JP2015182344A - Inkjet recording method, inkjet recording device and recorded matter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an inkjet recording method capable of recording an image having excellent adhesiveness and abrasion resistance and to provide an inkjet recording device for performing the method and a recorded matter obtained by the method.SOLUTION: There is provided an inkjet recording method which comprises: an adhesion layer formation step of discharging a second clear ink composition, which contains second resin particles having a glass transition temperature of less than 50°C and substantially contains no color material, on a recording surface of an ink low-absorptive or non-absorptive recording medium to form an adhesion layer; an image recording step of discharging an ink composition containing water and a color material to record an image on the adhesion layer; and a protective layer formation step of forming a protective layer, which contains first resin particles having a glass transition temperature of 50°C or more and substantially contains no color material, on the image.

Description

  The present invention relates to an ink jet recording method, an ink jet recording apparatus, and a recorded matter.

  2. Description of the Related Art Conventionally, a so-called inkjet recording method is known in which an image is recorded with fine ink droplets ejected from nozzles of an inkjet recording head. In recent years, inkjet recording methods have been used for recording images on various recording media in various fields.

  For example, Patent Document 1 discloses an ink jet recording method for an ink-absorbing recording medium such as PPC paper (plain paper). In patent document 1, in order to solve the problem that the image recorded on the PPC paper adheres to the discharge roller, a processing liquid (containing a resin having a high glass transition temperature, a resin having a low glass transition temperature, and an inorganic filler). It is disclosed that an image is covered with a resin film formed in (1).

  On the other hand, an ink low-absorbing or non-absorbing recording medium has lower ink absorbability than the above-described ink-absorbing recording medium, so that the fixability and abrasion resistance of the resulting image become a problem. Cheap. Therefore, for example, Patent Document 2 discloses that the obtained image is coated with a coating liquid in order to solve the problem that the fixability of an image recorded on a recording surface containing polyolefin is lowered. Further, in Patent Document 3, in order to solve the problem that the abrasion resistance of an image recorded on an ink low-absorbing or non-absorbing recording medium is reduced, a liquid composition containing no polymer and containing polymer particles is used. Coating is disclosed.

Japanese Patent No. 5286247 JP 2013-146925 A JP 2011-194826 A

  As described above, when an ink low-absorbing or non-absorbing recording medium is used, it is required to record an image excellent in fixability to the recording medium and abrasion resistance. However, images obtained by using the ink jet recording methods described in Patent Document 2 and Patent Document 3 may not yet have sufficient abrasion resistance and adhesion.

  In addition, when the adhesion of an image is improved by the resin component contained in the ink composition, the adhesion of the image is increased along with the improvement of the adhesion of the image, and the abrasion resistance may be lowered. On the other hand, when improving the scratch resistance of the image by the resin component contained in the ink composition, there is a problem that the image is easily peeled off together with the improvement of the scratch resistance of the image and the adhesion of the image is lowered. Sometimes. As described above, it may be difficult to satisfy both the rub resistance and adhesion properties of an image in a balanced manner.

  Some embodiments according to the present invention provide an ink jet recording method capable of recording an image excellent in abrasion resistance and adhesion by solving at least a part of the above-described problems, an ink jet recording apparatus that performs the same, and the same It is to provide a recorded matter obtained by.

  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 second clear ink composition containing a second resin particle having a glass transition temperature of less than 50 ° C. and containing substantially no color material is ejected onto the recording surface of a low-absorbing or non-absorbing recording medium. An adhesion layer forming step of forming an adhesion layer;
An image recording step of discharging an ink composition containing water and a coloring material and recording an image on the adhesion layer;
A protective layer forming step of forming a first resin particle having a glass transition temperature of 50 ° C. or higher and forming a protective layer substantially free of a coloring material on the image;
including.

  According to the ink jet recording method of Application Example 1, an image excellent in abrasion resistance and adhesion can be recorded.

  In the present invention, “substantially does not contain A” means that A is not intentionally added when the ink is produced, and the ink is inevitably mixed or generated during production or storage. It may contain a trace amount of A. Specific examples of “substantially free” include, for example, 1.0% by mass or more, preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and still more preferably 0% by mass. 0.05% by mass or less, particularly preferably 0.01% by mass or less.

  In the present invention, “image” indicates a print pattern formed from a group of dots, and includes text printing and solid printing.

[Application Example 2]
In application example 1,
The protective layer can further contain the second resin particles.

[Application Example 3]
In application example 2,
The protective layer forming step includes
A first protective layer forming step of forming a first protective layer by discharging a first clear ink composition containing the first resin particles and substantially free of a coloring material from a recording head;
A second protective layer forming step of discharging the second clear ink composition from a recording head to form a second protective layer;
Including
The first protective layer may be formed on the second protective layer.

[Application Example 4]
In any one of Application Examples 1 to 3,
The image forming step may be performed using at least one of a background ink composition containing a background color material as the color material and a color ink composition containing a color color material as the color material. Good.

[Application Example 5]
In any one of Application Examples 1 to 4,
When the recording surface of the recording medium is viewed in plan, the image is recorded in an area where the adhesion layer is formed, and is recorded so as to be smaller than the area of the adhesion layer in the area. Also good.

[Application Example 6]
In application example 5,
The protective layer may be formed so as to cover the image and the upper surface of the adhesion layer when the recording surface of the recording medium is viewed in plan.

[Application Example 7]
In any one of Application Examples 1 to 6,
The adhesion layer, the image, and the protective layer may be formed using an ink composition that does not contain a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher.

[Application Example 8]
In any one of Application Examples 1 to 7,
There may be at least one selected from an antifogging agent, an antistatic agent and an antioxidant on the recording surface of the recording medium.

[Application Example 9]
In any one of Application Examples 1 to 8,
The material constituting the recording surface of the recording medium may include at least one resin selected from olefin resins, ester resins, vinyl chloride resins, and amide resins.

[Application Example 10]
One aspect of the recorded matter according to the present invention is obtained by the ink jet recording method described in any one of Application Examples 1 to 9.

  According to the recorded matter of Application Example 10, an image having excellent abrasion resistance and adhesion is provided.

[Application Example 11]
One aspect of the ink jet recording apparatus according to the present invention is:
Recording is performed using the ink jet recording method described in any one of Application Examples 1 to 9.

  According to the ink jet recording apparatus of Application Example 11, an image excellent in abrasion resistance and adhesion can be obtained.

The figure which shows typically the side surface of the recording medium in which the contact bonding layer U was formed by the contact bonding layer formation process of the inkjet recording method which concerns on this embodiment. The figure which shows typically the side surface of the recording medium with which image BC was recorded on the contact | adherence layer U by the image recording process of the inkjet recording method which concerns on this embodiment. The figure which shows typically the side surface of the recording medium with which image BC was recorded on contact | adherence layer U 'by the image recording process of the inkjet recording method which concerns on this embodiment. The figure which shows typically the side surface of the recording medium with which image BC1 was formed by the image formation process of the inkjet recording method which concerns on this embodiment. The figure which shows typically the side surface of the recording medium in which the protective layer OP was formed by the protective layer formation process of the inkjet recording method which concerns on this embodiment. FIG. 3 is a diagram schematically illustrating a side surface of a recording medium on which a protective layer OP ′ is formed by a protective layer forming step of the ink jet recording method according to the embodiment. FIG. 4 is a diagram schematically illustrating a side surface of a recording medium on which a protective layer OP ″ is formed by a protective layer forming step of the ink jet recording method according to the embodiment. The figure which shows typically the side surface of the recording medium in which protective layer OP3 was formed by the protective layer formation process of the inkjet recording method which concerns on this embodiment. The figure which shows typically the side surface of the recording medium in which protective layer OP3 'was formed by the protective layer formation process of the inkjet recording method which concerns on this embodiment. The figure which shows typically the side surface of the recording medium in which protective layer OP3 '' was formed by the protective layer formation process of the inkjet recording method which concerns on this embodiment. The figure which shows typically the inkjet recording device used for the inkjet recording method which concerns on this embodiment.

  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 a second resin particle having a glass transition temperature of less than 50 ° C. on a recording surface of an ink low-absorbing or non-absorbing recording medium. An adhesion layer forming step of forming a contact layer by discharging a second clear ink composition that is substantially not contained, and an ink composition containing water and a coloring material is discharged to record an image on the contact layer. And an image recording step, and a protective layer forming step of forming a protective layer containing the first resin particles having a glass transition temperature of 50 ° C. or higher and substantially not containing a coloring material on the image, To do. Thereby, a recorded matter having an image recorded on the recording surface of the recording medium is obtained.

  Hereinafter, each step in the ink jet recording method according to the present embodiment will be described in detail.

1.1. Adhesion Layer (Underlayer) Formation Step The ink jet recording method according to this embodiment includes an adhesion layer formation step. In the adhesion layer forming step, the second clear ink composition containing the second resin particles having a glass transition temperature of less than 50 ° C. and containing substantially no coloring material is ejected, and the ink has low or non-absorbing ink properties. In this step, an adhesion layer is formed on the recording surface of the recording medium. That is, the adhesion layer forming step is a step of forming an adhesion layer in advance in at least an area where an image described later is recorded. Note that the adhesion layer according to the present embodiment is provided between the recording surface of the recording medium and the image, and thus may be referred to as an “underlayer”.

  Since the 2nd resin particle contained in a contact | adherence layer is less than 50 degreeC in glass transition temperature (Tg), it is equipped with adhesiveness besides being excellent in film property. Therefore, the adhesion between the recording surface of the recording medium and the image can be improved by providing an adhesion layer containing the second resin particles between the recording medium and the recording surface.

  FIG. 1 is a diagram schematically illustrating a side surface of a recording medium on which an adhesion layer U is formed. As shown in FIG. 1, by performing the adhesion layer forming step before the image recording step, the adhesion layer U can be formed in advance in a region where an image is formed. Although FIG. 1 shows a state in which one adhesive layer U is formed in a partial region of the recording medium, the present invention is not limited to this, and the adhesive layer U may be formed on the entire recording surface of the recording medium. In addition, two or more adhesion layers U (that is, two or more adhesion layers U that are not continuous on the recording surface) may be formed on the recording surface of the recording medium.

The weight in terms of solid content of the second resin particles contained per unit area of the adhesion layer is preferably 0.01 mg / cm ² or more and 0.5 mg / cm ² or less, and 0.05 mg / cm ² or more and 0.0. More preferably, it is ² mg / cm ² or less. By being in the said range, the adhesiveness of the image recorded by the image recording process mentioned later improves further.

1.2. Image Recording Step The ink jet recording method according to this embodiment includes an image recording step. The image recording step is a step of recording an image on the adhesion layer described above by discharging an ink composition containing water and a coloring material.

