JP2016221943A - Recording method and recording apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording method by which recording excellent in printing stability and recording productivity can be achieved on an ink non-absorbable or ink low-absorbable recording medium and images excellent in picture qualities and durability can be recorded.SOLUTION: The recording method includes: a reaction liquid adhesion step of discharging and adhering a reaction liquid as droplets by an inkjet process to an ink non-absorbable or ink low-absorbable recording medium 1 by controlling an adhesion amount of the reaction liquid to 1.9 mg/inchor less, where the reaction liquid comprises a reagent for aggregating or thickening a colored ink composition in a content of 0.1 to 0.9 mol/kg; and a colored ink composition adhesion step of adhering a colored ink composition to the recording medium 1 to which the reaction liquid is adhered. A period from when adhesion of the reaction liquid is ended until adhesion of the colored ink composition is started is within 30 seconds; and a surface temperature of the recording medium 1 from the reaction liquid adhesion step to the colored ink composition adhesion step is 38°C or lower.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a recording method and a recording apparatus for performing the recording method.

2. Description of the Related Art Conventionally, an ink jet recording method for recording an image on a recording medium by discharging minute ink droplets from a nozzle of a recording head of an ink jet recording apparatus is known. Ink for ink jet recording is generally prepared by dissolving or dispersing a colorant such as a dye or pigment in an aqueous medium containing water, an organic solvent, or the like. It is roughly divided into pigment inks containing Up to now, dye inks with excellent color reproducibility and ejection stability have been widely used, but the long-term storage stability of recorded images is regarded as important due to the expansion of the use of inkjet recording technology to digital photography services and commercial printing. As a result, pigment inks having superior water resistance and light resistance compared to dye inks have been used.

However, when pigment ink is used as ink for ink jet recording and recording is performed on a recording medium such as plain paper, coated paper, art paper, etc., the pigment penetrates into these, and the optical density tends to be insufficient. There was a problem.

In order to solve such a problem, for example, in Patent Document 1, a reaction liquid containing a pigment flocculant, water, and a water-soluble organic solvent is prepared separately from the ink containing a self-dispersing pigment, and the ink droplet amount is prepared. Is set to 35 pL or less, and a recording method is disclosed in which the reaction liquid is overprinted on an ink-recorded portion by an inkjet method.

In Patent Document 2, a reaction liquid having pigment ink aggregating ability and film forming ability is applied to a recording surface, and then an image is recorded by discharging the pigment ink, followed by heating and drying. An ink jet recording method for forming a film is disclosed.

JP 2010-234582 A JP 2003-326829 A

When a reaction liquid is attached to a recording medium that does not absorb ink or has low ink absorption, the reaction liquid hardly penetrates into the recording medium, and thus a drying step for drying the reaction liquid is essential. As the drying step, a method of heating the recording medium, a method of ensuring a wait time until the colored ink composition is attached, or the like can be considered. However, in the method of heating the recording medium to increase the drying property of the reaction liquid, when the heating is excessive, the nozzle of the ink jet head is easily dried by the radiant heat, and the reliability of the ink jet head is lowered. On the other hand, in the method of securing the wait time and drying the reaction solution, the printing speed is lowered, and as a result, the recording productivity is lowered.

Accordingly, some aspects of the present invention solve at least a part of the above-described problems, thereby achieving recording with excellent printing stability and recording productivity on a non-ink-absorbing or ink-absorbing recording medium. And a recording method capable of recording an image excellent in image quality and durability.

SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the recording method according to the present invention is:
Adhering a reaction liquid containing a reactive agent with a content of 0.1 to 0.9 mol / kg to a non-ink-absorbing or low-ink-absorbing recording medium to agglomerate or thicken the colored ink composition. A reaction liquid deposition step in which the amount is 1.9 mg / inch ² or less and is ejected and deposited as droplets by an inkjet method;
A colored ink composition attaching step for attaching the colored ink composition to the recording medium to which the reaction liquid is attached,
The time from the completion of the deposition of the reaction liquid to the start of the deposition of the colored ink composition is within 30 seconds, and the surface temperature of the recording medium from the reaction liquid deposition process to the colored ink composition deposition process is 38 ° C. It is characterized by the following.

According to the recording method of Application Example 1, by controlling the concentration of the reactant in the reaction liquid used in the reaction liquid attaching step and the amount of the reaction liquid attached, the ink can be removed without going through an excessive drying step of the reaction liquid. It is possible to realize recording excellent in printing stability and productivity on a recording medium having absorptivity or low ink absorption, and it is also possible to record an image excellent in image quality and durability.

[Application Example 2]
In the recording method of application example 1,
The mass per droplet (1 dot) of the reaction liquid in the reaction liquid adhesion step is 10 ng /
It can be less than dot.

[Application Example 3]
In the recording method of Application Example 1 or Application Example 2,
The droplet resolution in the region of the maximum amount of the reaction solution in the reaction solution attachment step is 200.
X200 dpi or more.

[Application Example 4]
In the recording method of any one of application examples 1 to 3,
The deposition amount of the reactant in the reaction liquid deposition step may be 1000 nmol / inch ² or less.

[Application Example 5]
In the recording method of any one of Application Example 1 to Application Example 4,
From the reaction liquid attaching step to the colored ink composition attaching step, the temperature of the recording medium is 3
It can be said that it is 2-38 degreeC.

[Application Example 6]
In the recording method of any one of application examples 1 to 5,
The colored ink composition contains a resin, and the volume of the 0.085 mol / kg calcium acetate aqueous solution necessary for agglomerating 3 mL of a 1% by mass resin-containing aqueous solution (aqueous dispersion) is 0.1 to 7 mL. Certain resins can be included.

[Application Example 7]
In the recording method of any one of application examples 1 to 6,
The water absorption rate of the recording medium is 30 from the start of contact in the Bristow method.
The water absorption up to msec ^1/2 can be 10 mL / m ² or less.

[Application Example 8]
In the recording method of any one of application examples 1 to 7,
The reactant may include at least one selected from the group consisting of polyvalent metal salts and organic acids.

[Application Example 9]
In the recording method described in any one of Application Examples 1 to 8,
In the recording area where the amount of the colored ink composition deposited in the colored ink composition deposition step is 5 mg / inch ² or more, the amount of the reaction liquid deposited is 0.3 to 1.9 mg / inch ^2. it can.

[Application Example 10]
One aspect of the recording apparatus according to the present invention is:
It is a recording apparatus for performing the recording method of any one of application examples 1 to 9.

1 is a diagram schematically illustrating an example of an image recording apparatus used in a recording method according to an embodiment.

Hereinafter, preferred embodiments of the present invention will be described. Embodiment described below demonstrates an example of this invention. In addition, the present invention is not limited to the following embodiments, and includes various modifications that are implemented within a range that does not change the gist of the present invention.

1. Recording Method The recording method according to the present embodiment is a method for recording on a non-ink-absorbing or ink-absorbing recording medium.
A reaction solution containing a reactive agent for aggregating or thickening the colored ink composition at a content of 0.1 to 0.9 mol / kg is obtained by an ink jet method with an adhesion amount of the reaction solution of 1.9 mg / inch ² or less. A reaction liquid attachment step for discharging and attaching as droplets, and a colored ink composition attachment step for attaching a colored ink composition to a recording medium to which the reaction liquid is attached. The time until the start of adhesion of the colored ink composition is within 30 seconds, and the surface temperature of the recording medium from the reaction liquid adhesion step to the color ink composition adhesion step is 38 ° C. or less.

The “image” in the present invention indicates a recording pattern formed from a group of dots, and includes text printing and solid images. Note that a “solid image” means that dots are recorded for all of the pixels that are the minimum recording unit area defined by the recording resolution. Normally, the recording area of the recording medium is covered with ink and the ground of the recording medium is recorded. This means an image pattern that should be an image that cannot be seen.

  Hereinafter, the recording method according to the present embodiment will be described in detail for each of the above steps.

