the printed image in the gloss gloss print mode and the mat gloss print mode.

-recoding media-
In the gloss gloss print mode, synthetic paper VJFN160 manufactured by Yupo Co., Ltd. (white polypropylene film, glossiness 16 (60° gloss value)) was used as the recording medium 1 .
In the matte glossy print mode, a window film GIY-0305 (transparent polyethylene terephthalate (PET) film, glossiness 159 (60° gloss value)) manufactured by Lintec Sign Systems Co., Ltd. was used as the recording medium 2 .

-Heating conditions-
As for the heating conditions, the heating temperatures of the heaters (heating means) arranged before, during, and after printing were set to 60° C., 60° C., and 70° C. in the gloss gloss printing mode. In the matte gloss printing mode, the heating temperature of each heater (heating means) was set to 65°C, 65°C, and 70°C. When measuring the temperature of the recording medium during printing, the recording medium temperature (=T _gloss ) in the gloss gloss print mode is 59° C., and the temperature of the heating means (=HT _gloss (° C.)) in the gloss gloss print mode during printing. is 60°C. Further, when measuring the temperature of the recording medium during printing, the recording medium temperature (=T _matte ) in the matte gloss print mode is 64° C., and the temperature of the heating means in the matte gloss print mode (=HT _matte (°C )) is 65°C.
The temperature of the recording medium during printing was measured using a digital radiation temperature sensor FT-H10 (manufactured by Keyence Corporation).
The image printed in the gloss gloss print mode was a solid image with an image resolution of 600 dpi×600 dpi and a print rate of 100%.
The image printed in the matte gloss print mode was a halftone image with an image resolution of 600 dpi×600 dpi and a print rate of 40%.

-Print rate-
Note that the print rate here means the following.
Print rate (%) = number of clear ink print dots/(vertical resolution x horizontal resolution) x 100
(However, in the above formula, the "number of dots printed with clear ink" is the number of dots actually printed with clear ink per unit area, and the "vertical resolution" and "horizontal resolution" are the resolutions per unit area, respectively. When printing with clear ink overlaid so that the same dot position is printed, the "number of dots printed with clear ink" is the total number of dots actually printed with clear ink per unit area.)
Clear ink A was printed directly on the recording medium in both the matte gloss print mode and the gloss gloss print mode.
Next, the glossiness and the root-mean-square slope Sdq of the resulting prints were measured as follows to evaluate the glossiness. Table 3 shows the results.

<Glossiness>
The 60° gloss value of the resulting printed matter was measured using a glossiness measuring instrument (Micro Trigloss, manufactured by BYK). At this time, the glossiness was measured at arbitrary three points on the surface of the printed area printed with clear ink A on the printed matter, and the average value was defined as Gp, and the glossiness of the surface of the recording medium in the non-printed area was defined as Gm.

<Root-mean-square slope Sdq>
The ISO25178 surface properties (ISO25178 parameters) of the obtained print were measured using a scanning white-light microscope (VS1530, manufactured by Hitachi High-Technologies Corporation) at an arbitrary point on the printed part. At this time, the Sdq of the surface of the printed part printed with the clear ink A of the printed material is Sdqp, the Sdq of the surface of the recording medium of the non-printed part is Sdqm, Sdqm - Sdqp in the case of the gloss gloss print mode, and Sdqm - Sdqp in the matte gloss print mode In some cases, the value of Sdqp-Sdqm was obtained.

<Glossiness (glossy or matte)>
The resulting prints were visually evaluated based on the following criteria. Glossy feeling was evaluated in the gloss gloss printing mode, and matte feeling was evaluated in the matte glossy printing mode. In addition, A and B were set as the pass, and C was set as the failure.
[Evaluation criteria]
A: Areas printed with clear ink have a clearer glossy or matte feel than areas not printed with clear ink. B: Areas printed with clear ink have a stronger gloss or matte feel than areas not printed with clear ink. , cannot be seen unless clearly seen C: Clear ink printed part does not feel glossy or matte feeling than clear ink unprinted part, or feels weak

( Reference example 2)
In Reference Example 1, the image printed in the gloss gloss print mode is changed to a halftone image with an image resolution of 600 dpi × 600 dpi and a print rate of 75%, and the image printed in the matte gloss print mode is changed to a halftone image with an image resolution of 600 dpi × Inkjet printing was performed in the same manner as in Reference Example 1, except that the image was changed to a halftone image with a print rate of 80% at 600 dpi.
Glossiness and root-mean-square slope Sdq of the obtained prints were measured in the same manner as in Reference Example 1 to evaluate glossiness. Table 3 shows the results.