  FIG. 2 is a diagram schematically illustrating a side surface of the recording medium on which the image BC is recorded. As shown in FIG. 2, the image BC is recorded in at least a part of the area on the adhesion layer by the image recording process. In FIG. 2, when the recording surface of the recording medium is viewed in plan, the region where the adhesion layer is formed and the region where the image is recorded coincide with each other. However, the present invention is not limited to this. For example, the adhesion layer may have a structure like the adhesion layer U ′ of FIG. The adhesive layer U ′ in FIG. 3 is formed so that the area of the adhesive layer U ′ is wider than the image BC when the recording surface is viewed in plan view, and the adhesive layer U ′ in the region where the adhesive layer U ′ is formed is formed. It is obtained by recording the image BC in the part. In other words, the image BC in FIG. 3 is recorded in a region where the adhesion layer U ′ is formed when the recording surface of the recording medium is viewed in plan, and is smaller than the area of the adhesion layer in the region. It was recorded to be.

  From the viewpoint of shortening the drying time of the second clear ink composition used for forming the adhesion layer and increasing the recording speed, it is preferable to form the adhesion layer U shown in FIG. On the other hand, from the viewpoint of further improving the abrasion resistance and adhesion of the image, it is preferable to form the adhesion layer U 'shown in FIG.

  For the ink composition used in the image recording process, at least one of a background ink composition containing a background color material as a color material and a color ink composition containing a color color material as a color material can be used. .

  Here, the recording medium itself may be colored or translucent or transparent. In such a case, the background ink composition can be used for recording a concealing layer that conceals the color of the recording medium itself. For example, when a color image is recorded using a color ink composition, there is an advantage that the color developability of the color image can be improved if a background image is recorded in advance in the area for recording the color image. From this point of view, the image recording step includes a background image recording step of discharging a background ink composition from a recording head and recording a background image on a recording surface of a recording medium, and a color ink composition as a recording head. And a color image recording step of recording a color image on the background image.

  FIG. 4 schematically shows a side surface of a recording medium on which an image BC1 including a background image b recorded on the adhesion layer U and a color image c recorded on the background image b is recorded. FIG. As shown in FIG. 4, the image BC1 is recorded in at least a part of the recording surface of the recording medium by the image recording process. In FIG. 4, the color image c is recorded so as to cover the entire upper surface of the background image b, but is not limited thereto, and the color image c is recorded on a part of the upper surface of the background image b. Or two or more color images c (that is, two or more color images c that are not continuous on the upper surface of the background image b) are recorded on the upper surface of the background image b. There may be.

When the background image recording step and the color image recording step are performed, the weight of the background color material contained per unit area of the recorded background image is 0.05 mg / cm ² or more and 0.5 mg / cm ^2. Or less, more preferably 0.1 mg / cm ² or more and 0.3 mg / cm ² or less. Since the weight of the color material for background is 0.05 mg / cm ² or more, the influence of the color of the recording medium can be reduced, or the transmission of a color image can be suppressed when a transparent film is used. In some cases, the color developability of the color image recorded on the image for use can be further improved. If the weight of the background color material exceeds 0.5 mg / cm ² , an improvement in the effect of concealing the color of the recording medium itself cannot be expected. Therefore, from the viewpoint of saving ink, 0.5 mg / cm ² or less is used. It is preferable.

1.3. Protective layer (upper layer) forming step The inkjet recording method according to this embodiment includes a protective layer forming step. The protective layer forming step is a step of forming on the image a protective layer containing the first resin particles having a glass transition temperature of 50 ° C. or higher and substantially not containing a color material. In addition, since the protective layer according to the present embodiment is provided on the image, it may be referred to as “upper layer”.

  Thus, by providing the protective layer on the image, it is possible to reduce the contact of the image with the solvent, so that the resistance of the image to the solvent (for example, an organic solvent such as alcohol), that is, the solvent resistance can be improved. Moreover, although mentioned later for details, since the glass transition temperature (Tg) is 50 degreeC or more among the components contained in a protective layer, the effect which improves the boil resistance of a protective layer, and protection Excellent in improving the abrasion resistance of the layer. Further, as will be described in detail later, when the protective layer contains the second resin particles, the Tg of the second resin particles is less than 50 ° C., so that the adhesion between the protective layer and the image, boil resistance, Excellent in improving solvent properties. Thus, if a protective layer containing both resin particles having a Tg of 50 ° C. or higher and resin particles having a Tg of less than 50 ° C. is provided on the image, the solvent resistance and the boil resistance are good. In addition, it is possible to obtain an image having a good balance between abrasion resistance and adhesion.

  In the ink jet recording method according to the present embodiment, an image is sandwiched between the adhesion layer and the protective layer, so that the adhesion effect of the image by the adhesion layer can be obtained and the abrasion resistance effect by the protection layer can be obtained. In addition, it is possible to achieve both high image adhesion and abrasion resistance.

  FIG. 5 is a diagram schematically showing a side surface of a recording medium in which a protective layer OP is formed on the image BC. By the protective layer forming step, the protective layer OP is formed so as to cover at least the upper surface of the image BC. Although FIG. 5 illustrates an example in which the protective layer OP is formed so as to cover the entire upper surface of the image BC, the present invention is not limited to this. For example, as shown in FIG. 6, the protective layer OP ′ is continuously covered so as to cover the surface of the image BC (that is, the upper surface and the side surface of the image BC) and the recording surface of the recording medium on which the image BC is not recorded. Can be formed. By doing so, the adhesion and abrasion resistance of the image BC to the recording medium are further improved.

  As shown in FIG. 7, when the recording surface of the recording medium is viewed in plan, the image BC is formed in the region where the adhesion layer U ′ is formed and is smaller than the area of the adhesion layer U ′ in the region. When the recording layer is recorded in such a manner, the protective layer OP ′ has the surface of the image BC (that is, the upper surface and the side surface of the image BC) and the upper surface of the adhesion layer U ′ when the recording surface of the recording medium is viewed in plan view. It is preferable to form so as to cover. As a result, the image BC is surrounded by the adhesion layer U ′ and the protective layer OP ′, so that the adhesion and the abrasion resistance are further improved. In addition, since the upper surface of the adhesion layer U ′ is covered with the protective layer OP ′, it is possible to suppress a decrease in boil resistance due to the exposed portion of the adhesion layer U ′.

  Although it is essential that the protective layer contains the first resin particles and does not substantially contain the coloring material, the second resin particles are further added from the viewpoint of further improving the boil resistance and the solvent resistance. It is preferable to contain. In this case, the protective layer forming step can use one type of clear ink composition that contains the first resin particles and the second resin particles and does not substantially contain the coloring material, or the first resin particles. At least two kinds of clear: a first clear ink composition containing substantially no color material and a second clear ink composition containing second resin particles and substantially no color material It can also be carried out using an ink composition.

  In the case of using one type of clear ink composition that contains the first resin particles and the second resin particles and does not substantially contain a color material, the first resin particles and the first resin particles are contained in the ink droplets ejected from the recording head. Two resin particles exist in a mixed state. That is, the protective layer OP1 in which the first resin particles and the second resin particles are uniformly dispersed is formed on the image plane.

  On the other hand, when two types of clear ink compositions, the first clear ink composition and the second clear ink composition, are used, at least the following two patterns of protective layers can be formed. The first is a protective layer OP2 formed by arranging ink drops made of the first clear ink composition and ink drops made of the second clear ink composition on the same plane. The second is a protective layer OP3 formed by laminating a first protective layer made of the first clear ink composition and a second protective layer made of the second clear ink composition.

  When the first resin particles and the second resin particles are present on the same plane (the protective layer OP1 and the protective layer OP2 above), the effect of each resin particle is exhibited, but compared to the case where it is used alone, Its function tends to decline. This tendency becomes more prominent as the first resin particles and the second resin particles are uniformly mixed on the same plane. Here, since the protective layer OP1 is obtained by uniformly mixing the first resin particles and the second resin particles as compared with the protective layer OP2, the function of each resin particle is deteriorated. From such a point, it is preferable to form the protective layer by using two or more clear ink compositions of the first clear ink composition and the second clear ink composition.

  Moreover, since the protective layer OP3 has a laminated structure of the first protective layer and the second protective layer, the function of the resin particles contained in each layer is unlikely to deteriorate. Therefore, when the protective layer OP3 is formed, the function of each resin particle is exhibited well. Moreover, the effect which suppresses permeation | transmission of a solvent improves further by making a protective layer into a laminated structure compared with the case where the protective layer of the same film thickness as this is formed with a single layer. Although the details of this mechanism have not yet been clarified, it is thought to be due to the ability to stop solvent penetration between layers. For these reasons, it is more preferable to employ a protective layer OP3 having a laminated structure of the first protective layer and the second protective layer as the protective layer according to this embodiment.

  As described above, the protective layer OP3 is obtained by laminating the first protective layer and the second protective layer. Specifically, the first protective layer containing the first resin particles is obtained by a first protective layer forming step of discharging the first clear ink composition from the recording head. Further, the second protective layer containing the second resin particles is obtained by a second protective layer forming step in which the second clear ink composition is discharged from the recording head.

  In the case of forming the protective layer OP3, the first protective layer forming step is preferably a step of forming the first protective layer on the second protective layer obtained by the second protective layer forming step. In other words, the first protective layer forming step is performed after the second protective layer forming step. By doing so, not only the adhesion of the first protective layer can be improved, but also the second resin particles contained in the second protective layer can easily penetrate into the image, so that the adhesion between the image and the recording medium is also improved. . Furthermore, since the first protective layer is present on the outermost surface, the second protective layer having higher adhesiveness than the first protective layer is less likely to be exposed on the upper surface of the image. As a result, the scuff resistance function of the first protective layer is further improved, and the scuff resistance of the image is excellent. As described above, the functions of the abrasion resistance and adhesion provided by the protective layer can be exhibited with a high standard and an excellent balance. Moreover, although mentioned later for details, by forming a 1st protective layer on a 2nd protective layer, the boil-resistant function with which a 1st resin particle is equipped, and the boil-proof function with which a 2nd resin particle is equipped, However, it acts synergistically and the function of boil resistance is further improved.

In the case of forming the protective layer OP3, the weight in terms of solid content of the first resin particles contained per unit area of the first protective layer is A (mg / cm ² ), and is contained per unit area of the second protective layer. It is preferable to satisfy the relationship of B / A <1 (that is, B <A), where B (mg / cm ² ) represents the weight of the second resin particles converted to solid content, and 0.2 ≦ B / It is more preferable to satisfy the relationship of A <1. When the weight ratio between the two resin particles is B <A, the function of improving the abrasion resistance of the first resin particles is more satisfactorily exhibited. Moreover, it exists in the tendency for the balance of abrasion resistance and adhesiveness to become favorable because it exists in the range of 0.2 <= B / A <1.

  FIG. 8 is a diagram schematically showing a side surface of the recording medium on which the protective layer OP3 is formed on the image BC. As shown in FIG. 8, by performing the second protective layer forming step and the first protective layer forming step in this order, the protective layer in which the second protective layer and the first protective layer are laminated in this order on the upper surface of the image. OP3 is obtained.

