JP2009113431A - Ink receiving particle, recording device, material for recording, and cartridge for storing ink receiving particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink receiving particle which can receive various types of ink and also keep its liquid absorbing property improved, and to provide a material for recording which utilizes the ink receiving particle, a recording device, and a cartridge for storing the ink receiving particle. <P>SOLUTION: For example, a particle layer is formed on an intermediate transfer body, an image is formed by discharging ink droplets onto the particle layer, and thus an ink is received by the ink receiving particle. After a recording medium is overlapped with the intermediate transfer body and an ink receiving particle layer is transferred on the recording medium, it is fixed. The ink receiving particle 200 which is applied for the recording device is, for example, structured by containing at least one resin selected from a hydrophilic organic resin, wherein at least a portion of a polar group of the resin has an alkali metal salt structure, a hydrophilic organic resin, wherein at least a portion of a polar group of the resin has a multi-valent metal salt structure, and a hydrophilic organic resin, wherein at least a portion of a polar group of the resin has an organic amine salt structure. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to ink receiving particles. The present invention also relates to a recording apparatus, a recording material, and an ink receiving particle storage cartridge using the ink receiving particles.

  There is an ink jet recording method in which an image or data using ink is recorded. The principle of the ink jet recording system is to record on paper, cloth, film, etc. by discharging liquid or molten solid ink from a nozzle, slit, porous film or the like. As for the method for ejecting ink, the so-called charge control method in which ink is ejected using electrostatic attraction, the so-called drop-on-demand method (pressure pulse method) in which ink is ejected using the vibration pressure of a piezo element. Various methods have been proposed, such as a so-called thermal ink jet method, in which ink is ejected using pressure generated by the formation and growth of bubbles due to high heat. By these methods, extremely high-definition images and data are A record can be obtained.

  In order to record with high image quality on various recording media such as penetrating media and non-penetrating media, recording methods using ink, including this ink jet recording method, are recorded on an intermediate and then transferred to the recording medium. A scheme has been proposed.

For example, Patent Document 1 discloses an ink receiving particle that includes ink receiving particles that receive ink including a recording material, has a trap structure that traps at least a liquid component of ink, and includes a liquid absorbing resin. 2. Description of the Related Art A recording apparatus has been proposed in which a conductive particle is supplied to an intermediate transfer member, and then ink is ejected onto the intermediate transfer member and transferred to a recording medium.
JP 2006-347085 A

  An object of the present invention is to provide ink receiving particles that can receive various inks and have improved liquid absorption. Another object of the present invention is to provide a recording material, a recording apparatus, and an ink receiving particle storage cartridge using the ink receiving particles.

The above problem is solved by the following means. That is,
The invention according to claim 1
A first organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%, and at least a part of the polar group has an alkali metal salt structure;
A second organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%, and at least a part of the polar group has a polyvalent metal salt structure; At least a portion of the polar monomer with respect to the total monomer component of 10 mol% or more and less than 100 mol%, and at least a part of the polar group is selected from a third organic resin having a salt structure of an organic amine. With one kind,
And ink receiving particles for receiving ink.

The invention according to claim 2
The ink receiving particles according to claim 1, comprising the first organic resin having an alkali metal salt structure and the second organic resin having a polyvalent metal salt structure.

The invention according to claim 3
The ink receptive particles have a core part and a covering part that covers the core part,
The core portion is configured to include the second organic resin having a multivalent metal salt structure,
The ink receptive particle according to claim 2, wherein the covering portion includes the first organic resin having an alkali metal salt structure.

The invention according to claim 4
The ink receptivity according to claim 3, wherein a ratio of the salt of the polyvalent metal to the polar monomer in the second organic resin contained in the core is 0.1 mol% or more and 20 mol% or less. particle.

The invention according to claim 5
4. The ink receiving particle according to claim 3, wherein a ratio of the alkali metal salt to the polar monomer in the first organic resin contained in the covering portion is 5 mol% or more and 90 mol% or less in molar ratio.

The invention according to claim 6
4. The ink receiving particle according to claim 3, wherein a ratio of the covering portion to the core portion is 0.5% or more and 25% or less by mass ratio.

The invention according to claim 7 provides:
The ink receiving particle according to claim 2, wherein at least one of the polar monomers of the first organic resin and the second organic resin contains a carboxylic acid as the polar group.

The invention according to claim 8 provides:
Among the organic resins contained in the ink receiving particles, the ratio of the organic resin in which the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol% is 80 by mass with respect to the entire ink receiving particles. The ink receiving particles according to claim 2, wherein the ink receiving particles are from 100% to 100%.

The invention according to claim 9 is:
2. The ink receiving particle according to claim 1, comprising the first organic resin having an alkali metal salt structure and the third organic resin having an organic amine salt structure.

The invention according to claim 10 is:
The ink receptive particles have a core part and a covering part that covers the core part,
The core portion includes the first organic resin having an alkali metal salt structure,
The ink receptive particle according to claim 9, wherein the covering portion includes the third organic resin having a salt structure of an organic amine.

The invention according to claim 11 is:
11. The ink receiving particle according to claim 10, wherein a ratio of the alkali metal salt to the polar monomer in the first organic resin contained in the core is 5 mol% or more and 90 mol% or less.

The invention according to claim 12
11. The ink receiving particle according to claim 10, wherein a ratio of the salt of the organic amine to the polar monomer in the third organic resin contained in the covering portion is 0.1 mol% or more and 45 mol% or less in terms of molar ratio. .

The invention according to claim 13 is:
11. The ink receiving particle according to claim 10, wherein a ratio of the covering portion to the core portion is 0.5% or more and 25% or less by mass ratio.

The invention according to claim 14 is:
The ink receiving particles according to claim 9, wherein at least one of the polar monomers of the first organic resin and the third organic resin contains a carboxylic acid as the polar group.

The invention according to claim 15 is:
Among the organic resins contained in the ink receiving particles, the ratio of the organic resin in which the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol% is 80 by mass with respect to the entire ink receiving particles. The ink receiving particles according to claim 9, wherein the ink receiving particles are from 100% to 100%.

The invention according to claim 16 provides:
A fourth organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%,
At least a part of the polar group in the fourth organic resin has an alkali metal salt structure and a polyvalent metal salt structure or an organic amine salt structure,
Ink-receiving particles that receive ink.

The invention according to claim 17 provides:
The ink receiving particles according to claim 16, wherein at least a part of the polar group in the fourth organic resin has an alkali metal salt structure and a polyvalent metal salt structure.

The invention according to claim 18
The ink receiving particles according to claim 16, wherein at least a part of the polar group in the fourth organic resin has an alkali metal salt structure and an organic amine salt structure.

The invention according to claim 19 is
The ink receiving particles according to claim 16, wherein at least one of the polar monomers of the fourth organic resin contains a carboxylic acid as the polar group.

The invention according to claim 20 provides
Among the organic resins contained in the ink receiving particles, the ratio of the organic resin in which the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol% is 80 by mass with respect to the entire ink receiving particles. The ink receiving particles according to claim 16, wherein the ink receiving particles are from 100% to 100%.

The invention according to claim 21 is
An intermediate transfer member;
Supply means for supplying the ink receiving particles according to any one of claims 1 to 20 onto the intermediate transfer member;
An ink ejection means for ejecting ink to the ink receiving particles supplied onto the intermediate transfer member;
Transfer means for transferring the ink receiving particles to a recording medium;
Fixing means for fixing the ink receiving particles transferred to the recording medium;
A recording apparatus.

The invention according to claim 22 is
Supply means for supplying the ink receiving particles according to any one of claims 1 to 20 onto a recording medium;
Ink ejection means for ejecting ink onto the ink receiving particles supplied on the recording medium;
Fixing means for fixing the ink receiving particles supplied on the recording medium;
A recording apparatus.

The invention according to claim 23 is
A recording material comprising ink and the ink receiving particles according to any one of claims 1 to 20.

The invention according to claim 24 provides
21. An ink receiving particle storage cartridge which is detached from a recording apparatus and stores the ink receiving particles according to any one of claims 1 to 20.

  According to the first aspect of the invention, various inks can be received and the liquid absorbency is improved.

  According to the second aspect of the present invention, the liquid absorbing property is improved and the fixing property is improved.

  According to the third aspect of the invention, it is possible to more effectively improve the liquid absorbency and the fixability.

  According to the invention which concerns on Claim 4, there exists an effect that fixability improves more effectively.

  According to the invention which concerns on Claim 5, there exists an effect that liquid absorptivity improves more effectively.

  According to the sixth aspect of the invention, it is possible to more effectively improve the liquid absorbency and the fixability.

  According to the seventh aspect of the invention, there are effects that the fixing property is further improved and the storage stability is excellent.

  According to the invention which concerns on Claim 8, there exists an effect that liquid absorptivity improves more effectively.

  According to the invention which concerns on Claim 9, while exhibiting a liquid-absorbing property, there exists an effect that the fluctuation | variation of charging property is suppressed.

  According to the invention which concerns on Claim 10, while exhibiting more effectively liquid-absorbing property, there exists an effect that the fluctuation | variation of charging property is suppressed.

  According to the eleventh aspect of the invention, there is an effect that the liquid absorbency is more effectively improved.

  According to the invention which concerns on Claim 12, there exists an effect that the fluctuation | variation of charging property is suppressed more effectively.

  According to the invention of claim 13, it is possible to more effectively improve the liquid absorbency and to suppress the fluctuation of the chargeability.

  According to the fourteenth aspect of the invention, there are effects that the fixing property is further improved and the storage stability is excellent.

  According to the invention which concerns on Claim 15, there exists an effect that liquid absorptivity improves more effectively.

  According to the sixteenth aspect of the invention, there are effects that various inks can be received and the liquid absorbency is improved.

  According to the seventeenth aspect of the present invention, there is an effect that the liquid absorbing property is improved and the fixing property is improved.

  According to the eighteenth aspect of the invention, there are the effects that the liquid absorbency is improved and the fluctuation of the charging property is suppressed.

  According to the nineteenth aspect of the invention, there are effects that the fixability is further improved and the storage stability is excellent.

  According to the invention of claim 20, there is an effect that the liquid absorbency is more effectively improved.

  According to the twenty-first aspect of the present invention, there is an effect that even if various inks are used, it is possible to record on various recording media at high speed.

  According to the twenty-second aspect of the present invention, there is an effect that it is possible to perform recording on various recording media at a high speed even if various inks are used with a simple configuration.

  According to the twenty-third aspect of the present invention, there is an effect that even if various inks are used, it is possible to record on various recording media at high speed.

  According to the twenty-fourth aspect of the invention, there is an effect that it is possible to record on various recording media at a high speed even if various inks are used.

Hereinafter, embodiments of the present invention will be described in detail.
(Ink-receptive particles)
The ink receiving particles according to the embodiment receive ink components when the ink comes into contact with the particles. Here, the ink receptivity indicates holding at least a part (at least a liquid component) of the ink component.

First, the ink receiving particles according to the first embodiment will be described.
The ink receiving particles according to the first embodiment are:
A first organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%, and at least a part of the polar group has an alkali metal salt structure;
A second organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%, and at least a part of the polar group has a polyvalent metal salt structure; At least a portion of the polar monomer with respect to the total monomer component of 10 mol% or more and less than 100 mol%, and at least a part of the polar group is selected from a third organic resin having a salt structure of an organic amine. With one kind,
And is characterized by receiving ink.

  The ink receptive particles according to the present embodiment are ink receptive particles that can receive various inks and have improved liquid absorbency by adopting the above-described configuration.

In particular, the ink receiving particles according to the present embodiment include the following forms.
1) The form including the first organic resin having an alkali metal salt structure and the second organic resin having a polyvalent metal salt structure. In this embodiment, the liquid absorbability is improved and the fixability is improved. The reason for this is not clear, but is presumed to be as follows.
By having the alkali metal salt structure, the first organic resin having an alkali metal salt structure has high hydrophilicity and water absorption. On the other hand, the second organic resin having a salt structure of a polyvalent metal has a reduced number of polar functional groups, and thus the hydrophilicity is lowered. On the other hand, it becomes possible to prevent entanglement of molecules, so that the whole As a result, sufficient water absorption can be maintained. Further, on the recording medium, partial cross-linking (ionic cross-linking) due to the salt of the polyvalent metal occurs, and the ionic cross-linking between the resins proceeds at the time of fixing, so that fixability is improved. For this reason, it is considered that the liquid absorbency is improved and the fixing property is improved.

  In this embodiment, the first organic resin having an alkali metal salt structure and the second organic resin having a polyvalent metal salt structure may be included in the form of single particles, and the core may be formed. And a covering portion that covers the core portion (so-called core / shell structure).

  In the case of the core / shell structure, the core part is configured to include a second organic resin having a polyvalent metal salt structure, and the covering part is configured to include a first organic resin having an alkali metal salt structure. Is good. Of course, the material configuration may be reversed between the core portion and the covering portion, but the region containing the second organic resin having a salt structure of a polyvalent metal mainly responsible for fixing properties is used as the core portion and is responsible for water absorption. By adopting a configuration in which the region including the first organic resin having an alkali metal salt structure is used as the covering portion, the liquid absorbability is further improved and the fixability is improved.

  Here, the ratio of the salt of the alkali metal to the polar monomer in the first organic resin contained in the coating portion is preferably 5 mol% or more and 90 mol% or less, and more preferably 20 mol% or more and 90 mol%. More preferably, it is 50 mol% or more and 90 mol% or less. When the ratio of the alkali metal salt is within the above range, the hydrophilicity is more effectively increased and the water absorption is improved.

  Further, the ratio of the polar monomer to the total monomer component in the first organic resin contained in the coating portion is 10 mol% or more and less than 100 mol%, preferably 15 mol% or more and less than 85 mol%, more preferably It is 30 mol% or more and less than 80 mol%. When the ratio of the polar monomer is within the above range, the hydrophilicity is more effectively enhanced and the water absorption is improved.

  On the other hand, the ratio of the salt of the polyvalent metal to the polar monomer in the second organic resin contained in the core is preferably 0.1 mol% or more and 20 mol% or less, and more preferably 0. It is 1 mol% or more and 5 mol% or less, and more preferably 0.25 mol% or more and 2.5 mol% or less. When the ratio of the polyvalent metal salt is within the above range, the fixing property is more effectively improved while ensuring sufficient water absorption.

  The ratio of the polar monomer to the total monomer component in the second organic resin contained in the core is 10 mol% or more and less than 100 mol%, preferably 20 mol% or more and less than 95 mol%, more preferably It is 40 mol% or more and less than 90 mol%. When the ratio of the polar monomer is within the above range, both water absorption and fixing ability can be achieved.

  Further, the ratio of the covering portion to the core portion is preferably 0.5% or more and 25% or less by mass ratio, more preferably 2% or more and 10% or less, and further preferably 5% or more and 10% or less. is there. When this ratio is in the above range, the liquid absorbability is further improved and the fixability is improved.

  Here, a method for producing particles having the core / shell structure will be described. For example, first, an alkali metal resin solution mixed in an organic resin (an organic resin having no salt structure), an alkali metal, and a solvent (for example, water or alcohol) is prepared. Further, an organic resin (an organic resin having no salt structure) is dissolved (or dispersed) in an organic solvent, and a polyvalent metal is added thereto to prepare a polyvalent metal resin dispersion. Then, using a double cylindrical needle in which the inner tube is concentrically arranged inside the outer tube, the polyvalent metal resin dispersion is fed to the inner tube (inner route), and the outer tube (outer route). Then, the alkali metal resin solution is fed to the nozzle and droplets are ejected (sprayed) from the tip of the needle. The discharged liquid droplet has a polyvalent metal resin dispersion inside, and an alkali metal resin solution exists so as to cover it. The droplets are dried to obtain particles having the core / shell structure (for example, Spray-Dry method).

  As another method, first, an organic resin (an organic resin having no salt structure) is dissolved (or dispersed) in an organic solvent, a polyvalent metal is added thereto, and a polyvalent metal resin dispersion is obtained. prepare. Next, the organic solvent of the polyvalent metal resin dispersion is removed and solidified. By pulverizing and classifying the solid matter, particles are formed to obtain core particles. Next, an alkali metal resin solution mixed in an organic resin (an organic resin having no salt structure), an alkali metal, and a solvent (for example, water or alcohol) is prepared. Next, the particles serving as the core are added and dispersed in the alkali metal resin solution. Here, since the particle | grains used as the said core part are partially bridge | crosslinked with the salt of a polyvalent metal, the solubility to water is low and does not melt | dissolve. Next, droplets of the alkali metal resin solution in which the core particles are dispersed are ejected (sprayed). In this droplet, an alkali metal resin solution is present so as to cover the core particle. By drying the droplet, particles having the core / shell structure can be obtained (for example, Spray-Dry method).

2) A form containing a first organic resin having an alkali metal salt structure and a third organic resin having an organic amine salt structure. In this embodiment, the liquid absorbability is improved and the variation in chargeability is suppressed. The reason for this is not clear, but is presumed to be as follows.
By having the alkali metal salt structure, the first organic resin having an alkali metal salt structure has high hydrophilicity and water absorption. On the other hand, the third organic resin having a salt structure of organic amine is less dissociated than the salt of alkali metal because the salt of organic amine is a weak base, so that the functional group distribution on the particle surface is made uniform. Is possible. In addition, the influence of moisture in the air is reduced. That is, since the neutralization distribution is made uniform by the salt of the organic amine, it becomes possible to suppress fluctuations in chargeability. As described above, by using the organic amine, the liquid absorbability is improved and the charging property can be improved.

  In this embodiment, the ink receiving particles may be in the form of particles comprising a first organic resin having an alkali metal salt structure and a third organic resin having an organic amine salt structure. It is good also as a structure (what is called a core / shell structure) which has a core part and the coating | coated part which coat | covers the said core part.

