JP2018035294A - Process liquid, process liquid cartridge, ink set, ink cartridge set, recording device, recording method, and process recording medium - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process liquid that can form both of an image with a narrow line width and a solid image with excellent uniformity even on a recording medium with low ink permeability.SOLUTION: A process liquid has a pH of 5 or more and 9 or less and contains a thermal acid generator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a processing liquid, a processing liquid cartridge, an ink set, an ink cartridge set, a recording apparatus, a recording method, and a processing recording medium.

Inkjet printing technology has been greatly increasing in recent years in the printing field because it is easy to increase the width and speed.
In particular, there is an increasing demand for recording using an ink-jet ink (water-based ink-jet ink) containing water on a recording medium (low-penetration recording medium, non-penetrable recording medium) such as a coated paper for printing, which has a slow liquid penetration.

As conventional ink sets or image forming methods, for example, those described in Patent Documents 1 to 3 are known.
For example, Patent Document 1 discloses that “an ink composition containing a colorant, poly (vinylpyridine) salt, polyalkylaminoethyl acrylate, polyalkylaminoethyl methacrylate, poly (vinylimidazole), polyethyleneimine, polybiguanide, and An ink set comprising at least one cationic polymer selected from polyguanides and a treatment liquid containing an acid generator has been proposed.

Patent Document 2 states that, “In an image forming method for forming an image by discharging an inkjet ink containing at least 20 mass% or more and 90 mass% or less of water, a resin, and a pigment onto a coated paper for printing, An aqueous treatment liquid having a function of aggregating or thickening inkjet ink is applied onto the coating paper for printing, and after drying the aqueous treatment liquid having a function of aggregating or thickening the inkjet ink, printing application is performed. An image forming method characterized in that the image is formed by ejecting the inkjet ink while heating the paper at 40 ° C. or higher and 60 ° C. or lower ”has been proposed.
Patent Document 3 states that “in the image forming method for forming an image on a recording medium using a water-based ink containing a color material and a treatment liquid containing a component that reacts with the color material, the recording is performed. A treatment liquid application step for applying the treatment liquid onto a medium, an ink droplet ejection step for depositing the aqueous ink on a recording medium to which the treatment liquid is applied, based on image information; An ink drying step of drying the ink layer formed on the previous recording medium by reacting with the treatment liquid; and a fixing step of fixing the ink layer on the dried recording medium by heating and pressurizing; In the ink drying step, there is proposed an image forming method characterized in that the residual water amount of ink-derived water after drying is 4.0 g / m ² or less.

JP 2011-074150 A JP 2010-247528 A JP 2010-005815 A

  The problem to be solved by the present invention is that a solid image having a narrow line width and excellent uniformity is obtained even on a recording medium having low ink permeability as compared with the case of using a treatment liquid not containing a thermal acid generator. It is to provide a processing liquid capable of forming both images.

  The above problem is solved by the following means.

The invention according to claim 1
The treatment liquid has a pH of 5 or more and 9 or less and contains a thermal acid generator.

The invention according to claim 2
The treatment liquid according to claim 1, wherein the thermal acid generator contains at least one compound selected from the group consisting of a carboxylic acid ammonium salt compound and a sulfonic acid ammonium salt compound.

The invention according to claim 3
It is a processing liquid of Claim 1 or Claim 2 containing an infrared absorber.

The invention according to claim 4
A processing liquid cartridge containing the processing liquid according to any one of claims 1 to 3.

The invention according to claim 5
An ink set comprising the treatment liquid according to any one of claims 1 to 3 and an ink having a pH of 7.5 or more and 10 or less.

The invention according to claim 6
An ink cartridge set comprising: a treatment liquid cartridge containing the treatment liquid according to any one of claims 1 to 3; and an ink cartridge containing an ink having a pH of 7.5 or more and 10 or less. .

The invention according to claim 7 provides:
An apparatus for containing the ink set according to claim 5 and applying the treatment liquid to a recording medium, an apparatus for heating at least a part of the treatment liquid applied on the recording medium, and the ink applied A recording apparatus having at least an apparatus for applying the treatment liquid and an apparatus for drying the applied ink.

The invention according to claim 8 provides:
6. The step of applying the treatment liquid to a recording medium using the ink set according to claim 5, the step of heating at least a part of the treatment liquid applied on the recording medium, and the treatment applied with the ink. It is a recording method including a step of applying at least a liquid and a step of drying the applied ink.

The invention according to claim 9 is:
This is a treated recording medium having a region having a thermal acid generator on at least a part of the surface of the recording medium.

The invention according to claim 10 is:
10. The treated recording medium according to claim 9, wherein the region is a region having a pH of 5 or more and 9 or less and a treatment liquid containing a thermal acid generator is applied to the surface of the recording medium.

The invention according to claim 11 is:
An apparatus for heating at least a part of the area in the treated recording medium according to claim 9 or 10, an apparatus for applying at least an ink having a pH of 7.5 to 10 on the area, and applied And a recording apparatus having an apparatus for drying the ink.

The invention according to claim 12
A step of heating at least a part of the region in the treated recording medium according to claim 9 or 10, a step of applying at least an ink having a pH of 7.5 to 10 on the region, and And a method of drying the ink.

According to the first aspect of the invention, compared to the case of using a treatment liquid that does not contain a thermal acid generator, a solid image having a narrow line width and excellent uniformity even on a recording medium having low ink permeability. A processing liquid capable of forming both images is provided.
According to the second aspect of the present invention, compared to the case where a thermal acid generator other than a compound selected from the group consisting of a carboxylic acid ammonium salt compound and a sulfonic acid ammonium salt compound is used, the recording medium has high ink permeability. In contrast, a processing liquid capable of forming an image with a narrower line width is provided.
According to the invention which concerns on Claim 3, compared with the case where an infrared absorber is not contained, the process liquid which can generate | occur | produce an acid easily only in the part which provided the process liquid is provided.

According to the fourth aspect of the invention, compared to the case of using a treatment liquid that does not contain a thermal acid generator, a solid image having a narrow line width and excellent uniformity even on a recording medium having low ink permeability. A processing liquid cartridge capable of forming both images is provided.
According to the invention of claim 5, compared with the case of using a treatment liquid that does not contain a thermal acid generator, the image with a narrow line width and uniformity are excellent even for a recording medium with low ink permeability. An ink set capable of forming both solid images is provided.
According to the invention of claim 6, compared to the case of using a treatment liquid that does not contain a thermal acid generator, a solid image having a narrow line width and excellent uniformity even on a recording medium having low ink permeability. An ink cartridge set capable of forming both images is provided.
According to the seventh aspect of the present invention, an image with a narrow line width and uniformity even with respect to a recording medium having low ink permeability as compared with the case where a treatment liquid containing no thermal acid generator is used as the treatment liquid. In addition, a recording apparatus capable of forming both solid images excellent in quality is provided.
According to the eighth aspect of the invention, it is possible to record an image with a narrow line width even on a recording medium having a low ink permeability as compared with the case where a treatment liquid containing no thermal acid generator is used as the treatment liquid. Provided is a recording apparatus capable of forming both an image with a narrow line width and a solid image with excellent uniformity.

According to the ninth aspect of the present invention, there is provided a processed recording medium capable of forming both an image having a narrow line width and a solid image having excellent uniformity as compared with the case where a recording medium having no thermal acid generator is used on the surface. Provided.
According to the tenth aspect of the present invention, there is provided a processing recording medium capable of forming a solid image that is superior in uniformity as compared with the case where a processing liquid containing no thermal acid generator is used.
According to the invention of claim 11, there is provided a recording apparatus capable of forming both an image with a narrow line width and a solid image having excellent uniformity as compared with the case where a recording medium having no thermal acid generator is used on the surface. Is done.
According to the twelfth aspect of the present invention, there is provided a recording apparatus capable of forming both an image having a narrow line width and a solid image having excellent uniformity as compared with the case of using a recording medium having no thermal acid generator on the surface. Is done.

1 is a schematic configuration diagram illustrating a recording apparatus according to an embodiment.

Hereinafter, the present embodiment will be described.
In addition, description with "mass part" and "mass%" is synonymous with "weight part" and "weight%", respectively.
Further, in the following description, ejecting ink onto a recording medium (in a target area) to form an image may be referred to as “image formation” or “form an image”. The process of ejecting ink, drying and fixing is sometimes referred to as “recording”, “image recording”, or “recording an image”.

<Processing liquid>
The treatment liquid according to the present embodiment has a pH of 5 or more and 9 or less and contains a thermal acid generator.
Note that the treatment liquid according to the present embodiment is preferably a treatment liquid that is used together with a colorant and an ink containing water to record an image.
Further, the processing liquid according to the present embodiment is suitably used as an inkjet processing liquid for recording an image by an inkjet recording method.

  With the above configuration, the processing liquid according to the present embodiment has a narrow line width image that realizes recording of a narrow line width image and a solid image with excellent uniformity (printing) even on a recording medium with low ink permeability. Both of which are formed). The reason is presumed as follows.

Examples of the recording medium having low ink permeability (non-permeable or low-permeable recording medium) include the following.
A resin film etc. are mentioned as a non-permeable recording medium. Specifically, the non-permeable recording medium means a recording medium having a maximum ink absorption amount of less than 3 ml / m ² within a contact time of 500 ms as measured by a dynamic scanning absorption meter.
Examples of the low permeability recording medium include coated paper such as coated paper, art paper, and cast paper. Specifically, the low-penetration recording medium is a recording in which the maximum ink absorption amount within a contact time of 500 ms measured with a dynamic scanning absorption meter is in the range of 3 ml / m ^{2 to} 15 ml / m ^2. Means medium.
On the other hand, as a permeable recording medium which is a recording medium having high ink permeability, plain paper or the like can be given. Specifically, the permeable recording medium means a recording medium having a maximum ink absorption amount exceeding 15 ml / m ² within a contact time of 500 ms as measured by a dynamic scanning absorption meter.

