JP6364776B2 - Inkjet recording method - Google Patents

Description

  The present invention relates to an ink jet recording method and an ink jet recording apparatus used therefor.

  The ink jet recording method is a method of performing printing by ejecting and ejecting small ink droplets from a fine nozzle head and attaching them to a recording medium such as paper. This method is characterized in that a high-resolution and high-quality image can be printed at a high speed with a relatively inexpensive apparatus. In the ink composition used in such an ink jet recording method, various components such as a coloring material, a resin, water, and an organic solvent are used depending on the recording medium used. Among these, dyes and pigments are widely used for the color material used in the ink composition, and pigments are preferably used from the viewpoint of excellent light resistance and the like.

  When recording an image using an ink composition for ink jet recording containing such a pigment, a solution containing a flocculant or the like is used on the recording medium in order to improve the image quality of the image. A technique for aggregating these components is known.

  For example, in Patent Document 1, in an ink jet recording method for plain paper, an ink composition containing a pigment or the like, a first liquid containing polymer fine particles (acrylic resin or the like), and a reactive agent (polyallylamine or many others). And printing with a second liquid containing a valent metal compound or the like. According to the inkjet recording method of Patent Document 1, it is described that an image with improved water resistance, abrasion resistance, and glossiness can be obtained.

  Patent Document 2 discloses a color ink containing a coloring material, resin particles, a water-soluble organic solvent, water, and the like and an aggregating component (an acidic compound, a polyvalent compound) in an inkjet recording method for coated paper having a coating layer. After printing using a pretreatment liquid containing a metal salt and polyallylamine) and a clear ink containing resin particles, a water-soluble organic solvent and water, the color image and the clear ink are heated and pressurized. It is disclosed to do. According to the ink jet recording method of Patent Document 2, it is possible to record an image excellent in glossiness and abrasion resistance while suppressing the occurrence of curling.

  Patent Document 3 also discloses an ink composition containing a pigment, resin particles, water, and the like, and an aggregating agent (a polyvalent metal salt, an acidic substance, and a cationic polymer) in an inkjet recording method for a recording medium such as coated paper. And a treatment liquid containing the composition), and printing and heating the obtained image. According to the ink jet recording method of Patent Document 3, high-definition full-color printing can be performed on commercial printing paper, and an image having high resolution and excellent image uniformity can be formed.

  Further, in Patent Document 4, in an ink jet recording method for a recording medium such as art paper, printing is performed using a treatment liquid containing an organic acidic compound, and an ink composition containing resin particles and a pigment. , Heating and pressurizing are disclosed. According to the ink jet recording method of Patent Document 4, an image in which roughness, abrasion resistance, and gloss unevenness are suppressed can be obtained.

  As described above, Patent Documents 1 to 4 described above use an ink-absorbing recording medium such as plain paper or coated paper.

Japanese Patent No. 36060311 JP 2010-46896 A JP 2011-630001 A JP 2013-18948 A

  However, when the ink jet recording method described in Patent Document 1 to Patent Document 4 described above is applied to a recording medium that does not absorb ink, such as a film, the gloss of the recorded image may be significantly reduced. . That is, when ink jet recording is performed using the reaction liquid containing the above-described flocculant and the ink composition containing the pigment, the components such as the pigment contained in the ink are quickly brought into water by the action of the flocculant. Separate and agglomerate and fix on the recording medium. A component such as a pigment aggregated by the action of the aggregating agent has an apparent increase in particle diameter, so that the glossiness tends to decrease. On the other hand, since a recording medium such as a film has high glossiness, a difference in glossiness from a recorded image is easily noticeable. For this reason, when the image is viewed, there is a tendency that a sense of incongruity due to the difference in glossiness is prominent.

  On the other hand, when an image is recorded on a recording medium such as a film that does not absorb ink, the ink composition is not absorbed by the recording medium. Therefore, the ink-absorbing recording medium (plain paper, coated paper, etc.) In comparison, there is a problem that bleeding (bleeding of the outline of an image) is likely to occur due to a decrease in abrasion resistance or a flow of ink on a recording medium.

  Some embodiments according to the present invention provide an ink jet recording method for recording an image having excellent gloss and abrasion resistance and suppressing bleeding by solving at least a part of the above-described problems, and an ink jet using the same. It is to provide a recording apparatus.

  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 inkjet recording method according to the present invention is:
A reaction liquid containing at least one of a polyvalent metal compound, an organic acid, and a cationic resin and an ink composition for ink jet recording containing water, a pigment, and polymer particles are attached to a film recording medium. An adhesion process;
A pressure application step of applying a pressure of 0.01 MPa or more and 3.0 MPa or less in a heated state to the ink composition attached to the film-based recording medium;
Including
The reaction liquid and the ink composition satisfy at least one of the following conditions (1) and (2).

(1) When the reaction solution contains at least one of a polyvalent metal compound and an organic acid, the reaction solution and the ink composition satisfy the following formula (α). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (α) is the sum of the contents of the polymer particles and the pigment dispersion resin.
0.3 ≦ [(content of polymer particles) / {(total content of polyvalent metal compound and organic acid) + (content when pigment is converted into solid content)}] ≦ 5 (α )

(2) When the reaction liquid contains a cationic resin, the reaction liquid and the ink composition satisfy the following formula (β). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (β) is the sum of the contents of the polymer particles and the pigment dispersion resin.
0.3 ≦ [(polymer particle content) / {(cationic resin content) + (content when the pigment is converted into solid content)}] ≦ 3.5 (β)

[Application Example 2]
In application example 1,
The heating temperature in the pressure application step may be equal to or higher than the glass transition temperature of the polymer particles.

[Application Example 3]
In application example 1 or application example 2,
The polymer particles may have a glass transition temperature of −40 ° C. or higher and 40 ° C. or lower.

[Application Example 4]
In any one of Application Examples 1 to 3,
The heating temperature in the pressure applying step may be 40 ° C. or higher and 80 ° C. or lower.

[Application Example 5]
In any one of Application Examples 1 to 4,
The material constituting the polymer particles may include at least one of an acrylic resin and a urethane resin.

[Application Example 6]
In any one of Application Examples 1 to 5,
The adhesion amount per unit area of the ink composition may be 3 to 30 times the adhesion amount per unit area of the reaction liquid.

[Application Example 7]
In any one of Application Examples 1 to 6,
The adhesion amount per unit area of the reaction solution may be 0.1 mg / inch ² or more and 3.0 mg / inch ² or less.

[Application Example 8]
One aspect of the ink jet recording apparatus according to the present invention is:
The inkjet recording method described in any one of Application Examples 1 to 7 is performed.

The recording apparatus which can implement the inkjet recording method which concerns on one Embodiment of this invention.

  Hereinafter, preferred embodiments of the present invention will be described. The embodiment described below describes an example of the present 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. Inkjet recording method An inkjet recording method according to an embodiment of the present invention includes an ink containing a reaction liquid containing at least one of a polyvalent metal compound, an organic acid, and a cationic resin, water, a pigment, and polymer particles. An adhesion process for adhering a recording ink composition to a film-based recording medium, and a pressure of 0.01 MPa to 3.0 MPa in a heated state with respect to the ink composition adhered to the film-based recording medium And a pressure application step of adding, wherein the reaction liquid and the ink composition satisfy at least one of the following conditions (1) and (2).