  In the case of the core / shell structure, the core portion is configured to include a first organic resin having an alkali metal salt structure, and the covering portion is configured to include a third organic resin having an organic amine salt structure. Is good. Of course, the material structure may be reversed between the core part and the covering part, but the organic amine mainly responsible for chargeability with the core part as the area containing the first organic resin having the alkali metal salt structure responsible for water absorption. By adopting a configuration in which the region including the third organic resin having the salt structure is used as the covering portion, the liquid absorbency is further improved and the variation in charging property is reduced.

  Here, the ratio of the salt of the alkali metal to the polar monomer in the first organic resin contained in the core is preferably 5 mol% or more and 90 mol% or less, more preferably 20 mol% or more and 85 mol%. More preferably, it is 50 mol% or more and 90 mol% or less. When the ratio of the alkali metal salt is within the above range, the hydrophilicity is more effectively increased and the water absorption is improved.

  The ratio of the polar monomer to the total monomer component in the first organic resin contained in the core is 10 mol% or more and less than 100 mol%, preferably 15 mol% or more and less than 95 mol%, more preferably It is 50 mol% or more and less than 90 mol%. When the ratio of the polar monomer is within the above range, the hydrophilicity is more effectively enhanced and the water absorption is improved.

  On the other hand, the ratio of the salt of the organic amine to the polar monomer in the third organic resin contained in the coating part is preferably 0.1 mol% or more and 45 mol% or less, and more preferably 1 mol% or more. It is 40 mol% or less, and more desirably 10 mol% or more and 30 mol% or less. When the ratio of the polyvalent metal salt is within the above range, it is possible to more effectively suppress fluctuations in chargeability.

  The ratio of the polar monomer to the total monomer component in the third organic resin contained in the coating portion is 10 mol% or more and less than 100 mol%, preferably 15 mol% or more and less than 85 mol%, more preferably It is 30 mol% or more and less than 80 mol%. When the ratio of the polar monomer is within the above range, water absorption and fixability are improved.

  Further, the ratio of the covering portion to the core portion is preferably 0.5% or more and 25% or less by mass ratio, more preferably 2% or more and 10% or less, and further preferably 5% or more and 10% or less. is there. When this ratio is in the above range, the liquid absorbability can be further improved, and fluctuations in chargeability can be suppressed.

  Here, a method for producing particles having the core / shell structure will be described. For example, first, an alkali metal resin solution mixed in an organic resin (an organic resin having no salt structure), an alkali metal, and a solvent (for example, water or alcohol) is prepared. Further, an organic resin (an organic resin having no salt structure) is dissolved (or dispersed) in an organic solvent, and an organic amine is added thereto to prepare an organic amine resin solution. Then, using a double cylindrical needle in which the inner tube is concentrically arranged inside the outer tube, an alkali metal resin solution is fed to the inner tube (inner route) and organic to the outer tube (outer route). The amine resin solution is fed to discharge (spray) droplets from the tip of the needle. The discharged droplets have an alkali metal resin solution inside, and an organic amine resin solution is present so as to cover it. By drying the droplets, particles having the core / shell structure can be obtained.

  As another method, first, an alkali metal resin solution mixed in an organic resin (an organic resin having no salt structure), an alkali metal, and a solvent (for example, water or alcohol) is prepared. Next, the solvent of the polyvalent metal resin solution is removed and solidified. By pulverizing and classifying the solid material, particles are formed to obtain particles serving as a core. Next, an organic resin (an organic resin having no salt structure) is dissolved (or dispersed) in an organic solvent, and an organic amine is added thereto to prepare an organic amine resin solution. Next, the particles serving as the core are added and dispersed in the organic amine resin solution. Here, since the particle | grains used as the said core part are comprised with the organic resin which has a salt structure of an alkali metal, the solubility to an organic solvent is low, and does not melt | dissolve. Next, droplets of the organic amine resin solution in which the core particles are dispersed are discharged (sprayed). In this droplet, an organic amine resin solution is present so as to cover the core particle. By drying the droplet, particles having the core / shell structure can be obtained (for example, Spray-Dry method).

Next, the ink receiving particles according to the second embodiment will be described.
The ink receiving particles according to the second embodiment include a fourth organic resin having a polar group and a ratio of the polar monomer to the total monomer component of 10 mol% or more and less than 100 mol%, and the fourth organic resin At least a part of the polar group has an alkali metal salt structure and a polyvalent metal salt structure or an organic amine salt structure, and accepts ink. This form is a form in which the salt structure is mixed in the same molecule.

  The ink receptive particles according to the present embodiment are ink receptive particles that can receive various inks and have improved liquid absorbency by adopting the above-described configuration.

In particular, the ink receiving particles according to the present embodiment include the following forms.
1) The form in which at least a part of the polar group in the fourth organic resin has an alkali metal salt structure and a polyvalent metal salt structure. In this embodiment, the liquid absorbability is improved and the fixability is improved. The reason for this is not clear, but is presumed to be as follows.
When the organic resin has an alkali metal salt structure, the hydrophilicity increases and the water absorption also increases. On the other hand, since the organic resin has a polyvalent metal salt structure, the polyvalent metal salt suppresses the entanglement of the organic resin to further improve the water absorption, and the partial cross-linking (ionic cross-linking by the polyvalent metal salt). ), And ionic cross-linking between the resins also proceeds during fixing, so that the fixing property is improved. For this reason, it is considered that the liquid absorbency is improved and the fixing property is improved.

  Here, in this embodiment, the ratio of the alkali metal salt to the polar monomer in the fourth organic resin is preferably 5 mol% or more and 90 mol% or less, and more preferably 20 mol% or more and 85 mol% or less. More preferably, it is 50 mol% or more and 90 mol% or less. When the ratio of the alkali metal salt is within the above range, the hydrophilicity is more effectively increased and the water absorption is improved.

  The ratio of the polyvalent metal salt to the polar monomer in the fourth organic resin is preferably 0.1 mol% or more and 20 mol% or less, and more preferably 0.1 mol% or more and 5 mol% or less. More preferably, it is 0.25 mol% or more and 2.5 mol% or less. When the ratio of the polyvalent metal salt is within the above range, the fixing property is more effectively improved.

  The ratio of the polar monomer to the total monomer component in the fourth organic resin is 10 mol% or more and less than 100 mol%, preferably 15 mol% or more and less than 95 mol%, more preferably 30 mol% or more and 90 mol%. Is less than. When the ratio of the polar monomer is within the above range, water absorption and fixing properties are improved.

2) A form in which at least a part of the polar group in the fourth organic resin has an alkali metal salt structure and an organic amine salt structure. In this embodiment, the liquid absorbability is improved and the variation in chargeability is suppressed. The reason for this is not clear, but is presumed to be as follows.
When the organic resin has an alkali metal salt structure, the hydrophilicity increases and the water absorption also increases. On the other hand, since the organic resin has an organic amine salt structure, the salt of the organic amine is a weak base, so it is difficult to dissociate compared to the alkali metal salt. And the influence of moisture in the air is reduced. That is, the degree of neutralization is increased by the salt of the organic amine, and the neutralization distribution is made uniform, so that it is possible to suppress fluctuations in chargeability.

  Here, in this embodiment, the ratio of the alkali metal salt to the polar monomer in the fourth organic resin is preferably 5 mol% or more and 90 mol% or less, and more preferably 20 mol% or more and 85 mol% or less. More preferably, it is 50 mol% or more and 90 mol% or less. When the ratio of the alkali metal salt is within the above range, the hydrophilicity is more effectively increased and the water absorption is improved.

  In addition, the ratio of the salt of the organic amine to the polar monomer in the fourth organic resin is preferably 0.1 mol% or more and 45 mol% or less, more preferably 1 mol% or more and 40 mol% or less, More desirably, it is 10 mol% or more and 30 mol% or less. When the ratio of the polyvalent metal salt is within the above range, it is possible to more effectively suppress fluctuations in chargeability.

  The ratio of the polar monomer to the total monomer component in the fourth organic resin is 10 mol% or more and less than 100 mol%, preferably 15 mol% or more and less than 95 mol%, more preferably 30 mol% or more and 90 mol%. Is less than. When the ratio of the polar monomer is within the above range, the hydrophilicity is more effectively enhanced and the water absorption is improved.

  In any of the above forms, the ratio of each salt structure to the polar monomer is determined as follows. First, regarding the unneutralized portion of the polar group, the polar functional group concentration can be quantified by dissolving or dispersing particles in water or an organic solvent and performing neutralization titration with an alkali. The total amount of polar groups can be quantified by performing back titration with an acidic liquid using a solution or dispersion obtained by quantifying polar groups in an unneutralized portion. Regarding the polyvalent metal concentration, the salt concentration can be analyzed using ICP analysis. Further, the organic amine concentration can be analyzed using NMR or mass spectrometry.

Next, the particle form of the ink receiving particles according to the first and second embodiments will be described.
The ink receptive particles according to the present embodiment may be referred to as single particles (hereinafter referred to as “primary particles”) of particles including the organic resin (hereinafter may be referred to as “liquid absorbing particles”). ) Or composite particles in which at least liquid-absorbing particles are aggregated. The single particles of the liquid-absorbing particles or the composite particles in which at least the liquid-absorbing particles are aggregated may be referred to as “mother particles”.

  Here, in the case where the ink receptive particles are composed of single particles of liquid-absorbing particles, when the ink receptive particles receive ink, if the ink adheres to the ink receptive particles, at least the liquid component of the ink absorbs. Absorbed by liquid particles.

  In this way, the ink receiving particles receive ink. Then, recording is performed by transferring the ink receiving particles that have received the ink to a recording medium.

  On the other hand, in the case where the ink receiving particles are composed of composite particles in which at least liquid-absorbing particles are aggregated, when the ink receiving particles receive the ink, first, when the ink adheres to the ink receiving particles, at least the ink The liquid component is captured (trapped) by voids between particles (at least liquid-absorbing particles) constituting the composite particles (hereinafter, the interparticle voids may be referred to as “trap structures”). At this time, among the ink components, the recording material is attached to the surface of the ink receiving particles or trapped by the trap structure. And the ink which exists in this space | gap is absorbed by particle | grains. In this way, the ink receiving particles receive ink. Then, recording is performed by transferring the ink receiving particles that have received the ink to a recording medium.

  The trapping of the ink component (liquid component, recording material) by this trapping structure is physical and / or chemical trapping by voids between particles (physical particle wall structure).

  And, by applying a form composed of at least composite particles in which liquid-absorbing particles are gathered, in addition to trapping (traps) by voids (physical particle wall structure) between the particles constituting the composite particles, The liquid component absorbs and holds the ink liquid component.

  Further, after the transfer of the ink receiving particles, the components of the liquid absorbing particles constituting the ink receiving particles also function as a binder resin or a coating resin for the recording material contained in the ink. In particular, it is desirable to apply a transparent resin as a component of the liquid-absorbing particles constituting the ink receiving particles.

  In order to improve the fixability (rub resistance) of an ink (for example, pigment ink) using an insoluble component such as a pigment or a dispersed particulate material as a recording material, it is necessary to add a large amount of resin to the ink. When a large amount of polymer is added to the ink (including the treatment liquid), reliability such as nozzle clogging of the ink discharge means is deteriorated. On the other hand, in the embodiment of the present invention, the organic resin component constituting the ink receiving particles can also function as the resin.

  Here, “a void between particles constituting the composite particle”, that is, “trap structure” is a physical particle wall structure capable of capturing at least a liquid. The size of the gap is the maximum aperture, for example, in the range of 0.1 μm to 5 μm, preferably 0.3 μm to 1 μm. In particular, the size of the voids is preferably a size capable of trapping a recording material, particularly, for example, a pigment having a volume average particle diameter of 100 nm. Micropores having a maximum opening diameter of less than 50 nm may exist. Moreover, it is good for the space | gap and the capillary tube to have communicated inside the particle | grains.

  The size of the gap is obtained as follows. It is obtained by reading a scanning electron microscope (SEM) image of the particle surface with an image analysis device, detecting voids by binarization processing, and analyzing the size and distribution of the voids.

  As described above, the trap structure preferably traps not only the liquid component of the ink components but also the recording material. When a recording material, particularly a pigment, is trapped (trapped) together with the ink liquid component in the trap structure, the recording material is held and fixed without being unevenly distributed inside the ink receiving particles. The liquid component of the ink is mainly an ink solvent or a dispersion medium (vehicle liquid).

  Hereinafter, the particle form of the ink receiving particles according to the present embodiment will be described in more detail. As described above, the ink receptive particles according to the present embodiment may be in a form in which the mother particles are composed of liquid absorbing particles alone, or at least composed of composite particles in which the liquid absorbing particles are aggregated. There may be a form.

  In addition to the organic resin, the liquid absorbing particles may contain other components (for example, an inorganic material). On the other hand, as particles constituting the composite particles other than the liquid absorbing particles,

  Further, for example, inorganic particles or the like may be attached to the surface of the liquid-absorbing particles or the composite particles.

  As a specific configuration of the ink receiving particles according to the present embodiment, for example, as shown in FIG. 1, a mother particle 202 composed of a single particle of the liquid absorbing particle 201 and a mother particle 202 (liquid absorbing particle 201). The form of the ink receptive particle 200 which has the inorganic particle 204 adhering to the surface is mentioned. Further, as shown in FIG. 2, mother particles 202 composed of composite particles in which liquid absorbing particles 201 and inorganic particles 203 are combined, and inorganic particles attached to the surfaces of the mother particles 202 (composite particles). 204, and the form of the ink receptive particles 210. In this composite particle, a void structure is formed by voids between the particles.

Here, examples of the sphere-converted average particle diameter of the entire ink receiving particles include a range of 0.5 μm or more and 50 μm or less.
Here, the sphere equivalent average particle diameter is obtained as follows. Although the optimum method differs depending on the particle size, various methods can be used such as, for example, dispersing particles in a liquid and obtaining the particle size by the light scattering principle, and obtaining a projected image of the particles by image processing. Examples of methods that can be used for general purposes include the Microtrac UPA method and the Coulter counter method.

  When the mother particles are composed of composite particles, the mass ratio of the liquid-absorbing particles to other particles (liquid-absorbing particles: other particles) is, for example, 5: 1 or more when the other particles are inorganic particles. The range of 10 or less is mentioned.

  Further, the particle diameter of the mother particles is, for example, in the range of sphere-converted average particle diameter of 0.1 to 50 μm, desirably 0.5 to 25 μm, more desirably 1 to 10 μm. When the average particle diameter in terms of sphere is in the above range, high image quality is achieved. That is, when the sphere-converted average particle size is large, a step in the height direction is generated between a portion where particles are present and a portion where particles are not present on the image surface, so that the smoothness of the image may be inferior. On the other hand, when the sphere-converted average particle size is small, the handling property of the powder tends to be lowered and the powder cannot be supplied to a desired position on the transfer body. Therefore, there are places where no liquid-absorbing particles exist on the image, and high-speed recording and high image quality may not be achieved. When the ink receiving particles are composed of primary particles, it is preferable to apply the range in terms of the sphere-converted average particle size.

In the case of constituting the matrix particles are composite particles, the BET specific surface area _{(N 2)} and the like in the range of for example ^{1 m} 2 / g or more 750 meters ² / g or less.

  When the mother particles are composed of composite particles, the composite particles are obtained, for example, by granulating the particles in a semi-sintered state. The semi-sintered state refers to a state in which a certain amount of particle shape remains and voids are retained between the particles. When the ink liquid component is trapped in the trap structure, at least a part of the particles may be dissociated, that is, the composite particles may be disassembled and the particles constituting the particles may be dispersed.

  The liquid-absorbing particles have a sphere-converted average particle size of, for example, from 0.1 μm to 50 μm, desirably from 0.5 μm to 25 μm, more desirably from 1 μm to 10 μm, when the primary particles are the mother particles. The following ranges are mentioned. On the other hand, when composing composite particles, the average particle diameter in terms of sphere is, for example, in the range of 10 nm to 30 μm, desirably 50 nm to 10 μm, more desirably 0.1 μm to 5 μm.

  Further, the ratio of the liquid-absorbing particles to the whole ink-receiving particles is, for example, 75% or more, desirably 85% or more, more desirably 90% or more and 99% or less in terms of mass ratio.

Hereinafter, each material will be described in detail.
First, organic resins (first to fourth organic resins: hereinafter may be referred to as hydrophilic organic resins) will be described. The hydrophilic organic resin is an organic resin having a polar group, the ratio of the polar monomer to the total monomer component being 10 mol% or more and 100 mol% or less, and at least a part of the polar group has a salt structure. ing. This salt structure has a salt structure corresponding to the first to fourth organic resins. The polar group is contained in the polar monomer.

  Here, examples of the alkali metal imparting an alkali metal salt structure include lithium chloride, sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium sulfate, potassium nitrate, and acetic acid. Examples thereof include alkali metals such as sodium, potassium oxalate, sodium citrate, potassium benzoate, and salts thereof.