In order to form a high-quality image with little color unevenness on a recording medium with low ink permeability such as coated paper for printing or resin film, before the landing interference (mixed color / interference) between inks starts on the recording medium And fixing the colorant to the recording medium.
In order to fix the colorant to the recording medium, it has been considered to use an agglomeration effect by an acidic treatment liquid or an ultraviolet (UV) curable ink. However, depending on the image pattern, particularly in the case of a solid image, there are cases where the image quality is better when it does not hinder ink spreading.

  Therefore, a treatment liquid having a pH of 5 or more and 9 or less and containing a thermal acid generator is used. When the treatment liquid is used, acid is generated from the thermal acid generator in the heated part, and the function of the treatment liquid is selectively applied only in the heated part, and the droplet ejection interference between the inks is suppressed, and the coated paper Even when an image is formed on a recording medium having low ink permeability such as an image, an image having a narrow line width can be obtained. Furthermore, in particular, in areas where there are many solid images, the function of the treatment liquid is not expressed intentionally, thereby forming an image with excellent uniformity utilizing the ink wetting and spreading characteristics. Furthermore, by suppressing the droplet ejection interference, the value of the line roughness (roughness degree and the radity) of the edge portion in the obtained line image (line image) is also reduced.

  In addition to the above, the treatment liquid is a neutral or a weakly acidic or weakly alkaline liquid having a pH of 5 or more and 9 or less before heating, and has little influence on the recording medium and the ejection head, and image recording. The recording medium is excellent in stability over time and ejection stability of the ejection head.

  Hereinafter, details of the treatment liquid according to the present embodiment will be described.

The pH of the treatment liquid according to this embodiment is 5 or more and 9 or less, and is preferably 5 or more and 8 or less from the viewpoint of obtaining a solid image having excellent uniformity even on a recording medium with low ink permeability. More preferably, it is 5.2 or more and 7.5 or less, and particularly preferably 5.5 or more and 7.0 or less.
In this embodiment, the pH is 23 ± 0.5 ° C. and the humidity is 55 ± 5% R.P. H. Under the environment, a value measured by a pH / conductivity meter (MPC227 manufactured by METTLER TOLEDO) is adopted.

  The heating temperature of the recording medium when the treatment liquid according to the present embodiment is applied onto the recording medium and the acid is generated from the thermal acid generator depends on the thermal acid generator and the like contained, but is 50 ° C. or higher and 200 ° C. It is preferable that it is 0 degreeC or less, 60 to 180 degreeC is more preferable, and 70 to 150 degreeC is still more preferable.

(Thermal acid generator)
The treatment liquid according to this embodiment contains a thermal acid generator.
The thermal acid generator may be a compound that generates an acid by heat, or may be a compound that directly generates an acid by thermal decomposition or the like, or it modifies a compound that has been generated by thermal decomposition or the like. The compound which generate | occur | produces an acid by this may be sufficient.
The acid generation temperature of the thermal acid generator depends on the decomposition temperature of the compound, but is preferably 50 ° C or higher and 200 ° C or lower, more preferably 60 ° C or higher and 180 ° C or lower, and 70 ° C or higher and 150 ° C or lower. The following is more preferable.

Preferable examples of the thermal acid generator include a compound that generates acid by thermal decomposition and a compound that generates acid by hydrolysis.
Examples of the compound that generates acid by thermal decomposition include an ammonium carboxylate compound and an ammonium sulfonate compound. It is presumed that carboxylic acid or sulfonic acid is generated by decomposition of ammonium cation by heat and volatilization of ammonia.
Examples of the compound that generates an acid by hydrolysis include an ester compound, an acetal compound, and an imide compound.
It is preferable to coexist an acidic catalyst or a basic catalyst for hydrolysis of the ester compound. The hydrolysis temperature is easily adjusted by these catalysts.
The acetal compound is hydrolyzed to produce an aldehyde, and further, the aldehyde is oxidized with an oxidizing agent to produce a carboxylic acid.
The imide compound is hydrolyzed to produce 2 molar equivalents of a carboxy group and 1 molar equivalent of an amine compound, so that more acid is produced than the amine compound, and the pH is lowered.

As the carboxylic acid ammonium salt compound and the sulfonic acid ammonium salt compound, an ammonium salt of a carboxylic acid having a boiling point of 100 ° C. or higher from the viewpoint of obtaining an image having a narrow line width even on a recording medium having low ink permeability, or It is preferably an ammonium salt of a sulfonic acid having a boiling point of 100 ° C. or higher, more preferably an ammonium salt of a carboxylic acid having a boiling point of 150 ° C. or higher, or an ammonium salt of a sulfonic acid having a boiling point of 150 ° C. or higher.
In addition, the number of carbon atoms of the carboxylic acid ammonium salt compound and the sulfonic acid ammonium salt compound is preferably 2 or more from the viewpoint of obtaining an image having a narrow line width even on a recording medium having low ink permeability. More preferably, it is 4 or more and 20 or less.
Among these, from the viewpoint of obtaining an image having a narrow line width even on a recording medium having low ink permeability, an ammonium carboxylate compound is preferable, and an ammonium salt of pyrrolidone carboxylic acid is particularly preferable.

Preferred examples of the ester compound include primary to tertiary alkyl ester compounds.
When hydrolyzing using an acidic catalyst or a basic catalyst, a primary alkyl ester compound or a secondary alkyl ester compound is preferably exemplified.
Moreover, when hydrolyzing without using an acidic catalyst or a basic catalyst, a secondary alkyl ester compound or a tertiary alkyl ester compound is mentioned preferably.
Preferred examples of the primary alkyl ester compound include acetic acid esters having 3 to 8 carbon atoms and propionic acid esters having 4 to 8 carbon atoms, and more preferred are acetic acid esters having 3 to 8 carbon atoms. Particularly preferred is ethyl acetate.
Preferred examples of the secondary alkyl ester compound include 2-butyl acetate and 2-ethylhexyl acetate.
The carbon number of the secondary alkyl ester compound is preferably 4 or more and 12 or less, and more preferably 4 or more and 10 or less.
Preferable examples of the tertiary alkyl ester compound include t-butyl acetate and t-butyl propionate.
Further, the carbon number of the tertiary alkyl ester compound is preferably 5 or more, 12 or less, more preferably 5 or more and 10 or less, and still more preferably 5 or more and 8 or less.
There is no restriction | limiting in particular as said acidic catalyst or a basic catalyst, Although a well-known catalyst may be used, an acidic catalyst is preferable and a sulfuric acid is more preferable.
Moreover, when an acidic catalyst or a basic catalyst is contained, in order to adjust the pH of the treatment liquid, it is preferable to further contain a pH adjuster described later.

The acetal compound is preferably a compound obtained by protecting an aldehyde compound with an acetal structure from the viewpoint of the safety of the oxidizing agent. That is, it is preferably not a ketal compound.
Further, the acetal compound may be a cyclic acetal compound or an acyclic acetal compound, but is preferably an acyclic acetal compound from the viewpoint of thermal decomposability, and a compound having a dialkoxyacetal structure It is more preferable that it is a compound having a dimethoxyacetal structure.
The oxidizing agent is preferably a mild oxidizing agent. Of these, chlorite is preferable, and sodium chlorite is more preferable.

The imide compound is preferably an aliphatic imide compound, and more preferably an aliphatic imide compound having 4 to 20 carbon atoms.
The imide compound is preferably an imide compound having a —CO—NH—CO— structure because the amine compound after hydrolysis is volatilized as ammonia.
An acidic catalyst or a basic catalyst may coexist in the hydrolysis of the imide compound. The hydrolysis temperature is easily adjusted by these catalysts.

  Among these, as the thermal acid generator, from the viewpoint of obtaining an image having a narrow line width even on a recording medium having low ink permeability, an ammonium carboxylate compound, an ammonium sulfonate compound, an ester compound, an acetal compound, And a compound selected from the group consisting of imide compounds, preferably a compound selected from the group consisting of carboxylic acid ammonium salt compounds, sulfonic acid ammonium salt compounds, primary alkyl ester compounds, and secondary alkyl ester compounds. Is more preferable, a compound selected from the group consisting of a carboxylic acid ammonium salt compound and a sulfonic acid ammonium salt compound is more preferable, and a carboxylic acid ammonium salt compound is particularly preferable.

The thermal acid generator may be contained singly or in combination of two or more.
The content of the thermal acid generator in the processing liquid according to the present embodiment is 0.1 mass with respect to the total mass of the processing liquid from the viewpoint of obtaining an image with a narrow line width even for a recording medium with low ink permeability. % To 30% by mass, more preferably 0.5% to 20% by mass, still more preferably 0.8% to 10% by mass. The content is particularly preferably 0% by mass or more and 5.0% by mass or less.
The amount of the thermal acid generator applied to the recording medium is 0.001 g / m ² or more and 3 g / m ² or less from the viewpoint of obtaining an image having a narrow line width even on a recording medium having low ink permeability. preferably, more preferably 0.005 g / m ² or more 2 g / m ² or less.