1.1. Reaction liquid adhesion step 1.1.1. Description of Process The reaction liquid adhesion step is a content of 0.1 to 0.9 mol / kg of a reactive agent that aggregates or thickens a colored ink composition described later on a non-ink-absorbing or low-ink-absorbing recording medium. Is a step of ejecting and adhering the reaction liquid contained in (4) as droplets by an ink jet method. When a reactive agent is previously attached to the recording area of the recording medium and the reactive agent and the colored ink composition are brought into contact with each other, the components (for example, the coloring agent and the resin) contained in the colored ink composition react with the reactive agent. To do. If it does so, the dispersion state of the coloring agent and resin in a coloring ink composition will be destroyed, and a coloring agent and resin will aggregate or a coloring ink composition will thicken. Thereby, since the penetration of the colorant into the recording medium can be inhibited, it is considered excellent in terms of improving the image quality of the recorded image.
The amount of the reaction solution deposited in the reaction solution deposition step is 1.9 mg / inch ² or less. This
The recorded images can be made excellent. In particular, when the amount of the reaction liquid deposited is larger than the above range, the solvent component contained in the reaction liquid adhered to the recording medium increases, and the ink composition is contained in the reaction liquid layer in which a large amount of solvent is present. The ink droplets that landed on the recording medium agglomerated or thickened in a granular state, and the ink droplets appeared to be granular in the image. Such a phenomenon can be prevented by setting the amount of the reaction solution to be within the above range.

The “ink non-absorbing or low ink absorbing recording medium” in the present invention refers to a recording medium having a property of not absorbing or hardly absorbing an ink composition. Quantitatively, a non-ink-absorbing or low-ink-absorbing recording medium is “Bristow”.
ow) refers to a recording medium having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the method. This Bristow method is the most popular method for measuring the amount of liquid absorbed in a short time, and is also adopted by the Japan Paper Pulp Technology Association (JAPAN TAPPI). Details of the test method are “JAPAN TAPPI Paper Pulp Test Method 2000”
Standard No. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method". On the other hand, an ink-absorbing recording medium refers to a recording medium that does not correspond to an ink non-absorbing or low-ink absorbing recording medium.

Examples of non-ink-absorbing recording media include plastic films that do not have an ink absorbing layer, those that are coated with plastic on a substrate such as paper, and those that have a plastic film adhered thereto. . Examples of the plastic here include polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene.

Examples of the recording medium with low ink absorption include a recording medium provided with a coating layer for receiving ink on the surface. For example, as the base material is paper, art paper, coated paper, mat For example, when the base material is a plastic film, a hydrophilic polymer is applied to the surface of polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, polypropylene, etc. , Silica and titanium particles are coated with a binder.

When the reaction liquid is attached to a non-ink-absorbing or low-ink-absorbing recording medium, the reaction liquid hardly penetrates into the recording medium, and therefore a reaction liquid pool in which a large amount of water exists in the recording area of the recording medium occurs. If the colored ink composition is driven into the reaction liquid reservoir containing a large amount of water, the colorant or resin contained in the colored ink composition aggregates in the reaction liquid reservoir in a granular manner, and the image quality deteriorates. was there. For this reason, when the reaction liquid is attached to a non-ink-absorbing or low-ink-absorbing recording medium, a drying step for drying the reaction liquid has been essential.

However, by ejecting the reaction liquid as droplets by the ink jet method and adhering it to the recording medium, it is possible to control the reaction liquid to be applied thinly on the recording medium. It was found that the image quality can be secured. As a result, since the amount of the reaction liquid applied is small, the amount of water adhering to the recording medium is small, and an excellent image quality can be ensured even without a drying step for drying the reaction liquid.

In addition, the reaction solution drying process may include a method of heating the recording medium to increase the drying property of the reaction solution or a method of drying the reaction solution while ensuring a long wait time. However, these drying steps are unnecessary. By doing so, printing stability and recording productivity are improved. That is, the method of heating the recording medium to increase the drying property of the reaction liquid is not performed, or the minimum necessary heating is performed to prevent the nozzle of the inkjet head from being easily dried by the radiant heat. Printing stability can be ensured. On the other hand, if the method of drying the reaction liquid while ensuring a long wait time is not performed, the printing speed is increased, and as a result, the recording productivity is improved.

When attaching the reaction liquid to the recording medium using the ink jet method, the line ink jet head is used to attach the head and the recording medium in a single relative scan, and the serial ink jet head is used for the reaction liquid. Any of the forms in which the head and the recording medium are attached by a multi-pass method may be used, but the former is preferable in terms of the high printing speed.

When the reaction solution is attached to the recording medium using the inkjet method, the amount of the reaction solution attached is 1.9.
It is within the range of mg / inch ² or less. The upper limit value of the amount of the reaction solution is preferably 1.8 m.
g / inch ² or less, more preferably 1.5 mg / inch ² or less, more preferably 1.
0 mg / inch ² or less. The lower limit value of the amount of the reaction solution in this region is preferably 0.
. 3 mg / inch ² or more, more preferably 0.4 mg / inch ² . If the amount of the reaction liquid adhering to the recording medium is within the above range, the reaction liquid may be removed without performing a drying process or when performing a minimum heating process in which the surface temperature of the recording medium is within a predetermined range. Even when there is no or little drying, and the solvent component contained in the reaction liquid remains on the recording medium, the amount of the solvent component adhered to the recording medium can be made relatively small, so the image quality of the recorded matter is excellent. In addition, it is possible to realize recording with excellent printing stability and recording productivity on a recording medium. These effects are particularly useful when recording on a non-ink-absorbing or ink-absorbing recording medium. In addition, since a necessary and sufficient amount of the reactive agent adheres to the recording area of the recording medium,
Images with excellent image quality and durability can also be recorded. Maximum amount of reaction solution is 0.3mg
In the case of / inch ² or more, the attached reactive agent is insufficient, or the reaction liquid permeates into the inside of the recording medium, so that almost no reactive agent remains on the surface of the recording area of the recording medium. Even if the composition is adhered to the recording area of the recording medium, it is difficult to cause a reaction and it is difficult to obtain an image with excellent image quality. On the other hand, the maximum adhesion amount of the reaction solution is 1.9 mg.
In the case of exceeding / inch ^{2, the} amount of the solvent of the reaction liquid attached to the recording area of the recording medium is large, and the reaction liquid pools, so that it is necessary to perform a drying process. And when a drying process is performed, the recording excellent in printing stability and recording productivity as mentioned above cannot be realized.
Further, the amount of adhesion 5 mg / inch ² or more colored ink composition of colored ink composition adhering step, preferably in the region of 5~16mg / inch ^2, the amount of deposition of the reaction solution in the reaction liquid applying step 0.3 1.9 mg / inch ² is preferable from the standpoint of further improving image quality, printing stability, and recording productivity. Further, in the above case, adhesion of the coloring ink composition colored ink composition adhering step is more preferably in terms of the fact that the 5~13mg / inch ² in the region of 5 to 10 mg / inch ² More preferably, the region. In this case, in the region where the amount of the colored ink composition deposited is less than 5 mg / inch ^{2, the} amount of the colored ink composition deposited is small and there is a tendency for no sticky spots or bleeding to occur. The amount is not limited except that the amount is 1.9 mg / inch ² or less.
Here, in the recording method, the amount of the reaction liquid deposited in the reaction liquid deposition step is different from the amount of the reaction liquid in a part of the region where the same amount is deposited in the recording area where recording is performed. It is the amount of adhesion. Similarly, the amount of the colored ink composition applied in the step of attaching the colored ink composition is the same when the recording method includes a region where the amount of the colored ink composition is different in the recording region where recording is performed. It is the adhesion amount of the colored ink composition in the area of the part.