(1) When the reaction solution contains at least one of a polyvalent metal compound and an organic acid, the reaction solution and the ink composition satisfy the following formula (α). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (α) is the sum of the contents of the polymer particles and the pigment dispersion resin.
0.3 ≦ [(content of polymer particles) / {(total content of polyvalent metal compound and organic acid) + (content when pigment is converted into solid content)}] ≦ 5 (α )

(2) When the reaction liquid contains a cationic resin, the reaction liquid and the ink composition satisfy the following formula (β). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (β) is the sum of the contents of the polymer particles and the pigment dispersion resin.
0.3 ≦ [(polymer particle content) / {(cationic resin content) + (content when the pigment is converted into solid content)}] ≦ 3.5 (β)

  By performing the ink jet recording method according to the present embodiment, a recorded matter in which an image is recorded on a film recording medium can be obtained. Hereinafter, the inkjet recording method according to the present embodiment will be described in detail for each step.

1.1. Adhesion process The adhesion process is a process in which the reaction liquid and the ink composition for inkjet recording are adhered to a film-based recording medium. Specifically, the reaction liquid and the ink composition are brought into contact with each other on a film-based recording medium to form an image composed of the ink composition. In the attaching step, a reaction liquid attaching step for attaching the reaction liquid to the image may be performed after the image recording step for recording the image made of the ink composition on the recording medium, but the image quality of the recorded image is improved. From this point of view, it is preferable to perform the image recording step after the reaction liquid attaching step. Hereinafter, the case where an image recording process is performed after the reaction liquid attaching process will be described in detail as an attaching process.

<Reaction liquid adhesion process>
In the attaching step, it is preferable to perform the reaction solution attaching step prior to the image recording step. The reaction solution attaching step is a step of attaching a reaction solution containing at least one of a polyvalent metal compound, an organic acid and a cationic resin to a recording medium. All of the polyvalent metal compound, organic acid and cationic resin contained in the reaction liquid react with the pigment contained in the ink composition, the pigment dispersion resin that can be contained in the ink composition, and the like, thereby aggregating the pigment. It has the function. Thereby, generation | occurrence | production of the bleeding etc. of the image recorded using an ink composition can be suppressed, and the image of the outstanding image quality is obtained.

  In the present specification, the polyvalent metal compound, organic acid and cationic resin contained in the reaction solution may be collectively referred to as “flocculating agent”.

  As a method for attaching the reaction liquid, for example, any method such as spin coating, spray coating, gravure roll coating, reverse roll coating, bar coating, and ink jet method can be used. Among these, it is preferable to use the ink jet method from the viewpoint of saving the reaction solution and shortening the time required for the reaction solution attaching step. When using the ink jet method, droplets of the reaction liquid are ejected from the nozzles of the ink jet recording head and attached to the recording medium.

The adhesion amount per unit area of the reaction solution is preferably 0.1 mg / inch ² or more and 3.0 mg / inch ² or less, more preferably 0.2 mg / inch ² or more and 1.0 mg / inch ² or less. preferable. By being 0.1 mg / inch ² or more, the pigment and the pigment dispersion resin are more easily aggregated. Moreover, since it is 3.0 mg / inch ² or less, since the drying time of a reaction liquid can be shortened, recording speed-up can be achieved. Here, the adhesion amount per unit area of the reaction liquid can be calculated by dividing the mass of the reaction liquid used in the reaction liquid adhesion step by the area of the region where the reaction liquid is adhered. The region to which the reaction solution is adhered will be further described later.

  A step of drying the reaction solution attached to the recording medium after the reaction solution attaching step and before the image recording step may be provided. In this case, it is preferable to perform drying to such an extent that no stickiness is felt when the reaction liquid adhering to the recording medium is touched. The drying step of the reaction solution may be performed by natural drying, but from the viewpoint of improving the drying speed, drying with heating is preferable. When the reaction solution drying step involves heating, the heating method is not particularly limited. For example, a print heater mechanism that heats a recording medium in contact with a heat source, infrared rays, or microwaves (2 , An electromagnetic wave having a maximum wavelength of about 450 MHz), a hot air drying mechanism using a dryer or the like.

In the present invention, the film-based recording medium is a film whose base material is a non-ink-absorbing film such as a plastic film. Or it is a transparent recording medium which consists of a film. The film-based recording medium preferably has a non-ink-absorbing property on the recording surface to which the ink composition or reaction liquid is attached. The ink non-absorbing recording medium refers to a recording medium having a property of not absorbing or hardly absorbing the ink composition. Quantitatively, the ink non-absorbing recording medium refers to “a recording medium having a water absorption amount of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method”. 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). For details of the test method, refer to Standard No. of “JAPAN TAPPI Paper Pulp Test Method 2000”. 51 "Paper and paperboard-Liquid absorbency test method-Bristow method". Examples of the recording medium having a non-ink-absorbing recording surface include a recording medium that does not have an ink-receptive ink-receiving layer on the recording surface, and a recording medium that has a non-ink-absorbing coating layer on the recording surface. It is done. On the other hand, the film-type recording medium of the present invention may be provided with an ink-absorbing layer having ink absorptivity on the recording surface and exhibiting ink absorptivity. A recording medium having the above-described non-ink-absorbing property is preferable in that the difference in glossiness from a recorded image is conspicuous, and the effect of the present invention is much greater and useful.

  In the recording medium of the present invention, the 60 ° glossiness of the recording surface based on JIS Z8741 is preferably 50 or more, and more preferably 60 or more. When the glossiness is not less than the above, it is possible to record a high glossy recorded material, but the difference in glossiness between the recording area and the non-recording area of the recording medium is conspicuous, and this embodiment is particularly useful.

  Specifically, the film-based recording medium is composed of a plastic film substrate, the film is coated with a coating layer, or the film is bonded to other layers such as paper. Is mentioned. Examples of the plastic herein include synthetic resins such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, and polypropylene. When using a film-based recording medium, the plastic film substrate is less susceptible to shrinkage and deformation in the thickness direction during heating and pressurization. It tends to be applied, and the gloss tends to increase with heating pressure.

<Image recording process>
In the attaching step, it is preferable to perform an image recording step after the reaction liquid attaching step described above. The image recording step is a step of recording an image on a recording surface of a recording medium using an ink composition for ink jet recording containing water, a pigment, and polymer particles after the reaction liquid attaching step described above. As a result, the pigment and the like contained in the ink composition react with the aggregating agent to cause the pigment to aggregate on the recording surface, so that the image quality such as the color developability of the recorded image can be improved.

  In the image recording step, an image is recorded by ejecting droplets of the ink composition from the nozzles of the inkjet recording head and adhering them to the reaction liquid adhering to the recording medium described above.

The adhesion amount per unit area of the ink composition is preferably 3.0 mg / inch ² or more and 15.0 mg / inch ² or less, and the lower limit is more preferably 5.0 mg / inch ² or more, and 6.0 mg / inch ² or less. Inch ² or more is more preferable. The upper limit is more preferably 10.0 mg / inch ² or less. By being 3.0 mg / inch ² or more, the abrasion resistance and glossiness of the recorded image tend to be improved. Further, it is 15.0 mg / inch ² or less, it is possible to suppress occurrence of bleeding of the recorded image. Here, the adhesion amount per unit area of the ink composition can be calculated by dividing the mass of the ink composition used in the image recording step by the area of the region (image) to which the ink composition is adhered. Here, the region to which the ink composition is attached may be at least a partial region in the image. By setting the partial area, glossiness is improved in the partial area and occurrence of image bleeding can be suppressed. Preferably, the adhesion amount per unit area of the ink composition is the adhesion amount of the ink in the region having the largest ink adhesion amount among the images recorded by the recording method of the present embodiment among the partial regions in the image. Can be divided by the area of the region. By doing so, it is possible to further improve the gloss even in the region with the largest ink adhesion amount where the gloss tends to decrease particularly. Note that the region to which the reaction liquid is attached when calculating the amount of the reaction liquid to be deposited per unit area is a region corresponding to a part of the region in the image.