(water)
The treatment liquid according to this embodiment preferably contains water.
Moreover, it is preferable that the processing liquid which concerns on this embodiment is an aqueous processing liquid. The aqueous treatment liquid refers to a treatment liquid containing 50% by mass or more of water with respect to the total mass of the treatment liquid.
The water is not particularly limited, and ion-exchanged water, ultrapure water, distilled water, ultrafiltered water, tap water, hard water, soft water, and the like are used. In particular, contamination of impurities or generation of microorganisms is prevented. From the viewpoint, ion exchange water, ultrapure water, distilled water, and ultrafiltered water are preferable.
The content of water in the treatment liquid according to this embodiment is preferably 10% by mass or more and 95% by mass or less, and more preferably 30% by mass or more and 90% by mass or less with respect to the mass of the entire treatment liquid. The content is more preferably 50% by mass or more and 85% by mass or less.

(Water-soluble organic solvent)
The treatment liquid according to this embodiment preferably contains a water-soluble organic solvent.
Examples of the water-soluble organic solvent include polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, and sulfur-containing solvents. Other examples of the water-soluble organic solvent include propylene carbonate and ethylene carbonate.

  Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2-hexanediol, 1,2,6-hexanetriol, glycerin, trimethylol Sugar alcohols such as propane and xylitol; sugars such as xylose, glucose and galactose;

  Polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diglycerin. And ethylene oxide adducts.

Examples of the nitrogen-containing solvent include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, triethanolamine and the like.
Examples of alcohols include ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol.
Examples of the sulfur-containing solvent include thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like.

  Among these, the treatment liquid according to the present embodiment preferably contains a polyhydric alcohol as the aqueous organic solvent from the viewpoint of adjusting the drying speed, and is selected from the group consisting of propylene glycol and 1,2-hexanediol. It is more preferable to include a prepared aqueous organic solvent, and it is particularly preferable to include propylene glycol and 1,2-hexanediol.

The water-soluble organic solvent may be used alone or in combination of two or more.
1 mass% or more and 60 mass% or less are preferable with respect to water, and, as for content of a water-soluble organic solvent, 5 mass% or more and 40 mass% or less are more preferable.

(Infrared absorber)
The treatment liquid according to the present embodiment preferably contains an infrared absorber from the viewpoints of drying speed and space saving in the recording apparatus.
By containing an infrared absorber, infrared irradiation by an infrared laser or the like is also used for drying the treatment liquid and heat treatment for the treatment liquid. Further, by using an infrared laser for the heat treatment on the treatment liquid, only the position to be heated on the recording medium may be selectively heated.
The “infrared absorber” refers to a compound that generates heat by absorbing infrared rays.
“Infrared radiation” refers to light in the wavelength range of 700 nm to 1 mm, and the infrared absorbent used in the present embodiment preferably has maximum absorption in the wavelength range of 800 nm to 1,500 nm.
There is no restriction | limiting in particular as an infrared absorber used for this embodiment, Although a well-known infrared absorber is used, From a viewpoint that formation of the image by an ink is not prevented, pigments, such as carbon black, are not preferable.
Moreover, it is preferable to use an inorganic material or an organic dye as the infrared absorber, and it is preferable to use an inorganic material from the viewpoint of the calorific value. The infrared absorber is decomposed by infrared irradiation, and the color of the infrared absorber itself is reduced. From the viewpoint of thinning and preventing the formation of an image by ink, it is preferable to use an organic dye. As the inorganic material, a metal oxide is preferable, such as antimony tin oxide (ATO) and indium tin oxide (ITO). Is preferably exemplified.
Preferred examples of the organic dye include cyanine compounds, aminium compounds, diimonium compounds, porphyrazine compounds, and squarylium compounds.

The treatment liquid according to the present embodiment may contain an infrared absorber alone or in combination of two or more.
The content of the infrared absorber is preferably 0.001% by mass or more and 3% by mass or less, and more preferably 0.005% by mass or more and 2% by mass or less with respect to the total mass of the treatment liquid. If it is the said range, the emitted-heat amount is sufficient and there is little influence on image formation.

  Commercially available infrared absorbers can also be used as the infrared absorber, such as NIR series (manufactured by Nagase ChemteX Corporation), YKR series (manufactured by Nagase ChemteX Corporation), KAYASORB series (Nippon Kayaku Co., Ltd.) )) And the like.

(Polymer particles)
The treatment liquid according to this embodiment preferably contains polymer particles.
The polymer particles are components that enhance the fixability of the image to the recording medium.
The polymer particles are obtained by granulating a polymer compound and are components different from the polymer dispersant described later.

Examples of the polymer particles include styrene-acrylic acid copolymer, styrene-acrylic acid-sodium acrylate copolymer, styrene-butadiene copolymer, polystyrene, acrylonitrile-butadiene copolymer, and acrylate copolymer. , Polyurethane, polyester, silicone-acrylic acid copolymer, acrylic modified fluororesin particles (latex particles).
Examples of the polymer particles include core / shell type polymer particles having different compositions at the center and outer edge of the particles.

The polymer particles may be dispersed in the treatment liquid using an emulsifier, or may be dispersed in the treatment liquid without using an emulsifier.
As an emulsifier, a polymer having a hydrophilic group such as a surfactant, a sulfonic acid group, or a carboxyl group (for example, a polymer having a hydrophilic group grafted thereto, a hydrophilic monomer and a hydrophobic portion) Polymers obtained from monomers).

The volume average particle diameter of the polymer particles is preferably 10 nm or more and 300 nm or less, more preferably 10 nm or more and 200 nm or less, from the viewpoint of glossiness and scratch resistance of the image.
The volume average particle diameter of the polymer particles is measured with a Microtrac UPA particle size analyzer UPA-UT151 (manufactured by Microtrac). The measurement is performed by placing 1,000-fold diluted aqueous ink in a measurement cell. As the input value at the time of measurement, the viscosity of the aqueous ink diluent is used as the viscosity, and the refractive index of the polymer particles is used as the particle refractive index.

The glass transition temperature of the polymer particles is preferably 40 ° C. or higher and 90 ° C. or lower, and more preferably 70 ° C. or higher and 90 ° C. or lower from the viewpoint of suppressing landing unevenness. On the other hand, the glass transition temperature of the polymer particles is preferably −20 ° C. or higher and 80 ° C. or lower, more preferably −10 ° C. or higher and 60 ° C. or lower, from the viewpoint of image scratch resistance.
The glass transition temperature of the polymer particles is determined from the DSC curve obtained by differential scanning calorimetry (DSC). More specifically, the method for determining the glass transition temperature in JIS K7121-1987 “Method for Measuring Plastic Transition Temperature”. It is calculated | required by description "extrapolated glass transition start temperature" of description.

  The content of the polymer particles is preferably 0.1% by mass or more and 10% by mass or less, and preferably 0.5% by mass with respect to the water-based ink, from the viewpoint of enhancing the fixing property of the image, the ejection stability, and the film forming property. More preferred is 5% by mass or less.

(Surfactant)
The surfactant will be described.
The treatment liquid according to this embodiment preferably contains a surfactant.
The treatment liquid preferably contains, for example, a surfactant having an HLB (hydrophilic-lipophilic balance) of 14 or less as a surfactant. It is easy to adjust the surface tension of the treatment liquid by adjusting the amount of the surfactant having an HLB of 14 or less, or by using a plurality of surfactants having different HLB.

The HLB (hydrophilic group / hydrophobic group balance “Hydrophile-Lipophile Balance”) is defined by the following formula (Griffin method).
・ HLB = 20 × (sum of formula weight of hydrophilic part / molecular weight)

  Examples of such a surfactant include at least one selected from the group consisting of an ethylene oxide adduct of acetylene glycol and a polyether-modified silicone.

The ethylene oxide adduct of acetylene glycol is, for example, an —O— (CH ₂ CH ₂ O) _n —H structure in which ethylene oxide is added to at least one hydroxyl group of acetylene glycol (for example, n is 1 to 30). A compound having an integer)
Examples of commercially available acetylene glycol ethylene oxide adducts (numbers in parentheses indicate HLB catalog values) include, for example, Olphine E1004 (from 7 to 9), Olphine E1010 (from 13 to 14), Olphine EXP. . 4001 (8 to 11), Olphin EXP. 4123 (11 to 14), Olphin EXP. 4300 (10 or more and 13 or less), Surfinol 104H (4), Surfinol 420 (4), Surfinol 440 (4), Dinol 604 (8) (above, manufactured by Nissin Chemical Industry Co., Ltd.) and the like. .

The polyether-modified silicone is, for example, a compound in which a polyether group is bonded to a silicone chain (polysiloxane main chain) in a graft form or a block form. Examples of the polyether group include a polyoxyethylene group and a polyoxypropylene group. The polyether group may be, for example, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are added in a block form or randomly.
As commercial products of polyether-modified silicone (the numbers in parentheses indicate catalog values of HLB), Silface SAG002 (12), Silface SAG503A (11), Silface SAG005 (7) (the above, Nissin) Chemical Industry Co., Ltd.).

In the treatment liquid, other surfactants other than acetylene glycol ethylene oxide adduct and polyether-modified silicone may be used.
Examples of other surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. Preferably, anionic surfactants and nonionic surfactants are used. is there.

Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, sulfuric acid of higher alcohol ether. Examples thereof include ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates, and the like.
Among these, as anionic surfactants, dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, monobutylbiphenylsulfonate, dibutylphenylphenol A disulfonate is preferable.

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, poly Examples thereof include oxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, alkyl alkanol amide, polyethylene glycol polypropylene glycol block copolymer, acetylene glycol and the like.
Among these, nonionic surfactants include polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene Oxyethylene sorbitan fatty acid ester, fatty acid alkylolamide, polyethylene glycol polypropylene glycol block copolymer, and acetylene glycol are preferred.