The maximum amount of the reactant contained in the reaction liquid in the recording area of the recording medium is 100
It is preferable to be 0 nmol / inch ² or less, and 90 to 1000 nmol / inch ²
More preferably. More preferably, the upper limit value of the maximum adhesion amount of the reactant is 700 nm.
ol / inch ² or less, more preferably 550 nmol / inch ² or less, more preferably 490 nmol / inch ² or less, more preferably 400 nmol / inch ² or less,
Particularly preferably, it is 300 nmol / inch ² or less. On the other hand, the lower limit is preferably 1.
00 nmol / inch ² or more. When the maximum amount of the reactive agent is within the above range, a necessary and sufficient amount of the reactive agent adheres to the recording area of the recording medium, so that an image excellent in image quality and durability can be recorded. Furthermore, when the minimum adhesion amount in the recording area of the reaction liquid is also within the above range, it is more preferable in terms of the above effects. When the maximum adhesion amount and the minimum adhesion amount of the reactant are within the above range, that is, the amount of the reactant contained in the reaction liquid in the recording area of the recording medium is within the above range. It is preferable that the amount of the reactant contained in the reaction solution in the recording area of the recording medium be within the above range.

When the reaction liquid is attached to the recording medium using the inkjet method, it is preferable that the resolution of the droplets in the region where the maximum amount of the reaction liquid is attached is 200 × 200 dpi or more. The lower limit value of the resolution is more preferably 300 × 300 dpi or more, and further preferably 360 × 360 d.
Pi or more, particularly preferably 600 × 600 dpi or more. The upper limit value of the resolution is not particularly limited, but is 2000 × 2000 dpi or less. Since the resolution of the droplets in the region where the maximum amount of the reaction liquid is attached is in the above range, the reaction agent can be uniformly attached to the recording area of the recording medium, and the drying property of the reaction liquid can be improved. .

When the reaction liquid is attached to the recording medium using the inkjet method, a droplet of the reaction liquid (1 dot
) Is preferably 20 ng / dot or less. The upper limit value of the mass per droplet of the reaction liquid is more preferably 10 ng / dot or less, and even more preferably 7 ng / dot.
Hereinafter, it is more preferably 5 ng / dot or less, particularly preferably 3 ng / dot or less.
The lower limit value of the mass per droplet of the reaction liquid is more preferably 0.5 ng / dot or more, and particularly preferably 1 ng / dot or more. When the mass per droplet of the reaction liquid is in the above range, it is preferable in that the reactant can be uniformly attached to the recording area of the recording medium and the drying property of the reaction liquid can be improved.

In addition, before the reaction liquid adhesion process, in order to improve the wettability of the recording medium to the reaction liquid, a surface modification process for modifying the surface of the recording medium may be performed. For example, by modifying the surface so that the wetting tension index on the surface of a low-ink or non-ink-absorbing recording medium is 40 mN / m or more, the wettability of the reaction liquid can be improved, and the reaction liquid is recorded. It can be uniformly deposited on the medium. Here, “wetting tension index” means “plastic film and sheet—
Wet tension measured in accordance with “wetting tension test method (JIS K6768: 1999)”.

Such a surface modification step is not particularly limited, for example, corona treatment,
Examples include atmospheric pressure plasma treatment, flame treatment, ultraviolet irradiation treatment, solvent treatment, and resin liquid adhesion treatment (for example, primer treatment). These processing methods can be performed using a known apparatus.

1.1.2. Next, the reaction solution used in the reaction solution attachment step will be described. The reaction liquid used in this embodiment contains a reactive agent for aggregating or thickening a colored ink composition described later, and other components. Hereinafter, components contained in the reaction solution used in the present embodiment and components that can be contained will be described in detail.

<Reactant>
The reaction liquid used in this embodiment contains a reactive agent that acts on components (for example, a colorant and a resin) included in the colored ink composition to cause aggregation or thickening. As a reactant,
Examples thereof include polyvalent metal salts, organic acids, and cationic compounds (cationic resins, cationic surfactants, etc.). These reactants may be used alone or in combination of two or more. Among these reactants, it is preferable to use at least one reactant selected from the group consisting of polyvalent metal salts and organic acids from the viewpoint of excellent reactivity with components contained in the colored ink composition. .

The polyvalent metal salt is a compound that is composed of divalent or higher polyvalent metal ions and anions that bind to these polyvalent metal ions and is soluble in water. Specific examples of polyvalent metal ions include C
Divalent metal ions such as a ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Zn ²⁺ , Ba ²⁺ ; Al ³⁺ , Fe ³⁺
And trivalent metal ions such as Cr ³⁺ . As anions, Cl ⁻ , I ⁻ , Br ⁻ ,
SO ₄ ²⁻ , ClO ³⁻ , NO ³⁻ , HCOO ⁻ , CH ₃ COO ^{− and the} like can be mentioned. Among these polyvalent metal salts, calcium salts and magnesium salts are preferable from the viewpoint of the stability of the reaction solution and the reactivity as a reactant.

Specific examples of polyvalent metal salts include strong acid and alkali salts such as nitrates (calcium nitrate,
Magnesium nitrate, etc.), sulfates (calcium sulfate, magnesium sulfate, etc.), hydrochlorides and the like. Also, weak acid and alkali salts such as formate and acetate can be used.

Examples of organic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, polyacrylic acid, acetic acid, glycolic acid, malonic acid, malic acid, maleic acid, ascorbic acid, succinic acid, glutaric acid, fumaric acid, citric acid, and tartaric acid. Lactic acid, sulfonic acid, orthophosphoric acid, pyrrolidone carboxylic acid,
Preferred examples include pyronecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, pyridinecarboxylic acid, coumaric acid, thiophenecarboxylic acid, nicotinic acid, derivatives of these compounds, or salts thereof. An organic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the cationic resin include a cationic urethane resin, a cationic olefin resin, and a cationic allylamine resin.

As a cationic urethane resin, a well-known thing can be selected suitably and can be used.
As the cationic urethane resin, commercially available products can be used, for example, hydrane.
CP-7010, CP-7020, CP-7030, CP-7040, CP-7050,
CP-7060, CP-7610 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.), Superflex 600, 610, 620, 630, 640, 650 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), urethane emulsion WBR -2120C, WBR-2122C (trade name, manufactured by Taisei Fine Chemical Co., Ltd.) and the like can be used.

The cationic olefin resin has an olefin such as ethylene or propylene in the structural skeleton, and a known one can be appropriately selected and used. The cationic olefin resin may be in an emulsion state dispersed in a solvent containing water, an organic solvent, or the like. As the cationic olefin resin, commercially available products can be used, and examples thereof include Arrow Base CB-1200, CD-1200 (trade name, manufactured by Unitika Ltd.) and the like.

As the cationic allylamine resin, known ones can be appropriately selected and used. For example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine acetate / diallylamine acetate Copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine hydrochloride,
Dimethylallylamine hydrochloride copolymer, allylamine / dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetate, polydiallyldimethylammonium chloride, diallylamine acetate / sulfur dioxide copolymer, Diallylmethylethylammonium ethyl sulfate / sulfur dioxide copolymer, methyldiallylamine hydrochloride /
And sulfur dioxide copolymer, diallyldimethylammonium chloride / sulfur dioxide copolymer, diallyldimethylammonium chloride / acrylamide copolymer, and the like. As such a cationic allylamine-based resin, commercially available products can be used. For example, PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, P
AA-HCL-3L, PAA-HCL-10L, PAA-H-HCL, PAA-SA, P
AA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15
C, PAA-25, PAA-H-10C, PAA-D11-HCL, PAA-D41-H
CL, PAA-D19-HCL, PAS-21CL, PAS-M-1L, PAS-M-1
, PAS-22SA, PAS-M-1A, PAS-H-1L, PAS-H-5L, PAS
-H-10L, PAS-92, PAS-92A, PAS-J-81L, PAS-J-81
(Trade name, manufactured by Nittobo Medical Company), Hymo Neo-600, Hymo Lock
Q-101, Q-311, Q-501, Himax SC-505, SC-505 (trade name, manufactured by Hymo Co., Ltd.) and the like can be used.

