JP2019014237A - Inkjet recording method and inkjet recording apparatus - Google Patents

Abstract

To provide an inkjet recording method capable of suppressing transfer of a coloring material and suppressing adherence of a coloring material to a porous layer even if a porous layer is repeatedly brought into contact with a first image.SOLUTION: There is provided an inkjet recording method for recording an image on a recording medium by utilizing an aqueous reaction liquid and an aqueous ink containing a first ink, which comprises: a reaction liquid imparting step of imparting a reaction liquid containing a reaction agent and resin particles over the whole of a first recording medium; an image forming step of forming a first image by imparting a first ink containing a coloring material to the first recording medium; and a liquid absorbing step of absorbing a liquid component from a part including the first image on the first recording medium by bringing a porous layer included in a liquid absorption member into contact with the first image, wherein the cumulative 10% pore diameter (μm) on the volume basis of the porous layer is larger than the cumulative 90% particle diameter (μm) on the volume basis of the resin particles.SELECTED DRAWING: None

Description

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

  Water-based inks are widely used as inks used in ink jet recording methods. In order to quickly remove the liquid component in the ink, there is a method of recording an image by drying the recording medium with warm air or infrared rays. Further, a method of forming a first image as an intermediate image on a transfer body using water-based ink, removing a liquid component contained in the first image by heat energy or the like, and then transferring the image to a recording medium to record the image. There is also. An ink jet recording method using a transfer body has been studied (see Patent Document 1). The inkjet recording method includes a step of forming a first image by applying ink to a transfer body after a reaction liquid containing a reactive agent and resin particles, and contacting a porous body with the first image. Removing the liquid component from the first image.

JP 2009-96175 A

  As a result of the study by the present inventors, when many images are recorded by the ink jet recording method described in Patent Document 1, the color material in the first image moves and the color material adheres to the porous body. I found out that

  Accordingly, an object of the present invention is to provide an ink jet recording method capable of suppressing the movement of the color material and suppressing the adhesion of the color material to the porous layer even when many images are recorded. Another object of the present invention is to provide an ink jet recording apparatus using the ink jet recording method.

  The above object is achieved by the present invention described below. That is, the inkjet recording method of the present invention is an inkjet recording method for recording an image on a recording medium using an aqueous reaction liquid and an aqueous ink containing a first ink, which contains a reactive agent and resin particles. A reaction liquid applying step of applying a reaction liquid to the first recording medium, an image forming step of applying a first ink containing a coloring material to the first recording medium to form a first image, and a liquid absorbing member A liquid absorption step of absorbing a liquid component from a portion including the first image on the first recording medium by bringing the porous layer provided into contact with the first image, and the volume reference of the porous layer The cumulative 10% pore diameter (μm) of the resin particles is larger than the volume-based cumulative 90% particle diameter (μm) of the resin particles.

  According to the present invention, after applying the reaction liquid, the first ink is applied, and the porous layer included in the liquid absorbing member is formed of the reaction liquid on the first recording medium and the first ink. An ink jet recording apparatus provided with a means for bringing into contact with a portion including the first image, wherein the reaction liquid is an aqueous reaction liquid containing a reactive agent and resin particles, and the first ink is a color. A water-based ink containing a material, wherein a volume-based cumulative 10% pore diameter (μm) of the porous layer is larger than a volume-based cumulative 90% particle diameter (μm) of the resin particles The present invention relates to a recording apparatus.

  According to the present invention, there is provided an ink jet recording method and an ink jet recording apparatus capable of suppressing the movement of the color material and suppressing the adhesion of the color material to the porous layer even when many images are recorded. .

It is a schematic diagram which shows an example of the transfer type inkjet recording device used for the inkjet recording method of this invention. It is a schematic diagram which shows an example of the direct recording type inkjet recording device used for the inkjet recording method of this invention.

  Hereinafter, embodiments of the present invention will be described in detail. In the present invention, hereinafter, the water-based ink and the first ink may be referred to as “ink”. The aqueous reaction liquid may be referred to as “reaction liquid”. Various physical property values are values at a temperature of 25 ° C. unless otherwise specified. References to “(meth) acrylic acid” and “(meth) acrylate” represent “acrylic acid, methacrylic acid” and “acrylate, methacrylate”, respectively.

  In the ink jet recording method of the present invention, an aqueous reaction liquid and an aqueous ink containing a first ink are used. After the reaction liquid containing the resin particles is applied to the first recording medium, when the first ink containing the color material is applied to the first recording medium, the color material in the first ink is applied due to the presence of the resin particles. It becomes difficult to move from the position. Accordingly, even if the porous layer included in the liquid absorbing member comes into contact with the reaction liquid on the first recording medium and the portion including the first image formed by the first ink, the color material in the first image Therefore, it is difficult for the coloring material to move in the first image. In particular, when the porous layer contacts the first image, the color material easily moves in the direction around the first image, but the presence of the resin particles suppresses the movement of the color material in the direction around the first image. it can.

  However, the first recording medium to which the reaction liquid is applied has a portion where ink is not applied, and the reaction liquid exists without reacting with the ink in that portion. For this reason, the porous layer comes into contact with not only the first image on the first recording medium, that is, the first image but also the portion where the reaction liquid not reacting with the ink exists. In the reaction liquid that has not reacted with the ink, there are resin particles that are not aggregated in addition to the liquid component. Therefore, when the porous layer comes into contact with the reaction liquid, not only the liquid component in the reaction liquid but also the resin particles Is also absorbed. In particular, when recording a large number of images, the porous layer is repeatedly contacted not only with the first image but also with the reaction solution. Therefore, if the pore size of the porous layer is smaller than the particle size of the resin particles in the reaction solution, the porous layer Resin particles tend to clog the pores of the layer. Even when a porous layer having pores clogged with resin particles is brought into contact with the first image, it is difficult to absorb the liquid component from the first image, so that aggregation of the color material in the first image is difficult to be promoted. Therefore, when a large number of images are recorded and the porous layer is repeatedly contacted with the reaction liquid, the color material moves together with the liquid component contained in the first image even if resin particles are present. End up. Thereby, the movement of the coloring material in the direction around the first image cannot be suppressed. Furthermore, since the aggregation of the color material in the first image is difficult to be promoted, the adhesion of the color material to the porous layer cannot be suppressed.

  Therefore, in order to suppress the movement of the color material and the adhesion of the color material to the porous layer, the present inventors set the volume-based cumulative 10% pore diameter of the porous layer to the volume-based cumulative 90% of the resin particles. It was thought that it was necessary to make it larger than the% particle size, and the present invention was reached. Hereinafter, the volume-based cumulative 10% pore diameter of the porous layer may be abbreviated as “pore diameter of the porous layer”, and the volume-based cumulative 90% particle diameter of the resin particles may be abbreviated as “resin particle diameter”. . The pore size of the porous layer is determined using a pore size distribution measuring device using a gas permeation method. The particle size of the resin particles is determined using a dynamic light scattering method or the like.

  Here, the cumulative 10% pore diameter is the diameter of the hole when the cumulative diameter from the small pore diameter side becomes 10% on the pore diameter cumulative curve as a reference. The volume of the hole is the volume of the through hole. Further, the cumulative 90% particle diameter is the diameter of a particle when the accumulated particle diameter curve is 90% when integrated from the small particle diameter side based on the total volume of the measured resin particles. The volume-based cumulative 10% pore diameter of the porous layer is larger than the volume-based cumulative 90% particle diameter of the resin particles means that most of the pore diameter of the porous layer is larger than the resin particle diameter. doing. Therefore, even when a large number of images are recorded and the porous layer is repeatedly contacted with the reaction liquid, the resin particles are absorbed together with the liquid components in the reaction liquid. Hard to clog. Even when the porous layer that has been used repeatedly is brought into contact with the first image, the liquid component is smoothly absorbed from the first image, so that aggregation of the coloring material in the first image is promoted. Thereby, a movement of a coloring material can be suppressed. Furthermore, adhesion of the coloring material to the porous layer can be suppressed by promoting aggregation of the coloring material in the first image.

  The ink jet recording method of the present invention can suppress the movement of the color material and the adhesion of the color material to the porous layer, regardless of which of the following methods (1) and (2).

(1) A method for recording an image by transferring a first image formed by applying ink to a first recording medium to a recording medium (2) A method for recording an image by directly applying ink to a recording medium (1) ), The first recording medium is a transfer member, and the ink jet recording method preferably includes a transfer step of transferring the first image of the transfer member to the recording medium after performing the liquid absorption step. An ink jet recording apparatus that can be used in each of the cases (1) and (2) will be described. Hereinafter, for convenience, the ink jet recording apparatus usable in the case (1) is referred to as a transfer type ink jet recording apparatus, and the ink jet recording apparatus usable in the case (2) is referred to as a direct recording type ink jet recording apparatus.

<Transfer type ink jet recording apparatus>
FIG. 1 is a schematic view showing an example of a transfer type ink jet recording apparatus used in the ink jet recording method of the present invention. The first recording medium when using the transfer type ink jet recording apparatus is a transfer body.