  Other nonionic surfactants include silicone surfactants such as polysiloxane oxyethylene adducts; fluorine-based surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers. Agents; biosurfactants such as spicrispolic acid, rhamnolipid, lysolecithin; and the like.

  The hydrophilic / hydrophobic balance (HLB) of other surfactants is preferably in the range of 3 to 20, for example, in consideration of solubility.

The surfactant may be used alone or in combination of two or more.
Among these, as the surfactant, an ethylene oxide adduct of acetylene glycol is preferable, and the water-based ink more preferably contains two or more ethylene oxide adducts of acetylene glycol.

  The total surfactant content is preferably from 0.1% by weight to 10% by weight, more preferably from 0.1% by weight to 5% by weight, and more preferably from 0.2% by weight to 3% by weight, based on the treatment liquid. A mass% or less is more preferable.

(Other additives)
The treatment liquid according to the present embodiment may further contain other additives.
Other additives include colorants, dischargeability improvers (polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, etc.), conductive agents, pH adjusters (potassium hydroxide, sodium hydroxide and hydroxide). Compounds of alkali metals such as lithium, inorganic and organic acids, and salts of these acids), reactive diluents, penetrants, pH buffers, antioxidants, fungicides, viscosity modifiers, chelates Well-known additives, such as a chemical | medical agent and a ultraviolet absorber, are mentioned.

(Physical properties of processing solution)
The surface tension of the treatment liquid is preferably 10 mN / m or more and 45 mN / m or less, more preferably 15 mN / m or more and 40 mN / m or less, and further preferably 20 mN / m or more and 35 mN / m or less. The surface tension of the treatment liquid is preferably smaller than the surface tension of the ink.
The surface tension is measured in a 23 ° C. and 55% RH environment using a Wilhelmy surface tension meter.

The viscosity of the treatment liquid is preferably 1.2 mPa · s or more and 15 mPa · s or less, more preferably 1.5 mPa · s or more and less than 10 mPa · s, and further preferably 1.8 mPa · s or more and less than 8 mPa · s.
The viscosity is measured using TV-20 (manufactured by Toki Sangyo Co., Ltd.) as a measuring device, at a measurement temperature of 23 ° C., and at a shear rate of 750 s ⁻¹ .

<Processing liquid cartridge>
The processing liquid cartridge according to the present embodiment contains the processing liquid according to the present embodiment, and further includes other members appropriately selected as necessary.
Further, it is preferable that the processing liquid cartridge according to the present embodiment is detachable from the recording apparatus.
Further, in the processing liquid cartridge according to the present embodiment, known members are used for the other members other than storing the processing liquid according to the present embodiment.

<Ink set>
The ink set according to the present embodiment preferably includes the treatment liquid according to the present embodiment and the ink having a pH of 7.5 or more and 10 or less.

The ink will be described.
The ink preferably has a pH of 7.5 or more and 10 or less, and preferably contains a colorant and water. The ink may contain other components.
In addition, the ink used in the present embodiment is preferably a water-based ink. The water-based ink refers to an ink containing 50% by mass or more of water with respect to the total mass of the ink.

  The ink used in this embodiment preferably contains a colorant, water, and an aqueous organic solvent, and may contain a colorant, polymer particles, water, and an aqueous organic solvent. More preferably, it contains a colorant, polymer particles, a polymer dispersant, a surfactant, water, and an aqueous organic solvent.

  Hereinafter, each component of the ink will be described.

  For the water, aqueous organic solvent, polymer particles, surfactant, and infrared absorber that the ink may contain, the water, aqueous organic solvent, polymer particles, surfactant, and The infrared absorbers have the same meanings, and the preferred embodiments are also the same.

(Coloring agent)
First, the colorant will be described.
As the colorant, those according to the water-based ink having the target hue may be used, and specific examples thereof include pigments. Examples of the pigment include organic pigments and inorganic pigments.

Specific examples of the cyan pigment include C.I. I. Pigment Blue-1, -2, -3, -15, -15: 1, -15: 2, -15: 3, -15: 4, -16, -22, -60, and the like. It is not limited.
Specific examples of the magenta color pigment include C.I. I. Pigment Red-5, -7, -12, -48, -48: 1, -57, -112, -122, -123, -146, -168, -177, -184, -202, C.I. I. Pigment Violet-19 and the like, but are not limited thereto.
Specific examples of yellow pigments include C.I. I. Pigment Yellow-1, -2, -3, -12, -13, -14, -16, -17, -73, -74, -75, -83, -93, -95, -97, -98, -114, -128, -129, -138, -151, -154, -180, and the like, but are not limited thereto.

  Specific examples of black pigments (black pigments) include Raven7000, Raven5750, Raven5250, Raven5000 ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1190, Raven1190, Raven1190, Raven1190 ) Regal 400R, Regal 330R, Regal 660R, Mogul L, Black Pearls L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Mon rch 1400 (above Cabot), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black 18, Color Black FW200, Color Black S150, Color Black S150, Color Black S160, Color Black S160, Color Black S160, Color Black S150, Color Black S150, Color Black S150, Color Black S150, Color Black S150, Color Black S150 , Printex 140V, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (manufactured by Orion Engineered Carbons Co., Ltd.), no. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Corporation) and the like, but are not limited thereto.

  Here, when a pigment is used as the colorant, it is preferable to use a pigment dispersant together. Examples of the pigment dispersant used include a polymer dispersant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant described later.

  As the polymer dispersant, a polymer having a hydrophilic structure portion and a hydrophobic structure portion is preferably used. As the polymer having a hydrophilic structure part and a hydrophobic structure part, for example, a condensation polymer and an addition polymer are used. Examples of the condensation polymer include known polyester dispersants. Examples of the addition polymer include addition polymers of monomers having an α, β-ethylenically unsaturated group. By copolymerizing a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group and a monomer having an α, β-ethylenically unsaturated group having a hydrophobic group, A molecular dispersant is obtained. A homopolymer of a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group is also used.

  Monomers having an α, β-ethylenically unsaturated group having a hydrophilic group include monomers having a carboxyl group, a sulfonic acid group, a hydroxyl group, a phosphoric acid group, such as acrylic acid, methacrylic acid, and croton. Acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, vinyl sulfonic acid, styrene sulfonic acid, sulfonated vinyl naphthalene, vinyl alcohol, acrylamide, methacryloxyethyl phosphate, bis Examples include methacryloxyethyl phosphate, methacryloxyethyl phenyl acid phosphate, ethylene glycol dimethacrylate, and diethylene glycol dimethacrylate.

  Examples of the monomer having an α, β-ethylenically unsaturated group having a hydrophobic group include styrene derivatives such as styrene, α-methylstyrene, vinyltoluene, vinylcyclohexane, vinylnaphthalene, vinylnaphthalene derivatives, and alkyl acrylate esters. Methacrylic acid alkyl ester, methacrylic acid phenyl ester, methacrylic acid cycloalkyl ester, crotonic acid alkyl ester, itaconic acid dialkyl ester, maleic acid dialkyl ester and the like.

Examples of preferred copolymers as the polymer dispersant include styrene-styrene sulfonic acid copolymer, styrene-maleic acid copolymer, styrene-methacrylic acid copolymer, styrene-acrylic acid copolymer, vinyl naphthalene- Maleic acid copolymer, vinyl naphthalene-methacrylic acid copolymer, vinyl naphthalene-acrylic acid copolymer, alkyl acrylate ester-acrylic acid copolymer, alkyl methacrylate ester-methacrylic acid copolymer, styrene-methacrylic acid Alkyl ester-methacrylic acid copolymer, styrene-alkyl acrylate ester-acrylic acid copolymer, styrene-phenyl methacrylate-methacrylic acid copolymer, styrene-methacrylic acid cyclohexyl ester-methacrylic acid copolymer, or these Examples of salt It is. Moreover, you may copolymerize the monomer which has a polyoxyethylene group and a hydroxyl group with these polymers.
Among these, a polymer dispersant selected from the group consisting of a styrene-acrylic acid copolymer and a styrene-acrylate copolymer is preferable, a styrene-acrylate copolymer is more preferable, and a styrene-acrylic acid is preferable. Alkali metal salt copolymers are particularly preferred.
In addition, the styrene-acrylate copolymer acts as a weak base in the ink containing water, and can be easily adjusted so that the pH of the ink is 7.5 or more and 10 or less.

  The weight average molecular weight of the polymer dispersant is preferably 2,000 or more and 50,000 or less. Unless otherwise specified, the weight average molecular weight in the present embodiment is a value measured by gel permeation chromatography (GPC) and converted to standard polystyrene.

  These polymer dispersants may be used alone or in combination of two or more. The content of the polymer dispersant varies greatly depending on the pigment and cannot be generally stated, but it is preferably 0.1% by mass or more and 100% by mass or less based on the pigment.

Examples of the pigment include pigments that are self-dispersed in water (hereinafter referred to as self-dispersing pigments).
The self-dispersing pigment refers to a pigment that has a water-solubilizing group on the pigment surface and disperses in water without the presence of a polymer dispersant. The self-dispersing pigment can be obtained, for example, by subjecting the pigment to surface modification treatment such as acid / base treatment, coupling agent treatment, polymer graft treatment, plasma treatment, oxidation / reduction treatment, and the like.