  In FIG. 8, the first protective layer and the second protective layer are formed so as to cover the entire upper surface of the image BC, but the present invention is not limited to this. For example, after forming the second protective layer so as to cover at least the surface of the image BC (that is, the upper surface and the side surface of the image BC), the first protective layer and the second protective layer are at least the surface of the second protective layer (that is, the first protective layer). 2 may be obtained by forming the first protective layer so as to cover the upper surface and the side surface of the protective layer. According to this, compared with what covers only the upper surface of image BC, the abrasion resistance and adhesiveness of an image may improve further. A specific example of such an embodiment is a protective layer OP3 'shown in FIG. The protective layer OP3 ′ continuously includes the surface of the image BC (that is, the upper surface and the side surface of the image BC), the side surface of the adhesion layer U, and the recording surface of the recording medium on which the adhesion layer U and the image BC are not recorded. After forming the second protective layer so as to cover, the surface of the second protective layer (that is, the upper surface and the side surface of the second protective layer) and the recording medium on which the adhesion layer U, the image BC, and the second protective layer are not formed. It can be obtained by forming the first protective layer so as to continuously cover the recording surface.

  From the viewpoint that the formation rate of the first protective layer can be improved while being excellent in functions such as abrasion resistance, adhesion and solvent resistance, the protective layer has a structure like the protective layer OP3 ″ shown in FIG. It may be. 10 includes the surface of the image BC (that is, the upper surface and the side surface of the image BC), the side surface of the adhesion layer U, and the recording surface of the recording medium on which the adhesion layer U and the image BC are not recorded. Are formed by forming the first protective layer only on the upper surface of the second protective layer. According to the protective layer OP3 ″, the second protective layer having excellent adhesiveness is provided up to the side surface of the image, so that the adhesiveness of the image is improved. Further, since the first protective layer is provided on the upper surface of the second protective layer, the abrasion resistance of the image is sufficiently improved even if the first protective layer is not provided on the side surface of the second protective layer. Furthermore, by not providing the first protective layer up to the side surface of the second protective layer, the discharge time and drying time of the first clear ink composition can be shortened.

The weight of the color material contained per unit area of the image is P (mg / cm ² ), and the weight of the first resin particles contained per unit area of the protective layer converted to solid content is A (mg / cm ² ). In this case, it is preferable to satisfy the relationship of 0.2 ≦ A / P, and it is more preferable to satisfy the relationship of 0.2 ≦ A / P ≦ 1. By satisfying the relationship of 0.2 ≦ A / P, the color material can be sufficiently covered with the first resin particles, so that the abrasion resistance of the image can be improved. Moreover, by satisfy | filling the relationship of A / P <= 1, it may be able to suppress that the color development property of an image falls by an excess 1st resin particle.

The weight of the color material contained per unit area of the image is P (mg / cm ² ), and the weight of the second resin particles contained per unit area of the protective layer in terms of solid content is B (mg / cm ² ). In this case, 0.1 ≦ B / P is preferably satisfied, and 0.1 ≦ B / P ≦ 0.7 is more preferably satisfied. By satisfying the relationship of 0.1 ≦ B / P, the color material can be sufficiently covered with the second resin particles, so that the image adhesion can be improved. In addition, by satisfying the relationship of B / P ≦ 0.7, it may be possible to suppress a reduction in image colorability due to excessive second resin particles.

1.4. First Heating Process The ink jet recording method according to this embodiment may include a first heating process. The first heating step is performed after the protective layer forming step described above, and is a step of heating the recording surface at a temperature equal to or higher than the glass transition temperature of the first resin particles.

  By performing the first heating step, film formation of the adhesion layer, the image, and the protective layer is promoted. Further, the first resin particles and the second resin particles contained in the protective layer are melted so that the melted resin particles can easily penetrate into the image, or the melted resin particles and the resin that may be included in the image, As a result, the adhesion between the adhesion layer and the recording surface, the adhesion between the adhesion layer and the image, the adhesion between the image and the protective layer, and the like can be improved.

  The heating of the recording surface in the first heating step needs to be performed at a temperature equal to or higher than the glass transition temperature of the first resin particles, but is preferably performed at 80 ° C. or higher, and more preferably at 80 ° C. or higher and 150 ° C. or lower. preferable. By heating the recording surface at a temperature equal to or higher than the glass transition temperature of the first resin particles, melting of the resin particles is promoted, so that the adhesion of each layer (adhesion layer, image and protective layer; the same applies hereinafter) can be improved. Further, by heating the recording surface at 150 ° C. or lower, it is possible to suppress the occurrence of cracks due to excessive progress of drying of each layer.

  In the present invention, the heating temperature of the recording surface refers to the surface temperature of the recording surface and can be measured, for example, with a non-contact thermometer. As an example of the non-contact thermometer, infrared thermography apparatus H2640 / H2630 (trade name, manufactured by NEC Avio Infrared Technologies Co., Ltd.), PT-2LD (trade name, manufactured by Optex Co., Ltd.) Is mentioned.

  The heating time is preferably 1 second or longer and 10 seconds or shorter, and more preferably 1 second or longer and 5 seconds or shorter. When the heating time is within the above range, film formation and mixing of the resin (resin particles) can be sufficiently promoted.

  The heating in the first heating step is preferably not accompanied by air. If the air is blown before the resin (resin particles) is made into a film, the solvent contained in the protective layer and the image is excessively evaporated, and it is difficult to obtain the effect of improving the fluidity of the resin by the liquid medium. As a result, since the penetration and mixing of the resin contained in the protective layer and the image are less likely to occur, the adhesion of each layer tends to decrease. From such a viewpoint, the first heating step includes a print heater mechanism that heats the recording medium in contact with a heat source, a mechanism that irradiates infrared rays or microwaves (electromagnetic waves having a maximum wavelength of about 2,450 MHz), and the like. It is preferable to use a heating means that does not involve air blowing.

1.5. First Drying Step The ink jet recording method according to this embodiment may include a first drying step. The first drying step is a step that is performed after the above-described first heating step and blows air while heating the recording surface at a temperature equal to or lower than the recording surface heating temperature in the first heating step. Thereby, the liquid medium (water, organic solvent, etc.) contained in each layer can be evaporated and each layer can be dried.

  “Blowing” in the present embodiment includes one that blows air to each layer provided on the recording surface, and one that allows air to pass through the surface of the recording surface without blowing air directly to each layer (that is, recording) And those that generate airflow near the surface).

  In the first drying step, since air is blown, the liquid medium contained in each layer can be effectively evaporated (volatilized). Here, when each layer is dried only by the first heating step without air blowing without performing the first drying step, the evaporated liquid medium stays in the vicinity of the surface of each layer, and the drying property is remarkably high. It will decline. Therefore, it is preferable to perform the 1st drying process with ventilation after a 1st heating process. If a 1st drying process is performed after a 1st heating process, since each layer will form a favorable membrane | film | coat, a liquid medium will be removed, Therefore The dryness of each layer will be excellent, being excellent in the adhesiveness of each layer.

  The recording surface heating temperature in the first drying step is preferably not higher than the recording surface heating temperature in the first heating step, and more preferably less than the recording surface heating temperature in the first heating step. By setting it as the heating temperature or less during the first heating step, it is possible to suppress the resin from flowing after the film is formed.

  The recording surface heating temperature in the first drying step needs to be equal to or lower than the recording surface heating temperature in the first heating step (preferably less than the recording surface heating temperature in the first heating step). Furthermore, it can be set to 60 ° C. or higher and 150 ° C. or lower. By making it 60 degreeC or more, the drying property of each layer becomes still more favorable, and it can suppress that a crack generate | occur | produces in each layer by making it 150 degreeC or less.

  The first drying step may be performed by blowing with heating (that is, warm air), or may be performed by combining the recording surface heating unit and the blowing unit similar to the first heating step. As a means for blowing air, for example, a known drying device such as a dryer can be used. Thus, in the first drying step, the means is not particularly limited as long as the air can be blown while the temperature of the recording surface is kept in the above range.

  The drying time in the first drying step (that is, the time for performing blowing and heating) is preferably 2 times or more, more preferably 3 times or more, more preferably 3 times or more of the heating time in the first heating step. More preferably, it is 30 times or less. In this way, by setting the drying time of the first drying step to be twice or more the heating time of the first heating step, the liquid medium is sufficiently evaporated, so that an image having excellent abrasion resistance can be obtained. it can. Moreover, by setting it as 30 times or less, it is possible to shorten the drying time while sufficiently evaporating the liquid medium.

  The blowing in the first drying step is preferably performed at a wind speed of 6 m / second or more, and more preferably performed at a wind speed of 6 m / second or more and 50 m / second or less. By drying at a wind speed of 6 m / sec or more, the evaporation rate of the liquid medium can be improved, and by performing the drying at 50 m / sec or less, it is possible to prevent disturbance of the protective layer and image due to the wind while maintaining the drying property.

1.6. Second Drying Step The ink jet recording method according to this embodiment may include a second drying step. The second drying step is performed when performing the adhesion layer forming step, the image recording step, and the protective layer forming step, and is a step of blowing air while heating the recording surface at a temperature lower than the recording surface heating temperature in the first drying step. is there. More specifically, the second drying step is a step performed before the first heating step and the first drying step described above, and at least one timing before, during, and after the discharge of each ink. Can be done. Thus, the adhesion layer, the image, and the protective layer can be dried to some extent by performing the second drying step.

  In the second drying step, drying is performed when each layer is formed (recorded), so that the flow of ink droplets forming the layer can be suppressed. As a result, it is possible to keep the ink droplets at the location where the ink droplets are attached, and therefore it is possible to suppress the occurrence of printing unevenness and the like. Further, in the second drying step, the next layer can be formed after the previously formed layer is dried to some extent, so that it is possible to suppress image bleed that occurs when components contained in each layer are too mixed.

  It is preferable that the heating temperature of the recording surface in the second drying step is lower than the heating temperature of the recording surface in the first drying step. That is, the heating temperature of the recording surface in the second drying process is also lower than the heating temperature of the recording surface in the first heating process. Thereby, since evaporation of a liquid medium and formation of a film | membrane progress can be suppressed, the fluidity | liquidity of the resin particle at the time of a 1st heating process is securable.

  The heating temperature of the recording surface in the second drying step is preferably less than the heating temperature of the recording surface in the first drying step from the viewpoint of suppressing drying from proceeding excessively. Specifically, the heating temperature in the second drying step can be 35 ° C. or more and 80 ° C. or less, and more preferably 35 ° C. or more and 60 ° C. or less.

  The second drying step may be performed by blowing with heating (that is, hot air), or may be performed by combining the blowing unit and the recording surface heating unit similar to the first heating step. As a means for blowing air, for example, a known drying device such as a dryer can be used. Thus, in the second drying step, the means is not particularly limited as long as air can be blown while keeping the temperature of the recording surface in the above range.

  The drying time in the second drying step (that is, the time for performing air blowing and heating) is not particularly limited as long as the drying rate of each layer is set in a range described later. Here, the drying rate in the present embodiment refers to the weight at the time when drying of the layer composed of the ink droplets attached to the recording surface is finished, assuming that the weight of the ink droplets ejected to form a layer is 100%. Can be calculated based on the weight of the layer made of ink droplets attached to the recording surface at a specific time.

