JP2008087412A - Ink-recipient particle, recording material, recording apparatus and storage member for ink-recipient particle - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To offer an ink-recipient particle that can receive various varieties of inks and that can control the unevenness of the recording images, a material for recording and a recording apparatus that utilize this ink recipient-particle, and a storage member for ink-recipient particle. <P>SOLUTION: The ink-recipient particle 100 receives ink and contains the mother particle 101 having a hydrophilic organic resin 101A containing a hydrophilic organic resin 101B with the ratio of a polar monomer to the total monomers of not less than 10 mol% and not more than 90 mol%, and the water repellent organic material contained inside of the mother particle 101 (at least either one of the first water repellent organic material with the melting point of 150°C or less which is solid at a room temperature and the second water repellent organic material which is liquid at a room temperature). The mother particle 101 can be the composite particle of the hydrophilic organic particle 101A with the other particles (for example, inorganic particle). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to ink receiving particles. The present invention also relates to a recording material, a recording apparatus, and an ink receiving particle storage member 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 Records 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 proposes a method for recording while supplying a plurality of types of powder mixtures onto an intermediate, such as polymers having different water absorption, water absorbing polymers having different sizes, and water absorbing polymers having different crosslinking degrees. Yes.

  Patent Document 2 proposes a method of recording while supplying solid particles (particles of polysaccharide polymer, alginic acid, carrageenan, etc.) that thicken the ink by contact with the ink on the intermediate.

  Further, in Patent Document 3, a hydrophobic resin particle layer is formed on an intermediate, and ink (for example, an SD type dye ink slow dry type (Slow Dry type)) is held in the voids of the hydrophobic resin particle layer. A method of transferring to a recording medium has been proposed.

  Patent Document 4 proposes a method in which a gap type ink absorption layer in which inorganic particles, a hydrophilic polymer, and the like are wet-coated is provided on an intermediate body (sheet), and dye ink is ejected thereon and transferred to a recording medium. Has been.

  Patent Document 5 discloses a porous ink absorbing layer formed by drying at a temperature not higher than the minimum film-forming temperature (MFT) of thermoplastic resin particles, which contains thermoplastic resin particles and non-thermoplastic particles. Inkjet intermediate transfer media having been proposed.

In Patent Document 6, after a powder that contacts a liquid with a high electric resistance and thickens is adhered onto an intermediate transfer body, an image is formed by bringing the liquid into contact with the powder to form an intermediate transfer body. A recording apparatus for transferring the above thickened image to a transfer medium has been proposed.
JP 2000-343808 JP 2000-94654 A JP 2003-57967 A JP 2002-370347 JP 2002-321443 A JP 2001-321443 A

  An object of the present invention is to provide ink-receptive particles that can receive various inks and can suppress disorder of a recorded image. Another object of the present invention is to provide a recording material, a recording apparatus, and an ink receiving particle storage member using the ink receiving particles.

The above problem is solved by the following means. That is,
The invention according to claim 1
A hydrophilic organic resin having a ratio of polar monomers to all monomer components of 10 mol% to 90 mol%, a first organic material having a water repellency that is solid at room temperature and has a melting point of 150 ° C. or less, and liquid at room temperature And at least one of the second organic materials having water repellency, and ink receiving particles that receive ink.

The invention according to claim 2
2. The ink receiving particle according to claim 1, wherein the hydrophilic organic resin has a ratio of a polar monomer to a total monomer component of 30 mol% to 80 mol%.

The invention according to claim 3
2. The ink receiving particle according to claim 1, wherein the melting point of the first organic material is 50 ° C. or higher and 110 ° C. or lower.

The invention according to claim 4
The hydrophilic organic resin has a ratio of polar monomers to 30 mol% or more and 80 mol% or less with respect to all monomer components, and the second organic material comprises silicone oil, fluorine oil, and solubility parameter (SP). Value) The ink receiving particles according to claim 1, comprising at least one selected from organic compounds having a value of 11 or less.

The invention according to claim 5
2. The ink receiving particle according to claim 1, wherein a ratio of a total amount of the first organic material and the second organic material is 1% or more and 15% or less by mass ratio with respect to the whole ink receiving particle. It is.

The invention according to claim 6
2. The ink receiving particle according to claim 1, wherein a ratio of a total amount of the first organic material and the second organic material is 2% or more and 5% or less by mass ratio with respect to the entire ink receiving particle. It is.

The invention according to claim 7 provides:
2. The ink receiving particle according to claim 1, wherein a ratio of the hydrophilic organic resin to the entire ink receiving particle is 50% or more and 99% or less by mass ratio.

The invention according to claim 8 provides:
The ink receptive particles are composite particles having first particles containing the hydrophilic organic resin and second particles containing at least one of the first organic material and the second organic material. The ink receiving particles according to claim 1.

The invention according to claim 9 is:
The ink receiving particles according to claim 8, wherein the ink components are captured in a gap between the particles of the composite particles.

The invention according to claim 10 is:
The ink receiving particles according to claim 9, wherein the ink includes a recording material and captures the recording material in a gap between the particles of the composite particles.

The invention according to claim 11 is:
It is a recording material provided with ink and the ink receptive particle of any one of Claims 1-10.

The invention according to claim 12
An intermediate transfer member, supply means for supplying the ink receiving particles according to claim 1 onto the intermediate transfer member, and the ink receiving particles supplied onto the intermediate transfer member. An ink discharge means for discharging ink, a transfer means for transferring the ink receiving particles to a recording medium, and a fixing means for fixing the ink receiving particles transferred to the recording medium. The neutral particles are supplied onto the intermediate transfer body and receive the ink ejected from the ink ejection means. The fixing means includes the first organic material and the first organic material contained in the ink receptive particles. The recording apparatus is characterized in that a release layer is formed of at least one of the two organic materials.

The invention according to claim 13 is:
An intermediate transfer member, supply means for supplying the ink receiving particles according to claim 8 onto the intermediate transfer member, and ink for discharging ink to the ink receiving particles supplied onto the intermediate transfer member Discharge means, transfer means for transferring the ink receptive particles to a recording medium, and fixing means for fixing the ink receptive particles transferred to the recording medium, wherein the ink receptive particles are The ink is supplied onto the intermediate transfer member and receives the ink discharged from the ink discharge unit, and the fixing unit includes the first organic material and the second organic material included in the ink receiving particles. The recording apparatus is characterized in that a release layer is formed by at least one of them.

The invention according to claim 14 is:
An intermediate transfer member, a supply unit that supplies the ink receiving particles according to claim 10 onto the intermediate transfer member, and an ink discharge unit that discharges ink onto the ink receiving particles supplied onto the intermediate transfer member. Transfer means for transferring the ink receiving particles to a recording medium; and fixing means for fixing the ink receiving particles transferred to the recording medium, wherein the ink receiving particles are the intermediate transfer The ink is supplied onto the body and receives the ink discharged from the ink discharge means, and the fixing means is at least one of the first organic material and the second organic material contained in the ink receiving particles. In this recording apparatus, a release layer is formed.

The invention according to claim 15 is:
The ink receptive particle storage member that is detachable from the recording apparatus and stores the ink receptive particles according to claim 1.

  According to the first aspect of the present invention, it is possible to receive various inks and to suppress the disturbance of the recorded image, compared to the case where this configuration is not provided.

  The invention according to claim 2 has an effect that the receiving speed of various inks can be improved as compared with the case where this configuration is not provided.

  According to the third aspect of the present invention, there is an effect that the disturbance of the recorded image can be further suppressed as compared with the case where the present configuration is not provided.

  The invention according to claim 4 has an effect that it is possible to achieve both of various ink receiving speeds and suppression of disturbance of recorded images, compared with the case without this configuration.

  The invention according to claim 5 has an effect that, in comparison with the case where the present configuration is not provided, it is possible to achieve both compatibility of various ink receiving speeds and suppression of disturbance of recorded images.

  The invention according to claim 6 has an effect that it is possible to achieve both of various ink receiving speeds and suppression of disturbance of recorded images, compared to the case without this configuration.

  The invention according to claim 7 has an effect that it is possible to achieve both of various ink receiving speeds and suppression of disturbance of recorded images as compared with the case without this configuration.

The invention according to claim 8 has an effect that various inks can be received at higher speed than the case where the present configuration is not provided.

  The invention according to claim 9 has an effect that the retention ability of the liquid component of the absorbed ink is improved as compared with the case where this configuration is not provided.

  The invention according to claim 10 has an effect that the recording material can be held and fixed without being unevenly distributed in the ink receiving particles as compared with the case without this configuration.

  According to the eleventh aspect of the present invention, it is possible to record on various recording media even when using various inks and to form an image with suppressed image disturbance as compared with the case without this configuration. The effects are as follows.

  The invention according to claim 12 enables to record on various recording media at a high speed even when using various inks as compared with the case without this configuration, and forms an image with suppressed image disturbance. It can be. In addition, there is an effect that the powder operability is improved as compared with the case where this configuration is not provided.

  The invention according to claim 13 has an effect that the drying time can be shortened as compared with the case where the present configuration is not provided. Further, there is an effect that blurring of the image can be suppressed.

  According to the fourteenth aspect of the present invention, it is possible to improve the color developability as compared with the case where the present configuration is not provided.

  According to the fifteenth aspect of the present invention, various inks can be received and the disorder of the recorded image can be suppressed as compared with the case where this configuration is not provided.