  As self-dispersing pigments, in addition to pigments that have undergone surface modification treatment on the pigments, Cab-o-jet-200, Cab-o-jet-300, Cab-o-jet-400 manufactured by Cabot Corporation. IJX-157, IJX-253, IJX-266, IJX-273, IJX-444, IJX-55, Cab-o-jet-250C, Cab-o-jet-260M, Cab-o-jet-270Y, Cab -O-jet-450C, Cab-o-jet-465M, Cab-o-jet-470Y, Cab-o-jet-480M, Microjet Black CW-1, CW-2 manufactured by Orient Chemical Industries, Ltd. Commercially available self-dispersing pigments can also be mentioned.

  The self-dispersing pigment is preferably a pigment having at least a sulfonic acid, a sulfonate, a carboxylic acid or a carboxylate as a functional group on the surface, and has at least a carboxylic acid or a carboxylate as a functional group on the surface. More preferably, it is a pigment.

Here, examples of the pigment include a pigment coated with a resin. This is called a microcapsule pigment, and there are commercially available microcapsule pigments such as those manufactured by DIC Corporation and Toyo Ink Corporation. In addition, it is not restricted to a commercially available microcapsule pigment, You may use the microcapsule pigment produced according to the objective.
Examples of the pigment also include a resin dispersion type pigment in which a polymer compound is physically adsorbed or chemically bonded to the pigment.
In addition to black, cyan, magenta, and yellow, the pigments include specific color pigments such as red, green, blue, brown, and white, metallic luster pigments such as gold and silver, and colorless or light-colored constitutions. Examples include pigments and plastic pigments.
Examples of the pigment include particles in which silica, alumina, polymer beads or the like are used as a core, and a dye or pigment is fixed on the surface thereof, an insoluble lake of the dye, a colored emulsion, a colored latex, or the like.

  As colorants, in addition to pigments, hydrophilic anionic dyes, direct dyes, cationic dyes, reactive dyes, dyes such as polymer dyes and oil-soluble dyes, wax powders colored with dyes, resin powders, Or an emulsion, a fluorescent dye, a fluorescent pigment, etc. are mentioned.

The volume average particle diameter of the colorant is, for example, from 10 nm to 1,000 nm.
The volume average particle diameter of the colorant refers to the particle diameter of the colorant itself, or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the colorant.
The volume average particle size is measured with a Microtrac UPA particle size analyzer UPA-UT151 (manufactured by Microtrac). The measurement is performed by placing 1,000-fold diluted aqueous ink in a measurement cell. As the input value at the time of measurement, the viscosity of the aqueous ink diluent is used as the viscosity, and the refractive index of the colorant is used as the particle refractive index.

  The content (concentration) of the colorant is, for example, preferably from 1% by mass to 25% by mass and more preferably from 2% by mass to 20% by mass with respect to the aqueous ink.

(Other additives)
Other additives will be described.
The water-based ink may contain other additives.
Other additives include ink ejection improvers (polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, etc.), conductivity / pH adjusters (potassium hydroxide, sodium hydroxide and lithium hydroxide). And the like, and reactive diluent solvents, penetrants, pH buffers, antioxidants, fungicides, viscosity modifiers, conductive agents, chelating agents, An ultraviolet absorber etc. are mentioned.

(Ink physical properties)
The preferred physical properties of the ink will be described.
The pH of the ink is preferably 7.5 or more and 10 or less, and preferably 8.0 or more and 9.5 or less from the viewpoint of obtaining an image having a narrow line width even on a recording medium having low ink permeability. More preferably, it is 8.5 or more and 9.2 or less.
Here, the pH of the ink is 23 ± 0.5 ° C. and 55 ± 5% humidity. H. Under the environment, a value measured by a pH / conductivity meter (MPC227 manufactured by METTLER TOLEDO) is adopted.

The conductivity of the ink is preferably in the range of 0.01 S / m to 0.5 S / m, more preferably in the range of 0.01 S / m to 0.25 S / m, and 0.01 S / m to 0.20 S. A range of not more than / m is more preferable.
The conductivity is measured by MPC227 (pH / Conductivity Meter, manufactured by METTLER TOLEDO).
The viscosity of the ink is preferably 1.3 Pa · s to 30 mPa · s, and more preferably 1.5 Pa · s to 20 mPa · s.
Viscosity is measured using TV-20 (manufactured by Toki Sangyo Co., Ltd.) as a measuring device, at a measurement temperature of 23 ° C. and a shear rate of 750 s ⁻¹ .

<Ink cartridge set>
The ink cartridge set according to the present embodiment includes a processing liquid cartridge that stores the processing liquid according to the present embodiment, and an ink cartridge that stores ink having a pH of 7.5 to 10.
The treatment liquid cartridge and the ink cartridge in the ink cartridge set according to the present embodiment are preferably provided in a form that is detachable from, for example, an ink jet recording apparatus.
The ink cartridge set according to this embodiment may include two or more ink cartridges.

<Processing recording medium>
The treated recording medium according to the present embodiment has a region having a thermal acid generator on at least a part of the surface of the recording medium.
Further, in the treated recording medium according to the present embodiment, the region has a pH of 5 or more and 9 or less, and a treatment liquid containing the thermal acid generator (the treatment liquid according to the present embodiment) is applied to the surface of the recording medium. The applied region is preferable, and the region having a pH of 5 or more and 9 or less and more preferably a region where a treatment liquid containing a thermal acid generator is applied and dried on the surface of the recording medium is more preferable.
Furthermore, the processed recording medium according to the present embodiment preferably further includes an infrared absorber in the area.

The recording medium used in the present embodiment is not particularly limited, and includes any known recording medium.
The recording medium used in the present embodiment may be a permeable recording medium or a low permeable or non-permeable recording medium. The use of a permeable or non-permeable recording medium is preferable because the effects of the present embodiment are more exhibited.
Examples of the permeable recording medium include plain paper.
Examples of the low permeability recording medium include coated paper such as coated paper, art paper, and cast paper.
A resin film etc. are mentioned as a non-permeable recording medium.
Especially, as a recording medium, a coated paper and a resin film are mentioned preferably, and a coated paper is mentioned more preferably.

Further, the amount of the thermal acid generator in the portion having the thermal acid generator in the processed recording medium according to the present embodiment is from the viewpoint of obtaining an image with a narrow line width even on a recording medium having low ink permeability. It is preferably from 001 g / m ^{2 to} 3 g / m ^2, more preferably from 0.005 g / m ^{2 to 2} g / m ² .

<Recording apparatus and recording method>
In the present embodiment, the recording apparatus according to the first embodiment contains an ink set according to the present embodiment and applies the processing liquid to a recording medium. The processing apparatus applied to the recording medium A device for heating at least a part, a device for applying at least the treatment liquid to which the ink has been applied, and a device for drying the applied ink.
In the present embodiment, the recording apparatus according to the second embodiment is an apparatus that heats at least a part of the area in the processed recording medium according to the present embodiment, and ink that has a pH of 7.5 to 10 in the area. It has at least a device for applying the ink and a device for drying the applied ink.

In the recording apparatus according to the first embodiment, using the ink set according to the present embodiment, the step of applying the processing liquid to the recording medium, and heating at least a part of the processing liquid applied on the recording medium. A recording method (recording method according to the first embodiment) including a step, a step of applying at least the treatment liquid to which the ink has been applied, and a step of drying the applied ink is performed.
In the recording apparatus according to the second embodiment, the step of heating at least a part of the region in the processed recording medium according to the present embodiment, the ink having a pH of 7.5 or more and 10 or less is applied at least on the region. A recording method (recording method according to the second embodiment) including a step and a step of drying the applied ink is performed.

The discharge head used for discharging the treatment liquid and the ink is not particularly limited, and a known inkjet head is used. Examples thereof include a piezoelectric inkjet head and a thermal inkjet head.
The discharge temperature of the treatment liquid and ink is not particularly limited, and can be adjusted according to the treatment liquid and ink to be used.
Ink discharge in the present embodiment may be performed a plurality of times as necessary. For example, one type of ink may be ejected multiple times to the same location on the recording medium, two or more types of ink may be ejected once, or two or more types of ink may be ejected multiple times. May be.

Although there is no restriction | limiting in particular as a heating means to generate | occur | produce an acid from the thermal acid generator in this embodiment, It is preferable that it is an infrared rays generation means. When using an infrared ray generating means, it is preferable that the treatment liquid contains an infrared absorbent or that the treated recording medium has an infrared absorbent on at least a part of its surface.
As the heating means, a known heating device such as a heater or a heating roller is also preferably used.
The infrared irradiation means is not particularly limited as long as it is a means capable of irradiating infrared rays having a wavelength range of at least 760 nm or more and 1,500 nm or less. For example, an infrared laser irradiation apparatus or the like is preferably used.
Further, as the infrared irradiation means, an infrared laser irradiation unit in which a plurality of infrared laser light emitting elements are arranged along the width direction of the recording medium can be used.
In the infrared laser irradiation unit, the laser irradiation timing, irradiation position, and irradiation amount of each infrared laser light emitting element are adjusted for each infrared laser light emitting element according to the current value supplied to each infrared near laser light emitting element, for example. It is preferable that it is adapted. Such an infrared laser irradiation unit has a mechanism for controlling the irradiation timing of an infrared laser, a mechanism for controlling the irradiation amount of the infrared laser, and a sensor for measuring the irradiation amount of the infrared laser as described above. It is possible to have a mechanism for correcting variations.
Examples of such an infrared laser irradiation unit include a laser drying unit described in JP-A-2015-112792.