(Example 3)
In Reference Example 1, the heating temperature of each heater before printing, during printing, and after printing is set to 50° C., 50° C., and 70° C. in the gloss gloss print mode, and each heater is set in the mat gloss print mode. Inkjet printing was performed in the same manner as in Reference Example 1, except that the heating temperature of was set to 70°C, 70°C, and 70°C.
The glossiness and the root-mean-square slope Sdq of the resulting prints were measured in the same manner as in Reference Example 1 to evaluate the glossiness. Table 3 shows the results.
Incidentally, when the recording medium temperature during printing is measured, the recording medium temperature (=T _gloss ) in the gloss gloss printing mode is 49° C., and the temperature of the heating means in the gloss gloss printing mode (=HT _gloss (° C.) ) is 50°C. Further, when measuring the temperature of the recording medium during printing, the recording medium temperature (=T _matte ) in the matte gloss print mode is 68° C., and the temperature of the heating means in the matte gloss print mode (=HT _matte (°C )) is 70°C.

(Example 4)
Inkjet printing was performed in the same manner as in Example 3 except that the clear ink A of Production Example 1 was changed to the clear ink B of Production Example 2.
The glossiness and the root-mean-square slope Sdq of the resulting prints were measured in the same manner as in Reference Example 1 to evaluate the glossiness. Table 3 shows the results.

(Example 5)
Inkjet printing was performed in the same manner as in Example 3, except that the clear ink A of Production Example 1 was changed to the clear ink C of Production Example 3.
The glossiness and the root-mean-square slope Sdq of the resulting prints were measured in the same manner as in Reference Example 1 to evaluate the glossiness. Table 3 shows the results.

(Example 6)
Inkjet printing was performed in the same manner as in Example 3, except that the clear ink A of Production Example 1 was changed to the clear ink D of Production Example 4.
The glossiness and the root-mean-square slope Sdq of the resulting prints were measured in the same manner as in Reference Example 1 to evaluate the glossiness. Table 3 shows the results.

(Example 7)
Inkjet printing was performed in the same manner as in Example 3, except that the clear ink A of Production Example 1 was changed to the clear ink E of Production Example 5.
The glossiness and the root-mean-square slope Sdq of the resulting prints were measured in the same manner as in Reference Example 1 to evaluate the glossiness. Table 3 shows the results.

(Example 8)
Inkjet printing was performed in the same manner as in Example 7, except that the recording medium printed with the magenta ink of Production Example 6 was used. That is, the clear ink E was printed on the coating film printed with the magenta ink.
The magenta ink of Production Example 6 was used as the magenta ink printed on the recording medium. The magenta ink was printed using the same printing apparatus as clear ink E, and the magenta ink film used in the gloss/gloss printing mode was heated at 50°C, 50°C, and 50°C for each heater before, during, and after printing. and 70° C., and the heating temperature of each heater for the magenta ink coating film used in the matte gloss printing mode was set to 70° C., 70° C., and 70° C., and only the magenta ink was printed on the recording medium. All of the magenta printed images were solid images with an image resolution of 600 dpi×600 dpi and a print rate of 100%.
Clear ink E was printed again on the recording medium printed with this magenta ink coating film by the printing apparatus.
The glossiness of the resulting printed matter was measured in the same manner as in Reference Example 1. Table 3 shows the results.

(Comparative example 1)
In Reference Example 1, the image printed in the gloss gloss print mode is changed to a halftone image with an image resolution of 600 dpi × 600 dpi and a print rate of 80%, and the image printed in the matte gloss print mode is changed to an image resolution of 600 dpi × Change to a halftone image with a print rate of 80% at 600dpi, and set the heating conditions to 70°C, 70°C, and 70°C for each heater before, during, and after printing in the gloss/gloss print mode. Inkjet printing was performed in the same manner as in Reference Example 1, except that the heating temperature of each heater was set to 55° C., 55° C., and 70° C. in the matte gloss printing mode.
The glossiness and the root-mean-square slope Sdq of the resulting prints were measured in the same manner as in Reference Example 1 to evaluate the glossiness. Table 3 shows the results.
Incidentally, when measuring the recording medium temperature during printing, the recording medium temperature (=T _gloss ) in the gloss gloss printing mode is 68° C., and the temperature of the heating means (=HT _gloss (° C.) in the gloss gloss printing mode during printing ) is 70°C. Further, when the temperature of the recording medium during printing is measured, the recording medium temperature (=T _matte ) in the matte gloss print mode is 54° C., and the temperature of the heating means in the matte gloss print mode (=HT _matte (°C )) is 55°C.