Examples of the cationic surfactant include primary, secondary and tertiary amine salt type compounds, alkylamine salts, dialkylamine salts, aliphatic amine salts, benzalkonium salts, fourth compounds, and the like.
Examples include quaternary ammonium salts, quaternary alkyl ammonium salts, alkyl pyridinium salts, sulfonium salts, phosphonium salts, onium salts, imidazolinium salts, and the like. Specific examples of the cationic surfactant include hydrochlorides such as laurylamine, coconutamine, and rosinamine,
Acetate, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, benzyl tributyl ammonium chloride, benzalkonium chloride, dimethyl ethyl lauryl ammonium ethyl sulfate, dimethyl ethyl octyl ammonium ethyl sulfate, trimethyl lauryl ammonium hydrochloride, cetyl pyridinium chloride,
Examples include cetylpyridinium bromide, dihydroxyethyl laurylamine, decyldimethylbenzylammonium chloride, dodecyldimethylbenzylammonium chloride, tetradecyldimethylammonium chloride, hexadecyldimethylammonium chloride, and octadecyldimethylammonium chloride.

The content of the reactant contained in the reaction solution is preferably 0.1 mol / kg or more and 0.9 mol / kg or less with respect to 1 kg of the reaction solution. The lower limit of the content of the reactant is 0.3 mo
More preferably, it is 1 / kg or more. On the other hand, the upper limit value is more preferably 0.7 mol / kg or less. When the content of the reactant is within the above range, even if the maximum amount of the reaction liquid deposited by the ink jet method is as small as 0.3 to 1.9 mg / inch ² , the necessary and sufficient amount in the recording area of the recording medium is sufficient. Since the reactive agent adheres and reacts sufficiently with the components in the colored ink composition to cause aggregation or thickening, the print quality (image quality and image durability) of the recorded matter tends to be good.

<Water>
The reaction solution used in the present embodiment is preferably water as a main solvent. This water is a component that evaporates and scatters by drying after the reaction liquid is attached to the recording area of the recording medium. The water is preferably water from which ionic impurities such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water are removed as much as possible. In addition, it is preferable to use water sterilized by ultraviolet irradiation or addition of hydrogen peroxide because generation of mold and bacteria can be prevented when the reaction solution is stored for a long time. The content of water contained in the reaction solution can be, for example, 50% by mass or more with respect to the total mass of the reaction solution.

<Organic solvent>
An organic solvent may be added to the reaction solution used in this embodiment. By adding an organic solvent, the wettability of the reaction liquid with respect to the recording medium can be improved. As the organic solvent, the same organic solvents as exemplified in the color ink composition described later can be used. Although content of an organic solvent is not specifically limited, For example, it is 1 mass% or more and 40 mass% or less with respect to the total mass of a reaction liquid.

<Surfactant>
A surfactant may be added to the reaction solution used in this embodiment. By adding a surfactant, the surface tension of the reaction solution can be reduced and the wettability with the recording medium can be improved. Among the surfactants, for example, acetylene glycol surfactants, silicon surfactants, and fluorine surfactants can be preferably used. About the specific example of these surfactant, the thing similar to the surfactant illustrated with the below-mentioned coloring ink composition can be used. The content of the surfactant is not particularly limited, but with respect to the total mass of the reaction solution,
It can be 0.1 mass% or more and 1.5 mass% or less.

<Other ingredients>
In the reaction solution used in the present embodiment, a pH adjuster, an antiseptic / an antifungal agent, if necessary,
A rust inhibitor, a chelating agent, or the like may be added.

1.2. Colored ink composition adhesion step 1.2.1. Description of Process The colored ink composition attaching step is a step of attaching the colored ink composition to the recording region to which the reaction liquid is attached after the reaction liquid attaching step described above. In the colored ink composition adhesion step, the droplets of the colored ink composition are ejected from the nozzles of the inkjet recording head, and are adhered to the recording area to which the reaction liquid of the recording medium is adhered. Is to be recorded. Thereby, an image made of the colored ink composition is formed in the recording area of the recording medium. The colored ink composition adhering step is not limited to the inkjet method in which droplets of the colored ink composition are ejected from the nozzles of the inkjet recording head, and various printing methods such as letterpress printing, intaglio printing, planographic printing, and stencil printing. May be performed. Of these, in terms of reducing printing costs, improving printing speed, and reducing energy consumed by recording devices,
An ink jet method is preferred.

The colored ink composition attaching step is performed within 30 seconds from the completion of the reaction liquid attaching step. That is, the time from the completion of the adhesion of the reaction liquid to the start of the adhesion of the colored ink composition is within 30 seconds. The upper limit is preferably within 25 seconds, more preferably within 20 seconds, and even more preferably within 10 seconds. The lower limit is 0 second or longer, preferably 0.05 second or longer, more preferably 0.1 second or longer, still more preferably 0.5 second or longer, particularly preferably 1 second or longer. By performing the colored ink composition attaching step within 30 seconds from the completion of the reaction liquid attaching step, the recording productivity can be improved. The amount of the reaction solution deposited by the inkjet method is 1.9 mg / i
By setting it to nch ² or less, an excellent image quality can be obtained even when the time from the end of adhesion of the reaction liquid to the start of adhesion of the colored ink composition is within the above range. In addition, adhesion of the colored ink composition can be started before the reaction liquid completely penetrates into the recording medium. Therefore, the reactant and the component contained in the colored ink composition can be sufficiently reacted in the recording area of the recording medium, so that the image quality and durability of the recorded image are further improved. In addition, since the drying step is unnecessary or less, printing stability and productivity are improved.

Further, the surface temperature of the recording medium from the reaction liquid attaching step to the colored ink composition attaching step is 38.
It is below ℃. The upper limit value of the surface temperature of the recording medium is preferably 35 ° C. or lower, more preferably 30 ° C. or lower, and even more preferably 25 ° C. or lower. The lower limit is not particularly limited,
Preferably it is 0 degreeC or more, More preferably, it is 5 degreeC or more, More preferably, it is 10 degreeC or more, Most preferably, it is 15 degreeC or more. In other words, when the surface temperature of the recording medium is 38 ° C. or lower, the heating step of heating the recording medium is not performed, or the minimum necessary heating is performed with the surface temperature of the recording medium in this range. The heating step is a step of increasing the surface temperature by applying heat to the recording medium. By not performing the heating step or performing the minimum necessary heating, it is possible to suppress the drying of the ink at the nozzles of the inkjet head, and thus the printing stability is improved. When the heating process for heating the recording medium is not performed, it is preferable in that the printing stability is further improved. On the other hand, when the heating step is performed with the surface temperature of the recording medium in the above range, the image quality can be further improved while maintaining the printing stability, and the recording productivity can be further improved. It is preferable in terms of advantages. In this respect, the surface temperature of the recording medium is 20
° C or higher is preferable, 25 ° C or higher is more preferable, 30 ° C or higher is further preferable, and 32 ° C or higher is particularly preferable. By setting the deposition amount of the reaction liquid in the reaction liquid deposition step to 1.9 mg / inch ² or less, the image quality can be improved even when the surface temperature of the recording medium is in the above range.