Irradiation with an infrared laser may be performed on the entire surface of the recording medium or a part of the recording medium as necessary. When an acid is generated from a thermal acid generator, an image other than a solid image is formed. It is preferable to irradiate only the area to be applied.
Infrared irradiation amount may be an amount suitable for the application of drying of occurrence or ink acid, 1,000 J / m ² or more 100,000J / m ² or less is preferable, 3,000 J / m ² or more 70 , more preferably 000J / m ² or less, more preferably 5,000J / m ² or more 50,000J / m ² or less. The amount of infrared irradiation is the amount of infrared irradiation on the surface of the recording medium.
Although there is no restriction | limiting in particular as irradiation time of infrared rays, 100 microseconds or more and 1 second or less are preferable, 500 microseconds or more and 0.5 second or less are more preferable, 0.1 ms or more and 0.3 second or less are still more preferable.

  The recording apparatus and the recording method according to the present embodiment use the processing liquid according to the present embodiment or the processing recording medium according to the present embodiment, so that an image with a narrow line width can be obtained even on a recording medium with low ink permeability. Recording is realized.

  The recording apparatus according to the present embodiment may include an ink cartridge set according to the present embodiment that is formed into a cartridge so as to be attached to and detached from the recording apparatus.

  Hereinafter, in the present embodiment, an example of a recording apparatus and a recording method according to the first embodiment will be described with reference to the drawings.

FIG. 1 is a schematic configuration diagram illustrating a recording apparatus according to the present embodiment.
A recording apparatus 10 shown in FIG. 1 includes an image recording unit 12 that records an image on a recording medium P, a supply unit 14 that supplies the recording medium P to the image recording unit 12, and between the supply unit 14 and the image recording unit 12. A buffer unit 16 that adjusts the conveyance amount of the recording medium P supplied from the supply unit 14 to the image recording unit 12, and a winding unit 18 that winds up the recording medium P discharged from the image recording unit 12. A buffer unit 20 that is disposed between the image recording unit 12 and the winding unit 18 and adjusts the conveyance amount of the recording medium P discharged from the image recording unit 12 to the winding unit 18; A cooling unit that is disposed between the buffer unit 20 and cools the recording medium P carried out of the image recording unit 12. It is provided with a 22, a.

  The image recording unit 12 includes a treatment liquid discharge head 118, an infrared laser irradiation device 120, a discharge device 121, a conveyance path 124 for the recording medium P, a drying drum 126 (an example of a drying device), and a hot air blower 128. (An example of a drying device).

The processing liquid discharge head 118 discharges the processing liquid according to the present embodiment, and is provided on the upstream side of the transport path 124 relative to the infrared laser irradiation device 120. The processing liquid discharge head 118 is connected to a processing liquid cartridge (not shown) attached to and detached from the recording apparatus 10 through a supply pipe (not shown), and the processing liquid is supplied from the processing liquid cartridge to the processing liquid discharge head 118. An aspect may be sufficient.
The infrared laser irradiation device 120 is provided between the treatment liquid discharge head 118 and the discharge device 121, and irradiates at least a part of the discharged treatment liquid with infrared rays to apply heat to generate thermal acid in the treatment liquid. Acid is generated from the agent.

  The discharge device 121 includes a discharge head 122K that records a K (black) color image, a discharge head 122Y that records a Y (yellow) color image, and a discharge head 122M that records a M (magenta) color image. An ejection head 122C that records an image of C (cyan) color. The ejection heads 122K, 122Y, 122M, and 122C are arranged, for example, in this order from the upstream side to the downstream side of the transport path 124. The ejection heads 122K, 122Y, 122M, and 122C are connected to ink cartridges (not shown) of each color that are attached to and detached from the recording apparatus 10 through supply pipes (not shown), and ink of each color is ejected from the ink cartridges of each color. The aspect supplied to 122 may be sufficient. When the matters common to the ejection heads 122K, 122Y, 122M, and 122C are described, they are simply referred to as “ejection heads 122”.

  The discharge device 121 is not limited to a form including the four discharge heads 122 corresponding to the four colors, and includes a form including four or more discharge heads 122 corresponding to four or more colors including other intermediate colors. Also good.

  As the ejection head 122, for example, an effective recording area (arrangement area of nozzles that eject ink) is longer than the width of the recording medium P (the length in the direction perpendicular to the conveyance direction of the recording medium P). And a carriage-type ejection head that moves in the width direction of the recording medium P and ejects ink.

  As the inkjet system employed by the ejection head 122, a piezoelectric system that uses the vibration pressure of a piezoelectric element, a charge control system that ejects ink using electrostatic attraction, and an electrical signal that is converted into an acoustic beam and irradiated onto the ink Examples include an acoustic ink jet method that ejects ink using radiation pressure, and a thermal ink jet method that heats ink to form bubbles and uses the generated pressure.

  The discharge head 122 is, for example, a low-resolution discharge head (for example, a 600 dpi discharge head) that discharges ink droplets in a range of ink droplet amount of 10 pL or more and 15 pL or less, and a high discharge amount of ink droplets in a range of ink droplet amount of less than 10 pL. This is a discharge head for resolution (for example, a discharge head of 1,200 dpi). dpi means “dots per inch”.

  The ejection device 121 is not limited to a mode in which ink droplets are directly ejected from the ejection head 122 onto the recording medium P. After ejecting ink droplets from the ejection head 122 onto the intermediate transfer body, the ink droplets on the intermediate transfer body are ejected onto the recording medium P. It may be in the form of being transferred.

  The drying drum 126 is wound around the back surface of the recording medium P, and dries the image (ink) on the recording medium P while rotating following the conveyance of the recording medium P. Inside the drying drum 126 is incorporated a heating source (for example, a halogen heater or the like, not shown). The drying drum 126 dries the image (ink) on the recording medium P from the back side (opposite side of the recording surface) by the heating source.

  The warm air blower 128 is disposed around the drying drum 126, for example. The warm air blown from the warm air blower 128 dries the image (ink) on the recording medium P wound around the drying drum 126 from the front surface side (recording surface side).

  The drying device provided in the image recording unit 12 is not limited to the drying drum 126 and the hot air blowing device 128, and includes a near infrared heater, a laser irradiation device, and the like.

  The supply unit 14 includes a supply roll 14A around which the recording medium P is wound, and supplies the recording medium P from the supply roll 14A to the image recording unit 12. The supply roll 14A is rotatably supported by a frame member (not shown).

  The buffer unit 16 includes, for example, a first pass roller 16A, a dancer roller 16B, and a second pass roller 16C along the conveyance direction of the recording medium P. The dancer roller 16B moves up and down in FIG. 1 to adjust the tension and transport amount of the recording medium P supplied to the image recording unit 12.

  The winding unit 18 includes a winding roll 18A that winds the recording medium P on which an image is recorded. The recording medium P is transported along the transport path 124 by rotating the take-up roll 18 </ b> A by driving a motor (not shown).

  The buffer unit 20 includes, for example, a first pass roller 20A, a dancer roller 20B, and a second pass roller 20C along the conveyance direction of the recording medium P. The dancer roller 20 </ b> B moves up and down in FIG. 1 to adjust the tension and transport amount of the recording medium P discharged to the winding unit 18.

  The cooling unit 22 is provided with a plurality of cooling rollers 22A. The recording medium P is cooled by conveying the recording medium P between the plurality of cooling rollers 22A.

The recording apparatus according to the present embodiment is not limited to a rotary press such as the recording apparatus 10 shown in FIG. 1, and may be a sheet-fed machine that records each recording medium.
In addition, when used as a recording apparatus according to the second embodiment, an apparatus in which the processing liquid ejection head 118 in FIG. 1 is not used or removed is preferably exemplified.

  It is needless to say that the above-described embodiment is not limited to the embodiment and is realized within a range satisfying the requirements of the present invention.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” represent “part by mass” and “% by mass”, respectively.

Example 1
<Preparation of treatment liquid 1>
Ammonium salt of pyrrolidone carboxylic acid: 1.9% by mass
Propylene glycol (Wako Pure Chemical Industries, Ltd.): 7.0% by mass
1,2-hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.): 3.0% by mass
Polyacrylate emulsion (solid content 25% by mass): 4.0% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.6% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.2% by mass
Pure water: 81.3% by mass
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid 1. The pH of the treatment liquid 1 was 6.8.

<Preparation of water-based cyan ink 1>
Pigment Blue 15: 4 (cyan pigment, manufactured by Dainichi Seika Kogyo Co., Ltd.): 4.5% by mass
Styrene-acrylate copolymer (pigment dispersant): 0.5% by mass
Propylene glycol: 10% by mass
1,2-hexanediol: 5% by mass
Polyacrylate emulsion (solid content 25% by mass): 4% by mass
Olfine E1010: 0.7% by mass
Olfine E1004: 0.3% by mass
Pure water: 75% by mass
After mixing the above components, the mixture was filtered with a 5 μm filter to obtain an aqueous cyan ink 1. The pH of the aqueous cyan ink 1 was 8.8.

<Image formation>
About 3 ml of the treatment solution 1 was applied onto A4 size “OK topcoat +” paper (manufactured by Oji Paper Co., Ltd.) with a bar coater, and heat treated at 80 ° C. with a heater to prepare a recording medium.
Using the cyan ink 1 and a recording apparatus (Dimatix Materials Printer DMP-2831, manufactured by Fuji Film Dimatics), printing was performed on the produced recording medium.
A 2 dot line was printed with 10 pl droplets and then dried at 80 ° C. with a heater to obtain a printed image.

<Evaluation>
For each 2-dot line image, the line width and the radialness (line roughness of the edge portion of the line) were measured by a handy type image evaluation system Model PIAS-II (hereinafter referred to as “PIAS”) manufactured by Quality Engineering Associates (QEA). . The evaluation results are summarized in Table 1.
The criteria for each evaluation index are as follows.