The adhesion amount (g / inch ² ) per unit area of the ink composition is preferably 3 to 30 times the adhesion amount (g / inch ² ) per unit area of the reaction solution. It is more preferably no less than 25 times and no more than 25 times, and even more preferably no less than 12 times and no more than 20 times. When the value is 3 times or more, the rub resistance and gloss of the recorded image tend to be good, and when it is 30 times or less, the occurrence of bleeding of the recorded image can be further suppressed. .

  A step of drying the image on the recording medium may be provided after the image recording step. In this case, it is preferable to perform drying to such an extent that stickiness is not felt when an image attached to the recording medium is touched. The image drying step may be performed by natural drying, but may be drying accompanied by heating from the same viewpoint as described in the case of drying the reaction solution. The method for heating the image is not particularly limited, and the same methods as those mentioned for the reaction liquid heating method can be used.

1.2. Pressure application process The inkjet recording method according to the present embodiment includes a pressure application process. The pressure application step is a step of applying a pressure of 0.01 MPa or more and 3.0 MPa or less to the ink composition (image) attached to the film recording medium in a heated state. As a result, the surface of the image becomes smooth and the glossiness of the image is improved, so that the difference in glossiness between the image and the area where no image is formed on the recording medium is reduced. As a result, it is possible to reduce a sense of incongruity due to a difference in visual glossiness.

  In the pressure application step, the pressure applied to the image needs to be 0.01 MPa or more and 3.0 MPa or less, and more preferably 0.02 MPa or more and 1.0 MPa or less. When the pressure applied to the image is 0.01 MPa or more, the glossiness of the image is good, and when the pressure is 3 MPa or less, the load on the image and the film-based recording medium can be reduced. On the other hand, if the pressure applied to the image is less than 0.01 MPa, the glossiness of the image cannot be improved, and if the pressure exceeds 3 MPa, the load on the image or film-based recording medium increases and deformation of the recording medium (curl) , Stretching, etc.) and damage may occur.

  A pressure addition process can be performed using well-known pressing apparatuses, such as a heatable pressure roller and a flat plate press, for example.

  The heating temperature in the pressure application step is preferably not less than the glass transition temperature (Tg) of the polymer particles contained in the ink composition, specifically, it can be 40 ° C. or more and 80 ° C. or less, It can be set to 60 ° C. or higher and 70 ° C. or lower. When the heating temperature in the pressure application step is equal to or higher than the Tg of the polymer particles contained in the ink composition, the melting of the polymer particles is promoted and the image is easily flattened. In particular, when the heating temperature is 40 ° C. or higher, flattening of the image can be further promoted, and when the heating temperature is 80 ° C. or lower, deformation and breakage can be effectively suppressed. In addition, the heating temperature in a pressure provision process means the temperature of the image surface, for example, can be measured using a non-contact thermometer (trade name “IT2-80”, manufactured by Keyence Corporation).

  The time during which the pressure is applied may be appropriately set depending on the heating temperature, the type of the recording medium, and the like, and is not particularly limited, but may be, for example, 1 msec or more and 20 sec or less, and further 5 msec or more and 10 or less. It can be less than a second.

2. Reaction Liquid and Ink Composition In the ink jet recording method according to this embodiment, a reaction liquid and an ink composition are used. Hereinafter, components included in the reaction liquid and the ink composition and components that may be included will be described in detail.

2.1. Reaction Liquid In the ink jet recording method according to the present embodiment, a reaction liquid is used in the adhesion process (reaction liquid adhesion process).

2.1.1. Polyvalent metal compound, organic acid and cationic resin (flocculating agent)
The reaction liquid according to the present embodiment contains at least one of a polyvalent metal compound, an organic acid, and a cationic resin. The polyvalent metal compound, the organic acid, and the cationic resin are components collectively referred to as the flocculant as described above, and react with the pigment contained in the ink composition, the pigment dispersion resin that can be contained in the ink composition, and the like. Thus, it has a function of aggregating the pigment. Thereby, generation | occurrence | production of the bleeding etc. of the image recorded with an ink composition can be suppressed.

  Among these aggregating agents, polyvalent metal compounds and organic acids are preferable because they have good reactivity with components (pigments, pigment-dispersed resins, etc.) contained in the ink composition and are excellent in suppressing bleeding. Can be used. Moreover, a cationic resin can be preferably used from the point of being excellent in the effect which improves the glossiness of the image recorded.

  Examples of the polyvalent metal compound include, but are not limited to, titanium compounds, chromium compounds, copper compounds, cobalt compounds, strontium compounds, barium compounds, iron compounds, aluminum compounds, calcium compounds, and magnesium compounds, and salts thereof. (Polyvalent metal salt). Among these polyvalent metal compounds, one or more selected from the group consisting of aluminum compounds, calcium compounds, magnesium compounds, and salts thereof is preferable because pigments can be effectively aggregated, such as calcium and magnesium. The alkaline earth metal dissociable salt is more preferable, and at least one of calcium salt and magnesium salt is more preferable. The polyvalent metal compound is preferably ionic.

  Specific examples of the polyvalent metal compound include calcium carbonate such as heavy calcium carbonate and light calcium carbonate, chalk, kaolin, calcined clay, talc, calcium nitrate, calcium chloride, calcium sulfate, magnesium sulfate, barium sulfate, and titanium oxide. Inorganic pigments such as zinc oxide, zinc sulfide, zinc carbonate, aluminum silicate, calcium silicate, magnesium silicate, synthetic silica, aluminum hydroxide, alumina, sericite, white carbon, saponite, calcium montmorillonite, sodium montmorillonite, and bentonite, And organic pigments such as acrylic plastic pigments and urea polymer substances. A polyvalent metal compound may be used individually by 1 type, and may use 2 or more types together.

  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, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof Etc. are preferable. 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 the cationic urethane resin, known ones can be appropriately selected and used. Commercially available products can be used as the cationic urethane-based resin. For example, Hydran CP-7010, CP-7020, CP-7030, CP-7040, CP-7050, CP-7060, CP-7610 (trade names) , 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, Taisei Fine Chemical Co., Ltd.) 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 resins can be appropriately selected and used. For example, polyallylamine hydrochloride, polyallylamine amide sulfate, allylamine hydrochloride / diallylamine hydrochloride copolymer, allylamine acetate / diallylamine acetic acid Salt copolymer, allylamine acetate / diallylamine acetate copolymer, allylamine hydrochloride / dimethylallylamine hydrochloride copolymer, allylamine / dimethylallylamine copolymer, polydiallylamine hydrochloride, polymethyldiallylamine hydrochloride, polymethyldiallylamine amide sulfate, polymethyldiallylamine acetic acid Salt, polydiallyldimethylammonium chloride, diallylamine acetate / sulfur dioxide copolymer, diallylmethylethylammonium ethyl sulfate - sulfur dioxide copolymers, methyl diallyl amine hydrochloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-sulfur dioxide copolymers, diallyldimethylammonium chloride-acrylamide copolymer and the like. As such a cationic allylamine resin, commercially available products can be used. For example, PAA-HCL-01, PAA-HCL-03, PAA-HCL-05, PAA-HCL-3L, PAA-HCL- 10L, PAA-H-HCL, PAA-SA, PAA-01, PAA-03, PAA-05, PAA-08, PAA-15, PAA-15C, PAA-25, PAA-H-10C, PAA-D11- HCL, PAA-D41-HCL, 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, Nittobo Medical Association Etsu Chemical Co., Ltd.), Haimo Neo-600, Haimorokku Q-101, Q-311, Q-501, high-Max SC-505, SC-505 (trade name, can be used Haimo Co., Ltd.), and the like.