  Hereinafter, the present invention will be described in detail.

(Ink-receptive particles)
The ink receiving particles of the present invention receive ink components when 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.

  The ink receiving particles of the present invention have a hydrophilic organic resin in which the ratio of the polar monomer to the total monomer component is 10 mol% or more and 90 mol% or less (hereinafter sometimes simply referred to as “hydrophilic organic resin”). And at least one of a first organic material having water repellency that is solid at normal temperature and having a melting point of 150 ° C. or lower and a second organic material having water repellency that is liquid at normal temperature (hereinafter referred to as “organic material having water repellency”). In some cases).

  The ink receiving particles of the present invention include, for example, particles containing a hydrophilic organic resin (hereinafter sometimes referred to as “hydrophilic organic particles”), and the particles of hydrophilic organic particles alone (hereinafter referred to as “primary particles”). Or a composite particle aggregated including at least hydrophilic organic particles. Hereinafter, the primary particles and the composite particles are referred to as “mother particles”.

The ink receiving particles of the present invention contain an organic material having water repellency inside the mother particles. The organic material having water repellency may be included as a domain inside the hydrophilic organic particles, or may be included as particles constituting the composite particles (water repellent particles).
When forming a fixed image using the ink receptive particles of the present invention, since the organic material having water repellency is contained inside the mother particle, the melted (or exuded) organic material having water repellency is obtained. By forming a release layer on the surface of the fixing unit of the recording apparatus, it is possible to suppress unnecessary adhesion of the ink receiving particles that have received the ink to the fixing unit and to prevent image distortion.

  Here, when the mother particles are composed of only hydrophilic organic particles, when the ink receiving particles receive ink, if the ink adheres to the ink receiving particles, at least the liquid component of the ink is hydrophilic. Absorbed by organic 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 mother particles are composed of composite particles that include at least hydrophilic organic particles, when the ink receiving particles receive the ink, first, when the ink adheres to the ink receiving particles, at least The liquid component of the ink is trapped by a gap between particles (at least hydrophilic organic particles) constituting the composite particle (hereinafter, the interparticle gap (void) may be referred to as “trap structure”). . 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. 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 the gap between particles (physical particle wall structure).

  Then, by applying a form in which the mother particles are composed of composite particles that are aggregated including at least hydrophilic organic particles, capturing by the gaps (physical particle wall structure) between the particles constituting the composite particles In addition to (trap), ink liquid components are absorbed and held by hydrophilic organic particles.

  Further, after the transfer of the ink receiving particles, the components of the hydrophilic organic 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 hydrophilic organic 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 present invention, the organic resin component constituting the ink receiving particles can also function as the resin.

  Here, the “gap 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, for example, a maximum aperture of 0.1 μm to 5 μm, preferably 0.3 μm to 1 μm. In particular, the size of the gap is preferably a size that can trap 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 particle | grains.

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

  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 ink receiving particles of the present invention will be described in more detail. The ink receiving particles of the present invention may have a form in which the mother particles are composed of only hydrophilic organic particles as described above, and the composite particles in which the mother particles are aggregated including at least hydrophilic organic particles. The form comprised by may be sufficient.

  In a form in which the mother particle is composed of particles of only hydrophilic organic particles, an organic material having water repellency is also included in the hydrophilic organic particles together with the hydrophilic organic resin. On the other hand, in the form in which the mother particles are composed of composite particles that include at least hydrophilic organic particles, the organic material having water repellency may be contained inside the hydrophilic organic particles. The composite particles may be configured to be included together with hydrophilic organic particles as particles (hereinafter sometimes referred to as water-repellent particles). Thus, the organic material having water repellency is contained in the mother particles. The water-repellent particles may include not only an organic material having water repellency but also a third component (for example, a hydrophobic organic material or an inorganic material).

  The particles constituting the composite particles include inorganic particles and porous particles in addition to the hydrophilic organic particles and the water-repellent particles. Of course, if the organic particles having water repellency in any form are contained inside, the mother particle is a composite particle in which a plurality of hydrophilic organic particles are aggregated, or a plurality of hydrophilic organic particles and water repellent particles. You may comprise the aggregated composite particle.

  In addition, examples of the particles to be attached to the surface of the mother particles include hydrophobic organic particles and inorganic particles.

  As a specific configuration of the ink receiving particles of the present invention, for example, as shown in FIG. 1, a hydrophilic organic resin 101B serving as a binder resin has hydrophilicity including an organic material 101C having water repellency and inorganic particles 101E. Examples of the ink receiving particle 100 include mother particles 101 composed of organic particles 101A alone, and hydrophobic organic particles 102A and inorganic particles 102B attached to the mother particles 101. In addition, as shown in FIG. 2, the base particle 101 of the composite particle in which the hydrophilic organic particle 101A containing the hydrophilic organic resin, the water repellent particle 101D containing the water repellent organic material, and the inorganic particle 101E are combined. In addition, a form of ink receiving particles 110 having hydrophobic organic particles 102 </ b> A and inorganic particles 102 </ b> B attached to the mother particles 101 is also included. Note that a void structure is formed in the mother particle of the composite particle by the gap 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 hydrophilic organic particles to other particles (hydrophilic organic particles: other particles) is, for example, 5: 1 to 1 when other particles are inorganic particles. A range of 1:10 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.

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.

  Next, the hydrophilic organic particles will be described. In the hydrophilic organic particles, the ratio of the polar monomer to the total monomer component is 10 mol% or more and 90 mol% or less, desirably 15 mol% or more and 85 mol% or less, more desirably 30 mol% or more and 80 mol% or less. It is comprised including a hydrophilic organic resin.

  Here, the polar monomer includes an ethylene oxide group, a carboxy group, a sulfo group, a substituted or unsubstituted amino group, a hydroxyl group, an amide group, an imide group, a nitrile group, an ether group, an ester group, and salts thereof. It is a monomer. For example, in the case of imparting positive chargeability, it is desirable to use a monomer having a chlorination structure such as a (substituted) amino group, a (substituted) pyridine group, an amine salt thereof, or a quaternary ammonium salt. In the case of imparting negative charge, a monomer having an organic acid (salt) structure such as carboxylic acid (salt) or sulfonic acid (salt) is desirable.

  In addition, the ratio of a polar monomer is calculated | required as follows. First, the constitution of the organic component is identified from analysis techniques such as mass spectrometry, NMR, and IR. 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.

  As described above, the hydrophilic organic particles include a hydrophilic organic resin (hereinafter sometimes referred to as “liquid-absorbing resin”). Since the ink liquid component (for example, water or an aqueous solvent) absorbed in the liquid-absorbing resin acts as a plasticizer for the resin (polymer), it can be softened and contribute to fixability.

  The liquid absorbing resin is preferably a weak liquid absorbing resin. This weak liquid-absorbing resin means that, for example, when water is absorbed as a liquid, it is several% (≈5%) or more and several hundreds% (≈500%) or less, preferably about 5% or more and 100% or less with respect to the resin mass. This means that liquid absorption is possible.

  The liquid-absorbing 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 liquid-absorbent 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 group as the acid constituents of the above, polyesters including 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 absorbent resin that is a copolymer of the hydrophilic monomer and the hydrophobic monomer include, for example, a styrene / alkyl (meth) acrylate / (meth) acrylic acid copolymer, styrene. / (Meth) acrylic acid / (anhydrous) maleic acid copolymers, olefinic copolymers such as ethylene / propylene (or modified products thereof, or carboxylic acid unit introduced by copolymerization), trimellitic acid, etc. Preferable examples include branched polyesters and polyamides that improve the viscosity.

  Examples of the liquid absorbent resin include a neutral salt structure (for example, carboxylic acid). This neutralized salt structure such as carboxylic acid forms an ionomer by interaction with the cation when ink containing a cation (for example, a monovalent metal cation such as Na or Li) is absorbed.

  It is also desirable that the liquid absorbent resin contains 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 liquid absorbent resin, the molar ratio (hydrophilic monomer: hydrophobic monomer) between the hydrophilic unit (hydrophilic monomer) and the hydrophobic unit (hydrophilic monomer) is, for example, 5: 95-70: 30.

  The liquid absorbing 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. 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 ratio of the liquid-absorbing resin (hydrophilic organic resin) to the whole ink-receiving particles is preferably 50% or more and 99% or less, more preferably 60% or more and 99% or less, and still more preferably. It is 70% or more and 99% or less.

  The liquid-absorbing resin described above is used with the ratio of the polar monomer being controlled within the above range regardless of the form.

  The particle diameter of the hydrophilic organic particles, when the primary particles are used as mother particles, has a sphere-converted average particle diameter of, for example, 0.1 μm to 50 μm, desirably 0.5 μm to 25 μm, more desirably 1 μm to 10 μm. Range. 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.

  The ratio of the hydrophilic organic particles to the total 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.

Next, the hydrophobic organic particles will be described. In the hydrophobic organic particles, the ratio of the polar monomer to the total monomer component is in the range of, for example, 0 mol or more and less than 10 mol%, desirably 0.1 mol% or more and 8 mol% or less, more desirably 2 mol% or more and 5 mol% or less. Can be mentioned. Specifically, the hydrophobic organic particles include an organic resin having a ratio of the polar monomer (hereinafter referred to as a non-liquid absorbing resin).
Hydrophobic organic particles refer to those in which the ratio of the polar monomer is within the above range.