-Line width evaluation-
A 2-dot line image was observed with PIAS, and the average value of the line widths of the 2-dot line image was measured.
A: 8.5 μm or more and 12.5 μm or less B: Over 12.5 μm and 14.0 μm or less C: Over 14.0 μm

-Rigidness evaluation-
The edge part of the 2 dot line image was observed by PIAS, and the line roughness (radidness) of the edge part in the 2 dot line image was measured.
A: The radius value is less than 0.1 μm. B: The radius value is not less than 0.1 μm and not more than 0.15 μm. C: The radius value is more than 0.15 μm.

(Example 2)
A print image was prepared and evaluated in the same manner as in Example 1 except that the following treatment liquid 2 was used instead of the treatment liquid 1. The evaluation results are summarized in Table 1.

<Preparation of treatment liquid 2>
Ethyl acetate: 2.0% by mass
Dilute sulfuric acid (0.01 mol / L, manufactured by Wako Pure Chemical Industries, Ltd.): 1.9% by mass
Propylene glycol: 7.0% by mass
1,2-hexanediol: 3.0% by mass
Polyacrylate emulsion (solid content 25% by mass): 4.0% by mass
Olfine E1010: 0.6% by mass
Olfine E1004: 0.2% by mass
Pure water: 81.3% by mass
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid 2. The pH of the treatment liquid 2 was 5.9.

(Reference Example 1)
A print image was prepared and evaluated in the same manner as in Example 1 except that the heat treatment after applying the treatment liquid 1 was not performed and the recording medium was produced by air drying. The evaluation results are summarized in Table 1.

(Reference Example 2)
A print image was prepared and evaluated in the same manner as in Example 2 except that the recording medium was prepared by air drying without performing the heat treatment after the treatment liquid 2 was applied. The evaluation results are summarized in Table 1.

(Comparative Example 1)
A print image was prepared and evaluated in the same manner as in Example 1 except that the treatment liquid 1 was not applied. The evaluation results are summarized in Table 1.

(Comparative Example 2)
A print image was prepared and evaluated in the same manner as in Example 1 except that the treatment liquid 1 was not applied and no heat treatment was performed during production of the recording medium. The evaluation results are summarized in Table 1.

  The embodiment of Examples 1 and 2 was an aspect in which the line width and the radialness were excellent and the image quality was excellent as compared with Comparative Examples 1 and 2.

<Preparation of treatment liquid A>
Pyrrolidone carboxylic acid 60% neutralized sodium salt (manufactured by Ajinomoto Co., Inc., 60% neutralized with sodium hydroxide): 2.0% by mass
Propylene glycol: 7.0% by mass
1,2-hexanediol: 3.0% by mass
Olfine E1010: 0.6% by mass
Olfine E1004: 0.2% by mass
Pure water: 87.2% by mass
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid A. The pH of the treatment liquid A was 3.6.

<Preparation of treatment liquid B>
Citric acid (Wako Pure Chemical Industries, Ltd.): 1.2% by mass
Sodium citrate (manufactured by Wako Pure Chemical Industries, Ltd.): 1.6% by mass
Propylene glycol: 7.0% by mass
1,2-hexanediol: 3.0% by mass
Polyacrylate emulsion (solid content 25% by mass): 4.0% by mass
Olfine E1010: 0.6% by mass
Olfine E1004: 0.2% by mass
Pure water: 82.4% by mass
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid B. The pH was 4.5.

<Preparation of treatment liquid C>
Allylamine polymer PAA-01 (manufactured by Nitto Bo Medical Co., Ltd.): 2.0% by mass
Propylene glycol: 7.0% by mass
1,2-hexanediol: 3.0% by mass
Olfine E1010: 0.6% by mass
Olfine E1004: 0.2% by mass
Pure water: 87.2% by mass
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid C. The pH was 9.9.

(Examples 3 and 4 and Comparative Examples 3 to 5)
The treatment liquid 1, the treatment liquid 2, the treatment liquid A, the treatment liquid B, and the treatment liquid C were filled in the ejection head, and the change in the contact angle of the used treatment liquid with respect to the elapsed time was measured.
If the contact angle is 50 degrees or less, a problem occurs in ejection. The measurement results are shown in Table 2.

The head filled with the treatment solution A or treatment solution B, which is an acidic treatment solution having a pH of less than 5, and the treatment solution C, which is a basic treatment solution having a pH of 9 or more, had a contact angle of 50 degrees or less in about 200 hours.
On the other hand, the treatment liquid 1 and the treatment liquid 2 of the example had a contact angle of 50 degrees or more even after 800 hours.

(Examples 5 and 6 and Comparative Examples 6 to 8)
An OK topcoat + paper that was not subjected to any treatment and an OK topcoat + paper in which treatment liquid 1, treatment liquid 2, treatment liquid A, or treatment liquid B was applied with a bar coater were prepared.
The coating amount of the treatment liquid was about 3 ml.
For each of the obtained OK topcoat + paper, a solid patch of 25 × 25 mm was printed with the water-based cyan ink 1 and the recording apparatus (EPSONPX-1004), and the print area ratio was 50%, 80%, and 100%. After printing, the film was dried by heating with a heater at 100 ° C. for about 2 minutes.
After drying, the image quality was evaluated by visual observation. The evaluation results are summarized in Table 3. The evaluation criteria are as follows.
A: There is no graininess and unevenness B: There is a little granularity and unevenness C: There is granularity and unevenness

It can be seen that the solid portion is less likely to produce graininess and unevenness when the effect of the treatment liquid is not obtained.
By not performing the heat treatment on the applied treatment liquid, in the examples, even if the treatment liquid was applied, no effect was produced and no deterioration of graininess or unevenness occurred.

<Preparation of treatment liquid 5>
Ammonium citrate: 1.9% by mass
Near-infrared absorbent aqueous dispersion (KAYASORB IRG-140 (manufactured by Nippon Kayaku Co., Ltd.) content 0.3 mass%, phenoxyethyl acrylate / methyl methacrylate / acrylic acid / acrylic acid-2-carboxyethyl copolymer ( Copolymerization ratio: 50/44/1/5) Content 8.0% by mass): 25.0% by mass
Propylene glycol: 7.0% by mass
1,2-hexanediol: 3.0% by mass
Polyacrylate emulsion (solid content 25%): 4.0% by mass
Olfine E1010: 0.6% by mass
Olfine E1004: 0.2% by mass
Pure water: 58.3 mass%
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid 5. The pH was 6.9.

<Preparation of treatment liquid 6>
Propionate-t-butyl: 2.0% by mass
Dilute hydrochloric acid: 1.9% by mass
Near-infrared absorber aqueous dispersion (NIR-IM1 (manufactured by Nagase ChemteX Corporation)) content 0.3 mass%, phenoxyethyl acrylate / methyl methacrylate / acrylic acid / acrylic acid-2-carboxyethyl copolymer (co-polymer) Polymerization ratio: 50/44/1/5) Content 8.0% by mass): 25.0% by mass
Propylene glycol: 7.0% by mass
1,2-hexanediol: 3.0% by mass
Polyacrylate emulsion (solid content 25%): 4.0% by mass
Olfine E1010: 0.6% by mass
Olfine E1004: 0.2% by mass
Pure water: 56.3 mass%
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid 6. The pH was 6.0.

(Examples 7 and 8, Comparative Examples 9 to 11)
An OK topcoat + paper that was not subjected to any treatment and an OK topcoat + paper in which treatment liquid 5, treatment liquid 6, treatment liquid A, or treatment liquid B was applied with a bar coater were prepared.
The coating amount of the treatment liquid was about 3 ml.
All the prepared papers were heat-treated only at the center of the image with an infrared laser having a wavelength of 810 nm.
Each of the obtained OK topcoat + paper was printed with a solid patch having a printing area ratio of 80% and a 2 dot line at 25 × 25 mm with the aqueous cyan ink 1, and then heated and dried with a heater at 100 ° C. for about 2 minutes. . After drying, the line width and the raidness were evaluated by PIAS, and the solid image was visually evaluated.

In the laser heating part, the same result as the whole heating by the heater was obtained.
Moreover, in a solid image, image quality can be further improved by selecting a heating part and a non-heating part.

Example 9
<Preparation of treatment liquid 7>
Ammonium salt of pyrrolidone carboxylic acid (manufactured by Ajinomoto Co., Inc.) (100% neutralized): 1.9% by mass
Near-infrared absorber aqueous dispersion (near-infrared absorber content of the following structure: 0.3 mass%, phenoxyethyl acrylate / methyl methacrylate / acrylic acid / acrylic acid-2-carboxyethyl copolymer (copolymerization ratio: 50 / 44/1/5) Content 8.0% by mass): 25.0% by mass
Propylene glycol (Wako Pure Chemical Industries, Ltd.): 12.0% by mass
1,2-hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.): 1.0% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.4% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.2% by mass
Pure water: 59.5% by mass
After mixing the above components, filtration with a 5 μm filter was performed to obtain treatment liquid 5. The pH of the treatment liquid 5 was 7.1.

  TBu represents a t-butyl group.