  The transfer type inkjet recording apparatus 100 is a sheet type inkjet recording apparatus that manufactures a recorded material by transferring a first image to a sheet-like recording medium 108 via a transfer body 101. The X direction, the Y direction, and the Z direction indicate the width direction (full length direction), the depth direction, and the height direction of the transfer type inkjet recording apparatus 100, respectively. The recording medium is conveyed in the X direction.

  As shown in FIG. 1, the transfer type inkjet recording apparatus 100 includes a transfer body 101 supported by a support member 102 and a reaction liquid applying device 103 that applies a reaction liquid to the transfer body 101. Furthermore, an ink application device 104 having a recording head for applying ink to the transfer body 101 to which the reaction liquid has been applied to form a first image, a liquid absorption device 105 for absorbing a liquid component from a portion including the first image, And a pressing member 106 that transfers the first image to the recording medium 108. The recording head ejects ink by an ink jet method. The transfer type inkjet recording apparatus 100 may include a transfer body cleaning member 109 that cleans the surface of the transfer body 101 after transfer. The transfer body 101, the reaction liquid applying device 103, the recording head included in the ink applying device 104, the liquid absorbing device 105, and the transfer body cleaning member 109 each have a length corresponding to the recording medium 108 used in the Y direction. Have.

  The transfer body 101 rotates in the direction of arrow A about the rotation shaft 102a of the support member 102. As the support member 102 rotates, the transfer body 101 rotates. A reaction liquid is applied from the reaction liquid applying device 103 to the rotating transfer body 101. Thereafter, ink is applied from the ink applying device 104 to the region of the transfer body 101 to which the reaction liquid has been applied. In this way, a first image is formed on the transfer body 101. The first image formed on the transfer body 101 moves to a position in contact with the liquid absorbing member 105 a included in the liquid absorbing device 105 by the rotation of the transfer body 101.

  The liquid absorbing member 105 a rotates in synchronization with the rotation of the transfer body 101. The first image formed on the transfer body 101 is in contact with the rotating liquid absorbing member 105a. During this contact state, the liquid absorbing member 105a absorbs the liquid component from the first image. At this time, from the viewpoint of efficiently absorbing the liquid component, the liquid absorbing member 105a is preferably pressed against the transfer body 101 with a predetermined pressing force.

  Since the first image is formed with the reaction liquid and the first ink, absorbing the liquid component in the ink means absorbing the liquid component in the reaction liquid and the first ink. Since the liquid component is removed from the first image by the absorption of the liquid component, it can be said that the absorption of the liquid component is the concentration of the ink. By reducing the liquid component in the ink due to the concentration of the ink, the ratio of the solid content such as the coloring material or resin in the ink to the liquid component increases.

  The first image in which the liquid component is absorbed and the ink is concentrated moves to a region in contact with the recording medium 108 by the rotation of the transfer body 101. The first image and the recording medium 108 come into contact with each other by being pressed from the pressing member 106 side while being sandwiched between the transfer body 101 and the pressing member 106. When the roller-shaped transfer body 101 and the columnar pressing member 106 are used, the first image and the recording medium 108 are linearly contacted along the Y direction. At this time, when the transfer body 101 made of an elastic material is used, the transfer body 101 is recessed by pressing, so that the first image and the recording medium 108 come into contact with each other on the surface. Therefore, a point or surface where the first image and the recording medium 108 come into contact with each other is referred to as an “area”, and a portion including this area is referred to as a transfer unit 111. While the first image in which the liquid component is absorbed is in contact with the recording medium 108, the pressing member 106 presses the transfer body 101, whereby the first image is transferred to the recording medium 108. The second image transferred to the recording medium 108 is a reverse image of the first image formed on the transfer body 101. Here, the second image is a final image, and the first image is an image other than the final image. After the final image is formed, fixing by heating or laminating may be performed.

  The liquid component contained in the ink or the reaction liquid does not have a certain shape, and has a fluidity and a substantially constant volume. Specifically, an aqueous medium or the like that is a component contained in ink or a reaction liquid corresponds to the liquid component.

  Hereinafter, [1] transfer body, [2] support member, [3] reaction liquid application device, [4] ink application device, [5] liquid absorption device, which are main devices constituting the transfer type ink jet recording apparatus, 6) A pressing member for transfer, [7] a recording medium, and [8] a recording medium conveyance device will be described.

[1] Transfer body 101
The transfer body 101 has a surface layer as a first image forming surface. Examples of the material constituting the surface layer include resins and ceramics, and a material having a high compression elastic modulus is preferable from the viewpoint of durability and the like. In order to improve the wettability and transferability of the reaction solution, surface treatment may be performed. Moreover, you may give an arbitrary shape to a surface layer.

  The transfer body preferably has a compression layer having a function of absorbing pressure fluctuation between the surface layer and the support member. By providing a compression layer, the compression layer absorbs deformation of the surface layer of the transfer body, disperses the fluctuation against local pressure fluctuations, and maintains good transferability even when recording at high speed. Can do. Examples of the material constituting the compression layer include elastic materials such as rubber materials. Among these, a rubber material molded into a porous body by blending a filler such as a foaming agent, hollow fine particles, and a salt with a vulcanizing agent, a vulcanization accelerator and the like at the time of molding is preferable. In such a material, since the void portion is compressed with a change in volume with respect to pressure fluctuation, deformation in the direction other than the compression direction is small, and transferability and durability can be improved. Examples of the porous rubber material include those having a continuous void structure in which each void is continuous with each other and those having an independent void structure in which each void is independent.

  The transfer body preferably has an elastic layer between the surface layer and the compression layer. Examples of the material constituting the elastic layer include a resin material and a ceramic material. Among them, it is preferable to use a material having elasticity such as a rubber material because it is easy to process, changes in elastic modulus with temperature are small, and has excellent transferability.

  Each layer (surface layer, elastic layer, compression layer) constituting the transfer body can be bonded using an adhesive or a double-sided tape. A reinforcing layer having a high compression elastic modulus may be provided in order to suppress lateral elongation when the device is mounted and to maintain stiffness. As the reinforcing layer, a woven fabric or the like can be used. The transfer body can be produced by arbitrarily combining an elastic layer and a compression layer other than the surface layer.

  The size of the transfer body can be freely selected according to the recording speed and the image size. Examples of the shape of the transfer body include a sheet shape, a roller shape, a belt shape, and an endless web shape. Especially, it is preferable that the shape of a transfer body is a sheet form, a roller form, or an endless web form.

[2] Support member 102
The transfer body 101 is supported by a support member 102. An adhesive or a double-sided tape can be used for supporting the transfer body. An installation member made of a material such as metal, ceramic, or resin may be attached to the transfer body, and the transfer body may be installed on the support member 102 using the installation member.

  The support member 102 is required to have a certain degree of structural strength from the viewpoint of conveyance accuracy and durability. Examples of the material constituting the support member include metal materials, ceramic materials, and resin materials. In particular, it is preferable to use a metal material such as aluminum in order to reduce rigidity during operation and improve control responsiveness in addition to rigidity and dimensional accuracy that can withstand the stress during transfer.

[3] Reaction liquid applying device 103
The ink jet recording method of the present invention includes a reaction liquid applying step of applying a reaction liquid to the first recording medium before performing the image forming step. When the reaction liquid comes into contact with the ink, it is possible to aggregate components having an anionic group (resin, self-dispersing pigment, etc.) in the ink with the reactant. After applying the first ink, the reaction liquid may be further applied so that at least a part of the region where the first ink is applied overlaps.

  The transfer type ink jet recording apparatus includes a reaction liquid applying device 103 that applies a reaction liquid to the transfer body 101. 1 is a gravure offset roller having a reaction liquid storage unit 103a that stores a reaction liquid, and reaction liquid application members 103b and 103c that apply the reaction liquid in the reaction liquid storage unit 103a to a transfer body 101. This case is shown.

  The reaction liquid applying device only needs to be able to apply the reaction liquid to the transfer body, and examples thereof include a gravure offset roller and an ink jet recording head. In particular, the reaction liquid is preferably applied to the transfer body with a roller. Applying the reaction liquid to the transfer body with a roller means that there is a part where the ink is not applied to the transfer body on which the reaction liquid is applied, and the reaction liquid exists without reacting with the ink in that part. Means that. When the reaction liquid is ejected from the recording head or the like, it is difficult to uniformly apply the reaction liquid to the transfer body. For this reason, the transfer body includes a region where the color material in the ink tends to aggregate and a region where the color material in the ink hardly aggregates. A region where the color material easily aggregates is recognized as a dark image, and a region where the color material hardly aggregates is recognized as a thin image. Even in the second image to be recorded, since there are a portion that is recognized deeply and a portion that is recognized lightly, uneven density in the image may not be sufficiently suppressed.

[4] Ink applicator 104
The transfer type ink jet recording apparatus includes an ink applying device 104 that applies ink to the transfer body 101.

  As the ink applying device, it is preferable to use an ink jet recording head to eject ink and apply it to a recording medium. Examples of the method for ejecting ink include a method for imparting mechanical energy to the ink and a method for imparting thermal energy to the ink. In particular, it is preferable to employ a method in which thermal energy is applied to the ink and the ink is ejected.