  The content of the flocculant can be appropriately determined so that the above-described effects are exhibited. For example, the content of the flocculant is 0.25% by mass or more and 25.0% by mass or less with respect to the total mass of the reaction solution. Preferably, it is 0.5 mass% or more and 20.0 mass% or less.

2.1.2. Water The reaction liquid according to this embodiment may contain water. 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, use of water sterilized by ultraviolet irradiation or addition of hydrogen peroxide is preferable because generation of mold and bacteria can be prevented when the reaction solution is stored for a long period of 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.

2.1.3. Organic Solvent The reaction solution according to this embodiment may contain an organic solvent. The organic solvent has functions such as adjusting the viscosity of the reaction solution and increasing the adhesion of the reaction solution to the above-described film-based recording medium.

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

  Examples of 1,2-alkanediols include 1,2-propanediol, 1,2-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 reaction liquid with respect to the recording medium to wet it uniformly. When it contains 1,2-alkanediols, the content can be 1% by mass or more and 20% by mass or less with respect to the total mass of the reaction solution.

  Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, trimethylolpropane, and glycerin. It is done. Polyhydric alcohols have functions such as increasing the wettability of the reaction liquid to the recording medium and increasing the moisture retention of the nozzle when the reaction liquid is discharged using an ink jet recording apparatus. When polyhydric alcohols are contained, the content can be 2% by mass to 30% by mass with respect to the total mass of the reaction solution.

  Examples of pyrrolidone derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-pyrrolidone, N-butyl-2-pyrrolidone, and 5-methyl-2-pyrrolidone. Etc. The pyrrolidone derivative can act 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 mono-2-methylpentyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether, propylene glycol Monopropyl ether, dipropylene glycol Propyl ether, and tripropylene glycol monomethyl ether, and the like. These can be used individually by 1 type or in mixture of 2 or more types. Glycol ethers can control the wettability of the reaction liquid to the recording medium.

2.1.4. Surfactant The reaction liquid according to the present embodiment may contain a surfactant. The surfactant has a function of reducing the surface tension of the reaction solution and improving the wettability with the recording medium. Among the surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used.

  Although it does not specifically limit as acetylene glycol type surfactant, For example, Surfynol 104,104E, 104H, 104A, 104BC, 104DPM, 104PA, 104PG-50,104S, 420,440,465,485, SE, SE- F, 504, 61, DF37, CT111, CT121, CT131, CT136, TG, GA, DF110D (all are trade names, manufactured by Air Products and Chemicals. Inc.), Olphin B, Y, P, A, STG, SPC , E1004, E1010, PD-001, PD-002W, PD-003, PD-004, EXP. 4001, EXP. 4036, EXP. 4051, AF-103, AF-104, AK-02, SK-14, AE-3 (all trade names, manufactured by Nissin Chemical Industry), acetylenol E00, E00P, E40, E100 (all trade names, river Ken Fine Chemical Co., Ltd.).

  Although it does not specifically limit as a silicone 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. Commercially available products of the polyether-modified organosiloxane include, for example, BYK-306, BYK-307, BYK-333, BYK-341, BYK-345, BYK-346, BYK-348 (above trade names, manufactured by BYK). KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF-6020, X-22-4515 , KF-6011, KF-6012, KF-6015, KF-6017 (above trade names, 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 thereof can be 0.1% by mass or more and 1.5% by mass or less with respect to the total mass of the reaction solution.

2.1.5. Other Components The reaction solution according to the present embodiment may contain a pH adjuster, an antiseptic / fungicide, a rust inhibitor, a chelating agent, and the like as necessary.

2.2. Ink composition In the ink jet recording method according to the present embodiment, an ink composition is used in the attaching step (image recording step).

2.2.1. Pigment The inkjet composition according to this embodiment contains a pigment.

  Among the pigments, examples of the inorganic pigment include carbon black, iron oxide, and titanium oxide. Although it does not specifically limit as said carbon black, For example, furnace black, lamp black, acetylene black, and channel black (CI pigment black 7) are mentioned. 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, FW2, FW2V, FW18, FW200, S150, S160, S170, Pretex 35, 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, Columbia Carbon ( Columbian Carbon Japan Ltd), Columbian Chemicals, Regal 400R, 330R, 660R, Mogul L, Monarch 700, 800, 880, 900, 1000, 1100, 1300, 1400, Elftex 12 (all above) Product name, Cabot Corporation)).

  Examples of organic pigments include quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diene pigments. Examples include ketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, isoindolinone pigments, azomethine pigments, and azo pigments.

  The pigment content is preferably 0.5% by mass or more and 25.0% by mass or less, more preferably 1.0% by mass or more and 20.0% by mass or less, based on the total mass of the ink composition. More preferred.

2.2.2. Pigment-dispersed resin It is preferable that the pigment can be stably dispersed and held in water in order to apply the pigment to the ink composition. As the method, a method of dispersing with a pigment-dispersed resin such as a water-soluble resin and / or a water-dispersible resin (hereinafter, a pigment treated by this method may be referred to as “resin-dispersed pigment”), a dispersant. (Hereinafter, the pigment treated by this method may be referred to as “dispersant-dispersed pigment”), a hydrophilic functional group is chemically and physically introduced on the surface of the pigment particles, and the resin Alternatively, there may be mentioned a method for allowing dispersion and / or dissolution in water without a dispersant (hereinafter, a pigment treated by this method may be referred to as “surface-treated pigment”).

  The ink composition according to the present embodiment can use any of the resin dispersion pigments, dispersant dispersion pigments, and surface treatment pigments, and can be used in a mixed form as necessary. It preferably contains a pigment.

  Examples of the pigment dispersion resin used for the resin dispersion pigment include polyvinyl alcohols, polyacrylic acid, acrylic acid-acrylonitrile copolymer, vinyl acetate-acrylic acid ester copolymer, acrylic acid-acrylic acid ester copolymer, and styrene. -Acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-acrylic acid ester copolymer, styrene-α-methylstyrene-acrylic acid copolymer, styrene-α-methylstyrene-acrylic acid- Acrylate ester copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride copolymer, vinyl naphthalene-acrylic acid copolymer, vinyl naphthalene-maleic acid copolymer, vinyl acetate-maleic acid ester copolymer Polymer, vinyl acetate-crotonic acid copolymer, vinyl acetate-acrylic Examples thereof include luric acid copolymers and salts thereof. Among these, a copolymer of a monomer having a hydrophobic functional group and a monomer having a hydrophilic functional group, and a polymer composed of a monomer having both a hydrophobic functional group and a hydrophilic functional group are preferable. As the form of the copolymer, any form of a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer can be used.

  A commercial item can be used for such a pigment dispersion resin, for example, Solsperse 20000, 24000, 32000, 32500, 33500, 34000, 35200, 37500 (all manufactured by LUBRIZOL), Disperbyk-161, 162, 163, 164, 166, 180, 190, 191, 192 (all manufactured by Big Chemie Japan), Floren DOPA-17, 22, 33, G-700 (all manufactured by Kyoeisha Chemical Co., Ltd.), Azisper PB821, PB711 (all Ajinomoto Co., Inc.), LP4010, LP4050, LP4055, POLYMER400, 401, 402, 403, 450, 451, 453 (all manufactured by EFKA Chemicals).