  Examples of the non-liquid-absorbing resin constituting the hydrophobic organic particles include a single or a plurality of copolymers of hydrophobic monomers. Examples of hydrophobic monomers include olefin compounds such as ethylene, propylene, and butadiene, styrene derivatives such as styrene, α-methylstyrene, α-ethylstyrene, and vinyltoluene, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and acrylonitrile. , Vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, lauryl methacrylate, vinyl cyclohexane, vinyl naphthalene, vinyl naphthalene derivatives, alkyl acrylate ester, acrylic acid phenyl ester, methacrylic acid alkyl ester, methacrylic acid phenyl ester, Methacrylic acid cycloalkyl ester, crotonic acid alkyl ester, itaconic acid dialkyl ester, maleic acid dialkyl ester, etc.

  Specific examples of the non-liquid-absorbing resin include vinyl resins (eg, styrene- (meth) acrylic acid copolymer, (meth) acrylic acid alkyl ester- (meth) acrylic acid copolymer), polyester, and the like. Resin (for example, polyethylene terephthalate, polybutylene terephthalate), silicone resin (for example, organopolysiloxane), fluorine-based resin (for example, vinylidene fluoride resin, polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkylvinyl copolymer, tetra Preferred examples include fluoroethylene / ethylene copolymers.

  A non-liquid-absorbing resin means a resin having a liquid-absorbing property capable of absorbing liquid less than 5% with respect to the resin mass, for example, when absorbing water as a liquid.

  The non-liquid-absorbing resin described above is used by controlling the ratio of the polar monomer within the above range regardless of the form.

  The particle diameter of the hydrophobic organic particles is, for example, 0.1 μm or less, desirably 0.01 μm or more and 0.05 μm or less, more desirably 0.015 μm or more and 0.02 μm or less in terms of a sphere equivalent average particle diameter.

  The ratio of the hydrophobic organic particles to the entire ink receiving particles is, for example, 0.1% or more and 5% or less, desirably 0.1% or more and 2.5% or less, more desirably 0.5% or more and 2 in terms of mass ratio. % Or less.

  The ratio of the hydrophobic organic particles to the entire ink receiving particles is obtained as follows. The ink receiving particles are applied to a dry sieving measuring instrument (Sonic Shifter L-200P / spin air sieve) and an airflow classifier (Classeal N-01), and classification is performed based on the particle diameter. A particle having a small particle size is a hydrophobic organic particle, and a particle having a large particle size is a hydrophilic particle. It is also possible to disperse the ink receptivity in a liquid medium, determine the particle size distribution using hydrodynamic chromatography, and calculate the ratio of hydrophobic particles to hydrophilic particles. The same applies hereinafter.

  The hydrophobic organic particles may be subjected to a surface treatment (partially hydrophobic treatment, specific functional group introduction treatment, etc.). Specifically, for example, an alkyl group can be introduced by treatment with a silylating agent such as trimethylchlorosilane or t-butyldimethylchlorosilane. In this reaction, dehydrochlorination occurs due to the silylating agent, and the reaction proceeds. Therefore, the reaction can be promoted by adding hydrochloric acid to make hydrochloric acid hydrochloride. Further, surface treatment with aliphatic alcohols, higher fatty acids and derivatives thereof is also possible. Furthermore, 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 carboxyls Surface treatment with coupling agents having an anionic functional group such as acid is also possible.

  Next, common characteristics of the liquid-absorbing resin constituting the hydrophilic organic particles and the non-liquid-absorbing resin (hereinafter collectively referred to as organic resin) constituting the hydrophobic organic particles will be described.

  The 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.

The organic resin may further contain a charge control agent for electrophotographic toner, such as low-molecular quaternary ammonium salts, organic borates, and salt-forming compounds of salicylic acid derivatives. Control of conductivity is conductivity such as tin oxide and titanium oxide (where conductivity means, for example, volume resistivity is less than 10 ⁷ Ω · cm. The same applies hereinafter unless otherwise specified. ), Semiconductive (here, semiconductive means, for example, a volume resistivity of 10 ⁷ Ω · cm or more and 10 ¹³ Ω · cm or less. The same shall apply hereinafter unless otherwise specified). Addition is effective.

  The 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.

  As for the weight average molecular weight of organic resin, 3000-300,000 are mentioned, for example. 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, the sample concentration was 0.5%, and the flow rate was 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 organic resin, 50 mgKOH / g or more and 777 mgKOH / g or less are mentioned, for example in conversion of a 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.

  Next, an organic material having water repellency will be described. “Having water repellency” means that the contact angle with water is 90 degrees or more.

  The contact angle can be measured using a dynamic contact angle tester (FIBRO 1100 DAT MK II, manufactured by FIBRO System) as follows. Hereinafter, unless otherwise specified, the evaluation is performed under a temperature of 23 ± 0.5 ° C. and a humidity of 50 ± 5% RH.

  In the case of a material having a melting point of 20 ° C. or higher and 150 or lower, the evaluation sample is adjusted by placing the material to be evaluated on the polyimide film, heating at 180 ° C. for 30 minutes, and then cooling to room temperature. Next, the evaluation sample is set on a contact angle meter. 3 μL of ion-exchanged water is dropped on the evaluation sample, and the contact angle of water with respect to the base material is measured 0.1 seconds after the dropping.

  In the case of a material that is liquid at room temperature, the evaluation sample is adjusted by dropping the material to be evaluated on the polyimide film and leaving it for 5 minutes. Next, the evaluation sample is set on a contact angle meter. Subsequently, 3 μL of ion-exchanged water is dropped on the evaluation sample, and the contact angle of water with respect to the base material is measured 0.1 seconds after dropping.

  The organic material having water repellency is contained inside the hydrophilic organic particles in a form in which the mother particles are composed of particles of the hydrophilic organic particles alone. On the other hand, in a form in which the mother particles are composed of composite particles that include at least hydrophilic organic particles, the organic material having water repellency may be contained inside the hydrophilic organic particles. As such, the composite particle may be included.

An organic material having water repellency that is solid at room temperature will be described. “Solid at room temperature” means “solid at 23 ± 0.5 ° C.”.
The melting point of the water-repellent organic material that is solid at room temperature is 150 ° C. or lower, preferably 45 ° C. or higher and 130 ° C. or lower, more preferably 50 ° C. or higher and 110 ° C. or lower.

  Here, the melting point of the organic material having water repellency that is solid at room temperature was determined from the main maximum peak measured in accordance with 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 organic material that is solid at room temperature and has water repellency include, for example, polyolefins such as polyethylene, polypropylene, and polybutene; silicones; oleic acid amide, erucic acid amide, ricinoleic acid amide, 1,2-hydroxystearic acid amide , Fatty acid amides such as stearamide and phthalic anhydride; plant waxes such as ester wax, carnauba wax, rice wax, candelilla wax, cotton wax, tree wax, jojoba oil; animal systems such as beeswax and lanolin Synthetic hydrocarbon waxes such as montan wax, ozokerite, ceresin, paraffin wax, microcrystalline wax, Fischer-Tropsch wax, and modified products thereof; mineral waxes such as ozokerite and cercin; Emissions, microcrystalline, petroleum waxes such as petrolatum, esters, ketones, and synthetic waxes such as ether. Among these, polyethylene, polypropylene, polybutene, paraffin wax, and microcrystalline wax are preferable, and polyethylene is more preferable as the organic material that is solid at room temperature and has water repellency.

  An organic material having water repellency that is liquid at room temperature will be described. “Liquid at room temperature” means “liquid at 23 ± 0.5 ° C.”.

  Specifically, organic materials such as silicone oils, modified silicone oils, fluorine oils, hydrocarbon oils, mineral oils, vegetable oils, polyalkylene glycols, alkylene glycol ethers, alkane diols, molten waxes, surfactants and the like. It is done. Among these organic materials, silicone oil, fluorine oil, and organic compounds having a solubility parameter (SP value) of 11 or less are particularly preferable. These organic materials that are liquid at room temperature can be used in a state of being impregnated in porous particles (for example, porous silica, porous apatite, etc.).

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.
An organic compound having a solubility parameter (SP value) of 11 or less desirably has a solubility parameter (SP value) of 10 or less, more desirably a solubility parameter (SP value) of 8 to 10. By setting the solubility parameter (SP value) within the above range, it becomes difficult for the ink receiving particles to adhere firmly to the intermediate transfer member.

The solubility parameter (SP value) can be calculated from the actual value such as calculation from heat of evaporation, calculation from refractive index, calculation from Kauributanol number, calculation from surface tension, or calculation from chemical composition. Any method may be used. The solubility parameter (SP value) in the present invention is a value calculated by the following formula of Fedors determined from the evaporation energy (Δei) and the molar volume (Δvi) of atoms or atomic groups having a chemical structure.
Formula: [SP value = (ΣΔei / ΣΔvi) ^1/2 ]

Examples of organic compounds having a solubility parameter (SP value) in the above range include polyalkylene glycols and surfactants.
Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymer, and polybutylene glycol. Among these, polypropylene glycol is desirable.

  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.

  Examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkyl naphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, and higher alcohol ether. Sulfuric acid ester salts and sulfonic acid salts, higher alkyl sulfosuccinic acid salts, higher alkyl phosphoric acid ester salts, phosphoric acid ester salts of higher alcohol ethylene oxide adducts, fatty acid metal soaps, N-acyl amino acids and their salts, alkyl ether carboxylates , Acylated peptide, formalin polycondensate of naphthalene sulfonate, dialkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acyl methyl taurine, sulfated oil, alkyl ether sulfate Secondary higher alcohol ethoxy sulfates, polyoxyethylene alkylphenyl ether sulfates, sulfates of fatty alkylol amide, alkyl ether phosphoric acid ester salts, alkyl phosphoric acid ester salts.

  Examples of the cationic surfactant include aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium and the like.

  Examples of amphoteric surfactants include carboxybetaine, aminocarboxylate, imidazolinium betaine, and lecithin.

  Nonionic surfactants include polyoxyethylene alkyl ether, single chain length polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative , Ethylene oxide derivatives of alkylphenol formalin condensate, polyoxyethylene-polyoxypropylene copolymer (polyoxyethylene polyoxypropylene block polymer), polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Castor oil and hydrogenated castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, Examples include reethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, sucrose fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamide, alkylamine oxide and the like. Among these, polyoxyethylene alkyl ether and polyoxyethylene-polyoxypropylene copolymer are preferable.

  The viscosity of the organic material that is liquid at normal temperature is preferably, for example, 5 to 200 mPa · s, more preferably 5 to 100 mPa · s, and still more preferably 5 to 50 mPa · s. When the viscosity is in the above range, the organic material that is a room temperature liquid is easily developed on the intermediate transfer member, and an uncoated region of the organic material that is a room temperature liquid is prevented.

  The vapor pressure at 23 ° C. of the organic material having water repellency is, for example, 1000 Pa or less, desirably 500 Pa or less, and more desirably 133 Pa or less.

The total content of the organic material that is liquid at normal temperature is preferably 1% by mass or more and 15% by mass or less, more preferably 1% by mass or more and 10% by mass or less, and more preferably 1% by mass with respect to the entire ink receiving particles. It is even more preferable that the content is not less than 5% and not more than 5% by mass.
By making the total content of the organic material which is a liquid at room temperature within the above range, it is possible to achieve both the liquid absorption performance of the ink receiving particles and the prevention of image ghost due to offset to the fixing roll.

  The total content of the organic material having water repellency is preferably 1% by mass or more and 15% by mass or less, more preferably 1.5% by mass or more and 10% by mass or less, based on the whole ink receiving particles. It is even more preferable that the content is not less than 5% by mass and not more than 5% by mass. Here, the total content of the organic material having water repellency refers to the total content of the organic material having water repellency contained in the hydrophilic organic particles and the organic material having water repellency contained in the water repellent particles, The same applies to the form in which the mother particle is composed of particles of hydrophilic organic particles and the form in which the mother particle is composed of composite particles in which at least hydrophilic organic particles are aggregated.

  Next, the inorganic particles constituting the composite particles together with the hydrophilic organic particles and the inorganic particles attached to the mother particles together with the 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 hydrophilic organic 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. .

  Next, other additives for the ink receiving particles of the present invention will be described. First, it is desirable that the ink receiving particles of the present invention include a component that aggregates or thickens the components of the ink.

  The component having this function may be included as a functional group of the organic resin or may be included as a compound, for example. Examples of the functional group include carboxylic acids, polyvalent metal cations, polyamines, and the like.

  Moreover, as the said compound, flocculants, such as an inorganic electrolyte, an organic acid, an inorganic acid, and an organic amine, are mentioned suitably.

  Inorganic electrolytes include alkali metal ions such as lithium ion, sodium ion, potassium ion, aluminum ion, barium ion, calcium ion, copper ion, iron ion, magnesium ion, manganese ion, nickel ion, tin ion, titanium ion, zinc Polyvalent metal ions such as ions, hydrochloric acid, odorous acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, thiocyanic acid, and acetic acid, succinic acid, lactic acid, fumaric acid, fumaric acid, citric acid, salicylic acid, benzoic acid And the like, and organic carboxylic acids such as salts of organic sulfonic acids.

  Specific examples include lithium chloride, sodium chloride, potassium chloride, sodium bromide, potassium bromide, sodium iodide, potassium iodide, sodium sulfate, potassium nitrate, sodium acetate, potassium oxalate, sodium citrate, potassium benzoate and the like. Alkali metal salts and aluminum chloride, aluminum bromide, aluminum sulfate, aluminum nitrate, sodium aluminum sulfate, potassium aluminum sulfate, aluminum acetate, barium chloride, barium bromide, barium iodide, barium oxide, barium nitrate, thiocyanate Barium acid, calcium chloride, calcium bromide, calcium iodide, calcium nitrite, calcium nitrate, calcium dihydrogen phosphate, calcium thiocyanate, calcium benzoate, calcium acetate, salicylic acid Lucium, 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, oxalic acid Iron, iron lactate, iron fumarate, iron citrate, 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, manganese benzoate, manganese lactate, nickel chloride, nickel bromide, nickel sulfate, nickel nitrate, nickel acetate, tin sulfate, titanium chloride, zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, thiocyanate Examples thereof include salts of polyvalent metals such as zinc acid and zinc acetate.

  Specific examples of organic acids include arginic acid, citric acid, glycine, glutamic acid, succinic acid, tartaric acid, cysteine, oxalic acid, fumaric acid, phthalic acid, maleic acid, malonic acid, lysine, malic acid, and general formula Examples thereof include compounds represented by (1) and derivatives of these compounds.

Here, in the formula, X represents O, CO, NH, NR ₁ , S, or SO ₂ . R ₁ represents an alkyl group, and R ₁ is preferably CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OH. R represents an alkyl group, and R is preferably CH ₃ , C ₂ H ₅ , or C ₂ H ₄ OH. In addition, R may be included in the formula or may not be included. X is preferably CO, NH, NR ₁ , O, and more preferably CO, NH, O. M represents a hydrogen atom, an alkali metal or an amine. M is preferably H, Li, Na, K, monoethanolamine, diethanolamine, triethanolamine or the like, more preferably H, Na, K, and still more preferably a hydrogen atom. n is an integer of 3-7. n is preferably a case where the heterocyclic ring is a 6-membered ring or a 5-membered ring, and more preferably a 5-membered ring. m is 1 or 2. The compound represented by the general formula (1) may be a saturated ring or an unsaturated ring as long as it is a heterocyclic ring. l is an integer of 1-5.

  Specifically, the compound represented by the general formula (1) has a furan, pyrrole, pyrroline, pyrrolidone, pyrone, pyrrole, thiophene, indole, pyridine, quinoline structure, and further has a carboxyl group as a functional group. Compounds. Specifically, 2-pyrrolidone-5-carboxylic acid, 4-methyl-4-pentanolide-3-carboxylic acid, furan carboxylic acid, 2-benzofuran carboxylic acid, 5-methyl-2-furan carboxylic acid, 2,5 -Dimethyl-3-furancarboxylic acid, 2,5-furandicarboxylic acid, 4-butanolide-3-carboxylic acid, 3-hydroxy-4-pyrone-2,6-dicarboxylic acid, 2-pyrone-6-carboxylic acid, 4-pyrone-2-carboxylic acid, 5-hydroxy-4-pyrone-5-carboxylic acid, 4-pyrone-2,6-dicarboxylic acid, 3-hydroxy-4-pyrone-2,6-dicarboxylic acid, thiophenecarboxylic Acid, 2-pyrrolecarboxylic acid, 2,3-dimethylpyrrole-4-carboxylic acid, 2,4,5-trimethylpyrrole-3-propionic acid, 3-hydroxy-2-yne Carboxylic acid, 2,5-dioxo-4-methyl-3-pyrroline-3-propionic acid, 2-pyrrolidinecarboxylic acid, 4-hydroxyproline, 1-methylpyrrolidine-2-carboxylic acid, 5-carboxy-1-methyl Pyrrolidine-2-acetic acid, 2-pyridinecarboxylic acid, 3-pyridinecarboxylic acid, 4-pyridinecarboxylic acid, pyridinedicarboxylic acid, pyridinetricarboxylic acid, pyridinepentacarboxylic acid, 1,2,5,6-tetrahydro-1-methyl Examples include nicotinic acid, 2-quinolinecarboxylic acid, 4-quinolinecarboxylic acid, 2-phenyl-4-quinolinecarboxylic acid, 4-hydroxy-2-quinolinecarboxylic acid, and 6-methoxy-4-quinolinecarboxylic acid. .

  The organic acid is preferably citric acid, glycine, glutamic acid, succinic acid, tartaric acid, phthalic acid, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, Nicotinic acid, derivatives of these compounds, or salts thereof. More desirably, pyrrolidone carboxylic acid, pyrone carboxylic acid, pyrrole carboxylic acid, furan carboxylic acid, pyridine carboxylic acid, coumaric acid, thiophene carboxylic acid, nicotinic acid, or derivatives of these compounds, or salts thereof. More desirable are pyrrolidone carboxylic acid, pyrone carboxylic acid, furan carboxylic acid, coumaric acid, or a derivative of these compounds, or a salt thereof.