  The second drying step is preferably performed so that the drying rate of each layer is in the range of 30% by mass to 80% by mass, preferably 35% by mass to 75% by mass, more preferably 40% by mass. More preferably, it is carried out so as to be in the range of 70% by mass or less. By setting the drying rate of each layer to 30% by mass or more, it is possible to suppress the ink droplets from flowing and the components contained in the previously formed layer and the later formed layer from being mixed too much.

  The blowing in the second drying step is preferably performed at a speed lower than the wind speed in the first drying step, and for example, the wind speed can be 2 m / second or more and 5 m / second or less. By setting the speed lower than the wind speed in the first drying step, it is possible to prevent the liquid medium from evaporating excessively in the second drying step, so that the adhesion between the layers can be improved.

2. Ink 2.1. Clear Ink Composition The adhesion layer forming step and the protective layer forming step in the ink jet recording method according to this embodiment are preferably performed using a clear ink composition that does not substantially contain a color material. Since the clear ink composition does not substantially contain a color material, it is a colorless transparent or colorless translucent liquid. As such a clear ink composition, for example, the first clear ink composition containing the first resin particles and containing substantially no color material, and the second resin particles containing substantially no color material are contained. And a second clear ink composition.

  As described above, the second clear ink composition is used in the adhesion layer forming step. In the protective layer forming step, it is preferable to use two types of inks, a first clear ink composition and a second clear ink composition.

  Hereinafter, components included in each clear ink composition and components that may be included will be described in detail.

2.1.1. First Clear Ink Composition The first clear ink composition contains first resin particles and does not substantially contain a color material. When the first clear ink composition is used for forming the protective layer, the first clear ink composition can be referred to as a clear ink composition for forming the protective layer.

<First resin particle>
The first resin particles are resin particles having a glass transition temperature (Tg) of 50 ° C. or higher. Since the first resin particles have a glass transition temperature sufficiently higher than room temperature (25 ° C.) of 50 ° C. or higher, the first resin particles have a function of improving abrasion resistance. The first resin particles also have a function of improving the boil resistance.

  The Tg of the first resin particles needs to be 50 ° C. or higher, but is preferably 70 ° C. or higher, more preferably 100 ° C. or higher, and the upper limit is further preferably 150 ° C. or lower. Since the Tg of the first resin particles is 50 ° C. or more, a protective layer having excellent abrasion resistance can be formed, and thus the abrasion resistance of the image formed with the protective layer can be improved. Further, if the Tg of the first resin particles is 100 ° C. or higher, the stickiness of the protective layer due to the second resin particles is further reduced, so that a protective layer having excellent boil resistance can be formed. It is suitable when using a flexible packaging film used for packaging foods to be used. Moreover, since Tg of the 1st resin particle is 150 degrees C or less, it can suppress that a crack etc. arise when a protective layer is dried, or since it can accelerate | stimulate resin film formation, it has favorable abrasion resistance An image can be obtained.

  In particular, when the first protective layer and the second protective layer are laminated, if the first protective layer containing the first resin particles having a Tg of 100 ° C. or higher is formed on the outermost surface, the boil resistance by the second protective layer And the function of boil resistance by the first protective layer act synergistically, and the effect of boil resistance is more remarkably produced. Note that “boil resistance” refers to the heat resistance of an image when a recording medium on which an image is formed is placed in warm water. Here, the protective layer containing the first resin particles is excellent in boil resistance since it can suppress adhesion to other images in warm water. In addition, the protective layer containing the second resin particles is excellent in boil resistance because it has a property of being easily formed into a film and excellent in adhesiveness, and can prevent peeling of an image in warm water.

  As the resin constituting the first resin particles, acrylic resin, fluorene resin, urethane resin, olefin resin, rosin modified resin, terpene resin, ester resin, amide resin, epoxy resin, vinyl chloride resin Resins, vinyl chloride-vinyl acetate copolymers, ethylene vinyl acetate resins, and the like can be used. These resins can be used singly or in combination of two or more. Among these resins, the resin constituting the first resin particles preferably includes at least one of an acrylic resin and an ester resin from the viewpoint of further improving the abrasion resistance of the protective layer.

  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 of further improving the abrasion resistance of the protective layer. At least one of the resin and the styrene-acrylic acid copolymer resin is more preferable, and the styrene-acrylic acid copolymer resin is more preferable. The acrylic resin is more preferably an emulsion type.

  Commercially available products may be used for the resin emulsion containing the acrylic resin, for example, Movinyl 972 (Tg: 101 ° C.), 7180 (Tg: 53 ° C.) (all trade names, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) Joncryl 530 (Tg: 75 ° C.), 538 (Tg: 64 ° C.), 1908 (Tg: 98 ° C.), 1925 (Tg: 75 ° C.), 1992 (Tg: 78 ° C.) (all trade names, manufactured by BASF) ) And the like. In addition, the numerical value in a parenthesis is a glass transition temperature (Tg).

  The ester resin is a polymer obtained by polycondensation of a polyol and a polycarboxylic acid. The ester resin can be synthesized by a known method. The ester resin is more preferably an emulsion type. Commercially available products may be used for the resin emulsion containing the ester resin, for example, Elitel KA-5034 (Tg: 67 ° C.), KA-5071S (Tg: 67 ° C.), KZA-1734 (Tg: 66 ° C.). , KZA-6034 (Tg: 72 ° C.), KZA-3556 (Tg: 80 ° C.) (all trade names, manufactured by Unitika Ltd.) and the like. In addition, the numerical value in a parenthesis is a glass transition temperature (Tg).

  The content of the first resin particles is preferably 1% by mass or more and 20% by mass or less, and more preferably 3% by mass or more and 10% by mass or less with respect to the total mass of the first clear ink composition. . When the content of the first resin particles is 1% by mass or more, the abrasion resistance of the protective layer is further improved. Further, when the content of the first resin particles is 20% by mass or less, the discharge property of the first clear ink composition from the recording head tends to be good.

<Water>
The first clear ink composition contains water. Water is a main medium of the first clear ink composition, and is a component that evaporates and scatters when dried. The water is preferably water from which ionic impurities such as pure water such as ion exchange water, ultrafiltration water, reverse osmosis water, distilled water or ultrapure water are removed as much as possible. In addition, it is preferable to use water sterilized by ultraviolet irradiation or addition of hydrogen peroxide because the generation of mold and bacteria can be suppressed when the ink is stored for a long period of time.

  The first clear ink composition is a so-called aqueous ink containing water as a main solvent (containing 50% by mass or more of water). The water-based ink has an advantage that it is good for the environment because odor is suppressed and 50% by mass or more of its composition is water.

<Wax>
The first clear ink composition may contain a wax. Since the wax has a function of imparting lubrication to the protective layer, peeling or rubbing of the protective layer can be reduced.

  Examples of the components constituting the wax include plant and animal waxes such as carnauba wax, candeli wax, beeswax, rice wax, and lanolin; petroleum oils such as paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, and petrolatum. Wax; Mineral waxes such as montan wax and ozokerite; synthetic waxes such as carbon wax, Hoechst wax, polyolefin wax, stearamide, natural / synthetic wax emulsions such as α-olefin / maleic anhydride copolymer and blended wax Etc. can be used alone or in admixture of plural kinds. Among these, it is preferable to use polyolefin wax (especially polyethylene wax, polypropylene wax) and paraffin wax from the viewpoint of being excellent in the effect of improving fixability to the soft packaging film described later.

  As the wax, commercially available products can be used as they are. For example, Nopcoat PEM-17 (trade name, manufactured by San Nopco), Chemipearl W4005 (trade name, manufactured by Mitsui Chemicals), AQUACER 515, 539, 593 (above products) Name, manufactured by Big Chemie Japan Co., Ltd.).

  From the viewpoint of suppressing the performance of the wax from being excessively melted in the heating step and the drying step described above, the melting point is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 70 ° C. or higher and 180 ° C. or lower. More preferably, a wax having a melting point of 100 ° C. or higher and 180 ° C. or lower is preferably used.

  The wax content is preferably 0.1% by mass or more and 10% by mass or less in terms of solid content with respect to the total mass of the first clear ink composition. When the content of the wax is within the above range, the function of the wax can be satisfactorily exhibited.

<Organic solvent>
The first clear ink composition may contain an organic solvent. Although it does not specifically limit as an organic solvent, For example, alkyl polyols, a pyrrolidone derivative, glycol ethers etc. are mentioned. These organic solvents may be used alone or in combination of two or more.

  Examples of the alkyl polyols include propylene glycol, dipropylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,3-butylene glycol, 3-methyl-1,3-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propane Examples include diol, 2,2-dimethyl-1,3-propanediol, 2-methylpentane-2,4-diol, and 3-methyl-1,5-pentanediol. Alkyl polyols have a function of improving the wettability of the ink with respect to the recording medium and suppressing the solidification drying of the ink.

  When the alkyl polyols are contained, the content thereof can be 1% by mass or more and 40% by mass or less with respect to the total mass of the first clear ink composition.

  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 component. When the pyrrolidone derivative is contained, the content thereof can be 0.5% by mass or more and 30% by mass or less with respect to the total mass of the first clear ink composition.

  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 and permeation rate of the ink to the recording medium.

  When glycol ethers are contained, the content thereof can be 0.05% by mass or more and 6% by mass or less with respect to the total mass of the first ink composition.

  The first clear ink composition preferably does not substantially contain a water-soluble organic solvent having a normal boiling point of 280 ° C. or higher. By including a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher, the drying property of the ink is greatly reduced. As a result, when recording is performed on a soft packaging film, which will be described later, image fixability may be reduced. Examples of the water-soluble organic solvent having a standard boiling point of 280 ° C. or higher include glycerin (standard boiling point 290 ° C.). In the present invention, “water-soluble” means having a property that the solubility in 100 g of water at 20 ° C. is 0.1 g or more.

<Surfactant>
The first clear ink composition may contain a surfactant. The surfactant has a function of reducing surface tension and improving wettability with a 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. 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 is preferably 0.1% by mass or more and 1.5% by mass or less with respect to the total mass of the first clear ink composition.

<Other ingredients>
The first clear ink composition may contain a pH adjuster, an antiseptic / fungicide, a rust inhibitor, and the like, if necessary.

  Examples of the pH adjuster include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate, Examples thereof include sodium hydrogen carbonate.

  Examples of antiseptics and fungicides include sodium benzoate, sodium pentachlorophenol, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazoline-3-one Etc. Examples of commercially available products include Proxel XL2, Proxel GXL (above trade name, manufactured by Avicia), Denside CSA, NS-500W (above trade name, manufactured by Nagase ChemteX Corporation), and the like.

  Examples of the rust inhibitor include benzotriazole.

2.1.2. Second Clear Ink Composition The second clear ink composition contains the second resin particles and does not substantially contain a coloring material. The second clear ink composition can be used for forming a protective layer, and can also be used for forming an adhesion layer. When the second clear ink composition is used for forming the protective layer, it can be said that the second clear ink composition is a clear ink composition for forming the protective layer. When the second clear ink composition is used for forming the adhesion layer, the second clear ink composition can be referred to as a clear ink composition for forming the adhesion layer.