(Comparative example 2)
In Reference Example 1, the image printed in the gloss print mode is changed to a halftone image with an image resolution of 600 dpi × 600 dpi and a print rate of 50%, and the image printed in the matte gloss print mode is changed to an image resolution of 600 dpi × Change to a halftone image with a print rate of 80% at 600dpi, and set the heating conditions to 70°C, 70°C, and 70°C for each heater before, during, and after printing in the gloss/gloss print mode. Inkjet printing was performed in the same manner as in Reference Example 1, except that the heating temperature of each heater was set to 40° C., 40° C., and 70° C. in the matte gloss printing mode.
The glossiness and the root-mean-square slope Sdq of the resulting prints were measured in the same manner as in Reference Example 1 to evaluate the glossiness. Table 3 shows the results.
Incidentally, when measuring the recording medium temperature during printing, the recording medium temperature (=T _gloss ) in the gloss gloss printing mode is 68° C., and the temperature of the heating means (=HT _gloss (° C.) in the gloss gloss printing mode during printing ) is 70°C. Further, when measuring the temperature of the recording medium during printing, the recording medium temperature (=T _matte ) in the matte gloss print mode is 40° C., and the temperature of the heating means in the matte gloss print mode (=HT _matte (°C )) is 40°C.

(Comparative Example 3)
In Reference Example 1, the magenta ink of Production Example 6 was printed on the recording medium using a full solid image printed in the gloss print mode. The same all-solid image was used in both the matte gloss print mode and the gloss gloss print mode. The magenta ink is printed with the same printing device as the clear ink, and in the gloss/gloss print mode, the heating temperature of each heater before, during, and after printing is set to 50°C, 50°C, and 70°C. In the glossy print mode, the heating temperature of each heater was set to 70° C., 70° C., and 70° C., and inkjet printing of a magenta ink image was performed.
Glossiness and root-mean-square slope Sdq of the obtained prints were measured in the same manner as in Reference Example 1 to evaluate glossiness. Table 3 shows the results.
Incidentally, when the recording medium temperature during printing is measured, the recording medium temperature (=T _gloss ) in the gloss gloss printing mode is 49° C., and the temperature of the heating means in the gloss gloss printing mode during printing (=HT _gloss (° C.) ) is 50°C. Further, when measuring the temperature of the recording medium during printing, the recording medium temperature (=T _matte ) in the matte gloss print mode is 68° C., and the temperature of the heating means in the matte gloss print mode (=HT _matte (°C )) is 70°C.

From the results in Tables 2 and 3, it can be seen that the same ink can be used with different printing rates and heating temperatures in terms of glossiness, according to a comparison of Reference Examples 1-2 and Examples 3-8 with Comparative Examples 1 and 2. , it was found that the glossiness can be changed.
As for Sdq, according to a comparison between Actual Reference Examples 1 and 2, Examples 3 and 8, and Comparative Examples 1 and 2, Sdq is generally large for those with low glossiness, and conversely, Sdq is large for those with high glossiness. We found that it tends to be small.
Regarding glossiness, according to a comparison between Reference Examples 1 and 2, Examples 3 and 8, and Comparative Examples 1 and 2, Sdqm≧Sdqp in the case of gloss gloss printing mode, and Sdqp≧Sdqm in the case of matte gloss printing mode. It was found that sufficient glossiness and matteness can be obtained by increasing the thickness. Further, according to the comparison of Reference Examples 1 and 2 and Examples 3 to 8, Sdqm-Sdqp≧0.03 in the case of gloss gloss print mode and Sdqp-Sdqm≧0.05 in the case of matte gloss print mode are satisfied. Thus, it was found that a more excellent glossiness and mattness can be obtained. In addition, according to a comparison of Example 8 and Comparative Example 3, compared to the case of printing only with color ink, printing with clear ink on top of color ink causes a greater difference in glossiness, and is superior. It was found that a glossy feeling and a matte feeling could be produced.