  The organic amine compound may be any of primary, secondary, tertiary and quaternary amines and salts thereof. Specific examples include tetraalkylammonium, alkylamine, benzalkonium, alkylpyridium, imidazolium, polyamine, and derivatives or salts thereof. Specifically, amylamine, butylamine, propanolamine, propylamine, ethanolamine, ethylethanolamine, 2-ethylhexylamine, ethylmethylamine, ethylbenzylamine, ethylenediamine, octylamine, oleylamine, cyclooctylamine, cyclobutylamine, cyclohexane Propylamine, cyclohexylamine, diisopropanolamine, diethanolamine, diethylamine, di-2-ethylhexylamine, diethylenetriamine, diphenylamine, dibutylamine, dipropylamine, dihexylamine, dipentylamine, 3- (dimethylamino) propylamine, dimethylethylamine, dimethyl Ethylenediamine, 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-ethylhexyl ) 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, dihydroxyethyl stearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryl Dimethylbenzylammonium chloride, cetylpyridinium mouth Ride, stearamide methylbiridium chloride, diallyldimethylammonium chloride polymer, diallylamine polymer, monoallylamine polymer and the like can be mentioned.

  More desirably, triethanolamine, triisopropanolamine, 2-amino-2-ethyl-1,3-propanediol, ethanolamine, propanediamine, propylamine and the like are used.

Among these flocculants, polyvalent metal salts (Ca (NO ₃ ), Mg (NO ₃ ), Al (OH ₃ ), polyaluminum chloride, etc.) are preferably used.

  The flocculant may be used alone or in combination of two or more. The content of the flocculant is, for example, in the range of 0.01% by mass to 30% by mass, desirably 0.1% by mass to 15% by mass, and more desirably 1% by mass to 15% by mass. It is done.

In an embodiment of the present invention,
In addition to the structure of any one of claims 1 to 15, it is preferable that the average particle diameter of the base particles is 0.1 to 50 μm, more preferably 0.5 μm to 25 μm, and further preferably 1 μm. 10 μm.

  When the sphere-converted average particle size is in the above range, high image quality is achieved as compared with the case where this configuration is not provided. 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 is lowered, and the powder tends to be unable to 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 addition to the structure of any one of claims 1 to 15, the hydrophilic organic particles have a ratio of polar monomers to all monomer components of 10 mol% or more and 90 mol% or less, preferably 15 mol% or more and 85 mol% or less. More preferably, it is 30 mol% or more and 80 mol% or less.

  When the ratio of the polar monomer is within the above range, the ink is trapped in the particles and between the particles at a high speed compared to the case without this configuration, so that various inks can be received at a high speed. It is. Also, printing at high speed is possible.

-In addition to the structure in any one of Claims 1-15, it is suitable that a hydrophilic organic particle contains weak liquid absorption resin. This weak liquid-absorbing resin means that, for example, when water is absorbed as a liquid, it is several% (≈5%) or more and several hundreds% (≈500%) or less, preferably about 5% or more and 100% or less with respect to the resin mass. Means a lyophilic resin capable of absorbing liquid.

  When the liquid absorbency of the weak liquid-absorbing resin is less than 5%, the ink-retaining ability of the ink-receptive particles is lowered. When the liquid-absorbing resin exceeds 500%, the ink-receptive particles are actively absorbed, and the environment dependency is low. growing.

In addition to the structure of any one of claims 1 to 15, in the hydrophobic organic particles, the ratio of the polar monomer to the total monomer component is 0 mol or more and less than 10 mol%, preferably 0.1 mol% or more and 8 mol% or less. More preferably, it is 2 mol% or more and 5 mol% or less.

  By setting the ratio of the polar monomer within the above range, the ink receiving particles are stored, and when the hydrophilic organic particles contained in the mother particles absorb moisture in the atmosphere, or when the ink receiving particles are in the ink. Even when the liquid component is absorbed, the charging property on the surface of the ink receiving particles is ensured. In addition, the ink receiving particles can be supplied to the intermediate transfer member, and an image with suppressed image disturbance can be formed without the ink receiving particles being detached from the intermediate transfer member.

(Recording material)
The recording material of the present invention comprises at least an ink containing a recording material and the ink receiving particles of the present invention. 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 the present invention.

  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 FW 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, but generally 0.1 to 100% by mass with respect to the pigment is mentioned.

  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 pigments obtained by subjecting the above pigments to surface modification treatment, Cab-o-jet-200, Cab-o-jet-300, IJX- manufactured by Cabot Corporation Commercially available self-dispersing pigments such as 157, IJX-253, IJX-266, IJX-273, IJX-444, IJX-55, Cabot 260, 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 manufactured by Dainippon Ink and Chemicals, Inc., or Toyo Ink, but also microcapsule pigments produced for the present invention 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 (density) of the recording material is, for example, in the range of 5% by mass to 30% 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 1000 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 recording material density.

  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 nitrogen-containing solvents include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine. Examples of alcohols 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 penetrants for adjusting penetrability, polyethyleneimine, polyamines, polyvinyl pyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, etc. 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 surface tension of the ink is, for example, in the range of 20 mN / m to 45 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 1.5 mPa · s to 30 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 receiving particle storage member)
The ink receptive particle storage member of the present invention is detachable from the recording apparatus. The ink receptive particle storage member stores the ink receptive particles of the present invention, and the ink receptive particles are stored in the particle coating apparatus (particle supply apparatus) of the recording apparatus. It is a member for supplying.

  Hereinafter, embodiments of the ink receiving particle storage member of the present invention 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 and 54 fitted to both ends of the particle storage cartridge main body 51. It consists of and.

  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 member of the present invention is not limited to the above configuration.

(Recording device)
The recording apparatus (recording method) of the present invention is a recording apparatus (recording method) using an ink containing a recording material and the ink receiving particles of the present invention, and an ink discharge means (ink discharge) for discharging ink. Step), transfer means for transferring the ink receiving particles that have received the ink to the recording medium (transfer process), and fixing means for fixing the ink receiving particles transferred onto the recording medium (fixing step). .

  Specifically, for example, first, ink receiving particles are supplied in a layer form to an intermediate (intermediate transfer member) by a supply unit. Ink is ejected by the ink ejecting means to the ink receptive particles (hereinafter referred to as ink receptive particle layer) supplied in layers. 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 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. Note that the transfer and fixing may be performed substantially simultaneously or separately.

  Here, the ink receiving particles are formed in, for example, a layer when receiving ink, and the thickness of the ink receiving particle layer is, for example, 1 μm to 100 μm, preferably 3 μm to 60 μm, more preferably The range of 5 micrometers or more and 30 micrometers or less is mentioned. Further, the porosity in the ink receiving particle layer (that is, the void ratio between the ink receiving particles + the void ratio in the ink receiving 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.

  Hereinafter, an embodiment of a recording apparatus of the present invention will be described with reference to the drawings. 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 the ink receiving particle layer according to the embodiment. In the following embodiment, a case where composite particles are applied to mother particles as ink receiving particles is described.

  As shown in FIG. 5, the recording apparatus 11 according to the embodiment includes an endless belt-shaped intermediate transfer body 12, a charging device 28 that charges the surface of the intermediate transfer body 12, and ink reception in a charged region on the intermediate transfer body 12. A particle coating device 18 for forming a particle layer by adhering the conductive particles 16, an ink jet recording head 20 for forming an image by ejecting ink droplets on the particle layer, and a recording medium 8 superimposed on the intermediate transfer body 12, and applying pressure and heat. In addition, a transfer device 23 that transfers the ink receiving particle layer 16A onto the recording medium 8 and a fixing device 25 that fixes the ink receiving particle layer 16A onto the recording medium 8 are configured. An ink receiving particle storage cartridge 19 is detachably connected to the particle coating device 18 via a supply pipe 19A.

  In order to improve the transfer efficiency of the ink receiving particle layer 16A from the surface of the intermediate transfer body 12 to the recording medium 8 on the upstream side of the charging device 28, the ink receiving particle layer 16A is promoted to be released from the surface of the intermediate transfer body 12. A release agent coating device 14 for forming a release layer 14A is disposed.

  The surface of the intermediate transfer body 12 on which the charge is formed by the charging device 28 is formed by the particle coating device 18 with the ink receiving particles 16 as a layer, 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 by the transfer device (transfer roller) 23 together with the color image, and then fixed to the recording medium 8 by the fixing device 25.
The transfer device 23 and the fixing device 25 may be configured to use a transfer fixing device (not shown) having both functions.

  Downstream of the transfer device 23, the ink receiving particles 16D remaining on the surface of the intermediate transfer body 12 are removed, and foreign matter other than the particles (such as paper dust of the recording medium 8) is removed. The cleaning device 24 is arranged.

  The recording medium 8 on which the color image has been transferred and fixed 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 coating device 14 (hereinafter, “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 body 12 has a 400 μm thick ethylene propylene rubber (EPDM) surface layer formed on a 1 mm thick polyimide film base layer. Here, for example, 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 circulated and conveyed, and a release layer 14A is first formed on the surface of the intermediate transfer body 12 by the release agent coating device 14. The release agent 14D is applied to the surface of the intermediate transfer body 12 by the application roller 14C of the release agent application device 14, and the layer thickness is defined by the blade 14B.

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

  The release agent application device 14 may be supplied with a release agent 14D from an independent liquid supply system (not shown) so that the supply of the release agent 14D is not interrupted. In this embodiment, amino silicone oil is used as the release agent 14D.

  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 potential of the ink receiving particles 16 to be supplied / adsorbed to the surface of the intermediate transfer body 12 is formed by an electrostatic force due to an electric field that can be formed between the supply roller 18A of the particle coating device 18 and the surface of the intermediate transfer body 12. Good.