<Second resin particle>
The second resin particles are resin particles having a glass transition temperature (Tg) of less than 50 ° C. Since the second resin particles have a sufficiently low glass transition temperature of less than 50 ° C., the second resin particles have a function of easily forming a film and improving adhesion, boil resistance, and solvent resistance.

  The Tg of the second resin particles needs to be less than 50 ° C., preferably 40 ° C. or less, and more preferably 30 ° C. or less. The lower limit is preferably −40 ° C. or higher, more preferably −30 ° C. or higher, and more preferably −20 ° C. or higher. Since Tg of the 2nd resin particle is less than 50 degreeC, since the protective layer excellent in adhesiveness can be formed, the adhesiveness of the image in which the protective layer was formed can be improved. Further, when the second clear ink composition is used for forming the adhesion layer, the Tg of the second resin particles is less than 50 ° C., so that the adhesion between the recording surface of the recording medium and the image and the boil resistance are achieved. Solvent resistance can be improved. Moreover, since the Tg of the second resin particles is −40 ° C. or higher, the adhesiveness of the protective layer can be maintained within a favorable range, so the effect of improving the abrasion resistance by the first resin particles is good. Demonstrated.

  Further, the Tg of the second resin particles is preferably 40 ° C. or more lower than the heating temperature in the first heating step, and 50 ° C. or more lower than the heating temperature in the first heating step in order to sufficiently coat the layer formed by the second clear ink composition. It is preferable. Thereby, the adhesion, boil resistance and solvent resistance of the recorded matter can be improved.

  Furthermore, the difference between the Tg of the first resin particles and the Tg of the second resin particles is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, and further preferably 40 ° C. or higher. Thereby, it is possible to obtain a recorded matter having a good balance of abrasion resistance, adhesion, boil resistance, and solvent resistance.

  As the resin constituting the second resin particles, acrylic resin, fluorene resin, urethane resin, olefin resin, rosin modified resin, terpene resin, ester resin, amide resin, epoxy resin, vinyl chloride resin Resins, vinyl chloride-vinyl acetate copolymers, ethylene vinyl acetate resins, and the like can be used. These resins can be used singly or in combination of two or more. Among these resins, the resin constituting the second resin particles preferably includes a urethane resin from the viewpoint that the adhesion of the protective layer and the performance of the adhesion layer can be further improved. In particular, the urethane-based resin can be suitably used when an antifogging agent or an antistatic agent described later is present on the recording surface. That is, an antifogging agent, an antistatic agent, and the like are mainly composed of a fat-soluble surfactant (described later), and are often composed of high-polarity low molecules. In this case, if a urethane-based resin having a large number of polar groups is used, it is compatible with an antifogging agent, an antistatic agent, etc., so that the recording surface itself is a low-absorbing or non-absorbing ink. This is probably because the resin constituting the second resin particles can be in direct contact, and as a result, the image can be firmly fixed.

  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 (Tg: -34 ° C.), (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Bondic 1940NE (Tg : Less than 5 ° C.) (trade name, manufactured by DIC Corporation), Takelac W-6061 (Tg: 25 ° C.) (trade name, manufactured by Mitsui Chemicals, Inc.) and the like.

  The content of the second resin particles is preferably 1% by mass or more and 20% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the total mass of the second clear ink composition. More preferably, the content is 3% by mass or more and 10% by mass or less. When the content of the second resin particles is 3% by mass or more, the adhesion, boil resistance, and solvent resistance of the protective layer and the adhesion layer are further improved. Further, when the content of the second resin particles is 20% by mass or less, the discharge property of the second clear ink composition from the recording head is improved, and the adhesiveness of the protective layer is kept within a favorable range. Since it can do, the effect which improves the abrasion resistance by said 1st resin particle is exhibited favorably.

<Water>
The second clear ink composition contains water. Water is a main medium of the second clear ink composition, and is a component that evaporates and scatters when dried. The description of water is the same as that of the first clear ink composition, and thus description thereof is omitted.

  The second clear ink composition is a so-called aqueous ink containing water as a main solvent (containing 50% by mass or more of water). The water-based ink has an advantage that it is good for the environment because odor is suppressed and 50% by mass or more of its composition is water.

<Wax>
The second clear ink composition may contain a wax. The effects, specific examples, content range, and the like of the wax are the same as those shown for the first clear ink composition, and thus description thereof is omitted.

<Organic solvent>
The second clear ink composition may contain an organic solvent. Since specific examples, effects, content ranges, and the like of the organic solvent are the same as the contents shown in the first clear ink composition, the description thereof is omitted.

  As with the first clear ink composition, the second clear ink composition preferably does not substantially contain a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher. That is, the protective layer is preferably formed using a clear ink composition that does not contain a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher. This is because, when a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher is contained, the drying property of the ink is greatly lowered, and the fixability of the image may be lowered.

<Surfactant>
The second clear ink composition may contain a surfactant. Specific examples, effects, content ranges, and the like of the surfactant are the same as the contents shown in the first clear ink composition, and thus description thereof is omitted.

<Other ingredients>
The second clear ink composition may contain a pH adjuster, an antiseptic / fungicide, a rust inhibitor, and the like, if necessary. Specific examples of these components are the same as those shown for the first clear ink composition, and thus the description thereof is omitted.

2.1.3. Other Clear Ink Composition The protective layer forming step is also referred to as one type of clear ink composition (hereinafter referred to as “other clear ink composition”) containing both the first resin particles and the second resin particles. ) Can be used. However, as described above, in the protective layer forming step, the use of two or more clear ink compositions of the first clear ink composition and the second clear ink composition is more effective for the first resin particles and the second resin particles. It is preferable in that the function provided is exhibited well.

  The other clear ink composition contains the first resin particles and the second resin particles and does not substantially contain a coloring material. Since the first resin particles and the second resin particles contained in the other clear ink compositions are the same as those shown in the first clear ink composition and the second clear ink composition, the description thereof is omitted. .

  In addition, since other components that can be included in the clear ink composition are the same as those shown in the first clear ink composition and the second clear ink composition, description thereof is omitted.

2.2. Ink Composition Used in Image Recording Step In the image recording step in the ink jet recording method according to this embodiment, an ink composition containing water and a color material is used. As such an ink composition, for example, a background ink composition and a color ink composition can be used. Hereinafter, components included in each ink composition and components that may be included will be described in detail.

2.2.1. Background Ink Composition The background ink composition contains a background color material and water. Examples of the background ink include a white ink composition and a glitter ink composition.

The white ink composition is an ink (ink) capable of recording a color called “white” by social wisdom, and includes a slightly colored one. Moreover, the ink (ink) containing the pigment includes an ink (ink) which is named and sold under a name such as “white ink (ink), white ink (ink)”. Further, for example, when ink (ink) is recorded on Epson genuine photographic paper <Glossy> (manufactured by Seiko Epson Corporation) with an amount of 100% duty or more or an amount sufficient to cover the surface of the photographic paper, The lightness (L ^* ) and chromaticity (a ^* , b ^* ) were measured using a spectrophotometer Spectrolino (trade name, manufactured by GretagMacbeth), measurement conditions were D50 light source, observation field was 2 °, density was DIN NB, When the white reference is set to Abs, the filter is set to No, and the measurement mode is set to Reflectance, measurement is performed with 70 ≦ L ^* ≦ 100, −4.5 ≦ a ^* ≦ 2, −6 ≦ b ^* ≦ 2.5, Ink (ink) indicating the range of

  The glitter ink composition refers to an ink composition that exhibits glitter when attached to a medium. The glitter is a property characterized by, for example, the specular gloss of an obtained image (see Japanese Industrial Standard (JIS) Z8741). For example, the types of glitter include glitter that reflects light in a specular manner and so-called matte glitter, and can be characterized by, for example, high or low specular gloss.

<Color material for background>
Examples of the background color material include a white color material and a bright pigment.

  Examples of white color materials include metal oxides, barium sulfate, calcium carbonate, and the like. Examples of the metal oxide include titanium dioxide, zinc oxide, silica, alumina, and magnesium oxide. The white color material includes particles having a hollow structure, and the particles having a hollow structure are not particularly limited, and known ones can be used. As the particles having a hollow structure, for example, particles described in specifications such as US Pat. No. 4,880,465 can be preferably used. Among these, titanium dioxide is preferably used as the white color material from the viewpoint of good whiteness and abrasion resistance.

  When a white color material is used, the content (solid content) of the white color material is preferably 1% or more and 20% or less, more preferably 5%, based on the total mass of the white color ink composition. % Or more and 15% or less. If the content of the white color material exceeds the above range, nozzle clogging of the ink jet recording apparatus may occur. On the other hand, when the content of the white color material is less than the above range, the color density such as whiteness tends to be insufficient.

  The volume-based average particle diameter (hereinafter referred to as “average particle diameter”) of the white color material is preferably 30 nm or more and 600 nm or less, and more preferably 200 nm or more and 400 nm or less. When the average particle diameter of the white color material exceeds the above range, the particles may settle, and dispersion stability may be impaired, or nozzle clogging may occur when applied to an ink jet recording apparatus. On the other hand, when the average particle diameter of the white color material is less than the above range, the whiteness tends to be insufficient.

  The average particle diameter of the white color material can be measured by a particle size distribution measuring apparatus using a laser diffraction scattering method as a measurement principle. Examples of the particle size distribution measuring apparatus include a particle size distribution meter (for example, “Microtrack UPA” manufactured by Nikkiso Co., Ltd.) having a dynamic light scattering method as a measurement principle.

  The glitter pigment is not particularly limited as long as it can exhibit glitter when attached to a medium. For example, aluminum, silver, gold, platinum, nickel, chromium, tin, zinc, indium, titanium, and Examples thereof include one or two or more alloys selected from the group consisting of copper (also referred to as metal pigments) and pearl pigments having pearly luster. Representative examples of pearl pigments include pigments having pearly luster and interference gloss such as titanium dioxide-coated mica, fish scale foil, and bismuth oxychloride. Further, the glitter pigment may be subjected to a surface treatment for suppressing reaction with water. By including a glitter pigment in the ink, an image having excellent glitter can be formed.

  When the glitter pigment is used, the content of the glitter pigment is preferably 0.5% by mass or more and 30% by mass or less, and preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the glitter ink composition. Is more preferable. When the content of the glitter pigment is within the above range, the ejection stability from the nozzle of the ink jet recording apparatus and the storage stability of the glitter ink composition can be improved.

<Water>
The background ink composition contains water. Water is a main medium of the background ink composition, and is a component that is evaporated and scattered by drying. The description of water is the same as that of the first clear ink composition, and thus description thereof is omitted.

  The background ink composition is a so-called aqueous ink containing water as a main solvent (containing 50% by mass or more of water). The water-based ink has an advantage that it is good for the environment because odor is suppressed and 50% by mass or more of its composition is water.

<Organic solvent>
The background ink composition may contain an organic solvent. Although it does not specifically limit as an organic solvent, For example, alkyl polyols, a pyrrolidone derivative, glycol ethers etc. are mentioned. These organic solvents may be used alone or in combination of two or more. In addition, about the specific example of each organic solvent, an effect, the range of content, etc., since it is the same as that of the content shown with the 1st clear ink composition, the description is abbreviate | omitted.