The adhesion amount of the colored ink composition to the recording area is preferably 16 mg / inch ² or less, more preferably 13 mg / inch ² or less, and further preferably 10 mg / inch ² or less. Further, it is more preferably 5 mg / inch ² or more and 10 mg / inch ² or less, and even more preferably 5 mg / inch ² or more and 8 mg / inch ² or less. When the amount of the colored ink composition attached to the recording area is within the above range, the relative ratio between the amount of the reactive agent attached to the recording area and the amount of the reactive component contained in the colored ink composition becomes an appropriate amount. The image quality and durability are further improved, and the printing speed can be increased.
Further, in the recording area where the amount of the colored ink composition adhering to the recording area is 5 mg / inch ² or more, preferably 5 mg / inch ² or more and 16 mg / inch ² or less, the adhesion of the reaction liquid in the reaction liquid adhesion process described above. It is preferable that the amount is 0.3 mg / inch ² or more and 1.9 mg / inch ² in that the image quality and durability of the recorded matter can be further improved while making the reaction of the colored ink composition sufficient. . In this case, the recording method may further include an area where the amount of the colored ink composition attached to the recording area is less than 5 mg / inch ^{2 in} the recording area where recording is performed. This area is a light-colored image area, etc., but is an area where the amount of the colored ink composition adhering to the recording area is small, and there is a tendency that the problem of image quality deterioration due to bethamra or bleed tends not to occur. In this region, the amount of the reaction solution deposited in the reaction solution deposition step may be 1.9 mg / inch ² or less, and the lower limit of the amount of the reaction solution deposited is not limited.
The reaction solution may not be attached or may be less than 0.3 mg / inch ² . More preferably, the adhesion amount of the colored ink composition to the recording area is 3 mg / inch ² or more, 16
In the recording area of mg / inch ² or less, the amount of the reaction solution deposited in the reaction solution deposition step is set to 0.
. 3 mg / inch ² or more and 1.9 mg / inch ^2, and more preferably, the amount of the colored ink composition attached to the recording area is 1 mg / inch ² or more and 16 mg / inc.
In the recording area that is equal to or less than h ² , the amount of the reaction liquid deposited in the reaction liquid deposition step is 0.3 mg / i.
nch ² or more and 1.9 mg / inch ² or less.

In addition, you may provide the drying process which dries the colored ink composition adhering to the recording area of the recording medium after the colored ink composition adhesion process. In this case, it is preferable to perform drying to such an extent that no stickiness is felt when the colored ink composition attached to the recording area of the recording medium is touched. The drying process of the colored ink composition may be performed by natural drying or may be drying with heating. The heating method of the colored ink composition is not particularly limited, and examples thereof include a heat press method, a normal pressure steam method, a high pressure steam method, and a thermofix method. Moreover, as a heat source for heating, for example, infrared rays (lamp) can be cited.

1.2.2. Next, the components contained in the colored ink composition used in the colored ink composition attaching step and the components that can be contained will be described in detail.

<Resin>
The resin contained in the colored ink composition has a volume of 0.085 mol / kg calcium acetate aqueous solution required to agglomerate 3 mL of an aqueous solution or aqueous dispersion containing 1% by mass of the resin in an amount of 0.1 mL to 7 mL or less (preferably Is not more than 5 mL, more preferably not more than 3 mL, still more preferably not more than 2 mL, particularly preferably not more than 1 mL, and the lower limit is 0 from the viewpoint of availability.
5 mL or more of resin is preferable. Since such a resin has high reactivity with the above-mentioned reactant, it reacts quickly with the reactant in the recording area of the recording medium. Thereby, the dispersed state of the resin in the colored ink composition is destroyed, and the colored ink composition is aggregated or thickened. Since this aggregate inhibits the penetration of the colorant into the recording medium, it is possible to prevent landing interference and bleeding of the colored ink composition to be adhered thereafter, and to draw lines and fine images uniformly.
For this reason, it is considered that the image quality of the recorded image is excellent. Also, the odor can be reduced by the rapid reaction between the resin and the reactant contained in the colored ink composition.

In order to obtain such a highly reactive resin, although not particularly limited, (1)
An anionic resin having an anionic functional group introduced on its surface, or (2) an acid value of 5 mgKOH /
g or more (preferably 20 mgKOH / g or more, more preferably 40 mg / KOH or more), or (3) a self-dispersing resin not using an emulsifier. here,
“Anionic resin” refers to a resin having a negative charge as a whole. The “self-dispersing resin” refers to a resin that does not require a dispersant and can be dispersed by itself.

Examples of the resin material include acrylic resin, urethane resin, polyolefin resin, polyester resin, vinyl acetate copolymer resin, and ionomer resin.

As the form of the resin, resin particles (resin emulsion) or water-soluble resin can be used, but resin particles (resin emulsion) are preferable in view of the above-mentioned effects.

Among these, the anionic resin emulsion having an anionic functional group on the surface can increase the reactivity (reduce the volume related to the reaction) and can quickly bind to the reactant by electrostatic interaction. preferable. Examples of the anionic functional group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, or a group derived therefrom.

In this specification, the “acid value” means the number of mg of KOH required to neutralize 1 g of resin solids, and can be measured by a method described in JIS K0070, for example, a potentiometric titration method.

The solid content of the resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, with respect to the total mass of the colored ink composition, in that the lower limit is sufficiently reacted with the reactant. Especially preferably, it is 0.5 mass% or more. On the other hand, the upper limit is preferably 13% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less, and particularly preferably 5% by mass, from the viewpoint of storage stability and ejection stability of the colored ink composition. % Or less.

<Colorant>
The colored ink composition used in the present embodiment contains a colorant. As the colorant, a pigment or an acid dye can be preferably used from the viewpoint that the effect of the present invention is easily obtained.

Among the pigments, examples of the inorganic pigment include carbon black, iron oxide, and titanium oxide. The carbon black is not particularly limited. For example, furnace black, lamp black, acetylene black, and channel black (C.I.
Pigment black 7). Further, as a commercially available product of carbon black, for example, No. 2300, 900, MCF88, no. 20B, no. 33, no. 40, No
. 45, no. 52, MA7, MA8, MA100, no. 2200B (all trade names, manufactured by Mitsubishi Chemical Corporation), color black FW1, FW
2, FW2V, FW18, FW200, S150, S160, S170, Pretex 3
5, U, V, 140U, Special Black 6, 5, 4A, 4, 250 (all trade names, manufactured by Degussa AG), Conductex SC, Raven 1255, 5750,
5250, 5000, 3500, 1255, 700 (all trade names, manufactured by Columbian Carbon Japan Ltd), Columbian Chemicals
als), Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800
880, 900, 1000, 1100, 1300, 1400, Elftex 12 (all trade names, manufactured by Cabot Corporation).

Organic pigments include, for example, quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketo Examples include pyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments. Specific examples of the organic pigment include the following.

Examples of pigments used for cyan ink include C.I. I. Pigment Blue 1, 2, 3, 15
15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 15:34, 16, 18, 22
, 60, 65, 66, C.I. I. Bat Blue 4 and 60 are listed.

Examples of pigments used in magenta ink include C.I. I. Pigment Red 1, 2, 3, 4
5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21
, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48 (Ca), 48
(Mn), 57 (Ca), 57: 1, 88, 112, 114, 122, 123, 144,
146, 149, 150, 166, 168, 170, 171, 175, 176, 177,
178, 179, 184, 185, 187, 202, 209, 219, 224, 245,
254, 264, C.I. I. Pigment Violet 19, 23, 32, 33, 36, 38
43, 50.

Examples of pigments used in yellow ink include C.I. I. Pigment Yellow 1, 2, 3,
4, 5, 6, 7, 10, 11, 12, 13, 14, 16, 17, 24, 34, 35, 37
53, 55, 65, 73, 74, 75, 81, 83, 93, 94, 95, 97, 98,
99, 108, 109, 110, 113, 114, 117, 120, 124, 128, 1
29, 133, 138, 139, 147, 151, 153, 154, 155, 167, 1
72, 180, 185, 213.

In addition, as a pigment used for inks of colors other than the above, such as green ink and orange ink, conventionally known pigments can be used. These pigments may be used alone or in combination of two or more.

Examples of the acid dye include acid dyes such as azo, anthraquinone, pyrazolone, phthalocyanine, xanthene, indigoid, and triphenylmethane. Specific examples of the acid dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142
, C.I. I. Acid Red 52, 80, 82, 249, 254, 289, C.I. I. Acid Blue 9, 45, 249, C.I. I. Acid black 1, 2, 24, 94 etc. are mentioned. These acidic dyes may be used alone or in combination of two or more.

<Water>
The colored ink composition used in the present embodiment is preferably water as a main solvent. This water is a component that evaporates and scatters by drying after the colored ink composition is attached to the recording area of the recording medium. The water is preferably water from which ionic impurities such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water are removed as much as possible. In addition, it is preferable to use water sterilized by ultraviolet irradiation or addition of hydrogen peroxide because generation of mold and bacteria can be prevented when the colored ink composition is stored for a long period of time. The content of water contained in the colored ink composition can be, for example, 50% by mass or more with respect to the total mass of the colored ink composition.