  In this embodiment, the charging device 28 is used to apply a voltage between a driven roll 31 (connected to the ground) disposed between the charging device 28 and the intermediate transfer body 12 to charge the surface of the intermediate transfer body 12. The configuration is to let

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. For example, the volume resistivity is 10 ⁶ Ω · cm or more and 10 ⁸ Ω · cm. It is set as the roll-shaped member adjusted to the following grade. Further, the surface of the elastic layer is covered with a water / oil repellent skin layer (PFA) having a thickness of 5 μm to 100 μm, for example.

  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 constituted by a corotron or a brush.

  Next, the ink receiving particles 16 are supplied to the surface of the intermediate transfer body 12 by the particle applying device 18 to form the ink receiving particle layer 16A. In the particle applying device 18, a supply roller 18 </ b> A is disposed at 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 roller 18 </ b> A. The charging blade 18B also has a function of regulating the layer thickness of the ink receiving particles 16 attached to the surface of the supply roller 18A.

  The ink receiving particles 16 are supplied to the supply roller 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 roller 18A can be a solid aluminum roll, and the charging blade 18B can be a metal plate (such as SUS) on which urethane rubber is caught to apply pressure. The charging blade 18B is in contact with the supply roller 18A by a doctor method.

  The charged ink receiving particles 16 form, for example, one particle layer on the surface of the supply roller 18A, and are conveyed to a portion facing the surface of the intermediate transfer body 12, and when close to this, the surfaces of the supply roller 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 roller 18A are relatively set so that a single particle layer is formed 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, the positional relationship between the supply roller 18A and the intermediate transfer member 12, and the like.

The number of particles supplied onto the intermediate transfer body 12 is increased by relatively increasing the peripheral speed of the supply roller 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 image formation is performed 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 trapped on the surface of the ink receptive particle layer, and is fixed on the surface of the ink receptive particle or inside the particle gap so that the distribution in the depth direction decreases.

  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 that are not subjected to image formation become a protective layer after transfer and fixing, and are formed on the image layer 16B (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, The ink receptive particles 16 are laminated so that a sufficient number of particles are trapped and do not reach the lowest layer. In this case, the image forming material (pigment) is not exposed on the surface of the image layer after transfer / fixing, and the ink receiving particles 16 that do not form an image 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 (see FIG. 6). The ink jet recording head 20 applies ink droplets 20A to predetermined positions based on predetermined image information.

  Thereafter, the recording medium 8 and the intermediate transfer body 12 are sandwiched by the transfer device 23, 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 device 23 includes a heating roll 23A containing a heating source and a pressure roll 23B facing each other with the intermediate transfer body 12 interposed therebetween. 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, a material in which the outer surface of the aluminum core is coated with silicone rubber and further coated with a PFA tube can be used.

  At this time, while the organic resin constituting the ink receptive particles 16 in the non-image area is heated to a temperature lower than the glass transition temperature (Tg), the ink receptive particles are released from the release layer 14A formed on the surface of the intermediate transfer body 12 by pressure. The layer 16A is released and transferred onto the recording medium 8. Note that the intermediate transfer body 12 may be preheated before the transfer device 23.

  Finally, the recording medium 8 and the intermediate transfer body 12 are sandwiched by the fixing device 25, and pressure and heat are applied to the ink receiving particle layer 16A, whereby the ink receiving particle layer 16A is fixed on the recording medium 8.

  The fixing device 25 includes a heating roll 25A containing a heating source and a pressure roll 25B facing each other with the intermediate transfer body 12 interposed therebetween. The heating roll 25A and the pressure roll 25B are in contact with each other to form a contact portion. As the heating roll 25A and the pressure roll 25B, it is possible to use a product in which the outer surface of the aluminum core is coated with silicone rubber and further coated with a PFA tube.

  At the contact portion between the heating roll 25A and the pressure roll 25B, the organic resin particles constituting the ink receiving particle layer 16A are softened (or melted) by being heated to a glass transition point (Tg) or higher by a heater, and the pressure As a result, the ink receiving particle layer 16A is fixed to the recording medium 8.

  At this time, the fixing property is improved by heating. In this embodiment, the surface of the heating roll 25A 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 in the ink receiving particle layer 16A as it is after transfer / fixing.

  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 this embodiment, as shown in FIG. 6, a release layer 14 </ b> A can be formed on the surface of the intermediate transfer body 12 by a release layer coating apparatus 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 to impart releasability to the surface of the intermediate transfer body 12 itself.

  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 roller 18 </ b> A of the particle coating 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 roller 18 </ b> A of the particle coating 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 roller 18A as described above. To do. Alternatively, it may be controlled by the peripheral speed ratio between the supply roller 18 </ b> A and the intermediate transfer body 12.

  On the formed ink receiving particle layer 16A, ink droplets 20A are ejected by the ink jet recording head 20 of each color driven by piezoelectric (piezo), thermal, or the like, and an image layer 16B is formed on the ink receiving particle layer 16A. It 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 forming the ink receiving particles 16. At the same time, the recording material (for example, pigment) is also trapped on the surface of the ink receiving particles 16 (constituting particles) or 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 receiving particle layer 16A, but the recording material such as pigment is trapped on the surface of the ink receiving 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, the ink receiving particle layer 16 </ b> A having the image layer 16 </ b> B is transferred from the intermediate transfer body 12 onto the recording medium 8, whereby a color image is formed on 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 device (transfer roller) 23 heated by a heating means such as a heater and transferred onto the recording medium 8.

  Further, the ink receiving particle layer 16 </ b> A transferred onto the recording medium 8 is heated and pressed by a fixing device (fixing roller) 25 heated by a heating means such as a heater and fixed on the recording medium 8. The heating in the fixing device is preferably higher than the heating temperature in the transfer device, and is preferably higher than the glass transition temperature (Tg) of the organic resin constituting the ink receiving particle layer 16A.

  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 present invention. As shown in FIG. 7A, a release layer 14 </ b> 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 coating 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.

  Also, the recording material such as pigment contained in the ejected ink droplet 20A penetrates to about 1/3 to half of the ink receiving particle layer 16A as shown in FIG. A particle layer 16C that is not infiltrated with the material remains.

  The ink receiving particle layer 16A formed on the recording medium 8 by heating and pressure transfer by the transfer device (transfer roller) 23 has a particle layer 16C not containing ink on the image layer 16B as shown in FIG. 7B. Therefore, 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 fixing device (fixing roller) 25, 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 apparatus conditions such as the above charging voltage, particle layer thickness, transfer temperature, fixing temperature, etc. are determined by the ink receiving particles 16 or the composition of the ink, the amount of ink discharged, etc. Optimize in.

<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 a belt shape or a cylindrical shape (drum shape) as in the embodiment. 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 semiconductivity, for example, the surface resistivity is 10 ¹⁰ Ω / □ or more and less than 10 ¹⁴ Ω / □, and the volume resistivity is 10 ⁹ Ω · cm or more and less than 10 ¹³ Ω · cm. In the case of insulation, for example, 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 improve the transfer efficiency of the ink receiving particles 16 (efficient transfer from the intermediate transfer body 12 to the recording medium 8), a release layer 14A is formed on the surface of the intermediate transfer body 12. desirable. The release layer 14A may be formed as the surface (material) of the intermediate transfer body 12 or may be externally added to form the release layer 14A on the surface of the intermediate transfer body 12 by an on-process.

  That is, when the surface of the intermediate transfer body 12 is the release layer 14A, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer Fluorine resins such as polymers, silicone rubber, fluorosilicone rubber, phenyl silicone rubber, and the like are desirable.

  When the release layer 14A is formed by external addition, in the case of a drum shape, an anodized surface of aluminum, and in the case of a belt shape, the belt base material itself is formed (drum shape, Silicone rubber, fluorosilicone rubber, phenyl silicone rubber, fluorine rubber, chloroprene rubber, nitrile rubber, ethylene propylene rubber, styrene rubber, isoprene rubber, butadiene rubber, ethylene propylene butadiene rubber, nitrile butadiene rubber, etc. used.

  In order to exhibit a heating method by electromagnetic induction in the transfer process in the transfer device (transfer roller) 23 and the fixing process in the fixing device (fixing roller) 25, the transfer device (transfer roller) 23 and / or the fixing device (fixing roller). ) A heat generating layer may be formed on the intermediate transfer body 12 instead of 25. 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>
An ink receiving particle layer 16 </ b> A is formed on the surface of the 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 roller 18A form an electric field with the surface of the intermediate transfer member 12, and are moved / supplied onto the intermediate transfer member 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.

  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 roller 18A, and the thickness of the particle layer is regulated and charged by the charging blade 18B.

  The charging blade 18B functions to regulate the layer thickness of the ink receiving particles 16 on the surface of the supply roller 18A. For example, the layer thickness of the ink receiving particles 16 on the surface of the supply roller 18A is changed by changing the pressure applied to the supply roller 18A. To change. For example, the thickness of the ink receiving particles 16 on the surface of the supply roller 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 roller 18A is increased, and the thickness of the ink receiving particles formed on the surface of the intermediate transfer member 12 is increased. It may be increased.

  As another method, when the peripheral speed of the supply roller 18A for forming 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 roller 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 a 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. For example, a volume resistivity of 10 ⁶ Ω · cm or more A roll having a diameter of 10 mm or more and 25 mm or less adjusted to about 10 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, polynorbornene rubber, etc. 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.