  Examples of the polyvalent metal imparting a polyvalent metal salt structure include aluminum chloride, aluminum bromide, aluminum sulfate, aluminum nitrate, sodium sulfate aluminum, potassium aluminum sulfate, aluminum acetate, barium chloride, barium bromide, and iodide. Barium, barium oxide, barium nitrate, barium thiocyanate, calcium chloride, calcium bromide, calcium iodide, calcium nitrite, calcium nitrate, calcium dihydrogen phosphate, calcium thiocyanate, calcium benzoate, calcium acetate, calcium salicylate, Calcium tartrate, calcium lactate, calcium fumarate, calcium citrate, copper chloride, copper bromide, copper sulfate, copper nitrate, copper acetate, iron chloride, iron bromide, iron iodide, iron sulfate, iron nitrate, iron oxalate, Iron lactate, iron fumarate, ku Iron phosphate, magnesium chloride, magnesium bromide, magnesium iodide, magnesium sulfate, magnesium nitrate, magnesium acetate, magnesium lactate, manganese chloride, manganese sulfate, manganese nitrate, manganese dihydrogen phosphate, manganese acetate, manganese salicylate, benzoic acid Manganese, manganese lactate, nickel chloride, nickel bromide, nickel sulfate, nickel nitrate, nickel acetate, tin sulfate, titanium chloride, zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, zinc thiocyanate, zinc acetate, etc. Metals and their salts

Examples of the organic amine imparting the salt structure of the organic amine include, for example, primary amines, secondary amines, tertiary amines, quaternary amines, and salts thereof.
Specific examples include alkylamine, alkylammonium, alkanolamine, alkanolammonium, arylamine, pyridium, imidazolium, polyamine, and derivatives or salts thereof.
Also, for example, amylamine, butylamine, propanolamine, propylamine, ethanolamine, ethylethanolamine, 2-ethylhexylamine, ethylmethylamine, ethylbenzylamine, ethylenediamine, octylamine, oleylamine, cyclooctylamine, cyclobutylamine, cyclopropyl Amine, cyclohexylamine, diisopropanolamine, diethanolamine, diethylamine, di (2-ethylhexyl) amine, diethylenetriamine, diphenylamine, dibutylamine, dipropylamine, dihexylamine, dipentylamine, 3- (dimethylamino) propylamine, dimethylethylamine, Dimethylethylenediamine, dimethyloctylamine, 1,3-dimethylbutylamine Dimethyl-1,3-propanediamine, dimethylhexylamine, amino-butanol, amino-propanol, amino-propanediol, N-acetylaminoethanol, 2- (2-aminoethylamino) -ethanol, 2-amino-2- Ethyl-1,3-propanediol, 2- (2-aminoethoxy) ethanol, 2- (3,4-dimethoxyphenyl) ethylamine, cetylamine, triisopropanolamine, triisopentylamine, triethanolamine, trioctylamine, Tritylamine, bis (2-aminoethyl) 1,3-propanediamine, bis (3-aminopropyl) ethylenediamine, bis (3-aminopropyl) 1,3-propanediamine, bis (3-aminopropyl) methylamine, Bis (2-ethyl Xyl) amine, bis (trimethylsilyl) amine, butylamine, butylisopropylamine, propanediamine, propyldiamine, hexylamine, pentylamine, 2-methyl-cyclohexylamine, methyl-propylamine, methylbenzylamine, monoethanolamine, laurylamine , Nonylamine, trimethylamine, triethylamine, dimethylpropylamine, propylenediamine, hexamethylesidiamine, tetraethylenepentamine, diethylethanolamine, tetramethylammonium chloride, tetraethylammonium bromide, dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, Lauryldimethylbenzylammonium chloride, stearamide methyl chloride Bilidium, alkyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, lauryltrimethylammonium chloride, alkyldiaminoethyl hydrochloride Examples include glycine. Furthermore, diallyldimethylammonium chloride polymer, diallylamine polymer, monoallylamine polymer and the like can be mentioned.

  The organic amine is preferably a long-chain alkyl ammonium salt, a long-chain alkyl pyridinium salt, pyridinium, an alkylamine compound, or an alkanolamine. Specifically, for example, triethanolamine, triisopropanolamine, 2-amino-2-ethyl-1,3-propanediol, ethanolamine, propanediamine, propylamine, lauryldimethylbenzylammonium chloride, stearamide methyl biliyl chloride. Examples thereof include palladium, alkyltrimethylammonium chloride, distearyldimethylammonium chloride, stearyldimethylbenzylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, cetylpyridinium chloride, benzalkonium chloride, benzethonium chloride, and lauryltrimethylammonium chloride.

  On the other hand, the polar monomer containing a polar group is, for example, a monomer containing an ethylene oxide group, a carboxylic acid, a sulfonic acid, a substituted or unsubstituted amino group, or a hydroxyl group as a polar group. For example, in the case of imparting positive chargeability, a monomer containing, for example, a (substituted) amino group or a (substituted) pyridine group is desirable. In the case of imparting negative charge, it is desirable to be a monomer of an organic acid including carboxylic acid, sulfonic acid and the like. In particular, carboxylic acid is advantageous in terms of storage stability because it is difficult to dissociate when it is unneutralized (when it does not have a salt structure), and dissociates with ink (a weakly alkaline liquid). Also, the carboxylic acid is crosslinked (pseudo-crosslinked) with ions in the ink, and the entire system (ink + ink receiving particles) is easily fixed, which is advantageous for fixing properties.

  In addition, the ratio of a polar monomer is calculated | required as follows. First, the constitution of the organic component is specified from analysis methods such as mass spectrometry, NMR (nuclear magnetic resonance), and IR (infrared absorption spectrum). Then, based on JIS K0070 or JIS K2501, the acid value and base number of an organic component are measured. The ratio of the polar monomer can be calculated from the constitution of the organic component and the acid value / base value. The same applies hereinafter.

  The hydrophilic organic resin can soften and contribute to fixability because the ink liquid component (for example, water, aqueous solvent) that has been absorbed acts as a plasticizer for the resin (polymer).

The hydrophilic organic resin is preferably a weak liquid-absorbing resin. The weak liquid-absorbent resin is, for example, from several percent (≈5%) to several hundred percent (≈500%), desirably from about 5% to about 100% when absorbing water as a liquid. A lyophilic resin capable of absorbing liquid.
When the liquid absorbency of the hydrophilic organic resin (weak liquid absorbent resin) is less than 5%, the ink holding capacity of the ink receiving particles is reduced, and when it exceeds 500%, the ink receiving particles actively absorb moisture. Therefore, there are cases where the environment dependency becomes large.

  The hydrophilic organic resin can be composed of, for example, a homopolymer of a hydrophilic monomer or a copolymer composed of both a hydrophilic monomer and a hydrophobic monomer. In order to obtain a weak water-absorbing resin, the copolymer is desirable. In addition, not only the monomer but also a graft copolymer or block copolymer in which other units such as a polymer / oligomer structure are copolymerized as a start may be used.

Here, as a hydrophilic monomer, -OH, -EO unit (ethylene oxide group), -COOM (M is alkali metal, such as hydrogen, Na, Li, and K, ammonia, organic amines, etc.). ), - SO ₃ M (M is, for example, hydrogen, Na, Li, alkali metals K, etc., ammonia, organic amines, etc.), - NR ₃ (R is, for example, H, alkyl, phenyl, etc.). - NR ₄ X (R is, for example, H, alkyl, phenyl, etc., and X is, for example, halogen, sulfate radical, acid anions such as carboxylic acid, BF ₄ , etc.) and the like. It is done. Specific examples include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, acrylamide, acrylic acid, methacrylic acid, unsaturated carboxylic acid, crotonic acid, maleic acid, and the like. Examples of hydrophilic units or monomers include cellulose derivatives such as cellulose, ethyl cellulose, carboxymethyl cellulose, starch derivatives, monosaccharide / polysaccharide derivatives, vinyl sulfonic acid, styrene sulfonic acid, acrylic acid, methacrylic acid, (anhydrous) Polymeric carboxylic acids such as maleic acid, (partially) neutralized salts thereof, vinyl alcohols, vinyl pyrrolidone, vinyl pyridine, derivatives such as amino (meth) acrylate and dimethylamino (meth) acrylate, and oniums thereof Salts, amides such as acrylamide and isopropylacrylamide, polyethylene oxide chain-containing vinyl compounds, hydroxyl group-containing vinyl compounds, polyesters composed of polyfunctional carboxylic acids and polyhydric alcohols, especially trimellitic acid Branched polyester containing a large amount of content and terminal carboxylic acid or hydroxyl functionality more acid as a constituent component, a polyester containing polyethylene glycol structure, etc. may be mentioned.

  Examples of the hydrophobic monomer include monomers having a hydrophobic group. Specifically, for example, olefin (ethylene, butadiene, etc.), styrene, α-methylstyrene, α-ethylstyrene, methyl methacrylate, Examples include ethyl methacrylate, butyl methacrylate, acrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, and lauryl methacrylate. Hydrophobic units or monomers include styrene derivatives such as styrene, α-methylstyrene, vinyltoluene, vinylcyclohexane, vinylnaphthalene, vinylnaphthalene derivatives, alkyl acrylate esters, phenyl acrylate esters, alkyl methacrylate esters, methacrylic acid Examples also include phenyl esters, cycloalkyl methacrylates, alkyl esters of crotonic acid, dialkyl esters of itaconic acid, dialkyl maleates, polyolefins such as polyethylene, ethylene / vinyl acetate and polypropylene, and derivatives thereof.

  Specific examples of the liquid absorbing resin that is a copolymer of the hydrophilic monomer and the hydrophobic monomer include, for example, (meth) acrylic acid esters, styrene / (meth) acrylic acid / (anhydrous). ) Preferred are maleic acid copolymers, olefin polymers such as ethylene / propylene (or modified products thereof, or carboxylic acid unit introduced products by copolymerization), branched polyesters and polyamides whose acid value has been improved with trimellitic acid, etc. Can be mentioned.

  It is also desirable for the hydrophilic organic resin to contain a substituted or unsubstituted amino group or a substituted or unsubstituted pyridine group. The group exerts a bactericidal effect and interaction with a recording material having an anionic group (for example, pigment or dye).

  Here, in the hydrophilic organic resin, the molar ratio (hydrophilic monomer: hydrophobic monomer) between the hydrophilic unit (hydrophilic monomer) and the hydrophobic unit (hydrophilic monomer) is, for example, 5:95 to 70:30.

  The hydrophilic organic resin may be ion-crosslinked with ions supplied from the ink. Specifically, a unit containing a carboxylic acid is present in the resin, such as a copolymer containing a carboxylic acid such as (meth) acrylic acid or maleic acid or a (branched) polyester having a carboxylic acid in the hydrophilic organic resin. be able to. Ionic crosslinking and acid / base interaction occur between the carboxylic acid in the resin and the alkali metal cation, alkaline earth metal cation, organic amine / onium cation, etc. supplied from the liquid such as water-based ink.

  The hydrophilic organic resin may have a straight chain structure, but a split structure. The organic resin is preferably non-crosslinked or low crosslinked. The organic resin may be a linear random copolymer or block copolymer, but a branched polymer (including branched random copolymer, block copolymer, and graft copolymer) is further included. It can be used suitably. For example, in the case of polyester synthesized by polycondensation, end groups can be increased in a branched structure. This branched structure is generally synthesized by adding so-called cross-linking agents such as divinylbenzene and di (meth) acrylates during synthesis (for example, adding less than 1%) or adding a large amount of an initiator together with the cross-linking agent. It is one of the practical methods.

  To the hydrophilic organic resin, a charge control agent for an electrophotographic toner such as a low-molecular quaternary ammonium salt, an organic borate salt, or a salt-forming compound of a salicylic acid derivative may be added to the organic resin.

  The hydrophilic organic resin is preferably an amorphous resin, and the glass transition temperature (Tg) thereof is, for example, 40 ° C. or higher and 90 ° C. or lower. The glass transition temperature (and melting point) was determined from the main maximum peak measured according to ASTM D3418-8. DSC-7 manufactured by Perkin Elmer Co. can be used for measurement of the main maximum peak. The temperature correction of the detection part of this apparatus uses the melting point of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium. As the sample, an aluminum pan was used, an empty pan was set as a control, and the measurement was performed at a heating rate of 10 ° C./min.

  Examples of the weight average molecular weight of the hydrophilic organic resin include 3000 or more and 300,000 or less. The weight average molecular weight is measured under the following conditions. For example, GPC uses “HLC-8120GPC, SC-8020 (manufactured by Tosoh Corporation)” apparatus, and two columns are “TSKgel, SuperHM-H (6.0 mm ID × 15 cm, manufactured by Tosoh Corporation)”. And THF (tetrahydrofuran) was used as the eluent. As experimental conditions, a sample concentration of 0.5% and a flow rate of 0.6 ml / min. The experiment was conducted using a sample injection amount of 10 μl, a measurement temperature of 40 ° C., and an IR detector. The calibration curve is “polystylen standard sample TSK standard” manufactured by Tosoh Corporation: “A-500”, “F-1”, “F-10”, “F-80”, “F-380”, “A-2500”. ”,“ F-4 ”,“ F-40 ”,“ F-128 ”, and“ F-700 ”.

  As for the acid value of hydrophilic organic resin, 50 mgKOH / g or more and 1000 mgKOH / g or less are mentioned, for example in conversion of carboxylic acid group (-COOH). The acid value in terms of this carboxylic acid group (—COOH) was measured as follows.

  The acid value was measured according to JIS K0070 and using a neutralization titration method. That is, an appropriate amount of a sample is taken, 100 ml of a solvent (diethyl ether / ethanol mixed solution) and a few drops of an indicator (phenolphthalein solution) are added, and shaken sufficiently until the sample is dissolved on a water bath. This was titrated with a 0.1 mol / l potassium hydroxide ethanol solution, and the end point was when the red color of the indicator lasted for 30 seconds. When the acid value is A, the sample amount is S (g), the 0.1 mol / l potassium hydroxide ethanol solution used for the titration is B (ml), and f is the factor of the 0.1 mol / l potassium hydroxide ethanol solution. , A = (B × f × 5.611) / S.

  The hydrophilic organic resin described above is used by controlling the ratio of the polar monomer within the above range in any form. The ink receiving particles (liquid absorbing particles) may include a hydrophobic organic resin other than the core vinegar resin as the organic resin. Among the organic resins contained, the hydrophilic resin (salt) The ratio of those having a structure and those having no structure is desirably 80% or more and 100% or less in terms of mass ratio with respect to the entire ink receiving particles. When this ratio is in the above range, the hydrophilicity of the ink receiving particles is increased and the water absorption is also increased.

  Next, inorganic particles (inorganic particles constituting composite particles together with liquid-absorbing particles, and inorganic particles attached to mother particles together with hydrophobic organic particles) will be described. As the inorganic particles, any of non-porous particles and porous particles can be used. Examples of the inorganic particles include colorless, light-colored or white particles (for example, colloidal silica, alumina, calcium carbonate, zinc oxide, titanium oxide, tin oxide, etc.). These inorganic particles may be subjected to surface treatment (partial hydrophobization treatment, specific functional group introduction treatment, etc.). For example, in the case of silica, the hydroxyl group of silica is treated with a silylating agent such as trimethylchlorosilane or t-butyldimethylchlorosilane to introduce an alkyl group. Hydrochloric acid is generated by the silylating agent, and the reaction proceeds. At this time, if amine is added, hydrochloric acid can be converted into hydrochloride to promote the reaction. It can be controlled by controlling the treatment amount and treatment conditions of a silane coupling agent having an alkyl group or a phenyl group as a hydrophobic group or a coupling agent such as titanate or zirconate. Further, surface treatment with aliphatic alcohols, higher fatty acids and derivatives thereof is also possible. Also, coupling agents having a cationic functional group such as a (substituted) amino group or a silane coupling agent having a quaternary ammonium salt structure, coupling agents having a fluorine-based functional group such as fluorosilane, and other carboxylic acids Surface treatment with a coupling agent having an anionic functional group such as the above is also possible. These inorganic particles may be so-called internally added contained in the liquid-absorbing particles.

  The particle diameter of the inorganic particles constituting the composite particles is, for example, in the range of 10 nm to 30 μm, desirably 50 nm to 10 μm, more desirably 0.1 μm to 5 μm in terms of a sphere equivalent average particle diameter. On the other hand, the particle diameter of the inorganic particles attached to the mother particles is, for example, in the range of 10 nm to 1 μm, preferably 10 nm to 0.1 μm, more preferably 10 nm to 0.05 μm, in terms of sphere-converted average particle diameter. .

  Hereinafter, other constituent materials will be described.

  The ink receiving particles according to the present embodiment described above can be used alone or in combination with a carrier. In addition, as a carrier, the carrier used for the developer of the toner for electrophotography can be applied, for example.

(Recording material)
The recording material of the present embodiment includes at least an ink containing a recording material and the ink receiving particles according to the present embodiment. The recording material can perform recording by causing the ink receiving particles to receive ink and then transferring the ink receiving particles to a recording medium.

  Hereinafter, the ink will be described in detail. The ink can be used for both water-based ink and oil-based ink, but water-based ink is used from the viewpoint of environment. Aqueous ink (hereinafter simply referred to as ink) contains an ink solvent (for example, water, a water-soluble organic solvent) in addition to the recording material. In addition, other additives may be included as necessary.

  First, the recording material will be described. As the recording material, a color material is mainly used. As the color material, either a dye or a pigment can be used, but a pigment is preferable. As the pigment, either an organic pigment or an inorganic pigment can be used. Examples of the black pigment include carbon black pigments such as furnace black, lamp black, acetylene black, and channel black. In addition to black, cyan, magenta, and yellow primary pigments, specific color pigments such as red, green, blue, brown, and white, metallic luster pigments such as gold and silver, colorless or light color extender pigments, plastic pigments, etc. May be used. In addition, a newly synthesized pigment may be used for this embodiment.

  It is also possible to use particles, such as silica, alumina, polymer beads, etc., having a dye or pigment fixed on the surface thereof, a dye insoluble lake, a colored emulsion, or a colored latex as the pigment.

  Specific examples of black pigments include Raven7000, Raven5750, Raven5250, Raven5000 ULTRAII, Raven3500, Raven2000, Raven1500, Raven1250, Raven1200, Raven1125, Raven10, Raven10, Raven10 Regal 330R, Regal 660R, Mogul L, Black Pearls L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 140 0 (manufactured by Cabot Corporation), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black 18, Color Black FW200, Color Black S150, Color Black P160, Color Black P160, Color Black FW2V, Color Black FW2V, Color Black FW200, Color Black FW200 Printex 140V, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (manufactured by Degussa), No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Corporation) and the like can be mentioned, but are not limited thereto.

  Specific examples of the cyan pigment include C.I. I. Pigment Blue-1, -2, -3, -15, -15: 1, -15: 2, -15: 3, -15: 4, -16, -22, -60, and the like. It is not limited.

  Specific examples of the magenta color pigment include C.I. I. Pigment Red-5, -7, -12, -48, -48: 1, -57, -112, -122, -123, -146, -168, -177, -184, -202, C.I. I. Pigment Violet-19 etc. are mentioned, However, It is not limited to these.