Embodiments of the present invention are, for example, as follows.
<1> a liquid storage unit that stores a liquid;
an ejection head that ejects a liquid to form a print layer;
a heating means for heating the material to be printed;
A printing device comprising:
the liquid is clear ink containing resin and water;
The printing device has a matte gloss print mode, which is a print mode for applying matte gloss, and a gloss gloss print mode, which is a print mode for applying gloss gloss,
T _matte (° C.) is the temperature of the printing material in the matte printing area printed in the matte gloss printing mode when the heating means attaches the liquid to the printing material, and Assuming that the temperature of the printed material in the gloss printing area printed in the gloss gloss printing mode is T _gloss (° C.), the following formula, T _matte >T _gloss , is heated so as to satisfy,
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte glossy print mode, the printing apparatus satisfies the following equation: Gm≧Gp.
<2> a liquid storage unit that stores a liquid;
an ejection head that ejects a liquid to form a print layer;
a heating means for heating the material to be printed;
A printing device comprising:
the liquid is clear ink containing resin and water;
The printing device has a matte gloss print mode, which is a print mode for applying matte gloss, and a gloss gloss print mode, which is a print mode for applying gloss gloss,
Assuming that the temperature of the heating means in the matte gloss printing mode is HT _matte (°C) and the temperature of the heating means in the glossy gloss printing mode is HT _gloss (°C), the following expression, HT _matte > HT _gloss , is satisfied. heated as
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte glossy print mode, the printing apparatus satisfies the following equation: Gm≧Gp.
<3> In the case of the gloss gloss print mode, the following expression, Gp−Gm≧20, is satisfied,
In the case of the matte gloss print mode, the printing apparatus according to any one of <1> to <2>, which satisfies the following formula: Gm−Gp≧30.
<4> When the root-mean-square gradient Sdq of the printed material is Sdqm, and the root-mean-square gradient Sdq of the printing layer surface after printing is Sdqp,
In the case of the gloss gloss print mode, the following expression, Sdqm≧Sdqp, is satisfied,
In the case of the matte gloss print mode, the printing apparatus according to any one of <1> to <3>, which satisfies the following equation: Sdqp≧Sdqm.
<5> In the case of the gloss gloss print mode, the following expression, Sdqm-Sdqp≧0.03, is satisfied,
The printing apparatus according to <4>, satisfying the following expression: Sdqp−Sdqm≧0.05 in the case of the matte glossy print mode.
<6> _Let G _matte be the glossiness of the printing material used in the matte gloss printing mode _, and G _gloss be the glossiness of the printing material used in the gloss gloss printing mode. The printing apparatus according to any one of <1> to <5>.
<7> The printing apparatus according to any one of <1> to <6>, wherein the resin content in the clear ink is 8% by mass or more.
<8> The printing apparatus according to any one of <1> to <7>, wherein the resin is a polyurethane resin.
<9> The printing apparatus according to any one of <1> to <8>, wherein the clear ink further contains a surfactant, and the content of the surfactant is 2% by mass or less.
<10> The printing apparatus according to <9>, wherein the surfactant is a fluorosurfactant.
<11> A printing step of ejecting a liquid onto an object to be printed to provide a printing layer;
a heating step of heating the printed substrate;
A printing method comprising
the liquid is clear ink containing resin and water;
The printing method has a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss,
In the heating step, the temperature of the substrate in the matte printing area printed in the matte gloss printing mode when the liquid is attached to the substrate is T _matte (° C.), and the liquid is attached to the substrate. Assuming that the temperature of the printed material in the gloss printing area printed in the gloss gloss printing mode is T _gloss (° C.), the following formula, T _matte >T _gloss , is heated so as to satisfy,
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte gloss print mode, the printing method is characterized by satisfying the following equation: Gm≧Gp.
<12> A printing step of ejecting a liquid onto a printed material to provide a printing layer;
a heating step of heating the printed substrate with heating means;
A printing method comprising
the liquid is clear ink containing resin and water;
The printing method has a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss,
Assuming that the temperature of the heating means in the matte gloss printing mode is HT _matte (°C) and the temperature of the heating means in the glossy gloss printing mode is HT _gloss (°C), the following expression, HT _matte > HT _gloss , is satisfied. heated as
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte gloss print mode, the printing method is characterized by satisfying the following equation: Gm≧Gp.
<13> In the case of the gloss gloss print mode, the following expression, Gp−Gm≧20, is satisfied,
In the case of the matte glossy print mode, the printing method according to any one of <11> to <12>, which satisfies the following formula: Gm−Gp≧30.
<14> When the root-mean-square gradient Sdq of the printed material is Sdqm, and the root-mean-square gradient Sdq of the printing layer surface after printing is Sdqp,
In the case of the gloss gloss print mode, the following expression, Sdqm≧Sdqp, is satisfied,
In the case of the matte gloss print mode, the printing method according to any one of <11> to <13>, which satisfies the following equation: Sdqp≧Sdqm.
<15> In the case of the gloss gloss print mode, the following expression, Sdqm−Sdqp≧0.03, is satisfied,
In the case of the matte glossy print mode, the printing method according to <14>, which satisfies the following equation: Sdqp-Sdqm≧0.05.
<16> Let G _matte be the glossiness of the printing _material used in _the matte gloss printing mode, and G _gloss be the glossiness of the printing material used in the gloss gloss printing mode. The printing method according to any one of <11> to <15>.
<17> The printing method according to any one of <11> to <16>, wherein the resin content in the clear ink is 8% by mass or more.
<18> The printing method according to any one of <11> to <17>, wherein the resin is a polyurethane resin.
<19> The printing method according to any one of <11> to <18>, wherein the clear ink further contains a surfactant, and the content of the surfactant is 2% by mass or less.
<20> The printing method according to <19>, wherein the surfactant is a fluorosurfactant.
<21> A printing step of ejecting a liquid onto an object to be printed to provide a printing layer;
a heating step of heating the printed substrate;
A printed image glossiness control method comprising:
the liquid is clear ink containing resin and water;
The method for controlling the glossiness of a printed image includes a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss,
When printing in the matte glossy print mode, control is performed to increase the root-mean-square slope Sdq of the print layer surface or to increase the heating temperature,
In the glossiness control method for a printed image, when printing is performed in the glossiness printing mode, the root-mean-square gradient Sdq of the print layer surface is reduced or the heating temperature is lowered.