  The recording head is a line-type recording head arranged along the Y direction, and ejection openings for ejecting ink are arranged over the entire area in the width direction of the recording medium. The recording head has an ejection port surface on which an ejection port array is formed, and a gap between the ejection port surface and the transfer body 101 facing the ejection port surface can be about several mm.

  The ink applying device 104 may include a plurality of recording heads for applying the first ink of each color such as cyan, magenta, yellow, and black (CMYK) to the transfer body. For example, when forming a first image using four types of first inks of CMYK, the ink applicator has four recording heads that respectively discharge the four types of first inks of CMYK. They are arranged in the X direction.

[5] Liquid absorber 105
The liquid absorbing device 105 includes a liquid absorbing member 105 a and a liquid absorbing pressing member 105 b that presses the liquid absorbing member 105 a against the first image of the transfer body 101. The shapes of the liquid absorbing member 105a and the pressing member 105b can be as follows. For example, as shown in FIG. 1, the pressing member 105 b has a cylindrical shape, the liquid absorbing member 105 a has a belt shape, and the belt-shaped liquid absorbing member 105 a is pressed against the transfer body 101 by the cylindrical pressing member 105 b. A configuration is mentioned. Further, there is a configuration in which the pressing member 105b has a cylindrical shape, the liquid absorbing member 105a is attached to the surface around the cylindrical pressing member 105b, and the liquid absorbing member 105a of the pressing member 105b is pressed against the transfer body. Considering the space in the ink jet recording apparatus, the liquid absorbing member 105a is preferably belt-shaped. The liquid absorbing device 105 having the belt-shaped liquid absorbing member 105a may include a stretching member that stretches the liquid absorbing member 105a. Reference numeral 105c denotes a tension roller as a tension member. In FIG. 1, the pressing member 105b is also shown as a roller member in the same manner as the stretching roller, but is not limited to this.

  The liquid absorbing device 105 causes the liquid absorbing member 105a to absorb the liquid component contained in the first image by bringing the liquid absorbing member 105a having the porous layer into contact with the first image by the pressing member 105b. As a method for absorbing the liquid component contained in the first image, in addition to the present method in which the liquid absorbing member is brought into contact, a method using heating, a method for blowing low-humidity air, a method for reducing pressure, and the like may be used in combination. Further, the liquid component may be further absorbed by applying these methods to the first image before and after the liquid component is absorbed.

[Liquid absorbing member]
When the porous layer which the liquid absorption member 105a comprises contacts with a 1st image, at least one part of a liquid component is absorbed from a 1st image. The liquid absorbing member having such a porous layer rotates in conjunction with the rotation of the transfer body 101. Therefore, it is preferable that the liquid absorbing member has a shape capable of repeatedly absorbing liquid, and specific examples include an endless belt shape and a drum shape. After a region where the liquid absorbing member having such a shape contacts the first image and absorbs the liquid component, the liquid absorbing member rotates in the direction of arrow B, so that this region is removed from the position of the first image. Moving. After that, the liquid absorbing member rotates, and the liquid component absorbed from the previous first image and contained in the porous layer until this region comes into contact with the new first image becomes porous. It is preferably removed from the member. The liquid component contained in the porous member can be removed by a method of absorbing from the back surface of the porous member, a method of using a member that handles the porous member, or the like. By removing the liquid component in this way, when a certain area of the porous member comes into contact with the new first image, the liquid component contained in the first image can be efficiently absorbed again. Become.

(Porous layer)
In the ink jet recording method of the present invention, it is necessary to make the pore size of the porous layer larger than the particle size of the resin particles. When the pore size of the porous layer is smaller than the particle size of the resin particles, a large number of images are recorded, and when the porous layer is repeatedly contacted with the reaction solution, the color material is moved and the porous layer is moved to The adhesion of the coloring material cannot be suppressed. Further, as the color material adheres to the porous layer, the color material is peeled off in the first image that comes into contact with the porous layer and becomes partially colorless, so that density unevenness in the image may not be sufficiently suppressed. .

  The volume-based cumulative 10% pore diameter (μm) of the porous layer is preferably a ratio (times) to the volume-based cumulative 90% particle diameter (μm) of the resin particles, and is preferably 2.2 times or more. When the ratio is 2.2 times or more, since the difference between the pore diameter of the porous layer and the particle diameter of the resin particles is large, many images are recorded, and the porous layer is repeatedly contacted with the reaction liquid. However, the liquid component contained in the first image is absorbed smoothly, and the aggregation of the color material in the first image is promoted. Thereby, a movement of a coloring material and adhesion of a coloring material to a porous layer can be suppressed more effectively. Furthermore, since the coloring material is less likely to adhere to the porous layer, uneven density of the image can be more effectively suppressed.

  The volume-based cumulative 10% pore diameter (μm) of the porous layer is preferably 0.10 μm or more and 1.00 μm or less. When the pore diameter is less than 0.10 μm, since the pores of the porous layer are small, even if a large number of images are recorded and the porous layer is repeatedly contacted with the reaction solution, the resin particles are not absorbed into the pores. It is hard to be clogged up. However, since the hole is small, it is difficult to absorb the liquid component from the first image in the first place, and the liquid component contained in the first image tends to remain. Since the color material in the first image hardly aggregates, if the porous layer that has been repeatedly used is brought into contact with the first image, the movement of the color material may not be sufficiently suppressed. In addition, if the color material in the first image is less likely to aggregate, adhesion of the color material to the porous layer may not be sufficiently suppressed. Furthermore, as the coloring material adheres to the porous layer, the coloring material may be peeled off in the first image that contacts the porous layer, and the density unevenness of the image may not be sufficiently suppressed. When the pore diameter exceeds 1.00 μm, since the pores of the porous layer are large, it is difficult for the liquid component to be absorbed from the first image by capillary force, so that the liquid component contained in the first image tends to remain. Therefore, when the porous layer that has been used repeatedly is brought into contact with the first image for the same reason as described above, the movement of the coloring material, the adhesion of the coloring material to the porous layer, and the density unevenness of the image cannot be sufficiently suppressed. There is.

  Furthermore, it is preferable to reduce the thickness of the porous layer in order to achieve uniform and high air permeability. The air permeability can be indicated by a Gurley value defined by JIS P8117, and the Gurley value is preferably 10 seconds or less. The Gurley value is preferably 1 second or longer. However, if the porous layer is thinned, the total void volume of the porous layer is reduced, so that the maximum amount of liquid component that can be absorbed is reduced, and the liquid component contained in the first image may not be sufficiently absorbed. is there. Therefore, in addition to the porous layer, it is possible to sufficiently absorb the liquid component contained in the first image by using a porous body composed of several layers having voids larger than the porous layer. It is. In the liquid absorbing member, the layer in contact with the first image may be a porous layer, and the layer not in contact with the first image may not be a porous layer.

  Of the porous body, the porous layer in contact with the first image will be described as the first layer, and the layer laminated on the surface of the first layer opposite to the first image will be described as the second layer. Furthermore, the multilayer structure is also expressed in the order of stacking from the first layer. In the present specification, the first layer may be referred to as an “absorbing layer”, and the second and subsequent layers may be referred to as a “supporting layer”.

<First layer>
As the material constituting the first layer, any of a hydrophilic material having a contact angle with water of less than 90 ° and a water repellent material having a contact angle of 90 ° or more can be used. Examples of the hydrophilic material include fiber materials such as cellulose and resin materials such as polyacrylamide resin, and a single material or a composite material can be used. Further, the surface of a water-repellent material as will be described later can be used after being hydrophilized. Examples of the hydrophilization treatment include sputter etching, irradiation with radiation and H ₂ O ions, and excimer (ultraviolet) laser light irradiation.

  When a hydrophilic material is used, a hydrophilic material having a contact angle with water of 60 ° or less is preferable. In the case of a hydrophilic material, an action of sucking up a liquid component, particularly water, is generated by capillary force. On the other hand, from the viewpoint of suppressing the adhesion of the coloring material to the first layer and improving the cleaning property, the material of the first layer is a water repellent resin having a low surface free energy. It is preferable. Especially, it is preferable that a 1st layer contains a fluorine resin. Examples of the fluororesin include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, and polychlorotrifluoroethylene. Among these, the fluororesin is preferably polytetrafluoroethylene or polyvinylidene fluoride. Compared with olefin resins such as polypropylene and polyester resins such as polyethylene terephthalate, fluororesins have lower surface free energy and higher water repellency, so that the adhesion of the coloring material to the first layer is more effective. Can be suppressed. Furthermore, since the coloring material is less likely to adhere to the first layer, the coloring material is unlikely to peel off in the first image that is in contact with the first layer, so that density unevenness of the image can be more effectively suppressed.