  Specific examples of yellow pigments include C.I. I. Pigment Yellow-1, -2, -3, -12, -13, -14, -16, -17, -73, -74, -75, -83, -93, -95, -97, -98, -114, -128, -129, -138, -151, -154, -180, and the like, but are not limited thereto.

  Here, when a pigment is used as the color material, it is desirable to use a pigment dispersant together. Examples of the pigment dispersant that can be used include a polymer dispersant, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant.

  As the polymer dispersant, a polymer having a hydrophilic structure portion and a hydrophobic structure portion is preferably used. As the polymer having a hydrophilic structure portion and a hydrophobic structure portion, a condensation polymer and an addition polymer can be used. Examples of the condensation polymer include known polyester dispersants. Examples of the addition polymer include addition polymers of monomers having an α, β-ethylenically unsaturated group. Desired polymer dispersion by copolymerizing a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group and a monomer having an α, β-ethylenically unsaturated group having a hydrophobic group An agent is obtained. A homopolymer of a monomer having an α, β-ethylenically unsaturated group having a hydrophilic group can also be used.

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

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

  Examples of desirable copolymers used as polymer dispersants include styrene-styrene sulfonic acid copolymers, styrene-maleic acid copolymers, styrene-methacrylic acid copolymers, styrene-acrylic acid copolymers, Vinyl naphthalene-maleic acid copolymer, vinyl naphthalene-methacrylic acid copolymer, vinyl naphthalene-acrylic acid copolymer, alkyl acrylate ester-acrylic acid copolymer, alkyl methacrylate ester-methacrylic acid copolymer, styrene -Methacrylic acid alkyl ester-Methacrylic acid copolymer, Styrene-Acrylic acid alkyl ester-Acrylic acid copolymer, Styrene-Methacrylic acid phenyl ester-Methacrylic acid copolymer, Styrene-Methacrylic acid cyclohexyl ester-Methacrylic acid copolymer Etc. . Moreover, you may copolymerize the monomer which has a polyoxyethylene group and a hydroxyl group with these polymers.

  Examples of the polymer dispersant include those having a weight average molecular weight of 2,000 to 50,000.

  These pigment dispersants may be used alone or in combination of two or more. The amount of the pigment dispersant added varies greatly depending on the pigment, so it cannot be generally stated.

  A pigment that can be self-dispersed in water can also be used as the color material. A pigment that can be self-dispersed in water refers to a pigment that has many water-solubilizing groups on the surface of the pigment and disperses in water without the presence of a polymer dispersant. Specifically, it can be self-dispersed in water by subjecting ordinary so-called pigments to surface modification treatments such as acid / base treatment, coupling agent treatment, polymer graft treatment, plasma treatment, oxidation / reduction treatment, etc. Pigments are obtained.

  Further, as pigments that can be self-dispersed in water, in addition to the above pigments subjected to surface modification treatment, Cab-o-jet-200, Cab-o-jet-300, Cab manufactured by Cabot Corporation Commercially available self-dispersing pigments such as -o-jet-250, Cab-o-jet-260, Cab-o-jet-270, Microjet Black CW-1, CW-2 manufactured by Orient Chemical Co., etc. can also be used.

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

  Furthermore, a pigment coated with a resin can also be used. This is called a microcapsule pigment, and not only commercially available microcapsule pigments such as those manufactured by Dainippon Ink & Chemicals, Inc., or Toyo Ink, but also microcapsule pigments or the like that have been prototyped for this embodiment may be used. it can.

  In addition, a resin-dispersed pigment in which a polymer substance is physically adsorbed or chemically bonded to the pigment can also be used.

  Other recording materials include hydrophilic anionic dyes, direct dyes, cationic dyes, reactive dyes, dyes such as polymer dyes and oil-soluble dyes, wax powders / resin powders and emulsions colored with dyes, Fluorescent dyes and fluorescent pigments, infrared absorbers, ultraviolet absorbers, magnetic materials such as ferromagnetic materials represented by ferrite and magnetite, semiconductors and photocatalysts represented by titanium oxide and zinc oxide, and other organic and inorganic electrons Examples include material particles.

  The content (concentration) of the recording material is, for example, in the range of 2% by mass to 20% by mass with respect to the ink.

  Examples of the volume average particle diameter of the recording material include a range of 10 nm to 300 nm.

  The volume average particle size of the recording material refers to the particle size of the recording material itself, or the particle size to which the additive has adhered when an additive such as a dispersant is attached to the recording material. A Microtrac UPA particle size analyzer 9340 (manufactured by Lees & Northrup) was used as a volume average particle diameter measuring apparatus. The measurement was performed according to a predetermined measurement method with 4 ml of ink placed in a measurement cell. As input values at the time of measurement, the viscosity of the ink was used as the viscosity, and the density of the dispersed particles was used as the density of the recording material.

  Next, the water-soluble organic solvent will be described. As the water-soluble organic solvent, polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents and the like are used.

  Specific examples of the water-soluble organic solvent include polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2-hexanediol, 1,2, Examples thereof include sugar alcohols such as 6-hexanetriol, glycerin, trimethylolpropane, and xylitol, and sugars such as xylose, glucose, and galactose.

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

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

  In addition, as the water-soluble organic solvent, propylene carbonate, ethylene carbonate, or the like can be used.

  At least one kind of water-soluble organic solvent may be used. As content of a water-soluble organic solvent, the range of 1 mass% or more and 70 mass% or less is mentioned, for example.

  Next, water will be described. As water, it is desirable to use ion-exchanged water, ultrapure water, distilled water, or ultrafiltered water in order to prevent impurities from being mixed.

  Next, other additives will be described. A surfactant can be added to the ink.

  Examples of these surfactants include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, and the like. Desirably, anionic surfactants and nonionic surfactants are used. An activator is used.

Specific examples of the surfactant are listed below.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, sulfuric acid of higher alcohol ether. Ester salts and sulfonates, higher alkyl sulfosuccinates, polyoxyethylene alkyl ether carboxylates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, polyoxyethylene alkyl ether phosphates can be used, preferably , Dodecylbenzenesulfonate, isopropylnaphthalenesulfonate, monobutylphenylphenol monosulfonate, monobutylbiphenylsulfonate, monobutylbiphenylsulfonate, dibutylphenylsulfonate Nord disulfonic acid salts and the like are used.

  Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, poly Oxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, alkyl alkanolamide, polyethylene glycol polypropylene glycol block copolymer, acetylene glycol, polyoxyethylene adduct of acetylene glycol Desirably, polyoxyethylene nonyl pheny is preferable. Ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkylolamide, polyethylene glycol polypropylene glycol block copolymer Acetylene glycol and polyoxyethylene adducts of acetylene glycol are used.

  In addition, silicone surfactants such as polysiloxane oxyethylene adducts, fluorine surfactants such as perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, and oxyethylene perfluoroalkyl ethers, spicrispolic acid and rhamnolipids Biosurfactants such as lysolecithin can also be used.

  These surfactants may be used alone or in combination. The hydrophilic / hydrophobic balance (HLB) of the surfactant is, for example, in the range of 3 or more and 20 or less in consideration of solubility.

  The amount of these surfactants added is, for example, in the range of 0.001% by mass to 5% by mass, desirably 0.01% by mass to 3% by mass.

  In addition, the ink has other properties such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethyleneglycol, ethylcellulose, carboxymethylcellulose, etc. for the purpose of controlling properties such as penetrants and ink ejection improvement for the purpose of adjusting permeability. In order to adjust pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, etc., pH buffer, antioxidant, antifungal agent, viscosity adjuster, conductive agent as necessary UV absorbers, chelating agents, and the like can also be added.

  Next, preferred characteristics of the ink will be described. First, the pH of the ink is preferably 7 or more, more preferably 7 or more and 11 or less, and still more preferably 8 or more and 10 or less.

  Here, the pH of the ink is 23 ± 0.5 ° C. and 55 ± 5% humidity. H. Under the environment, a value measured by a pH / conductivity meter (MPC227 manufactured by METTLER TOLEDO) was adopted.

  Examples of the surface tension of the ink include a range of 20 mN / m to 40 mN / m (desirably 25 mN / m to 35 mN / m).

  Here, as the surface tension, a value measured in an environment of 23 ° C. and 55% RH using a Wilhelmy type surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.) was adopted.

  Examples of the viscosity of the ink include a range of 3 mPa · s to 15 mPa · s (desirably 10 mPa · s to 10 mPa · s).

Here, as the viscosity, a value measured using a rheomat 115 (manufactured by Contraves) as a measuring device, a measurement temperature of 23 ° C., and a shear rate of 1400 s ⁻¹ was adopted.

  The ink is not limited to the above configuration. In addition to the recording material, for example, a functional material such as a liquid crystal material or an electronic material may be included.

(Ink-receptive particle storage cartridge)
The ink receptive particle storage cartridge according to the present embodiment is detachable from the recording apparatus. The ink receptive particle storage cartridge stores the ink receptive particles according to the present embodiment, and the ink is applied to the particle coating apparatus (particle supply apparatus) of the recording apparatus. It is a member for supplying receptive particles.

  Hereinafter, an embodiment of an ink receiving particle storage cartridge according to the present embodiment will be described with reference to the drawings. FIG. 3 is a perspective view showing a cartridge for storing ink receiving particles according to the embodiment. 4 is a cross-sectional view taken along line AA in FIG.

  As shown in FIGS. 3 and 4, the ink-receptive particle storage cartridge 50 according to the embodiment includes a cylindrical particle storage cartridge main body 51 and side wall portions 52 fitted to both ends of the particle storage cartridge main body 51. 54.

  Further, on the peripheral surface of the particle storage cartridge main body 51 on one end side, a carry-out port 60 is provided for carrying out the ink receiving particles toward a particle coating device (particle supply device: not shown) of the recording apparatus. A band 56 is slidably attached to the particle storage cartridge main body 51. The band portion 56 is provided with a storage portion 58 for storing the carry-out port 60 outside the carry-out port 60.

  Accordingly, when the particle storage cartridge 50 is not attached to the recording apparatus (or just after attachment), the carry-out port 60 is stored in the storage unit 58, and the ink receiving particles in the particle storage cartridge main body 51 are removed from the carry-out port 60. Does not leak.

  Further, a hole 62 is formed in the central portion of the side wall portion 54 on the other end side of the particle storage cartridge main body 51, and the coupling portion 66 of the coupling portion 64 is connected to the particle storage cartridge main body from the hole 62 of the side wall portion 54. 51 penetrates inside. Thereby, the coupling part 64 is rotatable with respect to the side wall part 54.

  An agitator 68 is disposed inside the particle storage cartridge main body 51. The agitator 68 is made of a metal linear member having a circular cross section, for example, stainless steel (SUS304WP), and is formed in a spiral shape. One end of one agitator is bent toward the rotation axis (rotation center) and is connected to the connection portion 66 of the coupling portion 64. The tip of the other end is a free end that is not constrained.

  The agitator 68 is rotated by applying a rotational force from the coupling portion 66 of the coupling portion 64, and conveys the ink receiving particles in the particle storage cartridge main body 51 toward the carry-out port 60 while stirring. In this way, the particles are discharged from the outlet 60, and the ink receiving particles are additionally supplied to the recording apparatus.

  The ink receiving particle storage cartridge according to the present embodiment is not limited to the above configuration.

(Recording device)
The recording apparatus (recording method) of the present embodiment is a recording apparatus (recording method) using an ink containing a recording material and the ink receiving particles according to the present embodiment, and includes an intermediate transfer member and an ink receiving property. Supply means (supply process) for supplying particles onto the intermediate transfer member, ink discharge means (ink discharge process) for discharging ink onto the ink receiving particles supplied onto the intermediate transfer member, and recording the ink receiving particles A transfer unit (transfer process) for transferring to the medium; and a fixing unit (fixing step) for fixing the ink receiving particles transferred to the recording medium. The ink receiving particles are supplied onto the intermediate transfer member. And a recording apparatus (recording method) for receiving ink ejected from the ink ejecting means.

  Specifically, for example, first, ink receiving particles are supplied in a layer form to an intermediate (intermediate transfer member) by a supply unit. Ink-receiving particles (hereinafter referred to as ink-receiving particle layers) supplied in layers are discharged and received by ink discharge means. The ink receiving particle layer that has received the ink is transferred from the intermediate to the recording medium by a transfer means. This transfer is selectively performed on the entire ink receptive particle layer or on the recording portion (ink receiving portion). Thereafter, the ink receiving particle layer transferred to the recording medium is pressurized (or heated / pressurized) by a fixing means to be fixed. In this way, recording is performed with the ink receiving particles that have received the ink. Note that the transfer and fixing may be performed substantially simultaneously or separately.

  Here, the ink receptive particles are formed in, for example, a layer when receiving ink, and the thickness of the ink receptive particle layer is, for example, 1 μm to 100 μm, desirably 3 μm to 60 μm, and more desirably. The range of 5 micrometers or more and 30 micrometers or less is mentioned. Further, the porosity in the ink receptive particle layer (that is, the void ratio between the ink receptive particles + the void ratio in the ink receptive particles (trap structure)) is, for example, 10% to 80%, preferably 30% to 70%. Hereinafter, the range of 40% or more and 60% or less is more preferable.

  Further, a release agent may be applied to the surface of the intermediate in advance before supplying the ink receiving particles. Examples of the release agent include (modified) silicone oil, fluorine oil, hydrocarbon oil, mineral oil, vegetable oil, polyalkylene glycol, alkylene glycol ether, alkane diol, and molten wax.

  As the recording medium, any of a penetrating medium (for example, plain paper or coated paper) or a non-penetrating medium (for example, art paper or resin film) can be applied. The recording medium is not limited to these, and includes industrial products such as semiconductor substrates.

  On the other hand, the recording apparatus (recording method) according to the present embodiment includes a supplying unit that supplies ink receiving particles onto a recording medium, an ink discharging unit that discharges ink onto the ink receiving particles supplied onto the recording medium, and a recording. And a fixing unit that fixes the ink receiving particles supplied onto the medium, and the ink receiving particles are supplied onto the recording medium and receive the ink discharged from the ink discharging unit ( Recording method).

  Specifically, first, the ink receiving particles are supplied to the recording medium in a layer form by the supplying means. Ink-receiving particles (hereinafter referred to as ink-receiving particle layers) supplied in layers are discharged and received by ink discharge means. The ink receiving particle layer that has received ink is pressed (or heated / pressurized) by a fixing means to be fixed. In this way, recording is performed with the ink receiving particles that have received the ink. In this way, the recording medium may be supplied directly onto the recording medium.

  Embodiments of the present invention will be described below with reference to the drawings. In addition, the same code | symbol is provided to the member which has the substantially same effect | action and function through all the drawings, and the overlapping description may be abbreviate | omitted.

  FIG. 5 is a configuration diagram illustrating the recording apparatus according to the embodiment. FIG. 6 is a configuration diagram illustrating a main part of the recording apparatus according to the embodiment. FIG. 7 is a configuration diagram illustrating an ink receiving particle layer according to the embodiment. In the following embodiments, a case where composite particles are applied as ink receiving particles described later is described.

  As shown in FIGS. 5 and 6, the recording apparatus 10 according to the embodiment includes, for example, an endless belt-shaped intermediate transfer body 12, a charging device 28 that charges the surface of the intermediate transfer body 12, and charging on the intermediate transfer body 12. A particle supply device 18 for supplying ink receiving particles 16 to the formed area to form a particle layer, an ink jet recording head 20 for forming an image by ejecting ink droplets onto the particle layer, and a recording medium 8 overlapped with the intermediate transfer body 12. In addition, the image forming apparatus includes a transfer fixing device 22 that transfers and fixes the ink receiving particle layer on the recording medium 8 by applying pressure and heat. An ink receiving particle storage cartridge 19 is detachably connected to the particle supply device 18 via a supply pipe 19A.

  On the upstream side of the charging device 28, a release agent supply device 14 that supplies the release agent 14D to form the release layer 14A is disposed.

  The surface of the intermediate transfer body 12 having a charge formed on the surface by the charging device 28 is formed with the ink receiving particles 16 as a layer by the particle supply device 18, and the ink jet recording head 20 for each color, that is, 20K, 20C, is formed on the particle layer. , 20M, and 20Y, ink droplets of each color are ejected to form a color image.

  The particle layer having the color image formed on the surface is transferred to the recording medium 8 together with the color image by a transfer fixing device (transfer fixing roll) 22. Downstream of the transfer fixing device 22, the ink receiving particles 16 remaining on the surface of the intermediate transfer body 12 are removed, and the intermediate transfer body adhering material such as foreign matters other than the particles (such as paper dust of the recording medium 8) is removed. A cleaning device 24 is provided.

  The recording medium 8 to which the color image has been transferred is carried out as it is, and the intermediate transfer body 12 is again charged on the surface by the charging device 28. At this time, the ink receiving particles transferred to the recording medium 8 absorb and hold the ink droplets 20A, so that they can be quickly carried out.

  Further, if necessary, the intermediate transfer body 12 is provided between the cleaning device 24 and the release agent supply device 14 (hereinafter, the term “between A and B” means “not including any unless otherwise specified”). You may arrange | position the static elimination apparatus 29 for removing the electric charge which remains on the surface.

In the present embodiment, the intermediate transfer member 12 has a 400 μm thick ethylene propylene rubber (EPDM) surface layer formed on a 1 mm thick polyimide film base layer. Here, it is desirable that the surface resistance value is about 10 ¹³ Ω / □ and the volume resistance value is about 10 ¹² Ω · cm (semiconductive).

  The intermediate transfer body 12 is rotated, and a release layer 14A is first formed on the surface of the intermediate transfer body 12 by the release agent supply device 14. The release agent 14D is supplied to the surface of the intermediate transfer body 12 by the supply roll 14C of the release agent supply device 14, and the layer thickness is defined by the blade 14B.

  At this time, the release agent supply device 14 may be in continuous contact with the intermediate transfer body 12 or may be configured to be separated from the intermediate transfer body 12 for the purpose of continuous image formation and printing. .