<Organic solvent>
An organic solvent may be added to the colored ink composition used in the present embodiment. By adding an organic solvent, the wettability of the colored ink composition with respect to the recording medium can be improved, the fixability of the recorded image on the recording medium can be improved, and the ejection stability can be improved by preventing drying with the ejection head. This function can be imparted to the ink.

The organic solvent is not particularly limited, and examples thereof include 1,2-alkanediols, polyhydric alcohols (excluding 1,2-alkanediols), pyrrolidone derivatives, glycol ethers, and the like.

Examples of 1,2-alkanediols include 1,2-propanediol, 1,2-
Examples include butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-octanediol, and the like. 1,2-alkanediols are excellent in the action of increasing the wettability of the colored ink composition to the recording medium and uniformly wetting it. When 1,2-alkanediols are contained, the content thereof is 1% by mass or more and 2 with respect to the total mass of the ink composition.
It can be 0 mass% or less.

Examples of polyhydric alcohols (excluding 1,2-alkanediols) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6. -Hexanediol, trimethylolpropane, glycerin and the like. When polyhydric alcohols are contained, the content can be 2% by mass or more and 30% by mass or less based on the total mass of the colored ink composition.

Examples of pyrrolidone derivatives include N-methyl-2-pyrrolidone and N-ethyl-2-
Examples include pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. The pyrrolidone derivative acts as a good solubilizer for the resin.

Examples of glycol ethers include ethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monoisohexyl ether, diethylene glycol monohexyl ether, triethylene glycol monohexyl ether, diethylene glycol monoisohexyl ether, triethylene glycol monoisopropyl ether. Hexyl ether, ethylene glycol monoisoheptyl ether, diethylene glycol monoisoheptyl ether, triethylene glycol monoisoheptyl ether, ethylene glycol monooctyl ether, ethylene glycol monoisooctyl ether, diethylene glycol monoisooctyl ether, triethylene glycol monoisooctyl ether , Ethile Glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol mono-2
Ethylhexyl ether, diethylene glycol mono-2-ethylpentyl ether, ethylene glycol mono-2-ethylpentyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-2-methylpentyl ether, diethylene glycol Examples thereof include mono-2-methylpentyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, and tripropylene glycol monomethyl ether. These can be used individually by 1 type or in mixture of 2 or more types. Glycol ethers can control the wettability of the ink composition to the recording medium.

Although content of an organic solvent is not specifically limited, For example, it is 1 mass% or more and 40 mass% or less with respect to the total mass of a coloring ink composition.

<Surfactant>
The colored ink composition according to this embodiment may contain a surfactant. Surfactant is
It has the function of improving the wettability with the recording medium by reducing the surface tension of the ink.
Among the surfactants, for example, acetylene glycol surfactants, silicon surfactants, fluorine surfactants and the like can be preferably used.

Although it does not specifically limit as an acetylene glycol type surfactant, For example, Surfynol 104, 104E, 104H, 104A, 104BC, 104DPM, 104PA,
104PG-50, 104S, 420, 440, 465, 485, SE, SE-F, 50
4, 61, DF37, CT111, CT121, CT131, CT136, TG, GA,
DF110D (all trade names, manufactured by Air Products and Chemicals. Inc.), Orphine B, Y, P, A, STG, SPC, E1004, E1010, PD-001, PD-00
2W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4
051, AF-103, AF-104, AK-02, SK-14, AE-3 (all are trade names, manufactured by Nissin Chemical Industry Co., Ltd.), acetylenol E00, E00P, E40, E100
(All of the above are trade names, manufactured by Kawaken Fine Chemical Co., Ltd.).

Although it does not specifically limit as a silicon-type surfactant, A polysiloxane type compound is mentioned preferably. Although it does not specifically limit as the said polysiloxane type compound, For example, polyether modified organosiloxane is mentioned. Examples of commercially available products of the polyether-modified organosiloxane include BYK-306, BYK-307, BYK-333, B
YK-341, BYK-345, BYK-346, BYK-348 (above trade name, BYK
KF-351A, KF-352A, KF-353, KF-354L, KF-35
5A, KF-615A, KF-945, KF-640, KF-642, KF-643, K
F-6020, X-22-4515, KF-6011, KF-6012, KF-6015
, KF-6017 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.).

As the fluorine-based surfactant, a fluorine-modified polymer is preferably used, and specific examples thereof include BYK-340 (manufactured by BYK Japan).

When the surfactant is contained, the content is based on the total mass of the colored ink composition.
It can be 0.1 mass% or more and 1.5 mass% or less.

<Other ingredients>
The ink composition used in the present embodiment may contain a pH adjuster, an antiseptic / antifungal agent, a rust inhibitor, a chelating agent, and the like, if necessary.

1.3. Physical Properties of Each Ink Composition The reaction liquid and the colored ink composition (also referred to as “each ink composition” in the present specification) used in the present embodiment have an image quality and reliability as an ink for ink jet recording. From the viewpoint of balance, the surface tension at 20 ° C. is preferably 18 mN / m or more and 35 mN / m, and more preferably 20 mN / m or more and 35 mN / m or less. The surface tension is measured by, for example, measuring the surface tension when the platinum plate is wetted with ink in an environment of 20 ° C. using an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.). It can be measured by checking.

From the same viewpoint, the viscosity at 20 ° C. of each ink composition used in the present embodiment is preferably 2 mPa · s to 10 mPa · s, and preferably 2 mPa · s to 8 m.
More preferably, it is Pa · s or less. The viscosity is measured, for example, by the viscoelasticity testing machine M.
Viscosity under an environment of 20 ° C. can be measured using CR-300 (trade name, manufactured by Pysica).

2. Recording Device An example of an image recording device that can perform the recording method according to the present embodiment will be described with reference to the drawings. The image recording apparatus that can be used in the recording method according to the present embodiment is not limited to the following mode.

FIG. 1 is a diagram schematically illustrating an image recording apparatus capable of performing the recording method according to the present embodiment. The image recording apparatus 100 includes a conveying unit 10 that conveys the recording medium 1, a reaction liquid adhering unit 20 that adheres a reaction liquid to a recording area of the recording medium, and a colored ink that adheres a colored ink composition to the recording area of the recording medium. Composition adhering means 30.

2.1. Conveying means The conveying means 10 can be constituted by, for example, a roller 11. Conveying means 10
May have a plurality of rollers 11. As long as the recording medium 1 can be transported, the transport unit 10 may be provided at any position and number. The transport unit 10 may include a paper feed roll, a paper feed tray, a paper discharge roll, a paper discharge tray, and various platens.

Although FIG. 1 illustrates the case where the recording medium 1 is a continuous body, even if the recording medium 1 is a single sheet, the above-described recording medium can be configured by appropriately configuring the conveying means 10. Can be carried.

2.2. Reaction liquid attaching means The reaction liquid attaching means 20 is means for attaching the reaction liquid to the recording area of the recording medium 1 and applying the reactant contained in the reaction liquid to the recording area. The reaction liquid adhering means 20 includes an ink jet recording head 21 having a nozzle for discharging the reaction liquid. Examples of the method for discharging the reaction liquid from the nozzles of the inkjet recording head 21 include the following. Specifically, a strong electric field is applied between the nozzle and the accelerating electrode placed in front of the nozzle to continuously discharge a droplet-like reaction liquid from the nozzle, and the reaction liquid droplets fly between the deflection electrodes. A system that discharges in response to the recorded information signal (electrostatic suction system); forcing the reaction liquid by applying pressure to the reaction liquid with a small pump and mechanically vibrating the nozzle with a quartz crystal A method of ejecting droplets of the reaction liquid; simultaneously applying pressure and a recording information signal to the reaction liquid with a piezoelectric element, and ejecting and recording the droplets of the reaction liquid (piezo method); a resin liquid with a microelectrode according to the recording information signal Heat foam
Examples include a method of discharging and recording a droplet of the reaction liquid (thermal jet method). The reaction liquid adhesion means 20 is used in the reaction liquid adhesion process in the recording method according to this embodiment.