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

  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 gaps (voids) formed in the ink receiving particles 16 to be recorded. The material (for example, pigment) is trapped in the surface of the ink receiving particle 16 or the interparticle gap constituting the ink receiving particle 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 interparticle gaps (voids) in the ink receiving particles 16 exhibit a filter effect, trap recording material (for example, pigment) on the surface of the ink receiving particle layer 16A, and the interparticle gaps in the ink receiving particles 16. It is expressed by being trapped and fixed in

  In order to ensure that the recording material (for example, pigment) is trapped in the surface of the ink receiving particle layer 16A and the inter-particle gap in the ink receiving particle 16, the ink and the ink receiving particles 16 are reacted to form a 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 receiving the ink droplet 20 </ b> A and having the image formed thereon is transferred to the recording medium 8, thereby forming an image on the recording medium 8. The transfer process may be performed while heating / pressing. 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 is removed by natural drying after the fixing process.

<Fixing process>
The ink receptive particle layer 16A transferred to the recording medium 8 is fixed by the fixing device 25 while performing at least one of heating and pressurization. Preferably, a method of performing heating / pressurization 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).

  The transfer process and the fixing process may be performed in separate processes or may be performed substantially simultaneously.

<Release layer>
Before supplying the ink receptive particles 16, a step of forming a release layer 14 </ b> A such as silicone oil on the surface of the intermediate transfer body 12 can be provided.
As the release layer, silicone oil, modified silicone oil, fluorine-based oil, hydrocarbon-based oil, mineral oil, vegetable oil, polyalkylene glycol, alkylene glycol ether, alkane diol, molten wax and the like can be considered.

  The method for supplying the release layer 14A includes a method of forming the release layer 14A by incorporating an oil tank, supplying oil to the oil application member, and supplying oil to the surface of the intermediate transfer body 12 by the application member. For example, a method of forming the release layer 14A on the surface of the intermediate transfer body 12 by using the impregnated application member is used.

<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 cleaning described above, the ink receiving particles 16 (residual particles 16D) remaining on the surface of the intermediate transfer body 12 are removed, and other than particles. 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 elimination 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.

<Other forms>
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, the present invention is not limited to recording characters and images on a recording medium. That is, the droplet discharge device according to the present invention can be applied to all industrially used droplet discharge (jetting) devices.

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

-Production of particles A-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio: 10 mol%): 5 parts by mass Polypropylene wax (melting point: 120 ° C.): 2 parts by mass Henschel so that the above materials have a predetermined mixing ratio The mixture was mixed and stirred with a mixer to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a hammer mill to obtain a pulverized product a1.

Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 40 mol%): 95 parts by mass Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 μm): 10 mass Part / pulverized product a1: 7 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles a2 (base particles) having a sphere equivalent average particle size of 6 μm.

Particle a2 (mother particle): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, a particle A having a sphere equivalent average particle diameter of 8 μm was prepared.

-Production of particle B-
Styrene / 2-ethylhexyl methacrylate / acrylic acid copolymer (polar monomer ratio 35 mol%): 95 parts by mass Styrene / 2-ethylhexyl methacrylate / acrylic acid copolymer (polar monomer ratio 10 mol%): 5 Part by mass / Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 μm): 10 parts by mass / polypropylene wax (melting point: 109 ° C.): 4.5 parts by mass Thus, the mixture was stirred with a Henschel mixer to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles b1 (mother particles) having an average sphere equivalent particle size of 8 μm.

-Particles b1 (mother particles): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined mixing ratio. Then, a particle B having a sphere-converted average particle diameter of 9 μm was produced.

-Particle C-
Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 67 mol%): 95 parts by mass Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 15 mol%): 5 Part by mass / Amorphous polyester resin: 10 parts by mass / N-hydroxyethyl-ricinoleyl amide (melting point: 45 ° C. (ITOWAX J-400 / manufactured by Ito Oil)): 1.5 parts by mass / polypropylene wax (melting point: 109) ° C.): 1.5 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles c1 (mother particles) having a sphere equivalent average particle size of 8 μm.

-Particle c1 (mother particle): 100 parts by mass-Zinc stearate: 0.2 part by mass-Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 [mu] m): 1 part by mass The mixture C was stirred and mixed so that the blending ratio was as follows to prepare particles C having an average particle diameter in terms of sphere of 10 μm.

-Particle D-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio: 12 mol%): 50 parts by mass Microcrystalline wax (Hi-Mic-2095 (manufactured by Nippon Seiwa Co., Ltd.) Melting point: 98 ° C.): 2 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then coarsely pulverized using a hammer mill to obtain a pulverized product d1.

・ Styrene / 2-ethylhexyl methacrylate / maleic acid copolymer (polar monomer ratio 55 mol%): 50 parts by mass ・ Pulverized product d1: 51.2 parts by mass Were mixed and stirred to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles d2 (mother particles) having a sphere equivalent average particle diameter of 5 μm.

Particle d2 (base particle): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles D having an average particle diameter in terms of spheres of 7 μm were prepared.

-Particle E-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 12.5 mol%): 5 parts by mass Polyethylene glycol (melting point 45 ° C. (PEG-1500 / manufactured by Sanyo Chemical Co., Ltd.)): 2.5 Part by mass / polypropylene wax (melting point: 109 ° C.): 2.5 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then coarsely pulverized using a hammer mill to obtain a pulverized product e1.

Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 25 mol%): 95 parts by mass Amorphous polyester resin: 5 parts by mass Grinded material e1: 10 parts by mass Thus, the mixture was stirred with a Henschel mixer to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles e2 (mother particles) having a sphere equivalent average particle diameter of 7 μm.

-Particle e2 (mother particle): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle size in terms of sphere: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles E having a sphere equivalent average particle diameter of 10 μm were prepared.

-Particle F-
-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 40 mol%): 95 parts by mass- Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 10 mol%): 5 parts by mass Crystalline polyester resin: 10 parts by mass Vinyl ether wax (melting point 45 ° C. (V-Wax / BASF)): 3 parts by mass Microcrystalline wax (Hi-Mic-2095 (Nihon Seiwa Co., Ltd.) melting point 98 ° C.) : 1.2 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles f1 (mother particles) having a sphere equivalent average particle size of 8 μm.

-Particle f1 (mother particle): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere 0.04 µm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles F having a sphere equivalent average particle diameter of 12 μm were prepared.

-Particle G-
Styrene / n-butyl methacrylate / acrylic acid copolymer particles (polar monomer ratio 50 mol%, sphere equivalent average particle diameter 2 μm): 70 parts by mass Amorphous silica (sphere equivalent average particle diameter: 0.6 μm) : 40 parts by mass / polypropylene wax (melting point: 120 ° C.) (average particle diameter in terms of sphere: 3 μm): 2 parts by mass The above particles are mixed by stirring (30 seconds in a sample mill) and then processed intermittently by a mechanofusion system. Particleized. The particle size was measured for each intermittent driving condition, and was taken out when the particle size reached 12 μm to obtain particles g1 (mother particles).

-Particles g1 (mother particles): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of spheres: 0.04 μm): 1 part by mass The above particles are stirred and mixed so as to have a predetermined blending ratio. Then, particles G having an average sphere equivalent particle size of 12 μm were prepared.

-Particle H-
Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 40 mol%): 90 parts by mass Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 10 mol%): 10 Part by mass / Amorphous polyester resin: 10 parts by mass / Vinyl ether wax (melting point: 45 ° C. (V-Wax / BASF)): 3 parts by mass / microcrystalline wax (Hi-Mic-2095 (manufactured by Nippon Seiwa)) Melting point: 98 ° C.): 15 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles h1 (mother particles) having an average sphere equivalent particle size of 8 μm.

Particle h1 (mother particle): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles H having an average particle diameter in terms of sphere of 13 μm were prepared.

-Particle I-
Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 40 mol%): 85 parts by mass Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 10 mol%): 15 Part by mass / Amorphous polyester resin: 10 parts by mass / Vinyl ether wax (melting point: 45 ° C. (V-Wax / BASF)): 3 parts by mass / microcrystalline wax (Hi-Mic-2095 (manufactured by Nippon Seiwa)) Melting point 98 ° C.): 22.5 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles i1 (mother particles) having a sphere equivalent average particle diameter of 11 μm.

Particle i1 (mother particle): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 μm): 1 part by mass is stirred and mixed, and particle I having a sphere equivalent average particle size of 15 μm Was made.

-Particle J-
Hydroxyapatite (BET specific surface area 180 g / m ² ): 100 parts by mass KF-96-1,000 cs (normal temperature liquid silicone oil, manufactured by Shin-Etsu Silicone): 100 parts by mass And the pressure is reduced to 1000 Pa or less. After returning to normal pressure, excess oil was removed to obtain a porous body j1 containing silicone oil.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 40 mol%): 85 parts by mass-Porous body j1: 15 parts by mass Using a Henschel mixer so that the above materials are mixed at a predetermined ratio The mixture was stirred and used as a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles j2 (mother particles) having a sphere equivalent average particle size of 10 μm.

-Particle j2 (mother particle): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle size in terms of sphere 0.04 µm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles J having an average sphere equivalent particle size of 15 μm were prepared.