  The release agent 14D may be supplied to the release agent supply device 14 from an independent liquid supply system (not shown) so that the supply of the release agent 14D is not interrupted.

  Next, by applying a positive charge to the surface of the intermediate transfer body 12 by the charging device 28, the surface of the intermediate transfer body 12 is charged with a positive charge. Here, if the ink receiving particles 16 form a potential that can be supplied / adsorbed to the surface of the intermediate transfer body 12 by an electrostatic force due to an electric field that can be formed between the supply roll 18A of the particle supply device 18 and the surface of the intermediate transfer body 12. Good.

  In the present embodiment, a voltage is applied between the charging device 28 and a driven roll 31 (connected to the ground) disposed between the charging device 28 and the intermediate transfer body 12 using the charging device 28, so that the surface of the intermediate transfer body 12 is covered. It is configured to be charged.

The charging device 28 forms an elastic layer (foamed urethane resin) in which a conductivity imparting material is dispersed on a rod-like outer peripheral surface made of stainless steel, and has a volume resistivity of 10 ⁶ Ω · cm to 10 ⁸ Ω · cm. A roll-shaped member adjusted to a degree is used. Furthermore, the surface of the elastic layer is covered with a water / oil repellent coating layer (for example, composed of tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA)) having a thickness of 5 μm to 100 μm.

  A DC power source is connected to the charging device 28, and the driven roll 31 is electrically connected to the frame ground. The charging device 28 is driven while sandwiching the intermediate transfer body 12 with the driven roll 31, and a predetermined potential difference is generated with the grounded driven roll 31 at the pressed position. An electric charge can be given. Here, for example, a voltage of 1 kv is applied to the surface of the intermediate transfer member 12 by the charging device 28 to charge the surface of the intermediate transfer member 12.

  Further, the charging device 28 may be composed of a corotron or the like.

  Next, the ink supply particles 16 are supplied to the surface of the intermediate transfer body 12 by the particle supply device 18 to form the ink reception particle layer 16A. In the particle supply device 18, a supply roll 18 </ b> A is disposed on a portion of the container in which the ink receiving particles 16 are accommodated, facing the intermediate transfer body 12, and a charging blade 18 </ b> B is disposed so as to press the supply roll 18 </ b> A. The charging blade 18B also has a function of regulating the layer thickness of the ink receiving particles 16 supplied to the surface of the supply roll 18A.

  The ink receiving particles 16 are supplied to the supply roll 18A (conductive roll), the ink receiving particle layer 16A is regulated by the charging blade 18B (conductive blade), and the negative polarity is opposite to the charge on the surface of the intermediate transfer body 12. Is charged. The supply roll 18A can be a solid aluminum roll, and the charging blade 18B can be a metal plate (SUS or the like) on which urethane rubber is caught to apply pressure. The charging blade 18B is in contact with the supply roll 18A by a doctor blade method.

  The charged ink receiving particles 16 form, for example, a single particle layer on the surface of the supply roll 18A, and are conveyed to a portion facing the surface of the intermediate transfer body 12. When close to this, the surfaces of the supply roll 18A and the intermediate transfer body 12 are conveyed. The charged ink receiving particles 16 are moved to the surface of the intermediate transfer member 12 by electrostatic force due to the electric field formed by the potential difference between them.

  At this time, the moving speed of the intermediate transfer body 12 and the rotation speed of the supply roll 18A are relatively set so as to form one particle layer on the surface of the intermediate transfer body 12 (peripheral speed ratio). This peripheral speed ratio depends on other parameters such as the charge amount of the intermediate transfer member 12, the charge amount of the ink receiving particles 16, and the positional relationship between the supply roll 18A and the intermediate transfer member 12.

The number of particles supplied onto the intermediate transfer body 12 is increased by relatively increasing the peripheral speed of the supply roll 18A on the basis of the peripheral speed ratio for forming the one ink receptive particle layer 16A. Can be made. When the transferred image density is low (the amount of ink shot is small (for example, 0.1 g / m ² or more and 1.5 g / m ² or less)), the layer thickness is set to the minimum necessary thickness (for example, 1 μm to 5 μm). In addition, when the image density is high (the ink shot amount is large (for example, 4 g / m ² or more and 15 g / m ² or less)), the ink liquid component (solvent or dispersion medium) can be held sufficiently. It is desirable to control the layer thickness (for example, 10 μm or more and 25 μm or less).

  For example, in the case of a character image or the like with a small amount of ink shot, when an image is formed on one ink receptive particle layer on the intermediate transfer member, the image forming material (pigment) in the ink is on the intermediate transfer member. The ink receptive particle layer is captured on the surface of the ink receptive particle layer, and is fixed to the ink receptive particle surface and the internal particle void so that the distribution in the depth direction is reduced.

  For example, when it is desired to provide the particle layer 16C as the protective layer on the image layer 16B as the final image, the ink receiving particle layer 16A has a thickness of about three layers, and the uppermost layer is imaged with ink. For example (see FIG. 7A), the two particle layers 16C not subjected to image formation are formed on the image layer 16B as a protective layer after the transfer and fixing (see FIG. 7B).

  Alternatively, in the case of forming an image with a high ink ejection amount, such as a secondary color or tertiary color image, the ink receptive particle layer can hold an ink liquid component (solvent or dispersion medium) and a recording material (for example, Ink-receptive particles 16 are laminated so that a sufficient number of particles can be captured and not reach the lowermost layer. In this case, the image forming material (pigment) is not exposed on the surface of the image layer after the transfer and fixing, and the ink receiving particles 16 that do not perform image formation may be formed on the image surface as a protective layer.

  Next, the ink jet recording head 20 applies ink droplets 20A to the ink receiving particle layer 16A. The ink jet recording head 20 applies ink droplets 20A to predetermined positions based on predetermined image information.

  Finally, the recording medium 8 and the intermediate transfer body 12 are sandwiched by the transfer fixing device 22, and pressure and heat are applied to the ink receiving particle layer 16A, whereby the ink receiving particle layer 16A is transferred onto the recording medium 8. .

  The transfer fixing device 22 includes a heating roll 22A containing a heating source and a pressure roll 22B facing each other with the intermediate transfer body 12 interposed therebetween. The heating roll 22A and the pressure roll 22B are in contact with each other to form a contact portion. As the heating roll 22A and the pressure roll 22B, a product in which the outer surface of the aluminum core is coated with silicone rubber and further coated with a PFA tube can be used.

  Since the ink receiving particle layer 16A is heated by the heater and pressure is applied at the contact portion between the heating roll 22A and the pressure roll 22B, the ink receiving particle layer 16A is transferred and fixed to the recording medium 8.

  At this time, the organic resin particles constituting the ink receptive particles 16 in the non-image area were softened (or melted) by being heated to the glass transition temperature Tg) or higher, and formed on the surface of the intermediate transfer body 12 by pressure. The ink receiving particle layer 16 </ b> A is released from the release layer 14 </ b> A, and is transferred and fixed onto the recording medium 8. Then, the ink receiving particle layer 16 </ b> A is released from the release layer 14 </ b> A formed on the surface of the intermediate transfer body 12 by pressure, and is transferred onto the recording medium 8. At this time, the transfer fixing property is improved by heating. In the present embodiment, the surface of the heating roll 22A is controlled at 160 ° C. At this time, the ink liquid component (solvent or dispersion medium) held in the ink receiving particle layer 16A is held and fixed in the ink receiving particle layer 16A as it is after the transfer. Further, the intermediate transfer body 12 may be preheated before the transfer fixing device 22.

  In addition, as the recording medium 8, a permeation medium (for example, plain paper, ink jet coated paper, etc.) and a non-penetration medium (for example, art paper, resin film, etc.) can be applied. The recording medium is not limited to these, and includes industrial products such as semiconductor substrates.

  Hereinafter, the image forming process of the recording apparatus according to the embodiment will be described in more detail. In the recording apparatus according to the present embodiment, as shown in FIG. 6, the release layer 14 </ b> A can be formed on the surface of the intermediate transfer body 12 by the release layer supply device 14. If the material of the intermediate transfer body 12 is aluminum or PET base, it is particularly desirable to form the release layer 14A. Alternatively, a fluororesin / silicone rubber-based material may be used so that the surface of the intermediate transfer body 12 has releasability.

  Next, the surface of the intermediate transfer member 12 is charged to a polarity opposite to that of the ink receiving particles 16 by the charging device 28. Thereby, the ink receiving particles 16 supplied by the supply roll 18 </ b> A of the particle supply device 18 can be electrostatically adsorbed to form a layer of the ink receiving particles 16 on the surface of the intermediate transfer body 12.

  Next, the ink receiving particles 16 are formed as a layer on the surface of the intermediate transfer body 12 by the supply roll 18 </ b> A of the particle supply device 18. For example, the formed ink receiving particle layer 16A is formed to have a thickness in which the ink receiving particles 16 are overlapped by about three layers. That is, the thickness of the ink receiving particle layer 16A transferred to the recording medium 8 is controlled by controlling the ink receiving particle layer 16A to a desired thickness by the gap between the charging blade 18B and the supply roll 18A as described above. To do. Alternatively, it may be controlled by the peripheral speed ratio between the supply roll 18A and the intermediate transfer body 12.

  Next, ink droplets 20A are ejected onto the formed ink receptive particle layer 16A by an ink jet recording head 20 of each color driven by a piezoelectric (piezo) or thermal method, and an image is formed on the ink receptive particle layer 16A. Layer 16B is formed. The ink droplets 20A ejected from the ink jet recording head 20 are driven into the ink receiving particle layer 16A, and the liquid component of the ink is quickly absorbed into the gaps between the ink receiving particles 16 and the gaps constituting the ink receiving particles 16. At the same time, the recording material (for example, pigment) is also captured on the surface of the ink receiving particles 16 (constituting particles) or in the gaps between the particles constituting the ink receiving particles 16.

  At this time, the ink liquid component (solvent or dispersion medium) contained in the ink droplet 20A permeates the ink receptive particle layer 16A, but the recording material such as a pigment is captured on the surface of the ink receptive particle layer 16A or the interparticle gap. The That is, the ink liquid component (solvent or dispersion medium) may penetrate to the back surface of the ink receiving particle layer 16A, but the recording material such as a pigment does not penetrate the back surface of the ink receiving particle layer 16A. Thereby, when the recording material 8 is transferred to the recording medium 8, the particle layer 16C into which the recording material such as the pigment does not penetrate forms a layer on the image layer 16B, so that the particle layer 16C encloses the surface of the image layer 16B. It becomes a protective layer, and an image in which a recording material (for example, a color material such as a pigment) is not exposed on the surface can be formed.

  Next, a color image is formed on the recording medium 8 by transferring / fixing the ink receiving particle layer 16A on which the image layer 16B is formed from the intermediate transfer body 12 onto the recording medium 8. The ink receiving particle layer 16 </ b> A on the intermediate transfer body 12 is heated and pressed by a transfer fixing device (transfer fixing roll) 22 heated by a heating means such as a heater and transferred onto the recording medium 8.

  At this time, the glossiness may be controlled by adjusting the unevenness of the image surface by adjusting heating and pressurization as described later. Further, the glossiness may be controlled by performing cooling peeling.

  Residual particles 16D remaining on the surface of the intermediate transfer member 12 after the ink-receptive particle layer 16A is peeled off are collected by the cleaning device 24 (see FIG. 5), and the surface of the intermediate transfer member 12 is charged again by the charging device 28. Then, the ink receiving particles 16 are supplied to form the ink receiving particle layer 16A.

  Here, FIG. 7 shows a particle layer used for image formation according to the embodiment of the present invention. As shown in FIG. 7A, a release layer 14 A is formed on the surface of the intermediate transfer body 12.

  Next, the ink receiving particles 16 are formed as a layer on the surface of the intermediate transfer body 12 by the particle supply device 18. The ink receptive particle layer 16A formed as described above preferably has a thickness in which the ink receptive particles 16 are overlapped by about three layers. The thickness of the ink receiving particle layer 16A transferred to the recording medium 8 is controlled by controlling the ink receiving particle layer 16A to a desired thickness. At this time, the surface of the ink receiving particle layer 16A is leveled so as not to hinder the image formation (formation of the image layer 16B) by the ejection of the ink droplet 20A.

  Further, the recording material such as pigment contained in the ejected ink droplet 20A penetrates to about 1/3 or more and half or less of the ink receiving particle layer 16A as shown in FIG. A particle layer 16C that does not penetrate the recording material remains.

  The ink receiving particle layer 16A formed on the recording medium 8 by heating and pressure transfer by the transfer fixing device (transfer fixing roll) 22 is a particle layer containing no ink on the image layer 16B as shown in FIG. 7B. Since 16C exists, the image layer 16B does not appear directly on the surface and functions as a kind of protective layer. For this reason, at least the ink receiving particles 16 after fixing must be transparent.

  Since the particle layer 16C is heated and pressed by the transfer fixing device (transfer fixing roll) 22, the surface can be flattened, and the glossiness of the image surface can be controlled by heating and pressing.

  Further, drying of the ink liquid component (solvent or dispersion medium) trapped inside the ink receiving particles 16 by heating may be promoted.

  The ink liquid component (solvent or dispersion medium) received / held in the ink receiving particle layer 16A is held in the ink receiving particle layer 16A even after transfer fixing, and is removed by natural drying.

  Through the above steps, image formation is completed. With respect to the intermediate transfer body 12, there are foreign particles such as residual particles 16 </ b> D remaining on the intermediate transfer body 12 after the ink receiving particles 16 are transferred to the recording medium 8, or paper dust released from the recording medium 8. May be removed by the cleaning device 24.

  Further, a static elimination device 29 may be arranged downstream of the cleaning device 24. For example, a conductive roll is used as the static elimination device 29 and is sandwiched between the driven roll 31 (ground) and a voltage of about ± 3 kV and 500 Hz is applied to the surface of the intermediate transfer body 12 to neutralize the surface of the intermediate transfer body 12. .

  Various other device conditions such as the above-mentioned charging voltage, particle layer thickness, fixing temperature, etc. are optimized because the optimum conditions are determined by the ink receiving particles 16 or ink composition, ink discharge amount, etc. To do.

<Each component>
Next, components of each step of the embodiment will be described in detail.

<Intermediate transfer member>
The intermediate transfer body 12 on which the ink receptive particle layer is formed may be belt-shaped as in the embodiment, or may be cylindrical (drum-shaped). In order to supply and hold the ink receiving particles on the surface of the intermediate transfer member by electrostatic force, the outer peripheral surface of the intermediate transfer member needs to have a semiconductive or insulating particle holding property. As the electrical characteristics of the surface of the intermediate transfer member, in the case of semi-conductivity, the surface resistivity is 10 ¹⁰ Ω / □ or more and 10 ¹⁴ Ω / □ or less, the volume resistivity is 10 ⁹ Ω · cm or more and 10 ¹³ Ω · cm or less, In the case of insulation, a member having a surface resistivity of 10 ¹⁴ Ω / □ or more and a volume resistivity of 10 ¹³ Ω · cm or more is used.

  In the case of a belt shape, the base material can be driven by a belt in the apparatus, has the required mechanical strength, and particularly has the required heat resistance when using heat during transfer / fixing. Good. Specifically, polyimide, polyamideimide, aramid resin, polyethylene terephthalate, polyester, polyethersulfone, stainless steel and the like are used.

  In the case of a drum shape, aluminum, stainless steel, etc. can be considered as the base material.

  In order to exhibit the heating method by electromagnetic induction in the fixing process in the transfer fixing device (transfer fixing roll) 22, a heat generating layer may be formed on the intermediate transfer body 12 instead of the transfer fixing device (transfer fixing roll) 22. Good. A metal that generates electromagnetic induction is used for the heat generating layer. For example, nickel, iron, copper, aluminum, chromium, or the like can be selected.

<Particle supply process>
First, the release agent supply device 14 forms a release layer 14A of the release agent 14D on the surface of the intermediate transfer body 12 before the ink receiving particles 16 are supplied.

  The method for supplying the release layer 14A includes a release agent 14D, a release agent 14D supplied to the release agent supply member, and the release member 14D supplied to the surface of the intermediate transfer body 12 by the supply member. A method of forming the layer 14A, a method of forming the release layer 14A on the surface of the intermediate transfer body 12 by a supply member impregnated with the release agent 14D, and the like are used.

  Examples of the release agent 14D include release materials such as silicone oil, fluorine oil, polyalkylene glycol, and surfactant.

Examples of the silicone oil include straight silicone oil and modified silicone oil.
Examples of the straight silicone oil include dimethyl silicone oil and methyl hydrogen silicone oil.
Examples of the modified silicone oil include methylstyryl-modified oil, alkyl-modified oil, higher fatty acid ester-modified oil, fluorine-modified oil, and amino-modified oil.
Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, and polybutylene glycol. Among these, polypropylene glycol is preferable.
Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Among these, a nonionic surfactant is desirable.

  The viscosity of the release agent 14D is preferably, for example, from 5 mPa · s to 200 mPa · s, more preferably from 5 mPa · s to 100 mPa · s, and even more preferably from 5 mPa · s to 50 mPa · s.

The viscosity is measured as follows. The viscosity of the ink obtained was measured using Rheomatt 115 (manufactured by Contraves) as a measuring device. The measurement was performed by placing the sample in a measurement container and mounting it on the apparatus by a predetermined method, under the conditions of a measurement temperature of 40 ° C. and a shear rate of 1400 s ⁻¹ .

  The surface tension of the release agent 14D is, for example, in the range of 40 mN / m or less (desirably 30 mN / m or less, more desirably 25 mN / m or less).

  The surface tension is measured as follows. In an environment of 23 ± 0.5 ° C. and 55 ± 5% RH, the surface tension of the obtained sample was measured using a Wilhelmy type surface tension meter (manufactured by Kyowa Interface Science Co., Ltd.).

  The boiling point of the release agent 14D is, for example, in the range of 250 ° C. or higher (preferably 300 ° C. or higher, more preferably 350 ° C. or higher) under 760 mmHg.