  The content ratio of the pigment-dispersed resin can be appropriately selected depending on the pigment to be dispersed, but is preferably 5 parts by mass or more and 200 parts by mass or less, more preferably 100 parts by mass with respect to the pigment content in the ink composition. Is 30 parts by mass or more and 120 parts by mass or less.

2.2.3. Polymer Particles The ink composition according to this embodiment contains polymer particles. The polymer particles have a function of improving the fixability of the ink composition attached to the recording medium and improving the glossiness.

  Materials constituting the polymer particles include acrylic resins, fluorene resins, urethane resins, olefin resins, rosin modified resins, terpene resins, ester resins, amide resins, epoxy resins, vinyl chloride resins, Examples include vinyl chloride-vinyl acetate copolymer and ethylene vinyl acetate resin. These resins can be used singly or in combination of two or more. Among these resins, the material constituting the polymer particles preferably includes at least one of an acrylic resin and a urethane resin from the viewpoint of further improving the abrasion resistance of the image.

  An acrylic resin is a polymer obtained by using at least one of (meth) acrylic acid, (meth) acrylic acid ester, acrylonitrile, cyanoacrylate, and acrylamide as a monomer (hereinafter also referred to as “acrylic monomer”). Say.

  The acrylic resin may be a homopolymer of an acrylic monomer or a monomer other than an acrylic monomer (for example, olefin, styrene, vinyl acetate, vinyl chloride, vinyl alcohol, vinyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl carbazole, And a copolymer with vinyl imidazole, vinylidene chloride, etc.). In addition, said copolymer may be any form among a random copolymer, a block copolymer, an alternating copolymer, and a graft copolymer. In this specification, “(meth) acryl” means at least one of acrylic and methacryl corresponding thereto.

  Among the above, the acrylic resin is preferably at least one of (meth) acrylic resin and styrene- (meth) acrylic acid copolymer resin, from the viewpoint that the image can be further improved in abrasion resistance. At least one of the resin and the styrene-acrylic acid copolymer resin is more preferable. The acrylic resin is preferably an emulsion type.

  Commercially available products may be used for the resin emulsion containing the acrylic resin. For example, Movinyl 972, 718, 742A, 8055A (all trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), Joncryl 530, 538, 1908, 1925, 1992 (all are trade names, manufactured by BASF).

  Urethane resin is a polymer synthesized by reacting polyisocyanate and polyol. The synthesis of the urethane resin can be carried out by a known method.

  Examples of the polyisocyanate include linear aliphatic isocyanates such as tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, dodecamethylene diisocyanate, trimethylhexamethylene diisocyanate, and lysine diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4. -Aliphatic isocyanates having a cyclic structure such as cyclohexylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 3,3'-dimethyl-4,4'-dicyclohexylmethane diisocyanate, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 3,3′-dimethoxy-4, Aromatic isocyanates such as 4′-biphenylene diisocyanate, 3,3′-dichloro-4,4′-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Is mentioned. When synthesizing a urethane resin, the above polyisocyanate may be used alone or in combination of two or more.

  Examples of the polyol include polyether polyol and polycarbonate polyol. Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the polycarbonate polyol include diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, or polytetramethylene glycol, Examples thereof include dialkyl carbonates such as phosgene and dimethyl carbonate, and reaction products with cyclic carbonates such as ethylene carbonate.

  The urethane resin is preferably an emulsion type. Commercially available products can be used for the resin emulsion containing the urethane resin, for example, Superflex 740 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Bondic 1940NE, Hydran WLI-602 (trade name, DIC). Etc.).

  The glass transition temperature (Tg) of the polymer particles is preferably −40 ° C. or higher and 40 ° C. or lower, and more preferably 0 ° C. or higher and 40 ° C. or lower. When the Tg of the polymer particles is −40 ° C. or higher, the abrasion resistance of the recorded image is improved, and when it is 40 ° C. or lower, the smoothness of the recorded image is improved and the glossiness is increased. That is, by using polymer particles having a Tg in the range of −40 ° C. or more and 40 ° C. or less, an image having a good balance between abrasion resistance and glossiness can be recorded.

  The content of the polymer particles is preferably 1.0% by mass or more and 25.0% by mass or less with respect to the total mass of the ink composition. When the content of the polymer particles is 1.0% by mass or more, the abrasion resistance and glossiness of the image are further improved, and when the content is 25.0% by mass or less, the ink composition is ejected from the recording head. Tend to be good and the image quality tends to be good.

2.2.4. Water The ink composition according to the present embodiment contains water. The water preferably used is the same as that described in the reaction solution, and thus the description thereof is omitted. The water content can be, for example, 50% by mass or more with respect to the total mass of the ink composition.

2.2.5. Organic Solvent The ink composition according to this embodiment may contain an organic solvent. The organic solvent has functions such as improving the adhesion of the ink composition to the above-described film-based recording medium and suppressing the drying of the head of the ink jet recording apparatus. About the specific example of an organic solvent, since the thing similar to the organic solvent illustrated by description of the reaction liquid can be used, the description is abbreviate | omitted. The content of the organic solvent is not particularly limited, but may be, for example, 1% by mass to 40% by mass with respect to the total mass of the ink composition.

2.2.6. Surfactant The ink composition according to this embodiment may contain a surfactant. The surfactant has functions such as reducing the surface tension of the ink composition and improving wettability with the recording medium. Among the surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used. About the specific example of these surfactant, since the thing similar to the surfactant illustrated by description of the reaction liquid can be used, the description is abbreviate | omitted. The content of the surfactant is not particularly limited, but may be 0.1% by mass or more and 1.5% by mass or less with respect to the total mass of the ink composition.

2.2.7. Other Components The ink composition according to the present embodiment may contain a pH adjuster, an antiseptic / fungicide, a rust preventive, a chelating agent, and the like as necessary.

2.3. Relationship between the reaction liquid and the ink composition The reaction liquid and the ink composition used in the ink jet recording method according to the present embodiment have reduced functions of the components depending on the amount of specific components contained therein. It becomes difficult to exhibit the functions provided by each component in a balanced manner.

  That is, the polymer particles contained in the ink composition have a function of improving the abrasion resistance and glossiness of the image, but the content of the flocculant contained in the reaction liquid and the pigment contained in the ink composition Depending on the content of, its function decreases. On the other hand, the flocculant contained in the reaction liquid and the pigment contained in the ink composition have a function of improving the image quality of the image, but the function depends on the content of the polymer particles contained in the ink composition. descend.

  Therefore, as a result of intensive studies, the inventor satisfied that the content of the polymer particles contained in the ink composition and the pigment contained in the ink composition and the flocculant contained in the reaction liquid satisfy a specific relationship. It has been found that the function of each component is exerted in a well-balanced manner. Specifically, the reaction liquid and the ink composition used in the ink jet recording method according to this embodiment must satisfy at least one of the following conditions (1) and (2). As a result, it is possible to obtain an image in which each performance of suppression of bleeding, improvement of abrasion resistance, and improvement of glossiness is expressed in a balanced manner.

(1) When the reaction solution contains at least one of a polyvalent metal compound and an organic acid, the reaction solution and the ink composition satisfy the following formula (α). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (α) is the sum of the contents of the polymer particles and the pigment dispersion resin.
0.3 ≦ [(content of polymer particles) / {(total content of polyvalent metal compound and organic acid) + (content when pigment is converted into solid content)}] ≦ 5 (α )

  By satisfying the above formula (α), it is possible to obtain an image in which each performance of suppression of bleeding, improvement of abrasion resistance, and improvement of glossiness is expressed in a balanced manner. On the other hand, if it is less than 0.3 in the above formula (α), the balance of each performance is lost, and the rubbing resistance and glossiness of the image are lowered. Further, if the value exceeds 5 in the above formula (α), the occurrence of bleeding cannot be suppressed, and the image quality of the image is deteriorated.