  The background ink composition preferably contains substantially no water-soluble organic solvent having a normal boiling point of 280 ° C. or higher. This is because, when a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher is contained, the drying property of the ink is greatly lowered, and the fixability of the image may be lowered.

<Surfactant>
The background ink composition may contain a surfactant. The surfactant has a function of reducing surface tension and improving wettability with a recording medium. Among the surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used. These surfactants may be used alone or in combination of two or more. Since specific examples, effects, content ranges, and the like of each surfactant are the same as the contents shown in the first clear ink composition, the description thereof is omitted.

<Resin particles>
The background ink composition may contain at least one of the first resin particles and the second resin particles described above. The effect of providing a protective layer and an adhesion layer cannot be obtained, but the abrasion resistance and adhesion of the image can be improved. Here, when a color image is recorded on the background image, the background image is present at a position closer to the surface of the recording medium. In this case, it is more preferable to include the second resin particles in the background ink composition from the viewpoint that the adhesion between the image and the recording medium can be further improved.

<Wax>
The background ink composition may contain a wax. The effects, specific examples, content range, and the like of the wax are the same as those shown for the first clear ink composition, and thus description thereof is omitted.

<Other ingredients>
The background ink composition may contain a pH adjuster, an antiseptic / fungicide, a rust inhibitor, and the like, if necessary. Specific examples of these components are the same as those shown for the first clear ink composition, and thus the description thereof is omitted.

2.2.2. Color ink composition The color ink composition contains a color material and water.

<Color material>
The color ink composition contains a color coloring material. The color color material refers to a color material other than the aforementioned background color material. Examples of the color material include dyes and pigments.

  As the dye and the pigment, those described in US Patent Application Publication No. 2010/0086690, US Patent Application Publication No. 2005/0235870, International Publication No. 2011/027842, and the like can be suitably used. Of the dyes and pigments, it is more preferable to include a pigment. The pigment is preferably an organic pigment from the viewpoint of storage stability such as light resistance, weather resistance, and gas resistance.

  Specifically, the pigment is an insoluble azo pigment, condensed azo pigment, azo lake, chelate azo pigment or other azo pigment, phthalocyanine pigment, perylene and perinone pigment, anthraquinone pigment, quinacridone pigment, dioxane pigment, thioindigo pigment, isoindolinone pigment, Polycyclic pigments such as quinophthalone pigments, dye chelates, dye lakes, nitro pigments, nitroso pigments, aniline black, daylight fluorescent pigments, carbon black and the like are used. The above pigments can be used alone or in combination of two or more.

  Examples of the dye include various dyes used for normal inkjet recording such as direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, and reactive disperse dyes. Can be used.

  The content of the color coloring material is preferably 1% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 15% by mass or less with respect to the total mass of the color ink composition.

<Resin dispersant>
When a pigment is used as the coloring material, it is preferable that the pigment can be stably dispersed and held in water in order to be applied to the ink composition. As the method, a method of dispersing with a resin dispersant 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 color ink composition can use any of the resin dispersion pigments, dispersant dispersion pigments, and surface treatment pigments described above, and can be used in the form of a mixture of a plurality of types as required. It is preferable.

  Examples of the resin dispersant 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 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.

  The content of the resin dispersant 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 with respect to 100 parts by mass of the pigment in the color ink composition. Preferably they are 30 to 120 mass parts.

<Water>
The color ink composition contains water. Water is a main medium of the background ink composition, and is a component that is evaporated and scattered by drying. The description of water is the same as that of the first clear ink composition, and thus description thereof is omitted.

  The color ink composition is a so-called aqueous ink containing water as a main solvent (containing 50% by mass or more of water). The water-based ink has an advantage that it is good for the environment because odor is suppressed and 50% by mass or more of its composition is water.

<Organic solvent>
The color ink composition may contain an organic solvent. Although it does not specifically limit as an organic solvent, For example, alkyl polyols, a pyrrolidone derivative, glycol ethers etc. are mentioned. These organic solvents may be used alone or in combination of two or more. In addition, about the specific example of each organic solvent, an effect, the range of content, etc., since it is the same as that of the content shown with the 1st clear ink composition, the description is abbreviate | omitted.

  As with the background ink composition, the color ink composition preferably does not substantially contain a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher. That is, the image is preferably recorded using an ink composition that does not contain a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher. This is because, when a water-soluble organic solvent having a standard boiling point of 280 ° C. or higher is contained, the drying property of the ink is greatly lowered, and the fixability of the image may be lowered.

<Surfactant>
The color ink composition may contain a surfactant. The surfactant has a function of reducing surface tension and improving wettability with a recording medium. Among the surfactants, for example, acetylene glycol surfactants, silicone surfactants, and fluorine surfactants can be preferably used. These surfactants may be used alone or in combination of two or more. Since specific examples, effects, content ranges, and the like of each surfactant are the same as the contents shown in the first clear ink composition, the description thereof is omitted.

<Resin particles>
Similar to the background ink composition, the color ink composition may contain at least one of the first resin particles and the second resin particles described above. The effect of providing a protective layer and an adhesion layer cannot be obtained, but the abrasion resistance and adhesion of the image can be improved. In particular, when a color image is formed on a background image, the color image is present in the upper part as compared with the background image, and therefore is more susceptible to external friction. It is more preferable to contain resin particles.

<Wax>
The color ink composition may contain a wax. The effects, specific examples, content range, and the like of the wax are the same as those shown for the first clear ink composition, and thus description thereof is omitted.

<Other ingredients>
The color ink composition may contain a pH adjuster, an antiseptic / fungicide, a rust preventive, and the like, if necessary. Specific examples of these components are the same as those shown for the first clear ink composition, and thus the description thereof is omitted.

2.3. Ink Preparation Method Each of the ink compositions described above (the clear ink composition, the color ink composition, and the background ink composition) is prepared by mixing the above-described components in an arbitrary order, and performing filtration or the like as necessary. It is obtained by removing impurities. As a method for mixing the components, a method in which materials are sequentially added to a container equipped with a stirring device such as a mechanical stirrer or a magnetic stirrer and stirred and mixed is suitably used. As a filtration method, centrifugal filtration, filter filtration, or the like can be performed as necessary.

2.4. Ink physical properties Each of the ink compositions described above (the clear ink composition, the color ink composition, and the background ink composition) is at 20 ° C. from the viewpoint of a balance between image quality and reliability as an inkjet ink. The surface tension is preferably 15 mN / m or more and 50 mN / m, and more preferably 20 mN / m or more and 40 mN / m or less. The surface tension is measured, for example, by using an automatic surface tension meter CBVP-Z (trade name, manufactured by Kyowa Interface Science Co., Ltd.) and the surface when the platinum plate is wetted with the ink composition in an environment of 20 ° C. It can be measured by checking the tension.

  From the same viewpoint, the viscosity of each ink composition described above at 20 ° C. is preferably 2 mPa · s or more and 15 mPa · s or less, and more preferably 2 mPa · s or more and 10 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.

3. Inkjet Recording Device An example of an inkjet recording device capable of performing the inkjet recording method according to the present embodiment will be described with reference to the drawings. The ink jet 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. 11 is a schematic diagram of an example of an ink jet recording apparatus used in the ink jet recording method according to the present embodiment.

  An inkjet recording apparatus 1000 that is an example of the present embodiment includes a transport unit 10 that transports the recording medium 1, an adhesive layer forming unit 20 that records an adhesive layer using the above-described second clear ink composition, and an adhesive layer formation. An adhesion layer drying means 25 provided at a position facing the means 20, an image recording means 120 for recording an image using the ink composition described above, and an image drying means 125 provided at a position facing the image recording means. A protective layer forming means 220 for forming a protective layer for covering an image using the clear ink composition described above, a protective layer drying means 225 provided at a position facing the protective layer forming means 220, a recording surface An overall heating means 325 for heating and an overall drying means 425 for heating and blowing the recording surface are provided.

  As the ink jet recording apparatus in the present embodiment, any of an ink jet recording apparatus having a serial type recording head and an ink jet recording apparatus having a line type recording head can be used.

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 transport unit 10 is provided on the upstream side of the adhesion layer forming unit 20 in the direction in which the recording medium 1 is transported (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 by the adhesion layer forming means 20 to a position where the adhesion layer is recorded on the recording surface.

  Although FIG. 11 illustrates the case where the recording medium 1 is a continuous body, even if the recording medium 1 is a single sheet, the recording medium is conveyed by appropriately configuring the conveying unit 10. be able to.

3.2. Adhesion layer forming means The adhesion layer forming means 20 is an example of means for performing the above-mentioned adhesion layer forming process. The adhesion layer forming unit 20 records the adhesion layer 2 on the recording surface of the recording medium 1 using the above-described second clear ink composition. The adhesion layer forming unit 20 includes a recording head 21 including a nozzle that discharges the second clear ink composition.

  Examples of the method of ejecting ink such as the second clear ink composition from the nozzles of the recording head include the following. Specifically, a strong electric field is applied between the nozzle and the accelerating electrode placed in front of the nozzle, and droplet ink is continuously ejected from the nozzle, while the ink droplets fly between the deflection electrodes. The recording information signal is applied to the deflection electrode for recording, or the ink droplets are ejected in response to the recording information signal without deflecting the ink (electrostatic suction method). A system that forcibly ejects ink droplets by mechanically oscillating the liquid crystal with a quartz vibrator, etc., and a method that ejects and records ink droplets by simultaneously applying pressure and recording information signals to the ink using piezoelectric elements. (Piezo method), a method in which ink is heated and foamed with a microelectrode according to a recording information signal, and ink droplets are ejected and recorded (thermal jet method).

3.3. Adhesion Layer Drying Unit The adhesion layer drying unit 25 is an example of a unit for performing the second drying step described above, and is used for drying the adhesion layer formed on the recording surface. In the example of FIG. 11, the adhesion layer drying unit 25 is provided at a position facing the adhesion layer forming unit 20. However, the adhesion layer drying unit 25 is not limited to this, and the adhesion layer drying unit 25 may be formed before image recording. As long as it can be dried, it may be provided at any position. The details of the adhesion layer drying means 25 are as described in the second drying step, and thus the description thereof is omitted.

3.4. Image Recording Unit The image recording unit 120 is an example of a unit for performing the above-described image recording process. The image recording unit 120 records an image on the recording surface of the recording medium 1 using the ink composition described above. The image recording unit 120 includes a recording head 121 including a nozzle that discharges an ink composition. Since the ejection method of the recording head 121 is the same as the example described in the adhesion layer forming unit 20, the description thereof is omitted.

  In the case of forming an image using the background ink composition and the color ink composition described above, the image recording means 120 may eject both inks from different nozzles of the recording head 121, or the background. And a recording head that discharges the color ink composition.

  When the image recording unit 120 includes a recording head that discharges the background ink composition and a recording head that discharges the color ink composition, the recording head (recording unit) that discharges the background ink composition upstream. ), And a recording head (recording means) for discharging the color ink composition can be provided downstream thereof.