  The boiling point is measured as follows. Measurement was performed according to JIS K2254, and the initial boiling point was used as the boiling point.

  Next, the charging device 28 charges the surface of the intermediate transfer body 12 to a polarity opposite to that of the ink receiving particles 16. Then, an ink receptive particle layer 16 </ b> A is formed on the surface of the charged intermediate transfer body 12. At this time, as a method of forming the ink receptive particle layer 16A, a method of supplying a general electrophotographic toner to the photoreceptor can be applied. That is, charges are previously supplied to the surface of the intermediate transfer body 12 by a general electrophotographic charging method (charging by the charging device 28, etc.). The ink receiving particles 16 are triboelectrically charged (one-component triboelectric charging method or two-component method) with a polarity opposite to the charge on the surface of the intermediate transfer member 12.

  The ink receiving particles 16 held on the supply roll 18A form an electric field with the surface of the intermediate transfer body 12, and are moved / supplied onto the intermediate transfer body 12 by electrostatic force and held. At this time, the thickness of the ink receptive particle layer 16A may be controlled by the thickness of the image layer 16B formed on the ink receptive particle layer 16A (in accordance with the amount of ink to be applied). At this time, the absolute value of the charge amount of the ink receiving particles 16 is desirably in the range of 5 μc / g to 50 μc / g.

  Here, the thickness of the ink receiving particle layer 16A is desirably 1 μm or more and 100 μm or less, more desirably 1 μm or more and 50 μm or less, and further desirably 5 μm or more and 25 μm or less. Further, the porosity in the ink receptive particle layer (that is, the void ratio between the ink receptive particles + the void ratio in the ink receptive particles (trap structure)) is preferably 10% or more and 80% or less. Is from 30% to 70%, more preferably from 40% to 60%.

  Hereinafter, a particle supply process corresponding to a one-component supply (development) method will be described.

  The ink receiving particles 16 are supplied to the supply roll 18A, the thickness of the particle layer is regulated by the charging blade 18B and charged.

  The charging blade 18B has a function of regulating the layer thickness of the ink receiving particles 16 on the surface of the supply roll 18A. For example, the thickness of the ink receiving particles 16 on the surface of the supply roll 18A is changed by changing the pressure applied to the supply roll 18A. To change. For example, the thickness of the ink receiving particles 16 on the surface of the supply roll 18A is, for example, one layer, and the thickness of the ink receiving particles 16 formed on the surface of the intermediate transfer body 12 is approximately one layer. Further, the pressing force of the charging blade 18B is controlled to be low, the thickness of the ink receiving particles 16 formed on the surface of the supply roll 18A is increased, and the thickness of the ink receiving particles formed on the surface of the intermediate transfer body 12 is increased. It may be increased.

  As another method, when the peripheral speed of the supply roll 18A that forms, for example, one particle layer on the surface of the intermediate transfer body 12 and the intermediate transfer body 12 is set to 1, the peripheral speed of the supply roll 18A is increased and the intermediate transfer is performed. It can be controlled to increase the number of ink receptive particles 16 supplied on the body 12 and increase the thickness of the ink receptive particle layer on the intermediate transfer body 12. It is also possible to control by combining the above methods. In the above configuration, for example, the ink receiving particles 16 are negatively charged, and the surface of the intermediate transfer body 12 is positively charged.

  By controlling the layer thickness of the ink receiving particle layer in this way, it is possible to form a pattern whose surface is covered with a protective layer while suppressing consumption of the ink receiving particle layer.

As the charging roll in the charging device 28, an elastic layer in which a conductivity imparting material is dispersed is formed on the outer peripheral surface of a rod-like or pipe-like member made of aluminum, stainless steel or the like, and the volume resistivity is 10 ⁶ Ω · cm or more 10 A roll having a diameter of 10 mm to 25 mm adjusted to about ⁸ Ω · cm or less can be used.

  The elastic layer is made of a resin material such as urethane resin, thermoplastic elastomer, epichlorohydrin rubber, ethylene-propylene-diene copolymer rubber, silicone rubber, acrylonitrile-butadiene copolymer rubber, or polynorbornene rubber. A preferred material used in the above mixture is urethane foam resin.

  As the foamed urethane resin, a resin obtained by mixing and dispersing a hollow body such as a hollow glass bead or a thermal expansion type microcapsule in a urethane resin to provide a closed cell structure is desirable.

  Furthermore, the surface of the elastic layer may be covered with a water-repellent coating layer having a thickness of 5 μm to 100 μm.

  A DC power source is connected to the charging device 28, and the driven roll 31 is electrically connected to the frame ground. The charging device 28 is driven while the intermediate transfer body 12 is sandwiched between the charging roll 31 and a predetermined potential difference is generated between the charging apparatus 28 and the grounded driven roll 31 at the pressing position.

<Marking process>
Based on the image signal, ink droplets 20A are ejected from the ink jet recording head 20 to the layer of ink receptive particles 16 (ink receptive particle layer 16A) formed on the surface of the intermediate transfer body 12, thereby forming an image. The ink droplets 20A ejected from the ink jet recording head 20 are driven into the ink receiving particle layer 16A, and the ink droplets 20A are quickly absorbed by the interparticle voids formed in the ink receiving particles 16, and the recording material (for example, , The pigment) is trapped (trapped) on the surface of the ink receiving particles 16 or the interparticle voids constituting the ink receiving particles 16.

  In this case, it is desirable to capture (trap) many recording materials (for example, pigments) on the surface of the ink receiving particle layer 16A. The inter-particle voids in the ink-receptive particles 16 exhibit a filter effect, trapping a recording material (for example, pigment) on the surface of the ink-receptive particle layer 16A, and trapping in the inter-particle voids in the ink-receptive particles 16 ( It is expressed by being trapped and fixed.

  In order to reliably trap the recording material (for example, pigment) on the surface of the ink receiving particle layer 16 </ b> A and the interparticle voids in the ink receiving particle 16, the ink and the ink receiving particle 16 are reacted to thereby record the recording material ( For example, a method of quickly insolubilizing (aggregating) the pigment) may be employed. Specifically, it is possible to apply a reaction between the ink and the polyvalent metal salt or a pH reaction type as the reaction.

  In addition, a line type ink jet recording head having a width equal to or larger than the width of the recording medium is desirable. However, using a conventional scan type ink jet recording head, images are sequentially formed on the particle layer formed on the intermediate transfer member. It may be formed. The ink discharge means of the inkjet recording head 20 is not limited as long as it is a means capable of discharging ink, such as a piezoelectric element drive type and a heating element drive type. As the ink itself, an ink using a conventional dye as a coloring material can be used, but a pigment ink is desirable.

  When the ink receiving particles 16 are reacted with the ink, the treatment is performed with an aqueous solution containing an aggregating agent (for example, a polyvalent metal salt or an organic acid) that gives the effect of aggregating the pigment by reacting the ink receiving particles 16 with the ink. Use and dry.

<Transfer process>
The ink receiving particle layer 16 </ b> A that receives the ink droplet 20 </ b> A and has an image formed thereon is transferred and fixed to the recording medium 8, thereby forming an image on the recording medium 8. The transfer and fixing may be performed by different processes, but it is desirable that the transfer and fixing be performed substantially simultaneously. Fixing includes either a method of heating or pressurizing the ink receptive particle layer 16A, or a method of using both heating and pressurization. Preferably, a method of performing heating / pressing substantially simultaneously is preferable.

  Further, by controlling the heating / pressurization, it is possible to control the surface physical properties of the ink receiving particle layer 16A and to control the gloss (glossiness). Further, when the recording medium 8 onto which the image (ink-receptive particle layer 16A) has been transferred after being heated / pressurized is peeled off from the intermediate transfer body 12, the ink-receptive particle layer 16A may be peeled off after being cooled. Good. The cooling method may be forced cooling such as natural cooling or air cooling. For these processes, the intermediate transfer member 12 preferably has a belt shape.

  The ink image is formed on the surface layer of the ink receiving particle 16 layer formed on the intermediate transfer body 12 (the recording material (pigment) is trapped on the surface of the ink receiving particle layer 16A) and transferred to the recording medium 8. By doing so, the ink image is preferably formed so as to be protected by the particle layer 16 </ b> C of the ink receiving particles 16.

  The ink liquid component (solvent or dispersion medium) received / held in the ink receiving particle 16 layer is held in the ink receiving particle 16 layer even after the transfer and fixing, and is removed by natural drying.

<Cleaning process>
In order to refresh the surface of the intermediate transfer body 12 to enable repeated use, a process of cleaning the surface with the cleaning device 24 is necessary. The cleaning device 24 includes a cleaning unit and a particle transport / recovery unit (not shown). By the above cleaning, the ink receiving particles 16 (residual particles 16D) remaining on the surface of the intermediate transfer body 12 are removed. The adhering matter adhering to the surface of the intermediate transfer body 12 such as the foreign matter (paper dust of the recording medium 8) is removed. The recovered residual particles 16D may be reused.

<Static removal process>
Before forming the release layer 14 </ b> A, the surface of the intermediate transfer body 12 may be neutralized using the neutralization device 29.

  In the recording apparatus according to the embodiment described above, after the release agent 14D is supplied to the surface of the intermediate transfer body 12 by the release agent supply apparatus 14 to form the release layer 14A, the surface of the intermediate transfer body by the charging device 28. Is charged. Next, the ink receiving particles 16 are supplied from the particle supply device 18 to the region where the release layer of the intermediate transfer body 12 is formed and charged, thereby forming a particle layer. Then, ink droplets are ejected onto the particle layer by the ink jet recording head 20 to form an image. As a result, ink is received by the ink receiving particles 16. Next, the recording medium 8 is overlapped with the intermediate transfer body 12, and pressure and heat are applied by the transfer fixing device 22 to transfer and fix the ink receiving particle layer on the recording medium 8.

  Note that the recording apparatus is not limited to the intermediate transfer system, and may be another form that supplies ink receiving particles described below directly onto the recording medium.

  FIG. 8 is a configuration diagram showing a recording apparatus according to another embodiment. FIG. 9 is a configuration diagram illustrating a main part of a recording apparatus according to another embodiment. In the following other embodiments, the case where composite particles are applied as ink receiving particles to be described later is described.

  As shown in FIGS. 8 and 9, the recording apparatus 11 according to another embodiment includes an endless belt-like conveyance belt 13. The conveyance belt 13 rotates and conveys the recording medium 8 sent from a storage container (not shown).

  First, an ion flow control electrostatic recording head 100 (hereinafter abbreviated as “electrostatic recording head 100”) controls a recording medium 8 being transported by the transport belt 13 to control the ion flow due to discharge. An electrostatic latent image is formed by irradiating on the surface 8. (See FIG. 10A).

  The electrostatic receptive image formed on the recording medium 8 is visualized by the ink receptive particle supply device 18 to form an ink receptive particle layer 16A composed of the ink receptive particles 16. (See FIG. 10B).

  The preliminary fixing device 150 preheats and fixes the ink receiving particle layer 16 </ b> A formed on the recording medium 8.

  From the ink-receiving particle layer 16A that has been preheated and fixed, image data from the ink jet recording heads 20K, 20C, 20M, and 20Y for each color of black (K), cyan (C), magenta (M), and yellow (Y). The ink droplets 20A (see FIG. 9) for each color are ejected to form an ink image. (See FIG. 10C). Hereinafter, when it is necessary to distinguish each color, Y, M, C, and K are appended after the reference numerals, but Y, M, C, and K are omitted when it is not particularly necessary to distinguish each color.

  The ink receiving particle layer 16A on which the ink image is formed by the ejection of the ink droplet 20A is fixed on the recording medium 8 by the fixing device 23 applying pressure and heat.

  The electrostatic recording head 100 and the ink jet recording head 20 are so-called FWA (Full Width Array) type recording heads that are more than the width of the recording medium 8.

  Next, details of each component and the image forming process will be described.

  The recording medium 8 is transported by an endless belt-shaped transport belt 13. In the present embodiment, the recording medium 8 is conveyed while being attracted to the conveying belt 13.

  Here, as an example of a method for adsorbing the recording medium 8 to the conveyance belt 13, for example, a suction mechanism in which a hole (not shown) is provided in the conveyance belt 13 and sucked and adsorbed from the hole can be cited. In addition, the method of adsorbing the recording medium 8 to the conveyance belt 13 may be, for example, a method of adsorbing with the adhesive force, or a method of electrostatically adsorbing the recording medium 8 to the conveyance belt 13.

  An electrostatic recording head 100 that forms an electrostatic latent image on the recording medium 8 being transported to the transport belt 13 is disposed above the recording medium 8 with an interval on the upstream side in the transport direction. .

  In the electrostatic recording head 100, a plurality of drive electrodes 104 are provided in parallel to each other on the surface of a flat rectangular insulating substrate 102, and a plurality of controls are provided on the back surface thereof so as to intersect with these drive electrodes 104. An electrode 106 is provided. The drive electrode 104 and the control electrode 106 form a matrix (lattice). The control electrode 106 is formed with a circular opening 106 </ b> A at a position intersecting with the drive electrode 104. A screen electrode 108 is provided on the lower surface of the control electrode 106 with an insulating substrate 101 interposed therebetween. In the insulating substrate 101 and the screen electrode 108, a space 111 and an ion derivation opening 110 are formed at a position corresponding to the opening 106A of the control electrode 106.

  A high frequency high voltage is applied between the drive electrode 104 and the screen electrode 108 by the AC power source 112. On the other hand, a pulse voltage corresponding to image information is applied to the control electrode 106 by an ion control power source 114. Further, a DC voltage is applied to the screen electrode 108 by a DC power source 116.

  Then, by applying an alternating electric field between the drive electrode 104 and the control electrode 106 thus insulated, a creeping corona discharge is induced in the space 111, and ions generated by the creeping corona discharge are caused to flow between the control electrode 106 and the control electrode 106. Acceleration or absorption by an electric field formed between the screen electrode 108 and the ion flow emission from the ion extraction opening 110 is controlled, and ions corresponding to an image signal (ink image) (in this embodiment) An electrostatic latent image (see FIG. 10A) is formed on the surface of the recording medium 8 by using positive ions.

  In the next step, the potential of the electrostatic latent image is determined by the electrostatic force generated by the electric field formed by the particle supply roll 18A of the ink receiving particle supply device 18 and the electrostatic latent image formed on the recording medium 8. 16 may be any potential that can be supplied / adsorbed to the recording medium 8.

  The electrostatic recording head 100 can select a region where an electrostatic latent image is formed. Therefore, the electrostatic latent image formed on the surface of the recording medium 8 is a region where an ink image is formed. For example, when the formed image is the letter “A”, it is conceptually shown in FIG.

  The recording medium 8 on which the electrostatic latent image is formed is sent to the ink receiving particle supply device 18 to visualize the electrostatic latent image, and the ink receiving particle layer 16A corresponding to the electrostatic latent image is formed. Form. (See FIG. 10B). Thereby, the ink receptive particle layer 16A is formed on the recording medium 8 only in the ink image region formed based on the image signal (the ink receptive particle layer 16A is almost formed in the non-image portion region). Not)

  Next, the description returns to the image forming process.

  Next, as shown in FIG. 10A, the ink receiving particle layer 16 </ b> A formed on the recording medium 8 is preliminarily fixed by the preliminary fixing device 150.

  The ink receiving particle layer 16 </ b> A formed on the recording medium 8 is fixed on the recording medium 8 by electrostatic force. Therefore, if the ink droplet 20A is ejected from the inkjet recording head 20 into the ink receiving particle layer 16A in the next step as it is, the ink receiving particle layer 16A may be disturbed depending on the amount of ink. For this reason, the ink receiving particle layer 16A is preliminarily fixed in advance to temporarily fix the ink receiving particle 16 on the surface of the recording medium 8.

  In addition, the preliminary fixing prevents the ink receiving particles 16 from being scattered by the ink droplets 20 </ b> A being ejected and the nozzle surface 20 </ b> B of the inkjet recording head 20 from being contaminated.

  The preliminary heating in the preliminary fixing device 150 is at a lower temperature than the fixing heating in the final fixing device 23. That is, the preliminary fixing in the preliminary fixing device 150 does not completely melt the resin particles in the ink receiving particles 16 and fix them by pressure, but leaves gaps between the particles, and between the particles and between the particles and the recording medium. It is sufficient to bind the surface. As a result, the ink droplet 20A is preliminarily fixed to an acceptable level.

  The preliminary fixing device 150 can be a general heat fixing device (fuser) used in an electrophotographic image forming apparatus. Further, in addition to the heat fixing device used in the electrophotographic image forming apparatus, a heater heating method, an oven method, an electromagnetic induction heating method, or the like can be used.

  Next, the recording medium 8 on which the ink receptive particle layer 16A is preliminarily fixed is conveyed below the ink jet recording head 20.

  Then, based on the image data, ink droplets 20A are ejected from the ink jet recording head 20, and are ejected onto the ink receiving particle layer 16A formed on the surface of the recording medium 8, thereby forming an ink image. (FIG. 10C). At this time, the ink is received by the ink receiving particles 16.

  In order to write an image at a high speed, a line type ink jet recording head having a width equal to or larger than the width of the recording medium is desirable as in the present embodiment, but an image may be sequentially formed using a scan type ink jet recording head. The ink discharge means of the inkjet recording head 20 is not limited as long as it is a means capable of discharging ink, such as a piezoelectric element driving type and a heating element driving type.

  Next, the recording medium 8 is peeled off from the conveying belt 13 and sent to the fixing device 23, and pressure and heat are applied to the ink receiving particle layer 16 </ b> A, whereby the ink receiving particle layer 16 </ b> A is formed on the recording medium 8. To settle.

  The fixing device 23 includes a heating roll 23A containing a heating source and a pressure roll 23B facing the heating roll 23A. The heating roll 23A and the pressure roll 23B are in contact with each other to form a contact portion. As the heating roll 23A and the pressure roll 23B, for example, the outer surface of an aluminum core is coated with silicone rubber, and further coated with a PFA tube. The configuration is the same as that of a fixing device (fuser) used in an electrophotographic image forming apparatus. Further, in addition to the heat fixing device used in the electrophotographic image forming apparatus, a heater heating method, an oven method, an electromagnetic induction heating method, or the like can be used.