  When using a water repellent material, the action of sucking up the liquid component by capillary force hardly occurs unlike the hydrophilic material, and it may take time to suck up the liquid component. Therefore, it is preferable to impregnate a treatment liquid having a contact angle with the first layer of less than 90 ° in the first layer. The treatment liquid is applied from the surface of the liquid absorbing member that comes into contact with ink before the porous layer of the liquid absorbing member is brought into contact with the first image, so that the liquid is soaked into the first layer. I can leave. The treatment liquid preferably contains water and a water-soluble organic solvent. The water is preferably deionized water. As the water-soluble organic solvent, alcohols such as ethanol and isopropyl alcohol can be used. The treatment liquid may be prepared by further mixing components such as a surfactant. Examples of the method for applying the treatment liquid include dipping and dropping.

  The thickness of the first layer is preferably 400 μm or less. The thickness is more preferably 1 μm or more and 350 μm or less. The thickness of the first layer can be obtained by measuring the thickness of any 10 points with a micrometer or the like and calculating the average value. Specifically, a digimatic linearly moving outside micrometer (OMV-25MX, manufactured by Mitutoyo) or the like can be used.

  The first layer can be produced by a known method for producing a thin film porous membrane. For example, the resin material can be produced by obtaining a sheet-like material by a method such as extrusion molding and then stretching it to a predetermined thickness. Moreover, it can manufacture as a porous film by adding plasticizers, such as paraffin, to the material at the time of extrusion molding, and removing a plasticizer by heating etc. at the time of extending | stretching. The pore diameter can be adjusted by appropriately adjusting the amount of plasticizer to be added, the draw ratio, and the like.

<< Second layer >>
The second layer is preferably a breathable layer. Specifically, a nonwoven fabric, a woven fabric, etc. are mentioned. As a material constituting the second layer, a material having a contact angle equal to or lower than that of the second ink with respect to the first layer so that the liquid absorbed by the first layer does not flow back, for example, Examples thereof include resin materials such as olefin resin and urethane resin. The pore size of the second layer is preferably larger than that of the first layer.

《Third layer》
The porous body may be composed of three or more layers. As the third and subsequent layers, it is preferable to use a nonwoven fabric from the viewpoint of rigidity. Examples of the material constituting the third layer include the same materials as those of the second layer.

《Other parts》
The liquid absorbing member may include a reinforcing member that reinforces the side surface of the liquid absorbing member in addition to the porous body having the above-described laminated structure. Moreover, when connecting the longitudinal direction edge part of a sheet-like porous body and making it into a belt form, you may utilize joining members, such as a tape comprised with a non-porous material. It is preferable to arrange the joining member at a position or period that does not contact the first image.

<< Method for producing porous body >>
As a method for producing a porous body having a laminated structure, a plurality of layers may be simply stacked, or may be bonded with an adhesive or heat. From the viewpoint of air permeability, it is preferable not to use an adhesive but to bond a plurality of layers with heat. Further, a part of the layer may be melted and bonded by heating. Further, a fusing material such as hot melt powder may be interposed between the layers and bonded together by heating. When the third layer or more are stacked, they may be stacked at one time or sequentially, in which case the stacking order can be determined as appropriate. When heating is required to bond a plurality of layers, it is preferable to bond the porous body while pressing the porous body with a heated roller. Hereinafter, various conditions and configurations in the liquid absorbing device 105 will be described in detail.

《Pressurizing condition》
If the pressure of the liquid absorbing member when contacting the first image of the transfer body is 2.9 N / cm ² (0.3 kg / cm ² ) or more, the liquid component contained in the first image can be removed in a shorter time. Solid-liquid separation can be performed, and the liquid component contained in the first image can be efficiently removed. The pressure of the liquid absorbing member is the nip pressure between the transfer member and the liquid absorbing member.For example, the surface pressure is measured using a pressure distribution measuring system, and the load in the pressurizing region is divided by the area. Can be calculated. Specifically, a surface pressure distribution measurement system (I-SCAN, manufactured by Nitta) or the like can be used.

《Action time》
The time for which the porous layer included in the liquid absorbing member 105a is brought into contact with the first image is preferably 50 milliseconds or less in order to further suppress adhesion of the coloring material to the porous layer. The action time can be calculated by dividing the pressure sensing width in the moving direction of the transfer body in the above-described surface pressure measurement by the moving speed of the transfer body.

[6] Press member 106 for transfer
After the liquid component is absorbed from the first image, the first image is transferred to the recording medium 108 in the transfer unit 111. The apparatus configuration and conditions for transferring will be described.

  By using the transfer pressing member 106, the first image is brought into contact with the recording medium 108, the first image is transferred to the recording medium, and finally the second image is recorded. Since the first image after the liquid component is absorbed is transferred to the recording medium, curling and cockling can be effectively suppressed.

  The pressing member 106 is required to have a certain degree of structural strength from the viewpoint of conveyance accuracy and durability of the recording medium 108. Examples of the material constituting the pressing member 106 include a metal material, a ceramic material, and a resin material. Among them, it is preferable to use a metal material such as aluminum in order to reduce the inertia during operation and improve the control response in addition to the rigidity and dimensional accuracy that can withstand the pressure during transfer. You may use combining these.

  When the first image is transferred to the recording medium 108, the time during which the pressing member 106 presses the transfer body (pressing time) is 5 milliseconds from the viewpoint of good transfer and suppressing damage to the transfer body. It is preferable that it is 100 milliseconds or less. The pressing time means a time during which the recording medium 108 and the transfer body 101 are in contact with each other. The pressing time can be calculated by measuring the surface pressure using a pressure distribution measuring system and dividing the length of the pressurizing region in the transport direction by the transport speed. Specifically, a surface pressure distribution measurement system (I-SCAN, manufactured by Nitta) or the like can be used.

The pressure (pressing force) at which the pressing member 106 presses the transfer body 101 when the first image is transferred to the recording medium 108 is preferably such that the transfer is performed well and damage to the transfer body is suppressed. Therefore, it is preferable that the pressure is less than ^{9.8N / cm 2 (1kg / cm} 2) or more ^{294.2N / cm 2 (30kg / cm} 2). The pressing force means a nip pressure between the recording medium 108 and the transfer body 101. The pressing force can be calculated by measuring the surface pressure using a pressure distribution measuring system and dividing the weight in the pressurizing region by the area. Specifically, a surface pressure distribution measurement system (I-SCAN, manufactured by Nitta) or the like can be used.

  The temperature at which the pressing member 106 presses the transfer body 101 when transferring the first image to the recording medium 108 may be equal to or higher than the glass transition point of the resin component included in the first image, or higher than the softening point. preferable. Although it depends on the characteristics of the resin component, it is preferable to include a heating unit that heats the first image of the transfer body 101, the transfer body 101, and the recording medium 108 in order to adjust the temperature. Examples of the shape of the pressing member 106 include a roller shape.

[7] Recording medium 108
Examples of the recording medium 108 include a sheet that may be wound in a roll, and a sheet that is cut into a predetermined size. Examples of the constituent material of the recording medium 108 include paper, plastic and metal films, wooden boards, cardboard, and the like.

[8] Recording medium transport device 107
The recording medium transport device 107 for transporting the recording medium 108 in the direction of arrow C only needs to be able to transport the recording medium, and includes a recording medium feed roller 107a and a recording medium take-up roller 107b as shown in FIG. be able to. The conveyance speed of the recording medium 108 is preferably determined in consideration of the speed required in each process.

<Direct recording type inkjet recording apparatus>
FIG. 2 is a schematic view showing an example of a direct recording type ink jet recording apparatus used in the ink jet recording method of the present invention. The first recording medium in the case of using the direct recording type inkjet recording apparatus 200 is a general recording medium that is not a transfer body, and the “recording on which the first image is transferred” in the case of using the transfer type. Medium ". Unlike the transfer type inkjet recording apparatus described above, the direct recording type inkjet recording apparatus does not include the transfer body 101, the support member 102, the transfer pressing member 106, and the transfer body cleaning member 109. An image is formed and finally a second image is recorded. Other than the above, that is, the reaction liquid applying device 203, the ink applying device 204, the liquid absorbing device 205 that absorbs the liquid component contained in the first image by the liquid absorbing member 205a, and the recording medium 208 are the same as those of the transfer type ink jet recording device. It can be configured.

  2 is a gravure offset roller having a reaction solution storage unit 203a for storing a reaction solution, and reaction solution applying members 203b and 203c for applying the reaction solution in the reaction solution storage unit 203a to a recording medium 208. This case is shown. The liquid absorbing device 205 includes a liquid absorbing member 205 a that rotates in the direction of arrow B, and a liquid absorbing pressing member 205 b that presses the liquid absorbing member 205 a against the first image of the recording medium 208. The shapes of the liquid absorbing member 205a and the pressing member 205b can be the same as those of the transfer mold. The liquid absorbing device 205 may include a stretching member that stretches the liquid absorbing member. In FIG. 2, 205c, 205d, 205e, 205f, and 205g are stretching rollers as stretching members. The number of tension rollers is not limited to five as shown in FIG. 2, and the necessary number may be arranged according to the configuration and size of the apparatus. The recording medium is supported from the back side by the ink application unit that applies ink to the recording medium 208 by the ink application device 204 and the liquid absorption unit in which the liquid absorbing member 205a contacts the first image of the recording medium and absorbs the liquid component. A recording medium support member (not shown) may be provided. As the recording medium conveying device 207 for conveying the recording medium 208 in the direction of arrow C, the recording medium having the recording medium feeding roller 207a, the recording medium take-up roller 207b, and the recording medium conveying rollers 207c, 207d, 207e, and 207f in FIG. Examples thereof include a conveyance device.