3.5. Image Drying Unit The image drying unit 125 is an example of a unit for performing the above-described second drying step, and is used for drying an image. In the example of FIG. 11, the image drying unit 125 is provided at a position facing the image recording unit 120. However, the image drying unit 125 is not limited to this, and any position can be used as long as the image can be dried before the protective layer is formed. It may be provided. Since the details of the image drying means 125 are as described in the second drying step, the description thereof is omitted.

  When the image recording unit 120 includes a recording head that ejects the background ink composition and a recording head that ejects the color ink composition, the image drying unit 125 uses the background ink composition to record the background. The image forming apparatus may include a drying unit that dries the image for use and a drying unit that dries the color image recorded by the color ink composition.

3.6. Protective layer forming means The protective layer forming means 220 is an example of means for carrying out the above-described protective layer forming step. The protective layer forming unit 220 forms a protective layer using the clear ink composition described above for the image. The protective layer forming unit 220 includes a recording head 221 including a nozzle that discharges a clear ink composition. Since the ejection method of the recording head 221 is the same as the example described in the adhesion layer forming unit 20, the description thereof is omitted.

  When the protective layer is formed using the first clear ink composition and the second clear ink composition described above, the protective layer forming unit 220 ejects both inks from different nozzles of the recording head 121. Alternatively, a recording head that discharges the first clear ink composition and a recording head that discharges the second clear ink composition may be provided.

  When the protective layer forming unit 220 includes a recording head for discharging the first clear ink composition and a recording head for discharging the second clear ink composition, the second clear ink composition is discharged upstream. A recording head (recording means) can be provided, and a recording head (recording means) for discharging the first clear ink composition can be provided downstream thereof.

3.7. Protective layer drying means The protective layer drying means 225 is an example of means for carrying out the second drying step described above, and is used for drying the protective layer. In the example of FIG. 11, the protective layer drying means 225 is provided at a position facing the protective layer forming means 220. However, the present invention is not limited to this, and the protective layer can be dried before the entire heating process described later. It may be provided at any position. The details of the protective layer drying means 225 are as described in the second drying step, and thus the description thereof is omitted.

  When the protective layer forming unit 220 includes a recording head that discharges the first clear ink composition and a recording head that discharges the second clear ink composition, the protective layer drying unit 225 includes the first clear ink composition. And a drying unit that dries the first protective layer recorded by the object and a drying unit that dries the second protective layer recorded by the second clear ink composition.

  In the present embodiment, the case where the adhesion layer forming unit 20, the image recording unit 120 described later, and the protective layer forming unit 220 described later use different recording heads is shown, but the present invention is not limited to this, and each unit uses one recording head. It may be used in common. In this case, the adhesion layer drying means 25, the image drying means 125, and the protective layer drying means 225, which are means used for performing the second drying step described above, can be shared.

3.8. Overall heating means The overall heating means 325 is an example of means for performing the first heating step described above, and is used to heat the adhesion layer, the image, and the protective layer. The whole heating means 325 can be installed on the downstream side of the protective layer forming means 220, for example, as shown in FIG. The details of the whole heating means 325 are as described in the first heating step, and the description thereof is omitted.

3.9. Whole drying means The whole drying means 425 is an example of means for performing the above-described first drying step, and is used to dry the adhesion layer, the image, and the protective layer. The whole drying means 425 can be installed on the downstream side of the whole heating means 325, for example, as shown in FIG. The details of the whole drying means 425 are as described in the first drying step, and the description thereof is omitted.

4). Recording Medium The ink jet recording method according to this embodiment is performed using an ink low-absorbing or non-absorbing recording medium. An ink low-absorbing or non-absorbing recording medium refers to a recording medium having the property of not absorbing or hardly absorbing the ink composition. Quantitatively, a non-ink-absorbing or low-absorbing recording medium is a “recording medium having a water absorption of 10 mL / m ² or less from the start of contact to 30 msec ^1/2 in the Bristow method”. Point to. 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". In contrast, an ink-absorbing recording medium refers to a recording medium that does not fall under ink non-absorbing property or low absorbing property.

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

  In addition, examples of the low-ink-absorbing recording medium include a recording medium provided with a coating layer for receiving ink on the surface. For example, as the base material is paper, art paper, coated paper Printing paper such as matte paper, and when the substrate is a plastic film, hydrophilic polymer is coated on the surface of polyvinyl chloride, polyethylene terephthalate, polycarbonate, polystyrene, polyurethane, polyethylene, polypropylene, etc. And particles in which particles such as silica and titanium are coated together with a binder.

  The ink jet recording method according to this embodiment can be suitably used for a flexible packaging film. The flexible packaging film is an embodiment of the above-described ink non-absorbing recording medium. More specifically, a soft packaging film is a flexible film material used for food packaging, toiletries, cosmetics packaging, etc., and an anti-fogging or antistatic material, an antioxidant or the like is a film. It is a film material which exists on the surface and has a thickness in the range of 5 to 70 μm (preferably 10 to 50 μm). When recording an ink composition on this film, it is difficult to fix the ink as compared to a plastic film having a normal thickness, and even if the ink is fixed, the ink cannot cope with the flexibility of the film, and peeling easily occurs. According to the ink jet recording method according to the present embodiment, an image can be covered with a protective layer having excellent adhesion and scratch resistance, and therefore an image having excellent adhesion and scratch resistance can be recorded even on a soft packaging film. it can. In addition, since the flexible packaging film is often used for food packaging, cosmetic packaging, and the like, it is predicted that the flexible packaging film is placed in an environment to which alcohol or the like adheres. Even in such a case, according to the ink jet recording method according to the present embodiment, an image excellent in solvent resistance can be obtained by forming a protective layer, which is more suitable for a flexible packaging film. .

  Antifogging and antistatic materials are often anionic, nonionic, and cationic surfactants and vinyl and acrylic polymers. Examples of surfactants include glycerin fatty acid esters and polyglycerin. Representative examples include fatty acid esters such as fatty acid esters and sorbitan fatty acid esters, fatty acid amides such as oleic acid amide and stearic acid amide, and fatty acid or aliphatic derivative-based surfactants (fat-soluble surfactants) such as these ethylene oxide adducts. Examples of the vinyl polymer include vinyl alcohol and vinyl chloride polymer. Typical examples of the acrylic polymer include ethylene oxide and acrylic polymers having a polar group (hydroxyl group, carboxyl group, etc.). Speaking of patent publications, for example, a method of using glycerin monofatty acid ester and organic phosphite in combination (Japanese Patent Laid-Open No. 58-79042), a method of using these antifogging agents and fluorine-containing compounds in combination (Japanese Patent Laid-Open No. Hei 3- No. 215562), a method of using a hindered amine compound in combination (Japanese Patent Laid-Open No. 4-272946), a method of using an aliphatic alcohol having 6 to 30 carbon atoms or an aliphatic amine having 6 to 30 carbon atoms (Japanese Patent Laid-Open No. 9-2008). 31242), a method using a phosphoric acid compound (Japanese Patent Laid-Open No. 2008-115218), and the like.

  Typical examples of the antioxidant include phenol-based compounds such as dibutylhydroxytoluene, thioether-based compounds such as dilauryl thiopropionate, and phosphate-based compounds. More specifically, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy- Hydrocinnamamide), triethylene glycol-bis 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythrityl tetrakis [3- (3,5-di-t-butyl) -4-hydroxyphenyl) propionate], tetrakis [methylene-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate) methane, 1,1,3-tris (2-methyl-4 -Hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzo) Di) benzene, bis [3,3′-bis- (4′-hydroxy-3′-t-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3′5′-di-t -Butyl-4'-hydroxybenzyl) -s-triazine 2,4,6- (1H, 3H, 5H) trione, 1,6-hexanediol-bis [3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate and the like.

  Materials that make up the recording surface of flexible packaging films include olefin resins (polyethylene, polypropylene, etc.), ester resins (polyester, etc.), vinyl chloride resins (polyvinyl chloride, etc.), and amide resins (polyamide, etc.) Those containing at least one resin selected from the above can be used. As the film base including the recording surface of the flexible packaging film, those obtained by processing these resins into a film or a sheet can be used. In the case of a film or sheet using a resin, any of an unstretched film or a stretched film stretched in a uniaxial direction or a biaxial direction can be used. It is preferable to use it. Moreover, it can also be used in the laminated state which bonded together the film and sheet | seat which consist of these various resin as needed.

5. 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.

5.1. Ink preparation 5.1.1. Preparation of Clear Ink Composition First clear ink compositions CL1-1 and CL1-2 and second clear ink compositions CL2-1 to CL2-3 having different material compositions with the material compositions shown in Table 1 were obtained. Each clear ink composition is prepared by putting the materials shown in Table 1 into a container, stirring and mixing with a magnetic stirrer for 2 hours, and then filtering with a membrane filter having a pore size of 5 μm to remove impurities such as dust and coarse particles. It was prepared by. The numerical values in Table 1 all indicate mass%, and ion exchange water was added so that the total mass of the clear ink composition was 100 mass%.

5.1.2. Ink composition <Preparation of pigment dispersion>
The background ink composition (white ink composition) used in Examples and Comparative Examples used a water-insoluble pigment (white color material) as a colorant. The color ink compositions used in the examples and comparative examples used a water-insoluble pigment (cyan pigment) as a colorant. When the pigment was added to the ink composition, a resin-dispersed pigment in which the pigment was previously dispersed with a resin dispersant was used. Specifically, a pigment dispersion was prepared as follows.

<Preparation of colorant dispersion for background>
First, an acrylic acid-acrylate copolymer (weight average molecular weight: 25,000, acid value) as a resin dispersant was added to 75 parts by mass of ion-exchanged water in which 1 part by mass of a 30% aqueous ammonia solution (neutralizing agent) was dissolved. : 180) 4 parts by mass was added and dissolved. Thereto, 20 parts by mass of titanium oxide (CI Pigment White 6), which is a white pigment, was added and dispersed for 10 hours in a ball mill using zirconia beads. Thereafter, centrifugal filtration with a centrifugal separator was performed to remove impurities such as coarse particles and dust, and the white pigment concentration was adjusted to 20% by mass to obtain a color material dispersion for background. The particle size of the white pigment was 350 nm in terms of average particle size.

<Preparation of cyan pigment dispersion>
First, an acrylic acid-acrylic acid ester copolymer (weight average molecular weight: 25,000, as a resin dispersant) was added to 76 parts by mass of ion-exchanged water in which 1.5 parts by mass of a 30% aqueous ammonia solution (neutralizing agent) was dissolved. Acid value: 180) 7.5 parts by mass was added and dissolved. Thereto, 15 parts by mass of (CI Pigment Blue 15: 3) was added as a cyan pigment, and dispersion treatment was performed for 10 hours with a ball mill using zirconia beads. Thereafter, centrifugal filtration with a centrifugal separator was performed to remove impurities such as coarse particles and dust, and the cyan pigment concentration was adjusted to 15% by mass to obtain a cyan pigment dispersion. The particle diameter of the cyan pigment at that time was 100 nm in terms of average particle diameter.