By the printing apparatus according to any one of <1> to <10>, the printing method according to any one of <11> to <20>, and the glossiness control method for a printed image according to <21> Then, various problems in the conventional art can be solved and the object of the present invention can be achieved.

400 Image forming apparatus 401 Exterior 401c Cover 404 Cartridge holder 410, 410k, 410c, 410m, 410y Main tank 411 Ink container 413 Ink outlet 414 Container case 420 Mechanism 434 Ejection head 436 Supply tube L Ink container

JP 2015-3397 A

Claims (11)

a liquid storage unit that stores liquid;
an ejection head that ejects a liquid to form a print layer;
a heating means for heating the material to be printed;
A printing device comprising:
the liquid is clear ink containing resin and water;
The printing device has a matte gloss print mode, which is a print mode for applying matte gloss, and a gloss gloss print mode, which is a print mode for applying gloss gloss,
T _matte (° C.) is the temperature of the printing material in the matte printing area printed in the matte gloss printing mode when the heating means attaches the liquid to the printing material, and Assuming that the temperature of the printed material in the gloss printing area printed in the gloss gloss printing mode is T _gloss (° C.), the following formula, T _matte >T _gloss , is heated so as to satisfy,
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte glossy print mode, the following expression, Gm≧Gp, is satisfied,
Let D _matte be the print rate of the matte print image printed in the matte gloss print mode, and let D gloss be the print rate of the gloss print image printed _in the gloss _gloss print mode _. ,
Let Sdqm be the root-mean-square gradient Sdq of the material to be printed, and Sdqp be the root-mean-square gradient Sdq of the printed layer surface after printing.
In the case of the gloss gloss print mode, the following expression, Sdqm-Sdqp≧0.03, is satisfied,
A printing apparatus characterized by satisfying the following formula: Sdqp-Sdqm≧0.05 in the case of the matte glossy print mode . a liquid storage unit that stores liquid;
an ejection head that ejects a liquid to form a print layer;
a heating means for heating the material to be printed;
A printing device comprising:
the liquid is clear ink containing resin and water;
The printing device has a matte gloss print mode, which is a print mode for applying matte gloss, and a gloss gloss print mode, which is a print mode for applying gloss gloss,
Assuming that the temperature of the heating means in the matte gloss printing mode is HT _matte (°C) and the temperature of the heating means in the glossy gloss printing mode is HT _gloss (°C), the following expression, HT _matte > HT _gloss , is satisfied. heated as
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte glossy print mode, the following expression, Gm≧Gp, is satisfied,
Let D _matte be the print rate of the matte print image printed in the matte gloss print mode, and let D gloss be the print rate of the gloss print image printed _in the gloss _gloss print mode _. ,
Let Sdqm be the root-mean-square gradient Sdq of the material to be printed, and Sdqp be the root-mean-square gradient Sdq of the printed layer surface after printing.
In the case of the gloss gloss print mode, the following expression, Sdqm-Sdqp≧0.03, is satisfied,
A printing apparatus characterized by satisfying the following formula: Sdqp-Sdqm≧0.05 in the case of the matte glossy print mode . In the case of the gloss gloss print mode, the following formula, Gp−Gm≧20, is satisfied,