2.3. Colored ink composition adhering means Colored ink composition adhering means 30 is a means for forming a recorded image by adhering droplets of the colored ink composition to the recording area to which the reaction liquid has adhered. The colored ink composition adhering means 30 includes an inkjet recording head 31 having a nozzle for discharging the colored ink composition. The method for discharging the colored ink composition from the nozzles of the inkjet recording head 31 is the same as the method described in the reaction liquid adhering means 20. The colored ink composition attaching means 30 is used in the colored ink composition attaching step in the recording method according to the present embodiment.

2.4. Ink jet recording head In the above-described reaction liquid adhering means 20 and colored ink composition adhering means 30, any of an ink jet recording apparatus having a serial type recording head and an ink jet recording apparatus having a line type recording head can be used. Can also be used.

An inkjet recording apparatus provided with a serial type recording head refers to recording by performing a plurality of scans (passes) for discharging the ink composition while moving the recording head relative to the recording medium. Is what you do. In a specific example of the serial type recording head, a recording head is mounted on a carriage that moves in the width direction of the recording medium (a direction that intersects the conveyance direction of the recording medium), and the recording head accompanies the movement of the carriage. In which liquid droplets are ejected onto the recording medium by moving.

On the other hand, an ink jet recording apparatus equipped with a line type recording head performs recording by performing a single scan (pass) to eject the ink composition while moving the recording head relative to the recording medium. Is what you do. A specific example of the line-type recording head is one in which the recording head is formed wider than the width of the recording medium, and droplets are ejected onto the recording medium without moving the recording head.

2.5. Drying Unit The image recording apparatus 100 may be provided with the drying unit 40 after the colored ink composition adhering unit 30. By providing the drying means 40, the liquid medium can be quickly evaporated and scattered from the colored ink composition adhered to the recording medium, and a recorded image can be formed quickly. The drying means 40 is not particularly limited as long as it has a configuration that promotes evaporation and scattering of the liquid medium contained in the colored ink composition. For example, a means for applying heat to the recording medium, a means for blowing air to the reaction liquid, a means for combining them, and the like can be mentioned. Specifically, forced air heating, radiation heating, conductive heating, public wave drying, microwave drying, and the like are preferably used. The image recording apparatus 100 may not include the drying unit 40 when the recorded image is naturally dried.
Furthermore, the image recording apparatus 100 includes means for drying the reaction liquid (not shown) at least one of the place of the reaction liquid attaching means 20, the place of the colored ink composition attaching means 30, and the place between them. Also good. The specific configuration of the drying unit may be the same as that of the above-described drying unit 40. By this drying means, the reaction liquid adhered to the recording medium is dried before the colored ink composition is adhered. However, even when drying, the temperature of the recording medium and the time until the start of the deposition of the colored ink composition are as described above.

3. Examples Hereinafter, the embodiments of the present invention will be described more specifically by way of examples. However, the present embodiments are not limited to these examples.

3.1. Preparation of each ink composition <Preparation of reaction liquid>
Each component was mixed and stirred so as to have the blending ratio shown in Table 1, and then filtered through a 10 μm membrane filter to prepare each reaction solution (H1 to H4). The numerical values in Table 1 all indicate mass%, and ion-exchanged water was added so that the total mass of the reaction solution was 100 mass%.

<Preparation of colored ink composition>
After mixing and stirring each component so that it may become a mixture ratio of Table 1, the colored ink composition (C1-C3) was prepared by filtering with a 10 micrometer membrane filter. The numerical values in Table 1 all indicate mass%, and ion exchange water was added so that the total mass of the colored ink composition was 100 mass%.

<Reactivity test of resin>
It mixed and stirred, dripping 0.085 mol / kg calcium nitrate aqueous solution to 3 mL of resin liquid containing 1 mass% of resin of Table 1, and it was confirmed visually whether the deposit generate | occur | produced in the liquid mixture. Table 1 also shows the volume of the 0.085 mol / kg calcium nitrate aqueous solution necessary for the aggregation of these resins.

<Composition and physical properties of each ink composition>
The composition and physical properties of each ink composition obtained above are shown in Table 1 below.

In addition, the components described in Table 1 other than the compound names are as follows.
<Color material>
・ Cyan pigment (CI Pigment Blue 15: 3)
<Surfactant>
・ Silicon surfactant (trade name “BYK-348”, manufactured by Big Chemie Japan Co., Ltd.)
<Resin>
-Polyethylene resin A (trade name “AQUASER507”, manufactured by Big Chemie Japan, average particle size: 50 nm, Tg: 60 ° C.)
-Polyethylene resin B (trade name “AQUASER515”, manufactured by Big Chemie Japan, average particle size: 50 nm, Tg: 60 ° C.)
・ Polyester resin (trade name “Elitel KT-8701”, manufactured by Unitika Ltd., average particle size: 50 nm, Tg: 60 ° C.)

3.2. Recording method A modified ink jet printer PX-G930 (manufactured by Seiko Epson Corporation) was used. An ink jet head having a nozzle density of 600 dpi was used. It is possible to increase the recording resolution by performing interlaced recording. Each of the reaction liquid and the colored ink composition was filled in one nozzle row. A heater was attached to the platen so that the temperature of the recording medium during recording could be adjusted. The temperature of the recording medium is 30 ° C
Exceeding examples used this heater to adjust the temperature. In the case where the temperature of the recording medium was 30 ° C. or less, the temperature was adjusted by adjusting the room temperature. After the reaction liquid recording is completed, a predetermined standing time is provided on the platen, and then the recording medium is reversely fed and transported again, and the colored ink composition is deposited on the pattern. The time (weight time) until the start of object adhesion was adjusted. A 15 × 15 cm test pattern was set as a recording area on the recording medium, and recording was performed on this recording area. After the coloring ink composition is attached, the recording medium discharged from the printer is 55 ° C.
For 15 minutes. The temperature of the recording medium during recording is the temperature of the surface of the recording medium at a position facing the inkjet head.

<Reaction solution recording conditions>
Control was performed so that the reaction solution adhesion amount was the adhesion amount shown in Tables 2 to 3, and the average recording resolution of the adhesion region was the value shown in Tables 2 to 3.
-Dot size (liquid amount per discharged droplet): described in Tables 2 to 3.
<Coloring ink composition recording conditions>
Recording resolution (density of ejected droplets): 1200 × 1200 dpi
Ink adhesion amount: 6.8 mg / inch ²
<Recording medium>
Recording medium type 1: Recording medium having a water absorption of 1 mL / m ² or less: Trade name “PET50A PL Thin”, manufactured by Lintec Corporation, non-absorbing (very low absorbing) PET film.
Recording medium type 2: Recording medium having a water absorption of 8 mL / m ² : Trade name “Cast 73”, manufactured by Daio Paper Co., Ltd., low-absorbency coated paper.

3.3. Evaluation test <image quality>
The recorded matter obtained by the above recording method was visually checked for image quality, and evaluated based on the following evaluation criteria. It was observed whether there was any deterioration in image quality such as bethamra and bleed, and whether ink droplets looked grainy.
(Evaluation criteria)
A: No unevenness inside the pattern. No bleed around the pattern. Very good.
B: No unevenness inside the pattern. Bleed around the pattern. Good.
C: There is considerable unevenness inside the pattern.
D: Ink droplets look grainy inside the pattern and the image is unsightly.

<Printing stability>
With the above-described inkjet printer PX-G930, the state of the nozzles when 10 sheets of A4 size solid images were printed was visually confirmed and evaluated based on the following evaluation criteria.
(Evaluation criteria)
A: No missing dots or bending. Very good.
B: Some missing dots or bends (within 4 nozzles). Good.
C: Dot is missing or bent (5 nozzles or more and 8 nozzles or less).
D: Missing dot. There is a bend (9 nozzles or more).