Here, when the ink composition contains a pigment-dispersed resin, the above formula (α) can be expressed as the following formula (α) ′.
0.3 ≦ [{(content of polymer particles) + (content of pigment-dispersed resin)} / {(total content of polyvalent metal compound and organic acid) + (content when the pigment is converted into solid content) Amount)}] ≦ 5 (α) ′

  Although the pigment dispersion resin is not as much as the polymer particles, it contributes to the improvement of glossiness and abrasion resistance of the image. Therefore, when it is used, it is included in the molecule.

(2) When the reaction liquid contains a cationic resin, the reaction liquid and the ink composition satisfy the following formula (β). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (β) is the sum of the contents of the polymer particles and the pigment dispersion resin.
0.3 ≦ [(polymer particle content) / {(cationic resin content) + (content when the pigment is converted into solid content)}] ≦ 3.5 (β)

  By satisfying the above formula (β), it is possible to obtain an image in which each performance of suppression of bleeding, improvement of abrasion resistance, and improvement of glossiness is expressed in a balanced manner. On the other hand, if it is less than 0.3 in the above formula (β), the balance of each performance is lost, and the abrasion resistance and glossiness of the image are lowered. Moreover, if it exceeds 3.5 in said formula ((beta)), generation | occurrence | production of a bleed cannot be suppressed and the image quality of an image will fall.

Here, when the ink composition contains a pigment-dispersed resin, the formula (β) can be expressed as (β) ′ for the same reason as the formula (α) ′.
0.3 ≦ [{(content of polymer particles) + (content of pigment dispersion resin)} / {(total content of cationic resin) + (content when pigment is converted into solid content)}] ≦ 3.5 (β) '

When the reaction solution contains at least one of a polyvalent metal compound and an organic acid, and further contains a cationic resin, it may satisfy at least one of the above formula (α) and the following formula (β). Further, the lower limit value (that is, 0.3 or more) in the above formula (α) and the following formula (β) is satisfied, and the upper limit value (that is, 5 or less) of the above formula (α) and the above formula (β). It is more preferable to satisfy at least one of the upper limit values (that is, 3.5 or less). It is also preferable to satisfy the following formula (γ).
0.3 ≦ [(polymer particle content) / {(cationic resin content) + (total content of polyvalent metal compound and organic acid) + (content when the pigment is converted to solid content) }] ≦ 3.5 (γ)

Here, when the ink composition contains a pigment-dispersed resin, the above formula (γ) can be expressed as the following formula (γ) ′ for the same reason as described above.
0.3 ≦ [{(polymer particle content) + (pigment dispersion resin content)} / {(cationic resin content) + (total content of polyvalent metal compound and organic acid) + ( Content when pigment is converted into solid content)}] ≦ 3.5 (γ) ′

  When the above-mentioned conditions, the expression (γ), and the expression (γ) ′ are satisfied, an image can be obtained in which the performances of suppressing bleeding, improving abrasion resistance, and improving gloss are well balanced.

2.4. Physical Properties of Reaction Liquid and Ink Composition The ink composition according to this embodiment has a surface tension at 20 ° C. of 20 mN / m or more and 40 mN / m from the viewpoint of a balance between image quality and reliability as an ink for inkjet recording. It is preferable that it is 25 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. Moreover, when using a reaction liquid for an inkjet recording system, it is preferable that it is the surface tension of the range similar to an ink composition.

  From the same viewpoint, the viscosity at 20 ° C. of the ink composition according to this embodiment is preferably 3 mPa · s or more and 10 mPa · s or less, and more preferably 3 mPa · s or more and 8 mPa · s or less. . The viscosity can be measured, for example, by using a viscoelasticity tester MCR-300 (trade name, manufactured by Pysica) under a 20 ° C. environment. Moreover, when using a reaction liquid for an inkjet recording system, it is preferable that it is the viscosity of the range similar to an ink composition.

3. Recording Device An example of a recording device capable of performing the ink jet recording method according to the present embodiment will be described with reference to the drawings. The recording apparatus that can be used in the ink jet recording method according to the present embodiment is not limited to the following modes.

  FIG. 1 is a diagram schematically illustrating an ink jet recording apparatus capable of performing the ink jet recording method according to the present embodiment. The inkjet recording apparatus 1000 according to the present embodiment includes a transport unit 10 that transports the recording medium 1, a reaction liquid attachment unit 20 that attaches the reaction liquid to the recording medium, and a first drying unit 30 that dries the attached reaction liquid. And an image recording means 120 for recording an image using the ink composition, a second drying means 130 for drying the image, and a pressure applying means 40 for applying pressure while heating the image.

3.1. Conveying means The conveying means 10 can be constituted by, for example, a roller 11. The transport unit 10 may have a plurality of rollers 11. In the illustrated example, the conveying unit 10 is provided on the upstream side of the reaction liquid adhering unit 20 in the direction in which the recording medium 1 is conveyed (indicated by an arrow in the drawing), but is not limited thereto. As long as the recording medium 1 can be conveyed, the position and the number of the recording medium 1 provided are arbitrary. 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.

  The recording medium 1 conveyed by the conveying means 10 is conveyed to a position where the reaction liquid is attached to the recording surface.

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

3.2. Reaction liquid attachment means The reaction liquid attachment means 20 attaches the reaction liquid 2 to the recording surface of the recording medium 1 using the reaction liquid. The reaction liquid adhering means 20 includes an ink jet recording head (recording head) 21 having a nozzle for discharging the reaction liquid. The reaction liquid adhesion means 20 is used in the reaction liquid adhesion process in the above-described adhesion process.

  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. During this time, a recording information signal is applied to the deflecting electrode for recording, or a droplet of the reaction liquid is ejected in response to the recording information signal without deflection (electrostatic suction system), and the pressure is applied to the reaction liquid with a small pump. In addition, the nozzle is mechanically oscillated with a quartz oscillator, etc. to forcibly eject the droplets of the reaction liquid. Pressure and recording information signals are simultaneously applied to the reaction liquid with a piezoelectric element, Examples include a method of ejecting and recording droplets (piezo method), a method of heating and foaming a reaction liquid with a microelectrode according to a recording information signal, and ejecting and recording droplets of the reaction liquid (thermal jet method), and the like.

  In addition, although the case where the inkjet method was used as the reaction liquid adhesion means 20 was shown in FIG. 1, it is not limited to this, Even if it changes into the aspect which can implement the method (for example, spray coat, roll coat) mentioned above. Good.

3.3. First drying means The first drying means 30 is used to dry the reaction solution 2. The 1st drying means 30 will not be specifically limited if it is provided with the structure which accelerates | stimulates the evaporation scattering of the liquid medium contained in a reaction liquid. For example, a means for applying heat to the recording medium, a means for blowing air on the reaction liquid, a means for combining them, and the like can be mentioned. Specifically, forced air heating, radiation heating, conductive heating, high frequency drying, microwave drying, and the like are preferably used. The ink jet recording apparatus 1000 according to the present embodiment may not include the first drying unit 30 when the reaction liquid is naturally dried. Further, the first drying means 30 is provided on the downstream side of the reaction liquid attaching means 20, but may be provided at a position facing the reaction liquid attaching means 20 instead of or in addition to this. .