<Reaction solution>
Hereinafter, each component which comprises the reaction liquid used by this invention is demonstrated in detail. The content (% by mass) of the coloring material in the reaction solution is preferably 0.1% by mass or less, and more preferably 0.0% by mass, based on the total mass of the reaction solution. The reaction solution preferably does not contain a coloring material.

(Reactant)
The reaction liquid agglomerates a component (resin, self-dispersing pigment, etc.) having an anionic group in the ink by contacting with the ink, and contains a reactive agent. Examples of the reactive agent include cationic components such as polyvalent metal ions and cationic resins, and organic acids. Of these, the reactant is preferably an organic acid.

Examples of the polyvalent metal ion include divalent metal ions such as Ca ²⁺ , Cu ²⁺ , Ni ²⁺ , Mg ²⁺ , Sr ²⁺ , Ba ²⁺ and Zn ²⁺ , Fe ³⁺ , Cr ³⁺ , Y ³⁺ and Al ^3+. Of the trivalent metal ions. In order to contain a polyvalent metal ion in the reaction solution, a polyvalent metal salt (which may be a hydrate) constituted by combining a polyvalent metal ion and an anion can be used. Examples of the anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ⁻ , ClO ₂ ⁻ , ClO ₃ ⁻ , ClO ₄ ⁻ , NO ₂ ⁻ , NO ₃ ⁻ , SO ₄ ²⁻ , CO ₃ ²⁻ , HCO _3. ⁻ , PO ₄ ³⁻ , HPO ₄ ²⁻ , and inorganic anions such as H ₂ PO ₄ ⁻ ; HCOO ⁻ , (COO ⁻ ) ₂ , COOH (COO ⁻ ), CH ₃ COO ⁻ , C ₂ H ₄ (COO ⁻ ) ₂ , organic anions such as C ₆ H ₅ COO ⁻ , C ₆ H ₄ (COO ⁻ ) ₂ and CH ₃ SO ₃ ^— . When polyvalent metal ions are used as the reactant, the content (% by mass) in terms of the polyvalent metal salt in the reaction solution is 1.0% by mass or more and 20.0% by mass or less based on the total mass of the reaction solution. Preferably there is.

  The reaction solution containing an organic acid has a buffering ability in an acidic region (pH less than 7.0, preferably pH 0.5 to 5.0), thereby converting an anionic group of a component present in the ink into an acid form. Aggregates. Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, benzoic acid, glycolic acid, lactic acid, salicylic acid, pyrrole carboxylic acid, furan carboxylic acid, picolinic acid, nicotinic acid, thiophene carboxylic acid, levulinic acid, and coumarin acid. Monocarboxylic acids and salts thereof; oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, itaconic acid, sebacic acid, phthalic acid, malic acid, tartaric acid, and other dicarboxylic acids and salts thereof And tricarboxylic acids such as citric acid and trimellitic acid and salts and hydrogen salts thereof; tetracarboxylic acids such as pyromellitic acid and salts and hydrogen salts thereof. Especially, it is preferable that an organic acid is at least one of dicarboxylic acid, its salt, and hydrogen salt, and tricarboxylic acid, its salt, and hydrogen salt. The content (% by mass) of the organic acid in the reaction solution is preferably 1.0% by mass or more and 50.0% by mass or less based on the total mass of the reaction solution.

  Examples of the cationic resin include a resin having a primary to tertiary amine structure and a resin having a quaternary ammonium salt structure. Specific examples include resins having a structure such as vinylamine, allylamine, vinylimidazole, vinylpyridine, dimethylaminoethyl methacrylate, ethyleneimine, and guanidine. In order to enhance the solubility in the reaction solution, a cationic resin and an acidic compound can be used in combination, or a quaternization treatment of the cationic resin can be performed. When a cationic resin is used as the reactant, the content (% by mass) of the cationic resin in the reaction solution may be 1.0% by mass or more and 40.0% by mass or less based on the total mass of the reaction solution. Preferably, it is 1.0 mass% or more and 10.0 mass% or less.

(Resin particles)
By applying the first ink to the first recording medium to which the reaction liquid containing the resin particles is applied, the presence of the resin particles tends to stay at the position where the color material in the first ink is applied. Even if the porous layer repeatedly used contacts the first image, the presence of the resin particles can suppress the movement of the coloring material in the first image. Therefore, it is important that the reaction liquid contains the resin particles. is there. As the resin particles, it is preferable to use wax particles in order to improve the scratch resistance of the obtained image.

  Wax is a fatty acid and an ester with a water-insoluble higher monohydric alcohol or dihydric alcohol according to the Chemical Dictionary (Edited by the Chemical Dictionary Editor, Kyoritsu Publishing Co., Ltd.). However, in the technical field of inkjet ink, in addition to esters, those having the property of being a smooth solid at room temperature are also included in this definition. Among these, the wax particles are more preferably polyolefin wax particles. Examples of the polyolefin include α-olefin polymers such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene. Examples of the polyolefin wax include oxidized polyolefin wax, high-density polyolefin wax, a mixture of oxidized polyolefin wax and paraffin wax, and a copolymer of polyolefin and acrylic. Among these, the polyolefin wax particles are preferably polyethylene wax particles, and more preferably oxidized polyethylene wax particles obtained by oxidizing the polyethylene wax particles.

  The volume-based cumulative 90% particle size (μm) of the resin particles is preferably 0.03 μm or more and 0.30 μm or less. When the particle size is less than 0.03 μm, the resin particles have a small particle size. Therefore, if the first ink containing the color material is applied after the reaction liquid is applied to the first recording medium, even if the resin particles are present, the first ink can easily move from the position where the color material is applied. Become. Accordingly, when the porous layer comes into contact with the first image, it is difficult to stay at the position where the color material in the first image is applied, and thus the movement of the color material may not be sufficiently suppressed. When the particle diameter exceeds 0.30 μm, the particle size of the resin particles is large, so that the reflected light generated from the resin particles becomes strong. Since the reflected light is white light, the portion where the resin particles are present in the second image to be recorded is easily recognized as colorless, and the density unevenness of the image may not be sufficiently suppressed.

The content (% by mass) of the resin particles in the reaction solution is preferably 1.0% by mass or more and 25.0% by mass or less, and more preferably 2.0% by mass or more and 20.0% by mass or less. preferable. The application amount (g / m ² ) of polyolefin wax particles per unit area of the recording medium is preferably 0.04 g / m ² or more and 0.15 g / m ² . The application amount (g / m ² ) of the polyolefin wax particles per unit area of the recording medium is 0.01 times as a ratio (times) to the application amount (g / m ² ) of the color material per unit area of the recording medium. It is preferable that it is above, and it is more preferable that it is 0.08 times or more. When the ratio is less than 0.08 times, since the polyolefin wax particles are small relative to the color material, even if the porous layer contacts the first image, the color material in the first image is applied to the position. It is hard to stay. Therefore, the color material easily moves in the first image, and the movement of the color material in the direction around the first image may not be sufficiently suppressed. The ratio is more preferably 0.30 times or less. The ratio can be adjusted by the content of the polyolefin wax particles in the reaction solution, the application amount of the reaction solution, and the like.

(Surfactant)
The reaction solution preferably contains a surfactant. The surfactant is preferably at least one of a fluorine-based surfactant and a silicone-based surfactant. The content (% by mass) of the surfactant in the reaction solution is preferably 0.1% by mass or more and 10.0% by mass or less, based on the total mass of the reaction solution, and 2.0% by mass or more and 8.% by mass. More preferably, it is 0 mass% or less.

First, the fluorosurfactant will be described in detail. Examples of the fluorine _{surfactants, C x F 2x + 1 -} (CH 2) y - (OCH 2 CH 2) can be preferably used those represented by Z -OH. C _x F _{2x + 1} is a perfluoroalkyl group. X defining the number of carbon atoms and the number of fluorine atoms in the perfluoroalkyl group is preferably 4 or more and 6 or less. y represents the number of alkylene groups and is preferably 1 or more and 6 or less. z represents the number of ethylene oxide groups, preferably 1 or more and 50 or less, more preferably 1 or more and 20 or less, further preferably 1 or more and 10 or less, and 4 or more and 6 or less. It is particularly preferred.

  Fluorosurfactants include Surflon S-242, S-243, and S-420 (all manufactured by AGC Seimi Chemical); MegaFuck F-444 (manufactured by DIC); Zonyl FS-300, FSN, and FSO-100 FS-3100 (both made by DuPont). Among them, the fluorosurfactant is preferably one in which x is 6, specifically, zonyl FS-3100.