  When the recording medium 8 passes through the contact portion between the heating roll 23A and the pressure roll 23B, the ink receiving particle layer 16A is heated and pressure is applied, and the ink receiving particle layer 16A is fixed to the recording medium 8. . Note that not only a method using both heating and pressurization but also a method using only heating or only pressurization may be used. However, it is desirable to perform heating and pressurization simultaneously.

  Through the above steps, image formation is completed, and the recording medium 8 is discharged out of the apparatus.

  In the recording apparatus 11 according to another embodiment described above, an electrostatic latent image is formed by the electrostatic recording head 100 while the recording medium 8 is conveyed by the conveying belt 13, and a particle supply device is applied to the electrostatic latent image. The ink receiving particles 16 are supplied from 18 to form a particle layer. Then, ink droplets are ejected onto the particle layer by the ink jet recording head 20 to form an image. As a result, ink is received by the ink receiving particles 16. Next, after the recording medium 8 is peeled from the conveying belt 13, the ink receiving particle layer is fixed on the recording medium 8 by applying pressure and heat by the fixing device 23. Except for what has been described above, the recording apparatus according to the above-described embodiment is the same as the recording apparatus according to the above-described embodiment, and thus description thereof is omitted.

  As described above, in the embodiment, the ink droplets 20A are selectively ejected based on the image data from the inkjet recording heads 20 of black, yellow, magenta, and cyan so that a full color image is recorded on the recording medium 8. However, embodiments of the present invention are not limited to recording characters and images on a recording medium. That is, the droplet discharge device according to the embodiment of the present invention can be applied to all droplet discharge (ejection) devices used industrially.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.

[Example A]
-Particle AA-
Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 50 mol%): 95 parts by mass Magnesium nitrate hexahydrate (polyvalent metal: 10 wt% aqueous solution): 10 parts by mass Propanol: 1000 parts by mass The above materials were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. This obtained particle | grains Aa1.

-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 50 mol%): 95 parts by mass-Sodium hydroxide (alkali metal): 12.5 parts by mass-Ion-exchanged water: 1000 parts by mass Were mixed and stirred. 9.1 parts by mass of the particle Aa1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. This obtained particle | grains Aa2.

Particle Aa2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Particles were prepared.

-Particle AB-
-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 60 mol%): 95 parts by mass-Calcium nitrate tetrahydrate (10 wt% aqueous solution): 15 parts by mass-2-propanol: 1000 parts by mass Part The above materials were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. This obtained particle | grains Ab1.

-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 55 mol%): 95 parts by mass-Lithium hydroxide-Monohydrate: 20 parts by mass-Ion exchange water: 1000 parts by mass Mixed and stirred. 14 parts by mass of the particle Ab1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. This obtained particle | grains Ab2.

Particle Ab2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AC-
Styrene / 2-ethylhexyl acrylate / acrylic acid copolymer: 95 parts by mass (polar monomer ratio 40 mol%)
Magnesium nitrate hexahydrate (10 wt% aqueous solution): 1 part by mass 2-propanol: 1000 parts by mass The above materials were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. Thereby, particles Ac1 were obtained.

-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 50 mol%): 95 parts by mass-Potassium hydroxide: 2 parts by mass-Ion exchange water: 1000 parts by mass The above materials were mixed and stirred. . 40 parts by mass of the particle Ac1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Ac2 were obtained.

Particle Ac2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AD-
-Styrene / n-butyl methacrylate / maleic acid copolymer (polar monomer ratio 20 mol%): 95 parts by mass-Aluminum lactate (10 wt% aqueous solution): 5 parts by mass-2-propanol: 1000 parts by mass The above materials are mixed And stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. Thereby, particles Ad1 were obtained.

-Styrene / n-butyl methacrylate / maleic acid copolymer (polar monomer ratio 20 mol%): 95 parts by mass-Sodium hydroxide: 3 parts by mass-Ion exchange water: 1000 parts by mass The above materials were mixed and stirred. . 55 parts by mass of the particle Ad1 was added to this mixed liquid, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. This obtained particle | grains Ad2.

Particle Ad2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AE-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 12.5 mol%): 95 parts by mass Zinc salicylate trihydrate (10 wt% aqueous solution): 12.5 parts by mass Propanol: 1000 parts by mass The above materials were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. Thereby, particles Ae1 were obtained.

Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 12.5 mol%): 95 parts by mass Lithium hydroxide monohydrate: 2.3 parts by mass Ion-exchanged water: 1000 parts by mass Part The above materials were mixed and stirred. 22 parts by mass of the particle Ae1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Ae2 were obtained.

Particle Ae2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AF-
Styrene / n-butyl acrylate / methacrylic acid copolymer (polar monomer ratio 87.5 mol%): 95 parts by mass Magnesium lactate trihydrate (10 wt% aqueous solution): 7.5 parts by mass Propanol: 1000 parts by mass The above materials were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. Thereby, particles Af1 were obtained.

-Styrene / n-butyl acrylate / methacrylic acid copolymer (polar monomer ratio 87.5 mol%): 80 parts by mass- Styrene / n-butyl acrylate / methacrylic acid copolymer (polar monomer ratio 7.5 mol) %): 15 parts by mass, potassium hydroxide: 7.5 parts by mass, ion-exchanged water: 1000 parts by mass The above materials were mixed and stirred. 162 parts by mass of the particle Af1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Af2 were obtained.

Particle Af2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AG-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Magnesium nitrate hexahydrate: 3 parts by mass 2-propanol: 1000 parts by mass The above materials are mixed And stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. Thereby, particles Ag1 were obtained.

Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 45 mol%): 95 parts by mass Sodium hydroxide: 13 parts by mass Ion exchange water: 1000 parts by mass The above materials were mixed and stirred. . In this mixed solution, 10.4 parts by mass of the particle Ag1 was added, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. This obtained particle | grains Ag2.

-Particle Ag2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

"
-Particle AH-
Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 77.5 mol%): 95 parts by mass Magnesium nitrate hexahydrate: 2 parts by mass 2-propanol: 1000 parts by mass Were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. Thereby, particles Ah1 were obtained.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 77.5 mol%): 95 parts by mass-Lithium hydroxide-Monohydrate: 16 parts by mass-Ion exchange water: 1000 parts by mass The materials were mixed and stirred. 3.7 parts by mass of the particle Ah1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Ah2 were obtained.

Particle Ah2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AI-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Calcium nitrate tetrahydrate (10 wt% aqueous solution): 100 parts by mass 2-propanol: 1000 parts by mass Part The above materials were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. Thereby, particles Ai1 were obtained.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass Stir. 5.1 parts by mass of the particle Ai1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Ai2 were obtained.

Particle Ai2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AJ-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Calcium nitrate tetrahydrate (10 wt% aqueous solution): 25 parts by mass-2-propanol: 1000 parts by mass Part The above materials were mixed and stirred.

Then, to this mixture,
-Potassium hydroxide (10% aqueous solution): 125 parts by mass was added and stirring was continued. The obtained liquid mixture was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Aj1 were obtained.

Particle Aj1: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AK-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Calcium nitrate tetrahydrate (10 wt% aqueous solution): 100 parts by mass 2-propanol: 1000 parts by mass Part The above materials were mixed and stirred to obtain a mixed solution Ak1.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed and stirred. As a result, a mixed solution Ak2 was obtained.

  Using a double cylindrical needle, the mixed solution Ak1 was sent to the inner route and the mixed solution Ak2 was sent to the outer route. Then, while spraying droplets from the tip of the needle into a heating and drying furnace, the particles were dried to form particles. Furthermore, it classified using the airflow classifier. This obtained particle | grains Ak1.

Particles Ak1: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by weight Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AL-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Calcium nitrate tetrahydrate (10 wt% aqueous solution): 0.4 parts by mass 2-propanol: 1000 parts by mass The above materials were mixed and stirred to obtain a mixed solution Al1.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed and stirred. As a result, a mixed solution Al2 was obtained.

  The above materials were mixed and stirred. 5.1 parts by mass of the particle Ai1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Al1 were obtained.

-Particle Al 1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AM-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Calcium nitrate tetrahydrate (10 wt% aqueous solution): 192 parts by mass 2-propanol: 1000 parts by mass Part The above materials were mixed and stirred to obtain a mixed solution Am1.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed and stirred. As a result, a mixed solution Am2 was obtained.

  The above materials were mixed and stirred. 5.1 parts by mass of the particle Ai1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. This obtained particle | grains Am1.

-Particle Am1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AN-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Calcium nitrate tetrahydrate (10 wt% aqueous solution): 100 parts by mass 2-propanol: 1000 parts by mass Part The above materials were mixed and stirred to obtain a mixed solution An1.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Potassium hydroxide: 0.45 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed and stirred. As a result, a mixed solution An2 was obtained.

  The above materials were mixed and stirred. 5.1 parts by mass of the particle Ai1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. This obtained particle | grains An1.

Particle An1: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AO-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Calcium nitrate tetrahydrate (10 wt% aqueous solution): 100 parts by mass 2-propanol: 1000 parts by mass Part The above materials were mixed and stirred to obtain a mixed solution Ao1.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Potassium hydroxide: 17.3 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed and stirred. As a result, a mixed solution Ao2 was obtained.

  The above materials were mixed and stirred. 5.1 parts by mass of the particle Ai1 was added to the mixed solution, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.) and further classified with an airflow classifier. Thereby, particles Ao1 were obtained.

Particle Ao1: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AP-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Calcium nitrate tetrahydrate (10 wt% aqueous solution): 100 parts by mass 2-propanol: 1000 parts by mass Part The above materials were mixed and stirred. Next, after removing the solvent, the solid content was dried with a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier. This obtained particle | grains Ap1.

-Particle Ap1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AQ-
-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass Stir. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.), and further classified using an airflow classifier. This obtained particle | grains Aq1.

Particle Aq1: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Particle AR-
-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 7.5 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed. And stirred. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.), and further classified using an airflow classifier. This obtained particle | grains Ar1.

-Particle Ar 1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass Ink-receptive particles were prepared.

-Preparation of ink AA-
The following ink components were mixed, stirred, and then filtered using a membrane filter having a pore size of 5 μm to prepare an ink.
CB (Cabojet-300 / Cabot Corporation): 8% by mass
・ Styrene-acrylic acid copolymer: 1% by mass
・ Glycerin: 15% by mass
Propylene glycol: 10% by mass
・ 1,2-hexanediol: 5% by mass
・ Orphine E1010 (manufactured by Nissin Chemical): 1.5% by mass
-NaOH: appropriate amount-water: remainder The pH of the obtained ink was adjusted with an aqueous sodium hydroxide solution to be 7.3. The surface tension of the ink was 31 mN / m.

  Table 1 shows the characteristics of the ink receiving particles obtained above.

(Examples A1 to A15, Comparative Examples A1 to A3)
According to Table 1, the following evaluation was performed using each of the above particles (ink-receptive particles) and the following ink. The results are shown in Table 2. The amount of particles and ink applied was in accordance with Table 1.

-Preparation of ink AB-
The following ink components were mixed, stirred, and then filtered using a membrane filter having a pore size of 5 μm to prepare an ink.
・ C. I. Pigment Blue 15: 3: 7% by mass
-Styrene-acrylic acid copolymer: 2.5% by mass
・ Glycerin: 10% by mass
Propylene glycol: 10% by mass
・ 1,2-hexanediol: 5% by mass
・ Orphine E1010 (manufactured by Nissin Chemical): 1.5% by mass
-NaOH: appropriate amount-water: remainder The pH of the ink obtained was adjusted with an aqueous sodium hydroxide solution to 8.5. The surface tension of the ink was 31 mN / m.

(Evaluation)
-Fixability-
Fixability was evaluated as follows. The particles were dispersed on the PET film using a cake printer. Then, a 100% coverage pattern was formed on the PET film on which the particles were dispersed, with an image area ratio of 1200 dpi × 1200 dpi (dpi: number of dots per inch) using a piezo-type ink jet device. Thereafter, the particles to which ink was applied were transferred and fixed on plain paper (C2 paper: manufactured by Fuji Xerox Co., Ltd.) at a pressure of 10 ⁵ Pa and a temperature of 50 ° C., and left in a general environment for 24 hours. After leaving, press another plain paper (C2 paper: manufactured by Fuji Xerox Co., Ltd.) with a load of 4.9 × 10 ⁴ N / m ^{2 on} the printing surface and rub it. The sensory evaluation was carried out against the set limit sample.
The evaluation criteria are as follows.
◎: Dirt is not generated. ○: Dirt is hardly generated. △: Dirt is generated, but is at an acceptable level.

-Drying time (liquid absorption speed)-
The drying time (liquid absorption speed) was evaluated as follows. The particles were dispersed on the PET film using a cake printer. Then, a 100% coverage pattern was formed on the PET film on which the particles were dispersed, with an image area ratio of 1200 dpi × 1200 dpi (dpi: number of dots per inch) using a piezo-type ink jet device. Thereafter, plain paper (C2 paper: manufactured by Fuji Xerox Co., Ltd.) was pressed against the particles to which ink was applied at a pressure of 10 ⁵ Pa, and the time until transfer was stopped was measured.
The evaluation criteria are as follows.
A: Drying time is less than 0.5 seconds B: Drying time is less than 1 second Δ: Drying time is 1 second or more and less than 3 seconds X: Drying time is 3 seconds or more

-Optical density-
The optical density was evaluated as follows. An image was formed in the same manner as the evaluation of fixability, and the optical density of the image portion was measured using X-Rite 404 (manufactured by X-Rite).
The evaluation criteria are as follows.
◎: Optical density is 1.45 or more ○: Optical density is 1.4 or more and less than 1.45 Δ: Optical density is 1.3 or more and less than 1.4 ×: Optical density is less than 1.3

-Bleeding-
Bleeding was evaluated as follows. In the evaluation of fixability, an image was formed in the same manner except that a 1 dot line pattern was formed, and sensory evaluation was performed with reference to a limit sample in which the degree of bleeding of the line was determined in advance.
The evaluation criteria are as follows.
(Double-circle): Even if an image part is confirmed as an enlarged image (25 times), bleeding is not confirmed.
○: When the image portion is confirmed as an enlarged image (25 times), it is possible to confirm the blur, but it cannot be visually discriminated and is within the allowable range. Δ: The blur is visually recognized in the image portion. , Within allowable range x: Blur is visually recognized in the image area, and the degree is severe and out of the allowable range

-Storage stability-
The storage stability was evaluated as follows. The ink receiving particles stored in an environment of a temperature of 23 ° C. and a humidity of 75% RH for 24 hours were used to evaluate the drying time (liquid absorption speed).
The evaluation criteria are as follows.
A: Drying time is less than 0.5 seconds B: Drying time is less than 1 second Δ: Drying time is 1 second or more and less than 3 seconds X: Drying time is 3 seconds or more

  From the above results, it can be seen that this example is more satisfactory than the comparative example with respect to all evaluations of fixability, drying time (liquid absorption speed), optical density, bleeding and storage stability.

[Example B]
-Particle BA-
-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 60 mol%): 95 parts by mass-Sodium hydroxide: 15 parts by mass-Ion exchange water: 1000 parts by mass The above materials were mixed and stirred. . After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Ba1.

-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 40 mol%): 95 parts by mass-Triethanolamine (10% aqueous solution): 70 parts by mass-Isopropyl alcohol: 1000 parts by mass And stirred. Into this mixed solution, 7.7 parts by mass of the particle Ba1 was mixed, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.) and then classified with an airflow classifier to obtain particles Ba2.

Particle Ba2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.25 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.75 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BB-
-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 60 mol%): 95 parts by mass-Lithium hydroxide-Monohydrate: 16.5 parts by mass-Ion-exchanged water: 1000 parts by mass The materials were mixed and stirred. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bb1.

-Styrene / n-butyl acrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Tetramethylammonium hydroxide (10% aqueous solution): 60 parts by mass-Isopropyl alcohol: 1000 parts by mass Were mixed and stirred. In this mixed solution, 17 parts by mass of the particle Bb1 was mixed, and stirring was further continued. This mixed liquid was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bb2.

Particle Bb2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass is stirred and mixed to receive ink Particles were prepared.

-Particle BC-
-Styrene / 2-ethylhexyl acrylate / acrylic acid copolymer (polar monomer ratio 40 mol%): 95 parts by mass-Potassium hydroxide: 1.5 parts by mass-Ion exchange water: 1000 parts by mass Stir. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bc1.

-Styrene / 2-ethylhexyl acrylate / acrylic acid copolymer (polar monomer ratio 40 mol%): 95 parts by mass-Ethanolamine (10% aqueous solution): 65 parts by mass-Isopropyl alcohol: 1000 parts by mass , Stirred. In the mixed solution, 36 parts by mass of the particle Bc1 was mixed, and stirring was further continued. The mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bc2.

-Particle Bc2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BD-
Styrene / 2-ethylhexyl methacrylate / maleic acid copolymer (polar monomer ratio 20 mol%): 95 parts by mass polar monomer ratio 20 mol%)
-Sodium hydroxide: 5 mass parts-Ion exchange water: 1000 mass parts The said material was mixed and stirred. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bd1.

-Styrene / 2-ethylhexyl methacrylate / maleic acid copolymer (polar monomer ratio 20 mol%): 95 parts by mass-Cetylpyridinium chloride monohydrate (10 wt% aqueous solution): 65 parts by mass-Isopropyl alcohol: 1000 parts by mass Part The above materials were mixed and stirred. In this mixed solution, 48 parts by mass of the particle Bd1 was mixed, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bd2.

-Particle Bd2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass Particles were prepared.