3.4. Image recording means The image recording means 120 forms an image by adhering droplets of the ink composition to the region to which the reaction liquid has adhered. The image recording unit 120 includes an inkjet recording head 121 including a nozzle that discharges an ink composition. The method of ejecting the ink composition from the nozzles of the inkjet recording head 121 is the same as the example described in the reaction liquid adhering means 20, and therefore the description thereof is omitted. The image recording means 120 is used in the image recording process in the above-described adhesion process.

  As the reaction liquid adhering means 20 and the image recording means 120, any of an ink jet recording apparatus provided with a serial type recording head and an ink jet recording apparatus provided with a line type recording head can be used.

  An ink jet recording apparatus provided with a serial type recording head performs recording by performing a scan (pass) for discharging the ink composition a plurality of times while moving the recording head relative to the recording medium. It is. In a specific example of the serial type recording head, the recording head is mounted on a carriage that moves in the width direction of the recording medium (direction intersecting the conveyance direction of the recording medium), and the recording head moves as the carriage moves. By doing so, there are those that discharge droplets onto a recording medium. On the other hand, an ink jet recording apparatus equipped with a line type recording head performs recording by performing scanning (pass) for discharging the ink composition once while moving the recording head relative to the recording medium. It is. A specific example of the line-type recording head includes 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.

3.5. Second drying means The second drying means 130 dries the image formed on the recording surface. The drying means that can be used for the second drying means 130 is the same as the example described for the first drying means 30, and therefore the description thereof is omitted. The ink jet recording apparatus 1000 according to the present embodiment may not include the second drying unit 130 when the image is dried by natural drying. Further, the second drying unit 130 is provided on the downstream side of the image recording unit 120, but may be provided at a position facing the image recording unit 120 instead of or in addition to this.

3.6. Pressure applying means The pressure applying means 40 is not particularly limited as long as it includes means for pressurizing the obtained image while heating. For example, a heat that is a heatable roller as shown in FIG. It can be constituted by a roller 41. The pressure applying means 40 is used in the pressure applying process.

  Although the case where the heat roller 41 is used as the pressure applying means 40 is shown in FIG. 1, the present invention is not limited thereto, and a known pressing device such as a heatable flat plate press may be used.

4). 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.

4.1. Preparation of reaction liquid Each component was mixed and stirred so as to have a blending ratio shown in Table 1 to obtain a reaction liquid. The numerical values in Table 1 indicate mass%, and ion-exchanged water was added so that the total mass of the reaction solution was 100 mass%. In addition, the components described in Table 1 other than the compound names are as follows. Moreover, content of the cationic resin in Table 1 shows the value converted into solid content.

・ PAA-HCL-3L (trade name, manufactured by Nitto Bo Medical Co., Ltd., polyallylamine, cationic resin)

4.2. Preparation of Ink Composition Each component was mixed and stirred so as to have the blending ratio shown in Table 2, and then filtered through a 10 μm membrane filter to prepare an ink composition. In preparing the ink composition, a pigment dispersion containing a pigment, a pigment dispersion resin, and water was prepared in advance, and the pigment dispersion and the remaining components were mixed. The numerical values in Table 2 indicate mass%, and ion exchange water was added so that the total mass of the ink composition was 100 mass%. In addition, the components described in Table 2 other than the compound names are as follows. Moreover, the content of the pigment, pigment dispersion resin, and polymer particle in Table 2 indicates a value converted to solid content.

・ P. B15: 3 (CI pigment blue 15: 3, cyan pigment)
Pigment dispersion resin (styrene-acrylic acid copolymer, weight average molecular weight: 25000, Tg: 80 ° C., acid value: 180)
・ Movinyl 742A (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd., acrylic resin, Tg 37 ° C.)
・ Movinyl 8055A (trade name, manufactured by Nippon Synthetic Chemical Co., Ltd., styrene-acrylic acid copolymer, Tg 75 ° C.)
・ Hydran WLI-602 (trade name, manufactured by DIC Corporation, urethane resin, Tg-50 ° C.)
・ BYK-348 (trade name, manufactured by BYK Japan, Inc., silicone surfactant)

4.3. Evaluation Test Samples for evaluation of Examples and Comparative Examples used for the following evaluation tests were prepared as follows.

  First, the ink jet recording apparatus used in FIG. 1 was prepared by using a serial type recording head as a head for discharging the reaction liquid and the ink composition. Then, the reaction liquid and the ink composition were supplied so as to be ejected to the recording head.

Thereafter, the reaction liquid was discharged from the recording head and adhered to a film-based recording medium (trade name “Lumirror S10”, manufactured by Toray Industries, Inc., polyester film). The reaction liquid adhered to the film-type recording medium in this way was dried by heating so that the temperature of the recording surface of the recording medium was 40 ° C., and it was confirmed that there was no stickiness with the finger. The recording conditions for the reaction liquid were set so that the image resolution was 720 × 720 dpi and the amount of the reaction liquid deposited was 0.7 mg / inch ² .

Next, the ink composition was ejected from the recording head, and the image was recorded by adhering to the reaction liquid adhering to the film-based recording medium. The image thus obtained was heat-dried so that the temperature of the recording surface of the recording medium was 40 ° C., and it was confirmed that there was no stickiness with a finger. The recording conditions of the ink composition were set such that the image resolution was 720 × 720 dpi and the ink composition adhesion amount was 10 mg / inch ² .

  Next, the image recorded on the film-type recording medium was pressurized using a heating / pressurizing roller while heating to obtain evaluation samples according to Examples and Comparative Examples. In addition, the conditions at the time of heating and pressing were performed under the temperature conditions of room temperature (20 ° C.), 50 ° C., and 80 ° C. under the pressure conditions of 0.005 MPa, 1.0 MPa, and 5.0 MPa.

The evaluation sample for Comparative Example 6 was prepared using coated paper (trade name “OK Top Coat”, manufactured by Oji Paper Co., Ltd., weighing 104.7 g / m ² ) instead of the film recording medium. It was.

4.3.1. Abrasion resistance Abrasion resistance was evaluated using a Gakushin type friction fastness tester AB-301 (trade name, manufactured by Tester Sangyo Co., Ltd.). Specifically, the recording surface on which the image was recorded was rubbed 100 reciprocations with a load of 500 g with a friction element attached with a white cotton cloth (JIS L 0803 compliant). And the stain | pollution | contamination of the stain | pollution | contamination of a white cotton cloth and an image (coating film) was observed visually. For the evaluation of rubbing resistance, a temperature of 50 ° C. during heating and pressurization was used. The evaluation criteria are as follows.
◎: White cotton cloth has no stain and image does not peel ○: White cotton fabric has stain but no image peeling ×: White cotton fabric shows dirt and image peeling

4.3.2. Glossiness Using a MULTI GLOSS 268 (manufactured by Konica Minolta Co., Ltd.), the 60 ° glossiness based on JIS Z8741 of the image recording portion of the evaluation sample was measured. Specifically, the 60 ° glossiness of the image recording portion before and after heating and pressing (pressure applying step) was measured, and evaluation was performed based on the change in glossiness after heating and pressing. The glossiness after heating and pressing was measured for each heating temperature. The evaluation criteria are as follows.
A: Glossiness improvement is 20% or more B: Glossiness improvement is 15% or more and less than 20% C: Glossiness improvement is 10% or more and less than 15% D: Glossiness improvement is less than 10%

4.3.3. Bleed The bleed was evaluated by visually confirming the presence or absence of bleeding in the contour of the image. The bleed was evaluated at a temperature of 50 ° C. during heating and pressurization. The evaluation criteria are as follows.
○: No bleeding (bleed) ×: There is bleeding (bleed)