Next, the silicone surfactant will be described in detail. As the silicone-based surfactant, those having a hydrophilic siloxane (—Si—O—) unit having a polyether chain and a hydrophobic siloxane unit having no polyether chain can be suitably used. Some silicone surfactants have a polyether chain bonded to the main chain, and some have a polyether chain bonded to the side chain. The structure of the polyether chain is represented by —O— (C ₂ H ₄ O) _a — (C ₃ H ₆ O) _b —R. Here, a is an integer of 1 or more, b is an integer of 0 or more, and R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. C ₂ H ₄ O is an ethylene oxide group, and C ₃ H ₆ O is a propylene oxide group. In the polyether-modified siloxane compound, the state in which the ethylene oxide unit and the propylene oxide unit exist in the structure may exist in any state such as a random form or a block form. Here, that each unit exists in a random state means that ethylene oxide units and propylene oxide units are irregularly arranged. In addition, the presence of each unit in a block state means that each block is composed of several units as described above, and the blocks configured in this way are regularly arranged. Yes. Examples of the silicone surfactant include BYK-349, BYK-333, BYK-3455 (all of which are manufactured by BYK Chemie). Especially, it is preferable that a silicone type surfactant is a thing by which the polyether chain | strand has couple | bonded with the side chain, specifically, BYK-349.

(Other ingredients)
As other components, those similar to the aqueous medium and other additives mentioned later as those that can be used for the first ink can be used.

<First ink>
Hereinafter, each component constituting the first ink used in the present invention will be described in detail.

(Coloring material)
As the color material, pigments and dyes can be used. The content of the coloring material in the ink is preferably 0.5% by mass or more and 15.0% by mass or less, and 1.0% by mass or more and 10.0% by mass or less based on the total mass of the ink. Is more preferable.

  Specific examples of the pigment include inorganic pigments such as carbon black and titanium oxide; organic pigments such as azo, phthalocyanine, quinacridone, isoindolinone, imidazolone, diketopyrrolopyrrole and dioxazine.

  As a dispersion method of the pigment, a resin dispersion pigment using a resin as a dispersant, a self-dispersion pigment in which a hydrophilic group is bonded to the pigment particle surface, or the like can be used. Further, a resin-bonded pigment in which an organic group containing a resin is chemically bonded to the pigment particle surface, a microcapsule pigment in which the surface of the pigment particle is coated with a resin, or the like can be used.

  As the resin dispersant for dispersing the pigment in the aqueous medium, it is preferable to use a resin dispersant that can disperse the pigment in the aqueous medium by the action of the anionic group. As the resin dispersant, a resin as described later, preferably a water-soluble resin can be used. The content (mass%) of the pigment is a mass ratio with respect to the content of the resin dispersant (pigment / resin dispersant), and is preferably 0.3 times or more and 10.0 times or less.

  As the self-dispersing pigment, a pigment in which an anionic group such as a carboxylic acid group, a sulfonic acid group, or a phosphonic acid group is bonded to the pigment particle surface directly or through another atomic group (-R-) is used. be able to. The anionic group may be either an acid type or a salt type, and when it is a salt type, it may be either partially dissociated or completely dissociated. Examples of the cation serving as a counter ion when the anionic group is a salt type include alkali metal cations; ammonium; organic ammonium. Specific examples of other atomic groups (—R—) include linear or branched alkylene groups having 1 to 12 carbon atoms; arylene groups such as phenylene groups and naphthylene groups; carbonyl groups; imino groups; amide groups. Sulfonyl group; ester group; ether group and the like. Moreover, it is good also as group which combined these groups.

  As the dye, one having an anionic group is preferably used. Specific examples of the dye include dyes such as azo, triphenylmethane, (aza) phthalocyanine, xanthene and anthrapyridone.

  Among these, the color material is preferably a pigment, and more preferably a resin-dispersed pigment.

(resin)
The ink can contain a resin. The content (% by mass) of the resin in the ink is preferably 0.1% by mass or more and 20.0% by mass or less, and 0.5% by mass or more and 15.0% by mass or less based on the total mass of the ink. More preferably.

  The resin may be added to the ink for the purpose of (i) stabilizing the dispersion state of the pigment, that is, as the above-described resin dispersant and its auxiliary, (ii) improving various characteristics of the recorded image. it can. Examples of the form of the resin include a block copolymer, a random copolymer, a graft copolymer, and combinations thereof. Further, the resin may be in a state of being dissolved as a water-soluble resin in an aqueous medium, or in a state of being dispersed as resin particles in an aqueous medium. The resin particles do not have to include a color material.

  In the present invention, that the resin is water-soluble means that, when the resin is neutralized with an alkali equivalent to the acid value, it does not form particles whose particle size can be measured by a dynamic light scattering method. To do. Whether or not the resin is water-soluble can be determined according to the following method. First, a liquid (resin solid content: 10% by mass) containing a resin neutralized with an alkali corresponding to an acid value (sodium hydroxide, potassium hydroxide, etc.) is prepared. Next, the prepared liquid is diluted 10 times (volume basis) with pure water to prepare a sample solution. When the particle size of the resin in the sample solution is measured by the dynamic light scattering method, it can be determined that the resin is water-soluble when particles having a particle size are not measured. The measurement conditions at this time can be set, for example, as SetZero: 30 seconds, the number of measurements: 3 times, and the measurement time: 180 seconds. As the particle size distribution measuring apparatus, a particle size analyzer (for example, trade name “UPA-EX150”, manufactured by Nikkiso) using a dynamic light scattering method can be used. Of course, the particle size distribution measuring apparatus and measurement conditions to be used are not limited to the above.

  The acid value of the resin is preferably from 100 mgKOH / g to 250 mgKOH / g in the case of a water-soluble resin, and preferably from 5 mgKOH / g to 100 mgKOH / g in the case of a resin particle. The weight average molecular weight of the resin is preferably 3,000 to 15,000 in the case of a water-soluble resin, and preferably 1,000 to 2,000,000 in the case of a resin particle. The volume-based cumulative 50% particle diameter measured by the dynamic light scattering method (measurement conditions are the same as above) of the resin particles is preferably 100 nm or more and 500 nm or less.

  Examples of the resin include acrylic resin, urethane resin, and olefin resin. Among these, the resin is preferably an acrylic resin or a urethane resin.

  As an acrylic resin, what has a hydrophilic unit and a hydrophobic unit as a structural unit is preferable. Among these, a resin having a hydrophilic unit derived from (meth) acrylic acid and a hydrophobic unit derived from at least one of a monomer having an aromatic ring and a (meth) acrylic acid ester monomer is preferable. In particular, a resin having a hydrophilic unit derived from (meth) acrylic acid and a hydrophobic unit derived from at least one monomer of styrene and α-methylstyrene is preferable. Since these resins are likely to interact with the pigment, they can be suitably used as a resin dispersant for dispersing the pigment.

  The hydrophilic unit is a unit having a hydrophilic group such as an anionic group. The hydrophilic unit can be formed, for example, by polymerizing a hydrophilic monomer having a hydrophilic group. Specific examples of hydrophilic monomers having a hydrophilic group include acidic monomers having a carboxylic acid group such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid, and anions such as anhydrides and salts of these acidic monomers. And other monomers. Examples of the cation constituting the salt of the acidic monomer include ions such as lithium, sodium, potassium, ammonium, and organic ammonium. The hydrophobic unit is a unit having no hydrophilic group such as an anionic group. The hydrophobic unit can be formed, for example, by polymerizing a hydrophobic monomer having no hydrophilic group such as an anionic group. Specific examples of the hydrophobic monomer include monomers having an aromatic ring such as styrene, α-methylstyrene, benzyl (meth) acrylate; methyl (meth) acrylate, butyl (meth) acrylate, (meth) acrylic acid 2 -(Meth) acrylic acid ester monomers such as ethylhexyl.

  As a urethane resin, it can obtain by making polyisocyanate and a polyol react, for example. Further, it may be further reacted with a chain extender. Examples of the olefin resin include polyethylene and polypropylene.

(Aqueous medium)
The ink can contain water or an aqueous medium that is a mixed solvent of water and a water-soluble organic solvent. As water, deionized water or ion exchange water is preferably used. The content (% by mass) of water in the aqueous ink is preferably 50.0% by mass or more and 95.0% by mass or less based on the total mass of the ink. The content (% by mass) of the water-soluble organic solvent in the aqueous ink is preferably 3.0% by mass or more and 50.0% by mass or less based on the total mass of the ink. As the water-soluble organic solvent, any of those usable for ink-jet inks such as alcohols, (poly) alkylene glycols, glycol ethers, nitrogen-containing compounds and sulfur-containing compounds can be used.

(Other additives)
In addition to the above-mentioned components, the ink has various antifoaming agents, surfactants, pH adjusting agents, viscosity adjusting agents, rust preventives, antiseptics, antifungal agents, antioxidants, anti-reducing agents, etc. The additive may be contained.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited at all by the following Example, unless the summary is exceeded. In addition, what is described as “parts” and “%” with respect to the component amounts is based on mass unless otherwise specified.