<Preparation of ink composition>
Using the pigment dispersion prepared in “Preparation of Pigment Dispersion” above, the background ink compositions BG-1 to BG-4 and the cyan ink compositions C-1 to C— with the material compositions shown in Table 1 were used. 3 was obtained. For each ink composition, the materials shown in Table 1 are put into a container, mixed with stirring with a magnetic stirrer for 2 hours, and then filtered with a membrane filter having a pore size of 5 μm to remove impurities such as dust and coarse particles. It was prepared by. The numerical values in Table 1 all indicate mass%, and ion exchange water was added so that the total mass of the ink composition was 100 mass%. The numbers in parentheses in the table indicate the solid content of the resin particles.

In Table 1, materials described other than the compound names are as follows.
・ Titanium oxide (CI Pigment White 6)
・ Cyan pigment (CI Pigment Blue 15: 3)
Superflex 740 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyurethane resin emulsion, Tg: -34 ° C., 40% dispersion)
Bondi 1940NE (trade name, manufactured by DIC Corporation, polyurethane resin emulsion, Tg less than 5 ° C, 50% dispersion)
-Takelac W-6061 (trade name, manufactured by Mitsui Chemicals, polyurethane resin emulsion, Tg: 25 ° C., 30% dispersion)
・ JONCRYL 1992 (trade name, manufactured by BASF Japan Ltd., styrene-acrylic acid copolymer emulsion, Tg: 78 ° C., 43% dispersion)
・ Movinyl 972 (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Tg 101 ° C., 50% dispersion)
AQUACER 515 (trade name, manufactured by Big Chemie Japan, polyethylene wax emulsion, melting point 135 ° C., 35% dispersion)
Nopcoat PEM-17 (trade name, manufactured by San Nopco, melting point 103 ° C., 40% dispersion)
・ BYK-348 (trade name, manufactured by BYK Japan, Inc., silicone surfactant)
Surfynol DF-110D (trade name, manufactured by Air Products and Chemicals, Inc., acetylene glycol surfactant)

5.2. Evaluation of recorded matter The recorded matter used for each evaluation was produced as follows. By appropriately filling each ink obtained as described above into an ink jet printer and recording a recording pattern in which the layers are laminated in order from the first layer so as to have the layer configuration shown in Table 2, on the recording medium. The recorded matter according to Examples and Comparative Examples was obtained. Note that the recording of each layer was performed under the condition of 100% duty with the image resolution of 720 dpi horizontal and 720 dpi vertical.

  As a recording medium (soft packaging film), a biaxially stretched polypropylene film (trade name: Pyrene film OT, model number: P2111, thickness: 20 μm, manufactured by Toyobo Co., Ltd.), and a nylon film bag (trade name: Rei beautiful woman, Model No .: X-2030, film thickness: 80 μm, manufactured by Krillon Kasei Co., Ltd.).

  As the ink jet printer, an ink jet printer PX-G930 (trade name, manufactured by Seiko Epson Corporation, nozzle resolution: 180 dpi) in which a heater capable of changing the temperature was attached to the paper guide portion was used.

  The recorded material was produced by combining the following drying and heating conditions. The following drying and heating conditions were performed as follows in the order of the second drying step, the first heating step, and the first drying step.

  When forming any of white images, color images, protective layers, and adhesive layers (images), the heater setting of the printer paper guide during recording is set to “the temperature of the recording surface is 40 ° C.” Then, a wind at a temperature of 40 ° C. was blown to the recorded matter being recorded so that the wind speed on the recording surface of the recording medium was adjusted to about 2 m / sec to 5 m / sec (the second drying step described above). Equivalent).

  After the completion of the second drying process, the drying time was 2 minutes, the heating temperature of the recording surface of the recording medium was set to 90 ° C. using an infrared heater, and the heat treatment without blowing was performed (the first heating described above). Equivalent to the process).

  After completion of the first heating step, a drying process is performed by adjusting the wind at a temperature of 90 ° C. so that the wind speed on the recording surface of the recording medium is about 6 m / sec to 10 m / sec and blowing for 10 minutes. (Corresponding to the first drying step described above).

5.2.1. Evaluation of adhesion The recorded matter obtained as described above was left in a laboratory at 20 ° C. to 25 ° C./40% RH to 60% RH for 5 hours, and then the recording surface of the recorded matter (image forming portion) A transparent adhesive tape (trade name: transparent beautiful color, manufactured by Sumitomo 3M Co., Ltd.) was attached to the film. Then, the adhered tape was peeled off by hand, and the adhesiveness was evaluated based on the tape peelability (peeling resistance) by checking the ink peeling on the recording surface and the ink transfer state to the tape. The evaluation criteria for adhesion are as follows. The results are shown in Table 2.
A: No ink peeling on the recording surface or ink transfer to the tape B: No ink peeling on the recording surface, but slight ink transfer on the tape was observed C: Partial ink peeling on the recording surface D: All ink on the recording surface was peeled off

5.2.2. Evaluation of abrasion resistance The recorded material obtained as described above was left in a laboratory at 20 ° C. to 25 ° C./40% RH to 60% RH for 5 hours, and then the recording surface of the recorded material (image forming portion) ) Using a Gakushin type friction fastness tester AB-301 (trade name, manufactured by Tester Sangyo Co., Ltd.). The rubbing resistance was evaluated by checking the ink transfer state. The evaluation criteria for abrasion resistance are as follows. The results are shown in Table 2.
A: Ink peeling and ink transfer to cotton cloth were not observed even after rubbing 20 times. B: After rubbing 20 times, a part of the recording surface was slightly peeled off or slightly transferred to cotton cloth. C: After rubbing 20 times, ink peeling on the recording surface or ink transfer to cotton cloth was observed. D: Ink peeling on the recording surface or ink transfer to cotton cloth was recognized before rubbing 20 times.

5.2.3. Evaluation of Solvent Resistance The recorded material obtained as described above was left in a laboratory at 20 ° C. to 25 ° C./40% RH to 60% RH for 5 hours, and then the recording surface of the recorded material (image forming portion) ) Was wiped 5 times with Bencot (trade name: BEMCOT M-1, manufactured by Asahi Kasei Fibers Co., Ltd.) soaked in 40% by weight ethanol aqueous solution, and the state of ink in the image area after wiping and the state of ink transfer to Bencott The solvent resistance of the recorded matter was evaluated by checking the results. The evaluation criteria are as follows. The evaluation results are shown in Table 2.
A: No change in the appearance of the image area, and no ink adherence to the bencott B: Slight unevenness is observed in the image area, but no ink adherence to the bencott C: Clear unevenness is observed in the image area , Ink adhesion to bencott is recognized D: a large number of unevenness is recognized in the image area, and a large amount of ink is recognized to bencott

5.2.4. Evaluation of Boil Resistance After the recorded material obtained as described above was left in a laboratory at 20 ° C. to 25 ° C./40% RH to 60% RH for 5 hours, the recorded material was overlapped with the image surface. It was poured into 75 ° C. warm water (boil resistance test 1) or 100 ° C. warm water (boil resistance test 2) and allowed to stand for 1 hour while maintaining the temperature. After standing, the recorded matter was taken out from the hot water and allowed to cool to room temperature for 10 minutes, and then the peeled state and the stuck state of the image were confirmed. The evaluation criteria are as follows. The results are shown in Table 2.
A: No image peeling or sticking was observed B: Image peeling or partial image sticking was slightly recognized C: Image peeling or sticking was observed D: Image peeling And the sticking was remarkable and the original image could not be distinguished.

5.3. Evaluation results Table 2 shows the above evaluation results.

  As shown in the evaluation results of Table 2, it was shown that all the recorded materials according to the examples were excellent in adhesion and abrasion resistance.

  On the other hand, since the recorded matter obtained in Comparative Example 1 was not provided with an adhesion layer, it was shown that the adhesion was significantly reduced. The recorded matter obtained in Comparative Example 2 does not include an adhesion layer, and includes a protective layer that includes the second resin particles and does not include the first resin particles, and thus shows that the abrasion resistance is significantly reduced. It was. Since the recorded matter obtained in Comparative Example 3 was not provided with an adhesion layer, it was shown that the abrasion resistance and adhesion decreased. Since the recorded matter obtained in Comparative Example 4 was provided with a protective layer containing the second resin particles and not containing the first resin particles, it was shown that the abrasion resistance was significantly reduced. Since the recorded matter obtained in Comparative Example 5 was provided with an adhesion layer not containing the second resin particles, it was shown that the adhesion was significantly reduced.

  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, 2 ... Adhesion layer, 10 ... Conveyance means, 11 ... Roller, 20 ... Adhesion layer recording means, 21, 121, 221 ... Recording head, 25 ... Adhesion layer drying means, 120 ... Image recording means, 125 ... Image drying means, 220 ... protective layer forming means, 225 ... protective layer drying means, 325 ... overall heating means, 425 ... overall drying means, 1000 ... ink jet recording apparatus

Claims (11)

A second clear ink composition containing a second resin particle having a glass transition temperature of less than 50 ° C. and containing substantially no color material is ejected onto the recording surface of a low-absorbing or non-absorbing recording medium. An adhesion layer forming step of forming an adhesion layer;
An image recording step of discharging an ink composition containing water and a coloring material and recording an image on the adhesion layer;
A protective layer forming step of forming a first resin particle having a glass transition temperature of 50 ° C. or higher and forming a protective layer substantially free of a coloring material on the image;
An ink jet recording method comprising: In claim 1,
The inkjet recording method, wherein the protective layer further contains the second resin particles. In claim 2,
The protective layer forming step includes
A first protective layer forming step of forming a first protective layer by discharging a first clear ink composition containing the first resin particles and substantially free of a coloring material from a recording head;
A second protective layer forming step of discharging the second clear ink composition from a recording head to form a second protective layer;
Including
The ink jet recording method, wherein the first protective layer is formed on the second protective layer. In any one of Claims 1 thru | or 3,
The image forming step is performed using at least one of a background ink composition containing a background color material as the color material and a color ink composition containing a color color material as the color material. Recording method. In any one of Claims 1 thru | or 4,
When the recording surface of the recording medium is viewed in plan, the image is recorded in a region where the adhesion layer is formed, and is recorded so as to be smaller than the area of the adhesion layer in the region. Inkjet recording method. In claim 5,
The inkjet recording method, wherein the protective layer is formed so as to cover a surface of the image and an upper surface of the adhesion layer when the recording surface of the recording medium is viewed in plan. In any one of Claims 1 thru | or 6,
The adhesion layer, the image, and the protective layer are formed using an ink composition that does not contain a water-soluble organic solvent having a normal boiling point of 280 ° C. or higher. In any one of Claims 1 thru | or 7,
An ink jet recording method, wherein the recording surface of the recording medium includes at least one selected from an antifogging agent, an antistatic agent and an antioxidant. In any one of Claims 1 thru | or 8,
The ink jet recording method, wherein the material constituting the recording surface of the recording medium includes at least one resin selected from an olefin resin, an ester resin, a vinyl chloride resin, and an amide resin.   A recorded matter obtained by the ink jet recording method according to any one of claims 1 to 9.   An inkjet recording apparatus that performs recording using the inkjet recording method according to claim 1.

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