-Particle BE-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 17.5 mol%): 95 parts by mass-Lithium hydroxide-Monohydrate: 5.75 parts by mass-Ion exchange water: 1000 parts by mass Part The above materials were mixed and stirred. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Be1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 12.5 mol%): 95 parts by mass-Benzalkonium chloride (10% aqueous solution): 175 parts by mass-Isopropyl alcohol: 1000 parts by mass The materials were mixed and stirred. In this mixed liquid, 20 parts by mass of the particle Be1 was mixed, and stirring was further continued. The mixed liquid was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Be2.

Particle Be2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.5 part by mass Amorphous silica (Aerosil OX50 / Degussa): 0.5 part by mass is stirred and mixed to receive ink Particles were prepared.

-Particle BF-
-Styrene / n-butyl acrylate / methacrylic acid copolymer (polar monomer ratio 97.5 mol%): 85 parts by mass- Styrene / n-butyl acrylate / methacrylic acid copolymer (polar monomer ratio 7.5 mol) %): 10 parts by mass, potassium hydroxide: 15 parts by mass, ion-exchanged water: 1000 parts by mass The above materials were mixed and stirred. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bf1.

Styrene / n-butyl acrylate / methacrylic acid copolymer (polar monomer ratio 97.5 mol%): 95 parts by mass 2-amino-2-ethyl-1,3-propanediol (10% aqueous solution): 20 Part by mass / Isopropyl alcohol: 1000 parts by mass The above materials were mixed and stirred. In the mixed solution, 156 parts by mass of the particle Bf1 was mixed, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.) and then classified with an airflow classifier to obtain particles Bf2.

-Particle Bf2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BG-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 85 mol%): 95 parts by mass-Sodium hydroxide: 25 parts by mass-Ion exchange water: 1000 parts by mass The above materials were mixed and stirred. . After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bg1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Triethanolamine (10% aqueous solution): 50 parts by mass-Isopropyl alcohol: 1000 parts by mass And stirred. In this mixed solution, 1.5 parts by mass of the particle Bg1 was mixed, and stirring was further continued. The mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bg2.

-Particle Bg2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass Particles were prepared.

-Particle BH-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 92.5 mol%): 95 parts by mass-Sodium hydroxide: 3.5 parts by mass-Ion-exchanged water: 1000 parts by mass And stirred. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bh1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 90 mol%): 95 parts by mass-Stearyltrimethylammonium chloride (10% aqueous solution): 350 parts by mass-Isopropyl alcohol: 1000 parts by mass Mixed and stirred. In this mixed solution, 14 parts by mass of the particle Bh1 was mixed, and stirring was further continued. The mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bh2.

-Particle Bh2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass Particles were prepared.

-Particle BI-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass Stir. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bi1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 82.5 mol%): 95 parts by mass-Diethanolamine (10% aqueous solution): 360 parts by mass-Isopropyl alcohol: 1000 parts by mass And stirred. In this mixed solution, 21 parts by mass of the particle Bi1 was mixed, and stirring was further continued. The mixed liquid was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bi2.

Particle Bi2: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass is stirred and mixed to receive ink Particles were prepared.

-Particle BJ-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed and stirred. did.

Next, 360 parts by mass of diethanolamine (10% aqueous solution) was added to the mixed solution, and further stirred. The obtained mixed liquid was made into particles using a Spray-Dry machine (NL-5 / Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bj1.

-Particle Bj1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BK-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass The above materials are mixed and stirred. As a result, a mixed solution Bk1 was obtained.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Diethanolamine (10% aqueous solution): 360 parts by mass-Isopropyl alcohol: 1000 parts by mass The above materials are mixed and stirred As a result, a mixed solution Bk2 was obtained.

  Using a double cylindrical needle, the mixed solution Bk1 was sent to the inner route and the mixed solution Bk2 was sent to the outer route. Then, droplets were sprayed from the tip of the needle into a heating and drying furnace, and then classified with an airflow classifier to obtain particles Bk1.

-Particle Bk1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass with stirring and ink reception Particles were prepared.

-Particle BL-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 0.65 parts by mass-Ion-exchanged water: 1000 parts by mass Stir. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bl1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Diethanolamine (10% aqueous solution): 360 parts by mass-Isopropyl alcohol: 1000 parts by mass Stir. In this mixed solution, 21 parts by mass of the particle Bl1 was mixed, and stirring was further continued. The mixed liquid was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bl2.

-Particle Bl2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BM-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 14.5 parts by mass-Ion-exchanged water: 1000 parts by mass Stir. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bm1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Diethanolamine (10% aqueous solution): 360 parts by mass-Isopropyl alcohol: 1000 parts by mass Stir. In this mixed solution, 21 parts by mass of the particle Bm1 was mixed, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.) and then classified with an airflow classifier to obtain particles Bm2.

-Particle Bm2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BN-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 0.5 parts by mass-Ion exchanged water: 1000 parts by mass Stir. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bn1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Diethanolamine (10% aqueous solution): 360 parts by mass-Isopropyl alcohol: 1000 parts by mass Stir. 21 parts by mass of the particle Bn1 was mixed in this mixed liquid, and stirring was further continued. The mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.) and then classified with an airflow classifier to obtain particles Bn2.

-Particle Bn2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BO-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 12.5 parts by mass-Ion exchange water: 1000 parts by mass Stir. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bo1.

-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Diethanolamine (10% aqueous solution): 500 parts by mass-Isopropyl alcohol: 1000 parts by mass Stir. In this mixed solution, 21 parts by mass of the particle Bo1 was mixed, and stirring was further continued. This mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bo2.

-Particle Bo2: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BP-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Potassium hydroxide: 1.5 parts by mass-Ion-exchanged water: 1000 parts by mass Stir. After removing the solvent, it was dried using a vacuum dryer. The obtained solid was pulverized with a jet mill and further classified with an airflow classifier to obtain particles Bp1.

-Particle Bp1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink Particles were prepared.

-Particle BQ-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 30 mol%): 95 parts by mass-Diethanolamine (10% aqueous solution): 200 parts by mass-Isopropyl alcohol: 1000 parts by mass Stir. The mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Bq1.

-Particle Bq1: 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass-Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass are stirred and mixed to receive ink. Particles were prepared.

-Particle BR-
-Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 7.5 mol%): 95 parts by mass-Sodium hydroxide (10% aqueous solution): 15 parts by mass-Isopropyl alcohol: 1000 parts by mass Were mixed and stirred. The mixed solution was made into particles using a Spray-Dry machine (NL-5 / manufactured by Okawara Chemical Co., Ltd.), and then classified with an airflow classifier to obtain particles Br1.

Particle Br1: 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa): 0.5 parts by mass Amorphous silica (Aerosil OX50 / Degussa): 0.5 parts by mass is stirred and mixed to receive ink Particles were prepared.

  Table 3 shows the characteristics of the ink receiving particles obtained above.

(Examples B1 to B15, Comparative Examples B1 to B3)
According to Table 3, the following evaluation was performed using each of the above particles (ink-receptive particles) and the following ink. The results are shown in Table 4. The amount of particles and ink applied was in accordance with Table 3.

-Preparation of ink BA-
The following ink components were mixed, stirred, and then filtered using a membrane filter having a pore size of 5 μm to prepare an ink.
CB (Cabojet-300 / Cabot Corporation): 8% by mass
・ Styrene-acrylic acid copolymer: 1% by mass
・ Glycerin: 15% by mass
Propylene glycol: 10% by mass
・ 1,2-hexanediol: 5% by mass
・ Orphine E1010 (manufactured by Nissin Chemical): 1.5% by mass
-NaOH: appropriate amount-water: remainder The pH of the obtained ink was adjusted with an aqueous sodium hydroxide solution to be 7.3. The surface tension of the ink was 31 mN / m.

-Preparation of ink BB-
The following ink components were mixed, stirred, and then filtered using a membrane filter having a pore size of 5 μm to prepare an ink.
・ C. I. Pigment Blue 15: 3: 7% by mass
-Styrene-acrylic acid copolymer: 2.5% by mass
・ Glycerin: 10% by mass
Propylene glycol: 10% by mass
・ 1,2-hexanediol: 5% by mass
・ Orphine E1010 (manufactured by Nissin Chemical): 1.5% by mass
-NaOH: appropriate amount-water: remainder The pH of the ink obtained was adjusted with an aqueous sodium hydroxide solution to 8.5. The surface tension of the ink was 31 mN / m.

(Evaluation)
-Chargeability (particle layer uniformity)-
The chargeability (particle layer uniformity) was the state of particles when sprayed on a pet film using a cake printer, and the chargeability was evaluated. The evaluation criteria are as follows.
(Double-circle): When observing with a microscope, the particle | grains have spread evenly on the film.
○: When observed with the naked eye, it can be uniformly distributed on the film.
(Triangle | delta): Although there is unevenness, it can spread.
X: Cannot be sprayed.

-Drying time (liquid absorption speed)-
The drying time (liquid absorption speed) was evaluated as follows. The particles were dispersed on the PET film using a cake printer. Then, a 100% coverage pattern was formed on the PET film on which the particles were dispersed, with an image area ratio of 1200 dpi × 1200 dpi (dpi: number of dots per inch) using a piezo-type ink jet device. Thereafter, plain paper (C2 paper: manufactured by Fuji Xerox Co., Ltd.) was pressed against the particles to which ink was applied at a pressure of 10 ⁵ Pa, and the time until transfer was stopped was measured.
The evaluation criteria are as follows.
A: Drying time is less than 0.5 seconds B: Drying time is less than 1 second Δ: Drying time is 1 second or more and less than 3 seconds X: Drying time is 3 seconds or more

-Optical density-
The optical density was evaluated as follows. The particles were dispersed on the PET film using a cake printer. Then, a 100% coverage pattern was formed on the PET film on which the particles were dispersed, with an image area ratio of 1200 dpi × 1200 dpi (dpi: number of dots per inch) using a piezo-type ink jet device. Thereafter, the ink-applied particles were transferred and fixed on plain paper (C2 paper: manufactured by Fuji Xerox Co., Ltd.) at a pressure of 10 ⁵ Pa and a temperature of 50 ° C. The optical density of the image portion was measured using X-Rite 404 (manufactured by X-Rite).
The evaluation criteria are as follows.
◎: Optical density is 1.45 or more ○: Optical density is 1.4 or more and less than 1.45 Δ: Optical density is 1.3 or more and less than 1.4 ×: Optical density is less than 1.3

-Bleeding-
Bleeding was evaluated as follows. In the evaluation of optical density, an image was formed in the same manner except that a 1 dot line pattern was formed, and sensory evaluation was performed with reference to a limit sample in which the degree of bleeding of the line was previously determined.
The evaluation criteria are as follows.
(Double-circle): Even if an image part is confirmed as an enlarged image (25 times), bleeding is not confirmed.
○: When the image portion is confirmed as an enlarged image (25 times), it is possible to confirm the blur, but it cannot be visually discriminated and is within the allowable range. Δ: The blur is visually recognized in the image portion. , Within allowable range x: Blur is visually recognized in the image area, and the degree is severe and out of the allowable range

-Storage stability-
The storage stability was evaluated as follows. The ink receiving particles stored in an environment of a temperature of 23 ° C. and a humidity of 75% RH for 24 hours were used to evaluate the drying time (liquid absorption speed).
The evaluation criteria are as follows.
A: Drying time is less than 0.5 seconds B: Drying time is less than 1 second Δ: Drying time is 1 second or more and less than 3 seconds X: Drying time is 3 seconds or more

  From the above results, it can be seen that this example is more satisfactory than the comparative example in all the evaluations of chargeability (particle layer uniform formation), drying time (liquid absorption rate), optical density, bleeding, and storage stability.

It is a conceptual diagram which shows an example of the ink receptive particle which concerns on embodiment. It is a conceptual diagram which shows another example of the ink receptive particle which concerns on embodiment. It is a perspective view which shows the ink receptive particle | grain storage cartridge which concerns on embodiment. It is AA sectional drawing of FIG. It is a block diagram which shows the recording device which concerns on embodiment. FIG. 2 is a configuration diagram illustrating a main part of a recording apparatus according to an embodiment. It is a block diagram which shows the ink receptive particle layer which concerns on embodiment. It is a block diagram which shows the recording device which concerns on other embodiment. It is a block diagram which shows the principal part of the recording device which concerns on other embodiment. It is a figure which shows notionally the process in which an image is formed in the recording device which concerns on other embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Recording apparatus 11 Recording apparatus 12 Intermediate transfer body 13 Conveying belt 14 Release agent supply apparatus 14A Release layer 14B Blade 14C Supply roller 14D Release agent 16 Ink receiving particle 16A Ink receiving particle layer 16B Image layer 16D Residual particle 18 Ink receiving particle supply device 18A Particle supply roll 18B Charging blade 19 Ink receiving particle storage cartridge 19A Supply tube 20 Inkjet recording head 20A Ink droplet 20B Nozzle surface 22 Transfer fixing device 22A Heating roll 22B Pressure roll 23 Fixing device 23A Heating roll 23B Pressurizing roll 24 Cleaning device 28 Charging device 29 Neutralizing device 31 Follower roll 50 Ink-receptive particle storage cartridge 51 Particle storage cartridge main body 52 Side wall portion 54 Side wall portion 56 Band portion 58 Storage portion 60 Unloading port 64 Coupling Part 66 connecting portion 68 agitator

Claims (24)

A first organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%, and at least a part of the polar group has an alkali metal salt structure;
A second organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%, and at least a part of the polar group has a polyvalent metal salt structure; At least a portion of the polar monomer with respect to the total monomer component of 10 mol% or more and less than 100 mol%, and at least a part of the polar group is selected from a third organic resin having a salt structure of an organic amine. With one kind,
And ink receiving particles for receiving ink.   The ink receiving particles according to claim 1, comprising the first organic resin having an alkali metal salt structure and the second organic resin having a polyvalent metal salt structure. The ink receptive particles have a core part and a covering part that covers the core part,
The core portion is configured to include the second organic resin having a multivalent metal salt structure,
The ink receptive particle according to claim 2, wherein the covering portion includes the first organic resin having an alkali metal salt structure.   The ink receptivity according to claim 3, wherein a ratio of the salt of the polyvalent metal to the polar monomer in the second organic resin contained in the core is 0.1 mol% or more and 20 mol% or less. particle.   4. The ink receiving particle according to claim 3, wherein a ratio of the alkali metal salt to the polar monomer in the first organic resin contained in the covering portion is 5 mol% or more and 90 mol% or less in molar ratio.   4. The ink receiving particle according to claim 3, wherein a ratio of the covering portion to the core portion is 0.5% or more and 25% or less by mass ratio.   The ink receiving particle according to claim 2, wherein at least one of the polar monomers of the first organic resin and the second organic resin contains a carboxylic acid as the polar group.   Among the organic resins contained in the ink receiving particles, the ratio of the organic resin in which the ratio of the polar monomer to the whole monomer component is 10 mol% or more and less than 100 mol% is 80 by mass with respect to the entire ink receiving particles. The ink receiving particles according to claim 2, wherein the ink receiving particles are from 100% to 100%.   2. The ink receiving particle according to claim 1, comprising the first organic resin having an alkali metal salt structure and the third organic resin having an organic amine salt structure. The ink receptive particles have a core part and a covering part that covers the core part,
The core portion includes the first organic resin having an alkali metal salt structure,
The ink receptive particle according to claim 9, wherein the covering portion includes the third organic resin having a salt structure of an organic amine.   11. The ink receiving particle according to claim 10, wherein a ratio of the alkali metal salt to the polar monomer in the first organic resin contained in the core is 5 mol% or more and 90 mol% or less.   11. The ink receiving particle according to claim 10, wherein a ratio of the salt of the organic amine to the polar monomer in the third organic resin contained in the pre-coating portion is 0.1 mol% or more and 45 mol% or less in molar ratio. .   11. The ink receiving particle according to claim 10, wherein a ratio of the covering portion to the core portion is 0.5% or more and 25% or less by mass ratio.   The ink receiving particles according to claim 9, wherein at least one of the polar monomers of the first organic resin and the third organic resin contains a carboxylic acid as the polar group.   Among the organic resins contained in the ink receiving particles, the ratio of the organic resin in which the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol% is 80 by mass with respect to the entire ink receiving particles. The ink receiving particles according to claim 9, wherein the ink receiving particles are from 100% to 100%. A fourth organic resin having a polar group, wherein the ratio of the polar monomer to the total monomer component is 10 mol% or more and less than 100 mol%,
At least a part of the polar group in the fourth organic resin has an alkali metal salt structure and a polyvalent metal salt structure or an organic amine salt structure,
Ink-receiving particles that receive ink.   The ink receiving particles according to claim 16, wherein at least a part of the polar group in the fourth organic resin has an alkali metal salt structure and a polyvalent metal salt structure.   The ink receiving particles according to claim 16, wherein at least a part of the polar group in the fourth organic resin has an alkali metal salt structure and an organic amine salt structure.   The ink receiving particles according to claim 16, wherein at least one of the polar monomers of the fourth organic resin contains a carboxylic acid as the polar group.   Among the organic resins contained in the ink receiving particles, the ratio of the organic resin in which the ratio of the polar monomer to the whole monomer component is 10 mol% or more and less than 100 mol% is 80 by mass with respect to the entire ink receiving particles. The ink receiving particles according to claim 16, wherein the ink receiving particles are from 100% to 100%. An intermediate transfer member;
Supply means for supplying the ink receiving particles according to any one of claims 1 to 20 onto the intermediate transfer member;
An ink ejection means for ejecting ink to the ink receiving particles supplied onto the intermediate transfer member;
Transfer means for transferring the ink receiving particles to a recording medium;
Fixing means for fixing the ink receiving particles transferred to the recording medium;
A recording apparatus. Supply means for supplying the ink receiving particles according to any one of claims 1 to 20 onto a recording medium;
Ink ejection means for ejecting ink onto the ink receiving particles supplied on the recording medium;
Fixing means for fixing the ink receiving particles supplied on the recording medium;
A recording apparatus.   A recording material comprising ink and the ink receiving particles according to any one of claims 1 to 20.   21. An ink receiving particle storage cartridge which is detached from a recording apparatus and stores the ink receiving particles according to any one of claims 1 to 20.