<Preparation of liquid containing resin particles>
(Liquid containing resin particles 1, 3-6)
In a container equipped with a stirrer, a thermometer, and a temperature controller, 167 g of oxidized polyethylene wax (High Wax 4202E, manufactured by Mitsui Chemicals), 167 g of polyoxyethylene cetyl ether (NIKKOL BB-20, manufactured by Nikko Chemicals), 48% hydroxylation 6 g of an aqueous potassium solution and 660 g of ion-exchanged water were added. The temperature was raised to 160 ° C., stirred for 2 hours, and then cooled to a temperature of 40 ° C. By changing the stirring speed at the time of stirring, a liquid containing each resin particle having a cumulative 90% particle size on the basis of volume of the resin particle is a value shown in Table 1 (resin particle content is 16.7%) Got.

(Liquid containing resin particles 2)
In a container equipped with a stirrer, a thermometer, and a temperature controller, 266 g of oxidized polyethylene wax (High Wax 4202E, manufactured by Mitsui Chemicals), 66 g of polyoxyethylene cetyl ether (NIKKOL BB-20, manufactured by Nikko Chemicals), 48% hydroxylation 10 g of potassium aqueous solution and 658 g of ion-exchanged water were added. The temperature was raised to 160 ° C., stirred for 2 hours, and then cooled to a temperature of 40 ° C. A liquid (resin particle content: 26.6%) containing the resin particles having a volume-based cumulative 90% particle size of the resin particles as shown in Table 1 was obtained.

(Liquid containing resin particles 7 and 8)
In a container equipped with a stirrer, a thermometer, and a temperature controller, 300 g of oxidized polyethylene wax (High Wax 4202E, manufactured by Mitsui Chemicals), 33 g of polyoxyethylene cetyl ether (NIKKOL BB-20, manufactured by Nikko Chemicals), 48% hydroxylation 11 g of potassium aqueous solution and 658 g of ion-exchanged water were added. The temperature was raised to 160 ° C., stirred for 2 hours, and then cooled to a temperature of 40 ° C. By changing the stirring speed at the time of stirring, a liquid containing each resin particle in which the cumulative 90% particle size of the resin particles is the value described in Table 1 (resin particle content is 30.0%) Got.

(Liquid containing resin particles 9)
In a container equipped with a stirrer, a thermometer, and a temperature controller, 167 g of polypropylene wax (High Wax NP0555A, manufactured by Mitsui Chemicals), 33 g of polyoxyethylene cetyl ether (NIKKOL BB-20, manufactured by Nikko Chemicals), 48% potassium hydroxide 15.5 g of aqueous solution and 650.5 g of ion-exchanged water were added. The temperature was raised to 160 ° C., stirred for 2 hours, cooled to a temperature of 40 ° C., and a liquid (resin particles) containing resin particles 9 in which the cumulative 90% particle size on the volume basis of the resin particles was the value shown in Table 1. Content of 16.7%).

(Liquid containing resin particles 10)
A solution was prepared by mixing 0.3 part of potassium persulfate and 74.0 parts of ion-exchanged water. Furthermore, 23.0 parts of ethyl methacrylate, 2.3 parts of methoxypolyethylene glycol methacrylate (Blenmer PME1000, manufactured by NOF Corporation), and 0.4 parts of reactive surfactant (AQUALON KH-05, manufactured by Daiichi Kogyo Seiyaku) were mixed. Thus, an emulsion was prepared. Under a nitrogen atmosphere, the emulsion was added dropwise to the solution over 1 hour, and the polymerization reaction was carried out with stirring at a temperature of 80 ° C., followed by further stirring for 2 hours. After cooling to room temperature, ion-exchanged water and an aqueous potassium hydroxide solution were added to obtain a liquid containing a nonionic resin particle 10 (resin content is 25.0%). The volume-based cumulative 90% particle size of the resin particles 10 was 0.03 μm or more and 0.30 μm or less.

(Liquid containing resin particles 11)
The liquid containing resin particles 11 (resin content: 30.0%) was obtained by adjusting the concentration of a commercially available aqueous dispersion containing urethane resin particles (Superflex 500M, manufactured by Daiichi Kogyo Seiyaku). The volume-based cumulative 90% particle size of the nonionic resin particles 11 was 0.03 μm or more and 0.30 μm or less.

[Measurement of cumulative 90% particle size of resin particles based on volume]
The volume-based cumulative 90% particle size of resin particles is obtained by diluting a liquid containing resin particles with pure water, using a liquid containing resin particles with a resin particle content of 1.0% as a measurement sample, and dynamic light scattering. The particle size distribution was measured using a particle size distribution meter (Nanotrack UPA-EX150, manufactured by Nikkiso). The measurement conditions are SetZero: 30 seconds, number of measurements: 3, measurement time: 180 seconds, shape: true sphere, and refractive index: 1.6.

<Preparation of reaction solution>
Each component (unit:%) described in Table 2 was mixed and sufficiently stirred. Then, pressure filtration was performed with a micro filter (manufactured by Fuji Film) having a pore size of 3.0 μm to prepare a reaction solution. Zonyl FS-3100 is a nonionic fluorosurfactant manufactured by DuPont. BYK-349 is a silicone nonionic surfactant manufactured by Big Chemie. The lower part of Table 2 shows the resin particle content (%) in the reaction solution.

<Preparation of pigment dispersion>
A styrene-ethyl acrylate-acrylic acid copolymer (resin dispersant) having an acid value of 150 mgKOH / g and a weight average molecular weight of 8,000 was prepared. A resin dispersant in which 20.0 parts of this copolymer is neutralized with potassium hydroxide equimolar to its acid value, an appropriate amount of pure water is added, and the resin (solid content) content is 20.0%. An aqueous solution of was prepared. 10.0 parts of a pigment (Monac 1100, manufactured by Cabot), 15.0 parts of an aqueous solution of a resin dispersant, and 75.0 parts of pure water were mixed. This mixture and 200 parts of 0.3 mm diameter zirconia beads were placed in a batch type vertical sand mill (manufactured by IMEX) and dispersed for 5 hours while cooling with water. Thereafter, centrifugal separation is performed to remove coarse particles, and pressure filtration is performed with a cellulose acetate filter (manufactured by Advantech) having a pore size of 3.0 μm. The pigment content is 10.0% and the resin dispersant content is 3. A 0.0% pigment dispersion was prepared.

<Preparation of liquid containing resin particles 12>
18.0 parts of ethyl methacrylate, 3.0 parts of 2,2-azobis- (2-methylbutyronitrile) and 2.0 parts of n-hexadecane were mixed and stirred for 30 minutes. This mixture was added dropwise to 75.0 parts of an 8% aqueous solution of a styrene-butyl acrylate-acrylic acid copolymer having an acid value of 130 mgKOH / g and a weight average molecular weight of 7,000, followed by stirring for 24 minutes. Then, the ultrasonic wave was irradiated with the ultrasonic irradiation machine for 3 hours, and the polymerization reaction was performed at a temperature of 80 ° C. for 4 hours in a nitrogen atmosphere. The solution was cooled to a temperature of 25 ° C. and filtered to obtain a liquid containing resin particles 12 (resin particle content: 25.0%).

<Preparation of first ink>
Each component (unit:%) shown in Table 3 was mixed and sufficiently stirred, and then pressure filtration was performed with a microfilter (manufactured by Fuji Film) having a pore size of 3.0 μm to prepare a first ink. Acetylenol E100 is a nonionic surfactant manufactured by Kawaken Fine Chemicals. The lower part of Table 3 describes the pigment content (%) in the first ink.

<Preparation of porous body of liquid absorbing member>
(Liquid absorbing members 1-6)
As a first layer, a fibrillated porous layer was prepared by compression-molding crystallized fluororesin (polytetrafluoroethylene) emulsion-polymerized particles and stretching at a temperature below the melting point. By changing the stretching speed and temperature, each first layer in which the volume-based cumulative 10% pore diameter of the porous layer had the values described in Table 4 was obtained.

  As the second layer, HOP60 (manufactured by Hirose Paper), which is a polyolefin nonwoven fabric, was used. The first layer and the second layer were bonded by heat to obtain a porous body.

(Liquid absorbing member 7)
As the first layer, a crystalline fluorinated resin (polyvinylidene fluoride) emulsion-polymerized particle was compression-molded and stretched at a temperature below the melting point to prepare a fibrillated porous layer. The volume-based cumulative 10% pore diameter of the porous layer was the value shown in Table 4.

  As the second layer, HOP60 (manufactured by Hirose Paper), which is a polyolefin nonwoven fabric, was used. The first layer and the second layer were bonded by heat to obtain a porous body.

(Liquid absorbing member 8)
As a first layer, a fibrillated porous layer was produced by compression-molding crystallized olefin resin (polypropylene) emulsion-polymerized particles and stretching at a temperature below the melting point. The volume-based cumulative 10% pore diameter of the porous layer was the value shown in Table 4.

  As the second layer, HOP60 (manufactured by Hirose Paper), which is a polyolefin nonwoven fabric, was used. The first layer and the second layer were bonded by heat to obtain a porous body.

(Liquid absorbing member 9)
As a first layer, a fibrillated porous layer was prepared by compression-molding crystallized polyester resin (polyethylene terephthalate) emulsion-polymerized particles and stretching at a temperature below the melting point. The volume-based cumulative 10% pore diameter of the porous layer was the value shown in Table 4.