<Preparation of water-based cyan ink 2>
Pigment Blue 15: 4 (cyan pigment, manufactured by Dainichi Seika Kogyo Co., Ltd.): 4.0% by mass
Styrene-methyl methacrylate-acrylate copolymer (pigment dispersant): 0.4% by mass
Propylene glycol (Wako Pure Chemical Industries, Ltd.): 13% by mass
1,2-hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.): 1% by mass
Polyacrylate emulsion (solid content 25% by mass): 10% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.7% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.3% by mass
Pure water: 70.6% by mass
After mixing the above components, the mixture was filtered through a 5 μm filter to obtain an aqueous cyan ink 2. The pH of the aqueous cyan ink 2 was 8.8.
The styrene-methyl methacrylate-acrylate copolymer is prepared by subjecting a styrene / methyl methacrylate / acrylic acid and a polymerization initiator to a polymerization reaction in a reaction solvent in a conventional manner, followed by hydroxylation. The compound was obtained by neutralizing with sodium.
The polyacrylate emulsion uses butyl acrylate / methyl acrylate / acrylic acid, a surfactant and a polymerization initiator, and after performing a polymerization reaction in a reaction solvent according to a conventional method, is then neutralized with sodium hydroxide. Reaction was performed to obtain the compound.

<Preparation of aqueous magenta ink 1>
PigmentRed 122 (magenta pigment, manufactured by Dainichi Seika Kogyo Co., Ltd.): 5.5% by mass
Styrene-ethyl methacrylate-methacrylate copolymer (pigment dispersant): 0.5% by mass
Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.): 12% by mass
1,2-hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.): 3% by mass
Polyacrylate emulsion (solid content 25% by mass): 10% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.6% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.4% by mass
Pure water: 68.0% by mass
After mixing the above components, the mixture was filtered with a 5 μm filter to obtain an aqueous magenta ink 1. The pH of the aqueous magenta ink 1 was 8.7.

<Preparation of aqueous yellow ink 1>
Pigment Yellow 74 (yellow pigment, manufactured by Dainichi Seika Kogyo Co., Ltd.)
: 4.0% by mass
Styrene-methyl methacrylate-methacrylate copolymer (pigment dispersant): 0.4% by mass
Propylene glycol (Wako Pure Chemical Industries, Ltd.): 14% by mass
1,2-hexanediol (manufactured by Wako Pure Chemical Industries, Ltd.): 1.5% by mass
Polyacrylate emulsion (solid content 25% by mass): 10% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.5% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.3% by mass
Pure water: 69.3 mass%
After mixing the above components, the mixture was filtered with a 5 μm filter to obtain an aqueous magenta ink 1. The pH of the aqueous magenta ink 1 was 8.7.

<Preparation of aqueous black ink 1>
Carbon black (black pigment, manufactured by Cabot): 5.3% by mass
Styrene-ethyl acrylate-acrylate copolymer (pigment dispersant): 0.5% by mass
Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.): 12% by mass
Diethylene glycol monoisopropyl ether (manufactured by Nippon Emulsifier Co., Ltd.): 3% by mass
Polyacrylate emulsion (solid content 25% by mass): 10% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.6% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.4% by mass
Pure water: 68.2% by mass
After mixing the above components, the mixture was filtered with a 5 μm filter to obtain an aqueous black ink 1. The pH of the aqueous black ink 1 was 8.5.

<Image formation>
The treatment liquid 7 and water-based cyan ink 2 / water-based magenta ink 1 / water-based yellow ink 1 / water-based black ink 1 are applied onto OK top coat + paper (manufactured by Oji Paper Co., Ltd.) using the recording apparatus of FIG. A 10 pl droplet was printed with 2 dot lines and solid patches of 20 × 20 mm for each color at a printing area ratio of 50%, 80% and 100%. In the case of a 2 dot line, the processing liquid 5 has an image density corresponding to 2 dots around the image area, and in the case of a solid patch, the image area has an image density corresponding to 30% of the ink printing area ratio, and also corresponds to 2 dots around the solid patch. Granted. After application of the treatment liquid, an infrared laser having a wavelength of 810 nm was irradiated, and after ink application, the ink was dried on a drying drum. The drying temperature was 110 ° C.
As in Example 1, when the line width and the raidness were evaluated, the evaluation result was A for all.
Further, the solid patch was visually observed and the image quality was evaluated according to the following criteria. As a result, the evaluation was A regardless of the ink printing area ratio.
A: There is no graininess and unevenness. Moreover, there is no disturbance of the patch edge part.
B: There is a little graininess and unevenness, and there is a slight disturbance in the patch edge portion.
C: Graininess, streak unevenness, and patch-like irregularities at the patch edge portion.

(Example 10)
<Preparation of water-based cyan ink 3>
Pigment Blue 15: 3 (cyan pigment, manufactured by Dainichi Seika Kogyo Co., Ltd.): 4.0% by mass
Styrene-acrylate copolymer (pigment dispersant): 0.4% by mass
Propylene glycol (Wako Pure Chemical Industries, Ltd.): 9% by mass
Ethylene glycol (Wako Pure Chemical Industries, Ltd.): 3.5% by mass
Polyacrylate emulsion (solid content 25% by mass): 10% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.55% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.35% by mass
N-Cyclohexyl-3-aminopropanesulphonic acid (pH buffer, manufactured by Dojindo Laboratories): 0.221% by mass
0.1 mol / l sodium hydroxide solution: 6% by mass
Pure water: 65.979% by mass
After mixing the above components, the mixture was filtered with a 5 μm filter to obtain an aqueous cyan ink 3. The pH of the aqueous cyan ink 3 was 10.6.

<Image formation>
In the same manner as in Example 1, a recording medium coated with the treatment liquid 1 was produced. Further, the aqueous cyan ink 3 was printed on the previously prepared recording medium in the same manner as in Example 1.
A 2 dot line was printed with 10 pl droplets and then dried at 80 ° C. with a heater to obtain a printed image.

<Evaluation>
When the same evaluation as in Example 1 was performed, the result of the line width was A, the result of the radialness was B, and the evaluation of the solid image with a printing area ratio of 80% was B.

(Example 11)
<Preparation of water-based cyan ink 4>
Cabojet 250C (aqueous pigment dispersion, manufactured by Cabot Corporation, pigment solid content: 10% by mass): 40% by mass
Propylene glycol (Wako Pure Chemical Industries, Ltd.): 10% by mass
Diethylene glycol monobutyl ether (Wako Pure Chemical Industries, Ltd.): 1.5% by mass
Polyacrylate emulsion (solid content 30% by mass): 12% by mass
Olfine E1010 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.5% by mass
Olfine E1004 (surfactant, manufactured by Nissin Chemical Industry Co., Ltd.): 0.25% by mass
Pure water: 35.75% by mass
After mixing the above components, the mixture was filtered with a 5 μm filter to obtain an aqueous cyan ink 4. The pH of the aqueous cyan ink 4 was 7.1.

<Image formation>
In the same manner as in Example 1, a recording medium coated with the treatment liquid 1 was produced. Further, the aqueous cyan ink 4 was printed on the previously prepared recording medium in the same manner as in Example 1.
A 2 dot line was printed with 10 pl droplets and then dried at 80 ° C. with a heater to obtain a printed image.

<Evaluation>
When the same evaluation as in Example 1 was performed, the result of the line width was B, the result of the radialness was B, and the evaluation of the solid image with a printing area ratio of 80% was B.

10: inkjet recording apparatus 12: image recording unit 14: pre-processing unit 14B: supply roll 16: buffer unit 16A: first pass roller 16B: dancer roller 16C: second pass roller 18: post-processing unit 18A: take-up roll 20: buffer Unit 20A: first pass roller 20B: dancer roller 20C: second pass roller 22: cooling unit 22A: cooling roller 118: treatment liquid discharge head 120: infrared laser irradiation device 121: discharge devices 122K, 122Y, 122M, 122C: discharge head 124 : Transport path 126: drying drum 128: hot air blower P: recording medium

Claims (12)

A treatment liquid having a pH of 5 or more and 9 or less and containing a thermal acid generator.   The treatment liquid according to claim 1, wherein the thermal acid generator contains at least one compound selected from the group consisting of a carboxylic acid ammonium salt compound and a sulfonic acid ammonium salt compound.   The processing liquid of Claim 1 or Claim 2 containing an infrared absorber.   A processing liquid cartridge containing the processing liquid according to any one of claims 1 to 3. The processing liquid according to any one of claims 1 to 3, and
An ink set having an ink having a pH of 7.5 or more and 10 or less. A processing liquid cartridge containing the processing liquid according to any one of claims 1 to 3,
an ink cartridge containing ink having a pH of 7.5 to 10;
An ink cartridge set. Containing the ink set according to claim 5;
An apparatus for applying the treatment liquid to a recording medium;
An apparatus for heating at least a part of the treatment liquid applied on the recording medium;
An apparatus for applying at least the treatment liquid to which the ink has been applied; and
A recording apparatus comprising a device for drying the applied ink. Using the ink set according to claim 5,
Applying the treatment liquid to a recording medium;
Heating at least a part of the treatment liquid applied on the recording medium;
Applying at least the treatment liquid to which the ink has been applied; and
A recording method comprising a step of drying the applied ink.   A treated recording medium having a region having a thermal acid generator on at least a part of the surface of the recording medium.   The treated recording medium according to claim 9, wherein the region is a region having a pH of 5 or more and 9 or less and a treatment liquid containing a thermal acid generator applied to the surface of the recording medium. An apparatus for heating at least a part of the region in the processed recording medium according to claim 9 or 10,
an apparatus for applying at least an ink having a pH of 7.5 or more and 10 or less onto the region; and
A recording apparatus comprising a device for drying the applied ink. Heating at least a part of the region in the treated recording medium according to claim 9 or 10,
applying at least an ink having a pH of 7.5 to 10 on the region; and
A recording method comprising a step of drying the applied ink.