3. The printing apparatus according to any one of claims 1 and 2, wherein in the case of the matte glossy print mode, the following formula is satisfied: Gm-Gp≧30. the following formula, D _gloss -D _matte >10%. the following formula, T _matte -T _gloss 2. The printing apparatus according to claim 1, wherein the heating is performed so as to satisfy .gtoreq.10.degree. 6. The printing apparatus according to any one of claims 1 to 5, wherein the content of the resin in the clear ink is 8% by mass or more. 7. The printing apparatus according to any one of claims 1 to 6, wherein said resin is polyurethane resin. The printing apparatus according to any one of claims 1 to 7, wherein the clear ink further contains a surfactant, and the content of the surfactant is 2% by mass or less. A printing step of ejecting a liquid onto an object to be printed to provide a printing layer;
a heating step of heating the printed substrate;
A printing method comprising
the liquid is clear ink containing resin and water;
The printing method has a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss,
In the heating step, the temperature of the substrate in the matte printing area printed in the matte gloss printing mode when the liquid is attached to the substrate is T _matte (° C.), and the liquid is attached to the substrate. Assuming that the temperature of the printed material in the gloss printing area printed in the gloss gloss printing mode is T _gloss (° C.), the following formula, T _matte >T _gloss , is heated so as to satisfy,
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte glossy print mode, the following expression, Gm≧Gp, is satisfied,
Let D _matte be the print rate of the matte print image printed in the matte gloss print mode, and let D gloss be the print rate of the gloss print image printed _in the gloss _gloss print mode _. ,
Let Sdqm be the root-mean-square gradient Sdq of the printed material, and Sdqp be the root-mean-square gradient Sdq of the printed layer surface after printing.
In the case of the gloss gloss print mode, the following expression, Sdqm-Sdqp≧0.03, is satisfied,
A printing method characterized by satisfying the following formula: Sdqp−Sdqm≧0.05 in the case of the matte glossy print mode . A printing step of ejecting a liquid onto an object to be printed to provide a printing layer;
a heating step of heating the printed substrate with heating means;
A printing method comprising
the liquid is clear ink containing resin and water;
The printing method has a matte gloss print mode that is a print mode that imparts matte gloss and a gloss gloss print mode that is a print mode that imparts gloss gloss,
Assuming that the temperature of the heating means in the matte gloss printing mode is HT _matte (°C) and the temperature of the heating means in the glossy gloss printing mode is HT _gloss (°C), the following expression, HT _matte > HT _gloss , is satisfied. heated as
Assuming that the glossiness of the printed material is Gm and the glossiness of the surface of the printing layer after printing is Gp,
In the case of the gloss gloss print mode, the following expression, Gp≧Gm, is satisfied,
In the case of the matte glossy print mode, the following expression, Gm≧Gp, is satisfied,
Let D _matte be the print rate of the matte print image printed in the matte gloss _print mode, and let D _gloss be the print rate of the gloss print image printed in the _{gloss gloss} print mode. ,
Let Sdqm be the root-mean-square gradient Sdq of the material to be printed, and Sdqp be the root-mean-square gradient Sdq of the printed layer surface after printing.
In the case of the gloss gloss print mode, the following expression, Sdqm-Sdqp≧0.03, is satisfied,
A printing method characterized by satisfying the following formula: Sdqp−Sdqm≧0.05 in the case of the matte glossy print mode . the following formula, D _gloss -D _matte >10%.

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