  As the second layer, HOP60 (manufactured by Hirose Paper), which is a polyolefin nonwoven fabric, was used. The first layer and the second layer were bonded by heat to obtain a porous body.

[Measurement method of volume-based cumulative 10% pore diameter of porous layer]
The volume-based cumulative 10% pore size of the porous layer was measured using a pore size distribution measuring device (POROMETER 3Gz, manufactured by Quantachrome INSTRUMENTS) by a gas permeation method.

<Evaluation>
In the present invention, according to the following evaluation criteria, AA, A, or B is an acceptable level and C is an unacceptable level. Tables 5 and 6 show combinations of reaction liquids, first inks, and liquid absorbing members used in Examples, Comparative Examples, and Reference Examples, evaluation conditions, and evaluation results. In Tables 5 and 6, the volume-based cumulative 90% particle diameter of the resin particles is described as D ₉₀ (μm), and the volume-based cumulative 10% pore diameter of the porous layer is described as D ₁₀ (μm). Furthermore, the ratio of the volume-based cumulative 10% pore diameter of the porous layer to the volume-based cumulative 90% particle diameter of the resin particles is described as D ₁₀ / D ₉₀ (times).

(Examples 1-25, Comparative Examples 1-3, and Reference Examples 1-2)
Images were recorded using the transfer type ink jet recording apparatus shown in FIG. A cylindrical drum made of aluminum was used as the support member 102. As a member of the surface layer of the transfer body 101, a PET sheet having a thickness of 0.5 mm was coated with a silicone rubber (KE12, manufactured by Shin-Etsu Chemical Co., Ltd.) having a rubber hardness (durometer type A) of 40 ° to a thickness of 0.2 mm. A thing was used. And this surface was subjected to plasma surface treatment under the conditions of treatment distance: 5 mm, plasma mode: High, treatment speed: 100 mm / sec, using a normal pressure plasma treatment apparatus (ST-7000, manufactured by Keyence). Furthermore, this surface was immersed for 10 seconds in a solution diluted with pure water so that the concentration of a commercially available neutral detergent containing sodium alkylbenzenesulfonate was 3%. Thereafter, this surface was dried to obtain a surface layer member of the transfer body 101. The obtained transfer body 101 was fixed to the support member 102 using a double-sided adhesive tape.

The reaction solution was mounted on the reaction solution applying apparatus 103, and 1.0 g / m ² of the reaction solution was applied to the transfer body 101. The first ink was mounted on the ink applicator 104, applied thermal energy to the ink, and discharged onto the transfer body 101 by an on-demand method. Although there was a reaction liquid applied to the transfer body, there was a portion where no ink was applied.

The porous body used for the liquid absorbing member 105a was the one produced above. The speed of the transport roller 105c that transports the liquid absorbing member was adjusted to be equal to the moving speed of the transfer body 101. The conveyance speed of the conveyance roller 105c was 0.4 m / s. Further, the liquid absorbing member 105a was immersed in a treatment liquid containing 95.0 parts of ethanol and 5.0 parts of water, and the liquid was permeated into the voids of the porous body, and then replaced with water. The nip pressure between the transfer member 101 and the liquid absorbing member 105a was applied to the pressing member 105b so that the average pressure was 2 kg / cm ² .

Next, the recording medium 108 is conveyed by the recording medium feeding roller 107 a and the recording medium take-up roller 107 b so that the moving speed of the transfer body 101 is equal to the moving speed, and the recording medium is transferred between the transfer body 101 and the pressing member 106. 108 and the first image were brought into contact. As a result, the first image was transferred from the transfer body 101 to the recording medium 108. Coated paper (Aurora coated paper, manufactured by Nippon Paper Industries) was used as the recording medium 108. In this embodiment, the nip pressure between the transfer member 101 and the pressing member 106 was adjusted to 3 kg / cm ² .

(Examples 26 to 50 and Comparative Examples 4 to 6)
Images were recorded using the direct recording type ink jet recording apparatus shown in FIG. The reaction liquid applying device 203, the ink applying device 204, the recording medium conveyance speed, and the liquid absorbing device 205 were set to the same conditions as those of the transfer type ink jet recording device. As the recording medium 208, cast-coated paper (Gloria pure white paper, manufactured by Gojo Paper Co., Ltd.) was used.

[Move color material]
In the case of using a transfer type ink jet recording apparatus, a first image having a recording duty of the first ink of 200% was formed on the transfer body, and transferred to aurora coated paper to record an image (solid image of 5 cm × 5 cm). When using a direct recording type inkjet recording apparatus, an image (5 cm × 5 cm solid image) in which the recording duty of the first ink was 200% was recorded on Gloria pure white paper. In this embodiment, an image recorded under the condition that a 3.0 ng ink droplet is applied to a unit area of 1 / 1,200 inch × 1 / 1,200 inch at a resolution of 1,200 dpi × 1,200 dpi is recorded on a recording duty. It is defined as 100%. The movement of the color material due to the contact of the porous layer with the first image was evaluated by visually observing whether the color material was moving in the direction around the image after recording a predetermined number of images. . The movement of the coloring material was evaluated according to the following evaluation criteria.
A: Color material movement was not observed even when 30 sheets of images were recorded. B: Color material movement was observed when 30 sheets of images were recorded. C: When 10 sheets of images were recorded. There was a movement of the coloring material.

[Adhesion of coloring material to porous layer]
In the case of using a transfer type ink jet recording apparatus, a first image having a recording duty of the first ink of 200% was formed on the transfer body, and transferred to aurora coated paper to record an image (solid image of 5 cm × 5 cm). When using a direct recording type inkjet recording apparatus, an image (5 cm × 5 cm solid image) in which the recording duty of the first ink was 200% was recorded on Gloria pure white paper.

After recording a predetermined number of images, the adhesion of the coloring material to the porous layer included in the liquid absorbing member 105a was observed. According to the evaluation criteria shown below, the adhesion of the coloring material to the porous layer was evaluated.
A: Even when 30 sheets of images were recorded, no color material adhered B: When 30 sheets of images were recorded C: Color material adhered was observed C: When 10 sheets of images were recorded, Adhesion of coloring material was observed.

[Image density unevenness]
In the case of using a transfer type ink jet recording apparatus, a first image having a recording duty of 100% of the first ink was formed on the transfer body and transferred to aurora coated paper to record an image (solid image of 5 cm × 5 cm). When using a direct recording type inkjet recording apparatus, an image (5 cm × 5 cm solid image) in which the recording duty of the first ink was 100% was recorded on Gloria pure white paper. By setting the recording duty of the first ink to 100%, it is easy to recognize density unevenness of the image even if the image is observed visually.
AA: Image density unevenness was not observed. A: Image density unevenness was observed and the color was partially faint. B: Image density unevenness was observed and there was a colorless portion.

Claims (9)

An inkjet recording method for recording an image on a recording medium using an aqueous reaction liquid and an aqueous ink containing a first ink,
A reaction liquid application step of applying a reaction liquid containing a reaction agent and resin particles to the first recording medium;
An image forming step of forming a first image by applying a first ink containing a color material to the first recording medium, and a porous layer provided in a liquid absorbing member include the first layer on the first recording medium. Having a liquid absorption step of absorbing a liquid component from the first image by contacting a portion including one image;
An ink jet recording method, wherein the volume-based cumulative 10% pore diameter (μm) of the porous layer is larger than the volume-based cumulative 90% particle diameter (μm) of the resin particles.   The volume-based cumulative 10% pore diameter (μm) of the porous layer is 2.2 times or more in a ratio (times) to the volume-based cumulative 90% particle diameter (μm) of the resin particles. The inkjet recording method as described.   3. The inkjet recording method according to claim 1, wherein a volume-based cumulative 10% pore diameter (μm) of the porous layer is 0.10 μm or more and 1.00 μm or less.   4. The inkjet recording method according to claim 1, wherein a volume-based cumulative 90% particle size (μm) of the resin particles is 0.03 μm or more and 0.30 μm or less.   The inkjet recording method according to claim 1, wherein the porous layer contains a fluorine-based resin.   The ink jet recording method according to claim 1, wherein the reaction liquid is applied to the first recording medium with a roller. The first recording medium is a transfer body;
The ink jet recording method according to claim 1, further comprising a transfer step of transferring the first image of the first recording medium to the recording medium after performing the liquid absorption step. Inkjet recording method.   The inkjet recording method according to claim 1, wherein the resin particles are polyolefin wax particles. After applying the reaction liquid to the first recording medium, a means for applying the first ink to the first recording medium, and a porous layer included in the liquid absorbing member are formed between the reaction liquid on the recording medium and the first liquid. An ink jet recording apparatus comprising means for contacting a portion including a first image formed of ink,
The reaction solution is an aqueous reaction solution containing a reactant and resin particles,
The first ink is a water-based ink containing a coloring material;
An ink jet recording apparatus, wherein the volume-based cumulative 10% pore diameter (μm) of the porous layer is larger than the volume-based cumulative 90% particle diameter (μm) of the resin particles.