4.3.4. Damage to the recording medium The evaluation sample obtained as described above was placed in an environment with an air temperature of 25 ° C. and a humidity of 60%, and the presence or absence of curling of the recording medium on which the image was recorded and the conveyance direction of the recording medium The damage to the recording medium was determined by confirming the presence or absence of expansion and contraction of 5% or more. The presence or absence of curling was visually observed, and the presence or absence of expansion and contraction was measured with a measure. The glossiness after heating and pressing was measured for each temperature. The evaluation criteria are as follows.
A: No curling of recording medium, no expansion / contraction ○: Curling of recording medium, no expansion / contraction x: Curling of recording medium, expansion / contraction

4.4. Evaluation results The results of the above evaluation tests are shown in Tables 3 to 7.

  The evaluation sample according to the example is prepared by using the reaction liquid and ink composition set satisfying the formula (α) or the formula (β) described above and performing a pressure application step after image recording. According to the evaluation sample according to the example, it was shown that an image having excellent abrasion resistance and glossiness, a bleed-inhibited image can be recorded, and damage to the recording medium can be reduced.

  On the other hand, the evaluation samples according to Comparative Example 1 and Comparative Example 2 were prepared using a set of a reaction liquid and an ink composition that are less than the lower limit value of the formula (α), and therefore, abrasion resistance and glossiness Was shown to decrease. Since the evaluation sample according to Comparative Example 3 was formed using a set of a reaction liquid and an ink composition that exceeded the upper limit of the formula (α), it was shown that bleeding occurred. Since the evaluation sample according to Comparative Example 4 was prepared using a set of a reaction liquid and an ink composition that are less than the lower limit value of the formula (β), it is shown that the abrasion resistance and the glossiness are lowered. It was done. Since the evaluation sample according to Comparative Example 5 was formed using a set of a reaction liquid and an ink composition exceeding the upper limit value of the formula (β), it was shown that bleeding occurred. Since the evaluation sample according to Comparative Example 6 used coated paper as the recording medium, the glossiness of the image was insufficient.

  Moreover, since the evaluation sample which concerns on Comparative Example 7- Comparative Example 17 applied only the pressure of less than 0.01 MPa in a pressure addition process, it was shown that it is not excellent in the glossiness of the image recorded.

  Since the evaluation sample according to Comparative Example 18 was applied with a pressure exceeding 3.0 MPa in the pressure applying step, it was shown that the recording medium was damaged.

  Since the evaluation samples according to Comparative Examples 19 to 30 were performed at room temperature (20 ° C.) without heating during the pressure application step, it was shown that the glossiness of the image was insufficient.

  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, 21 (131) ... Inkjet recording head, 30 ... First drying means, 120 ... Image recording means, 130 ... Second drying means 40 ... Pressure applying means, 41 ... Heat roller, 1000 ... Image recording apparatus

Claims (11)

A reaction liquid containing at least one of a polyvalent metal compound, an organic acid, and a cationic resin and an ink composition for ink jet recording containing water, a pigment, and polymer particles are attached to a film recording medium. An adhesion process;
A pressure application step of applying a pressure of 1.0 MPa or more and 3.0 MPa or less in a heated state to the ink composition attached to the film-based recording medium,
The adhesion amount per unit area of the reaction solution is 0.1 mg / inch ² or more and 3.0 mg / inch ² or less,
In the reaction solution, the total content of the polyvalent metal compound, the organic acid and the cationic resin is 0.25% by mass or more and 15% by mass with respect to the total mass of the reaction solution,
An inkjet recording method, wherein the reaction liquid and the ink composition satisfy at least one of the following conditions (1) and (2).
(1) When the reaction solution contains at least one of a polyvalent metal compound and an organic acid, the reaction solution and the ink composition satisfy the following formula (α). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (α) is the sum of the content (% by mass) of the polymer particles and the pigment dispersion resin with respect to the total mass of the ink composition. .
0.3 ≦ [(content of polymer particles with respect to the total mass of the ink composition (% by mass)) / {(total of content (% by mass) with respect to the total mass of the reaction liquid of polyvalent metal compound and organic acid) + (Content (mass%) with respect to the total mass of the ink composition when the pigment is converted into solid content)}] ≦ 5 (α)
(2) When the reaction liquid contains a cationic resin, the reaction liquid and the ink composition satisfy the following formula (β). However, when the ink composition further contains a pigment dispersion resin, the molecule in the following formula (β) is the sum of the content (% by mass) of the polymer particles and the pigment dispersion resin with respect to the total mass of the ink composition. .
0.3 ≦ [(content of polymer particles with respect to the total mass of the ink composition (% by mass)) / {(content with respect to the total mass of the reaction solution of the cationic resin (% by mass)) + (pigment converted to solid content Content with respect to the total mass of the ink composition (% by mass))}] ≦ 3.5 (β) In claim 1,
The ink jet recording method, wherein a heating temperature in the pressure applying step is equal to or higher than a glass transition temperature of the polymer particles. In claim 1 or claim 2,
The inkjet recording method whose glass transition temperature of the said polymer particle is -40 degreeC or more and 40 degrees C or less. In any one of Claims 1 thru | or 3,
The inkjet recording method whose heating temperature in the said pressure addition process is 40 degreeC or more and 80 degrees C or less. In any one of Claims 1 thru | or 4,
The ink jet recording method, wherein the material constituting the polymer particles includes at least one of an acrylic resin and a urethane resin. In any one of Claims 1 thru | or 5,
The ink jet recording method, wherein an adhesion amount per unit area of the ink composition is 3 times or more and 30 times or less with respect to an adhesion amount per unit area of the reaction liquid. In any one of Claims 1 thru | or 6,
The ink jet recording method, wherein an amount of the reaction liquid adhered per unit area is 0.7 mg / inch ² or more and 3.0 mg / inch ² or less. In any one of Claims 1 thru | or 7,
An ink jet recording method in which, when the reaction solution contains at least one of a polyvalent metal compound and an organic acid and contains a cationic resin, the following formula (γ) is satisfied.
0.3 ≦ [(content of polymer particles with respect to the total mass of the ink composition (% by mass)) / {(content with respect to the total mass of the reaction liquid of polyvalent metal compound, organic acid and cationic resin (% by mass)) ) + (Content (mass%) with respect to the total mass of the ink composition when the pigment is converted into solid content)}] ≦ 3.5 (γ) In any one of Claims 1 thru | or 8,
The ink jet recording method, wherein the amount of adhesion per unit area of the ink composition is 12 times to 30 times the amount of adhesion per unit area of the reaction solution. In any one of Claims 1 thru | or 9,
The adhesion amount per unit area of the ink composition is 6.0 mg / inch ² or more 15.0 mg / inch ² or less, the ink jet recording method. In any one of Claims 1 thru | or 10,
When the above (1) is satisfied, in the formula (α), 2.3 ≦ [(content (% by mass) of polymer particles with respect to the total mass of the ink composition) / {(reaction of polyvalent metal compound and organic acid) The total content (mass%) of the liquid relative to the total mass) + (content (mass%) relative to the total mass of the ink composition when the pigment is converted into solid content)}] ≦ 5,
When satisfying the above (2), in the formula (β), 2.3 ≦ [(content (% by mass) of the polymer particles with respect to the total mass of the ink composition) / {(total mass of the reaction solution of the cationic resin) Content (mass%)) + (content (mass%) relative to the total mass of the ink composition when the pigment is converted into solid content)}] ≦ 3.5.

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