<Durability of recorded material>
For the recorded matter obtained by the above recording method, the Gakushin type friction fastness tester (device name “A
B-301 ", manufactured by Tester Sangyo Co., Ltd.) was used to evaluate durability. In particular,
The recording area on which the image was recorded was rubbed 50 times with a friction element attached with a white cotton cloth (according to JIS L 0803) under a load of 500 g.
(Evaluation criteria)
A: Dirt is recognized on the white cotton cloth, but the image is not peeled off. Very good.
B: Dirt on the white cotton cloth and partial peeling on the image are observed (about 10%). Good.
C: Peeling is recognized on the image. Bad.

<Recorded Productivity>
100 sheets were recorded on an A4 size recording medium by the above recording method. The time from the start of recording to the discharge of the 100th sheet was measured. During recording, maintenance such as head cleaning for maintaining the performance of the recording apparatus was performed as necessary.
(Evaluation criteria)
A: Within 1 hour.
B: Over 1 hour and within 2 hours.
C: Over 2 hours.

3.4. Evaluation Results Examples 1 to 13 and Comparative Examples 1 to 8 were carried out based on the above recording method and evaluation test. The recording methods and evaluation results for each example are summarized in Tables 2 to 3 below.

According to the recording methods of Examples 1 to 13 shown in Table 2, the reaction solution drying step is controlled by controlling the concentration of the reactant in the reaction solution used in the reaction solution attachment step and the amount of reaction solution attached. Without passing
It has been found that recording excellent in printing stability and productivity on a non-ink-absorbing or low-ink-absorbing recording medium can be realized. It has also been found that according to such a recording method, a color image having excellent image quality and durability can be recorded.

In Example 13, since the amount of the reaction liquid deposited was as small as 0.2 mg / inch ² , the amount of the reactant adhering to the recording area of the recording medium was small, and the aggregation of the components contained in the colored ink composition was insufficient. As a result, considerable unevenness occurred in the pattern of the solid image. This was not described in the table, but when the evaluation was performed in the same manner as in Example 1 except that the reaction liquid adhesion step was not performed, the image quality evaluation result was similar to that in Example 13. From this, it is presumed that the aggregation of the colored ink was insufficient. However, the ink droplets did not appear to be granular in the pattern, and it was not felt unsightly.
From the comparison between Example 12 and Example 5 and the comparison between Example 11 and Example 6 and Example 1, the image quality is further improved by performing low heating while keeping the surface temperature of the recording medium at 38 ° C. or lower. It was found that the printing stability could be improved.
In Comparative Example 7, the recording productivity was greatly impaired by increasing the wait time. Further, the adhesion amount of the flocculant adhering to the recording medium was large and the durability of the recorded matter was lowered.

In Comparative Example 1, since the concentration of the reactant in the reaction solution was too high, the amount of the reactant attached to the recording area of the recording medium was too large. Then, since the colored ink composition layer is placed on the reactive agent layer, it is presumed that the durability of the recorded material is lowered.

In Comparative Example 2, since the amount of the reaction liquid deposited is too large, the reaction liquid pooled in the recording area of the recording medium, and the ink composition was deposited in a state where a large amount of the solvent component of the reaction liquid was adhered to the recording medium. It was. For this reason, the ink enemies landed in the reaction liquid reacted instantaneously to become granular, and a phenomenon was observed in which the ink droplets looked granular inside the solid image pattern. In addition, since the reactant is not completely fixed on the recording medium, it is presumed that the durability of the recorded material is also lowered.

In Comparative Example 3, the colored ink composition was adhered in a state where the temperature of the recording medium was adjusted to 45 ° C. by the heating process. As a result, the nozzles of the inkjet head were dried by the radiant heat, and the printing stability was greatly impaired.

In Comparative Example 4, since the wait time from the end of the adhesion of the reaction liquid to the start of the deposition of the colored ink composition was 60 seconds, the recording productivity was greatly impaired.

In Comparative Example 5, as in Comparative Example 2, the amount of the reaction liquid deposited was too large, and therefore, the reaction liquid pooled in the recording area of the recording medium, causing a phenomenon that the ink droplets looked granular inside the solid image pattern. It is guessed. However, the adhesion amount of the flocculant adhered to the recording medium was smaller than that of Comparative Example 2, and the recorded matter durability was better than that of Comparative Example 2.

In Comparative Example 6, even if an excessive amount of the reaction solution adhered was dried by the heating step (40 ° C.), the nozzle was dried and the printing stability was greatly impaired, and the recorded material durability was insufficient due to insufficient drying of the reaction solution. Also declined.

In Comparative Example 7, even if an attempt was made to dry the adhesion amount of the reaction solution by increasing the wait time, the recording productivity was greatly impaired, and the durability of the recorded material was also deteriorated due to insufficient drying of the reaction solution.
In Comparative Example 8, the wait time was long and the recording productivity was impaired.

The present invention is not limited to the embodiments described above, and various modifications are possible. For example, the present invention includes substantially the same configuration (for example, a configuration having the same function, method and result, or a configuration having the same purpose and effect) as the configuration described in the embodiment. In addition, the invention includes a configuration in which a non-essential part of the configuration described in the embodiment is replaced. In addition, the present invention includes a configuration that exhibits the same operational effects as the configuration described in the embodiment or a configuration that can achieve the same object. In addition, the invention includes a configuration in which a known technique is added to the configuration described in the embodiment.

DESCRIPTION OF SYMBOLS 1 ... Recording medium, 10 ... Conveyance means, 11 ... Roller, 20 ... Reaction liquid adhesion means, 30 ... Colored ink composition adhesion means, 21.31 ... Inkjet recording head, 40 ... Drying means, 1
00: Image recording apparatus.

Claims (10)

Adhering a reaction liquid containing a reactive agent with a content of 0.1 to 0.9 mol / kg to a non-ink-absorbing or low-ink-absorbing recording medium to agglomerate or thicken the colored ink composition. A reaction liquid deposition step in which the amount is 1.9 mg / inch ² or less and is ejected and deposited as droplets by an inkjet method;
A colored ink composition attaching step for attaching the colored ink composition to the recording medium to which the reaction liquid is attached,
The time from the completion of the deposition of the reaction liquid to the start of the deposition of the colored ink composition is within 30 seconds, and the surface temperature of the recording medium from the reaction liquid deposition process to the colored ink composition deposition process is 38 ° C. The recording method is as follows. The recording method according to claim 1, wherein a mass per droplet (1 dot) of the reaction liquid in the reaction liquid adhesion step is 10 ng / dot or less. The recording method according to claim 1, wherein a resolution of the droplet in the reaction liquid attaching step is 200 × 200 dpi or more. The recording method according to any one of claims 1 to 3, wherein the amount of the reactant deposited in the reaction liquid deposition step is 1000 nmol / inch ² or less. From the reaction liquid attaching step to the colored ink composition attaching step, the temperature of the recording medium is 3
The recording method according to any one of claims 1 to 4, wherein the recording temperature is 2 to 38 ° C. The colored ink composition contains a resin;
The said resin contains resin whose volume of 0.085 mol / kg calcium acetate aqueous solution required in order to aggregate 3 mL of 1 mass% resin containing aqueous solution or water dispersion liquid is 0.1-7 mL. The recording method according to claim 5. The water absorption rate of the recording medium is 30 from the start of contact in the Bristow method.
The recording method according to any one of claims 1 to 6, wherein the water absorption up to msec ^1/2 is 10 mL / m ² or less. The recording method according to any one of claims 1 to 7, wherein the reactant includes at least one selected from the group consisting of a polyvalent metal salt and an organic acid. Wherein the recording area of the deposition amount is 5 mg / inch ² or more colored ink composition of colored ink composition adhering step, the the adhesion amount of the reaction solution with 0.3~1.9mg / inch ^2, claims 1 The recording method according to claim 8.   A recording apparatus for performing the recording method according to any one of claims 1 to 9.

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