-Particle K-
Styrene / n-butyl methacrylate / acrylic acid copolymer particles (polar monomer ratio 50 mol%, sphere equivalent average particle size 2 μm): 50 parts by mass Amorphous silica (sphere equivalent average particle size 0.16 μm): 50 parts by mass / polypropylene wax (melting point 120 ° C.) (average particle diameter in terms of spheres = 3 μm): 2 parts by mass The above particles were mixed by stirring (30 seconds in a sample mill), and then processed intermittently by a mechanofusion system. Particleized. The particle diameter was measured for each intermittent driving condition, and was taken out when the sphere-converted average particle diameter was 11 μm to obtain particles k1 (mother particles).

-Particles k1 (mother particles): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of spheres: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles K having an average sphere equivalent particle size of 12 μm were prepared.

-Particle L-
-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 87.5 mol%): 50 parts by mass- Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 12.5 mol) %): 50 parts by mass Amorphous polyester resin: 10 parts by mass Microcrystalline wax (Hi-Mic-2095 (manufactured by Nippon Seiwa Co., Ltd.) Melting point 98 ° C.): 3 parts by mass The above materials are mixed at a predetermined ratio. Thus, the mixture was stirred with a Henschel mixer to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles l1 (mother particles) having a sphere equivalent average particle diameter of 8 μm.

-Particle l1 (mother particle): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle size in terms of sphere: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles L having an average particle diameter in terms of sphere of 13 μm were prepared.

-Particle M-
Styrene / 2-ethylhexyl methacrylate / acrylic acid copolymer (polar monomer ratio 40 mol%): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere 0.04 μm): 10 mass Part The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles m1 (mother particles) having a sphere equivalent average particle size of 6 μm.

-Particle m1 (mother particle): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles M having an average particle diameter in terms of spheres of 8 μm were prepared.

-Particle N-
Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 8 mol%): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere 0.04 μm): 10 parts by mass Parts / polyethylene glycol (melting point: 51 ° C. (PEG-2000 / manufactured by Sanyo Chemical Co., Ltd.)): 5 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles n1 (mother particles) having an average sphere equivalent particle size of 5 μm.

-Particle n1 (mother particle): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere: 0.04 μm): 1 part by mass The above materials are mixed with stirring so as to have a predetermined blending ratio. Then, particles N having a sphere-converted average particle diameter of 7 μm were prepared.

-Particle O-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 95 mol%): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere 0.04 μm): 10 mass Parts / polyethylene glycol (melting point: 51 ° C. (PEG-2000 / manufactured by Sanyo Chemical Co., Ltd.)): 5 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles o1 (mother particles) having a sphere equivalent average particle size of 10 μm.

-Particle o1 (mother particle): 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, average particle size in terms of sphere: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles O having a sphere-converted average particle diameter of 12 μm were prepared.

-Particle P-
Styrene / n-butyl methacrylate / acrylic acid copolymer (polar monomer ratio 50 mol%): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 μm): 10 parts by mass Polypropylene (melting point: 170 ° C.): 5 parts by mass The above materials were mixed and stirred with a Henschel mixer so as to obtain a predetermined blending ratio to obtain a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles p1 (mother particles) having a sphere equivalent average particle size of 9 μm.

-Particle p1 (mother particle) 100 parts by mass-Amorphous silica (Aerosil TT600 / Degussa, sphere equivalent average particle size 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Particles P having a sphere equivalent average particle diameter of 12 μm were prepared.

-Particle Q-
・ Hydroxyapatite (BET specific surface area 180 g / m ² ): 100 parts by mass • Degnum S-20 (normal temperature liquid fluorine-based oil, manufactured by Daikin): 100 parts by mass The above materials are mixed so as to have a predetermined mixing ratio. The pressure is reduced to 1000 Pa or less. After returning to normal pressure, excess oil was removed to obtain a porous body q1 containing fluorinated oil.

-Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 40 mol%): 85 parts by mass-Porous material q1: 15 parts by mass Using a Henschel mixer so that the above materials have a predetermined mixing ratio The mixture was stirred and used as a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles q2 (base particles) having a sphere-converted average particle size of 10 μm.

Particle q2 (mother particle): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles Q having an average particle diameter in terms of spheres of 15 μm were prepared.

-Particle R-
Hydroxyapatite (BET specific surface area 180 g / m ² ): 100 parts by mass PF-753 (normal temperature liquid oil, manufactured by Asahi Glass Co., Ltd./SP value = 8.8): 100 parts by mass Mix and depressurize to 1000 Pa or less. After returning to normal pressure, excess oil was removed to obtain a porous body r1 containing an organic material (oil) having an SP value of 11 or less.

Styrene / n-butyl methacrylate / methacrylic acid copolymer (polar monomer ratio 40 mol%): 85 parts by mass Porous material r1: 15 parts by mass Using a Henschel mixer so that the above materials are mixed at a predetermined ratio The mixture was stirred and used as a kneaded material. Subsequently, it was put into an extruder and melt kneaded. The obtained kneaded product was cooled and then pulverized using a jet mill. This was applied to an airflow classifier to obtain particles r2 (mother particles) having a sphere equivalent average particle size of 10 μm.

Particle r2 (mother particle): 100 parts by mass Amorphous silica (Aerosil TT600 / Degussa, average particle diameter in terms of sphere: 0.04 μm): 1 part by mass The above materials are stirred and mixed so as to have a predetermined blending ratio. Then, particles R having a sphere equivalent average particle diameter of 15 μm were prepared.

  The characteristics of the produced particles A to Q are summarized in Table 1.

[Examples 1-14, Comparative Examples 1-4]
Each of the above particles was used as ink receiving particles, and the following evaluation was performed using the following ink A. The results are shown in Table 2.

-Ink A-
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.

-Ink component-
-Cyan pigment (CI Pig. Blue 15: 3): 7.5 parts-Styrene / acrylic acid (acid value 150 mg KOH / g): 2.5 parts-Butyl carbitol: 2.5 parts-Diethylene glycol: 10 Parts ・ Glycerol: 25 parts ・ Nonionic surfactant (acetylene glycol derivative): 1 part ・ pH adjuster, fungicide (manufactured by Proxel GXL (S) Arch Chemicals Japan): Small amount ・ Pure water: 60 parts

  The obtained ink had a surface tension of 33 mN / m, a viscosity of 7.2 mPa · s, a pH of 8.8, and a volume average particle diameter of 92 nm.

The image forming method was performed as follows. The particles were dispersed on the intermediate medium using a cake printer. At this time, the amount of particles dispersed was different depending on the type of particles, but was in the range of 5 to 12 g / m ² . A piezo-type ink jet device was used on the intermediate medium on which the particles were dispersed, and 3 pL of ink was applied at an image area ratio of 1200 × 1200 dots per inch to form a predetermined print pattern. An OK topcoat N paper (manufactured by Oji Paper Co., Ltd.) was pressed against the obtained image at 3 × 10 ⁵ Pa, and the recording medium was heated at 90 ° C. for 1 minute.
For image disturbance, after 20 identical images are printed in succession, one different image is printed. The non-image part of the printed sample printed at the end was visually observed and the image disorder was judged as an enlarged image using a microscope.
The evaluation criteria are as follows.
◎: No image distortion occurred in the enlarged image ○: Image distortion occurred in the enlarged image, but could not be discerned visually, and within an allowable range ○ ⁻ : Image disturbance occurred in the enlarged image, Partially visible, but within acceptable range Δ: Overall image disturbance can be visually determined, but acceptable range ×: Image disturbance can be visually identified, outside of allowable range Things

-Optical density-
The optical density was evaluated as follows. A 100% coverage pattern was formed as a print pattern, and the optical density of the obtained image was measured using X-Rite 404 (manufactured by X-Rite).
The evaluation criteria are as follows.
◎: Optical density is 1.4 or more ○: 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. A 1 dot line pattern was printed as a print pattern, and bleeding was judged as an enlarged image using the obtained image and a microscope.
The evaluation criteria are as follows.
A: Even if an image portion is confirmed as an enlarged image, bleeding is not confirmed.
○: When the image portion is confirmed as a magnified image at a high magnification, bleeding can be confirmed, but it cannot be visually determined, and is within an allowable range. ○ ⁻ : The image portion is confirmed as a magnified image at a low magnification. In this case, it is possible to confirm bleeding, but it cannot be visually determined, and is within the allowable range. Δ: Bleeding is recognized in the image portion visually, but within the allowable range ×: bleeding into the image portion visually Is recognized, is severe, and out of tolerance

-Storage stability-
The storage stability was evaluated as follows. Evaluation criteria for evaluating the above-mentioned image disturbance using ink receiving particles stored for 24 hours in an environment of temperature 23 ° C. and humidity 75% RH are as follows.
◎: Image distortion is not generated at all in the enlarged image. ○: Image disturbance is generated at the enlarged image, but cannot be visually recognized, and is within an allowable range. X: Image disturbance can be visually determined. Out of range

  As can be seen from Table 2, it can be seen that in this embodiment, an image can be formed without the disturbance of the fixed image due to an offset or the like as compared with the comparative example.

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.

Explanation of symbols

8 Recording medium 11 Recording device 12 Intermediate transfer member 14 Release agent coating device 14A Release layer 14B Blade 14C Application roller 14D Release agent 16 Ink receiving particles 16A Ink receiving particle layer 16B Image layer 16C Particle layer 16D Residual particles 18 Particle coating device 18A Supply roller 18B Charging blade 19 Ink receiving particle storage cartridge 19A Supply tube 20 Inkjet recording head 20A Ink droplet 23 Transfer device (transfer roller)
23A Heating roll 23B Pressure roll 24 Cleaning device 25 Fixing device (fixing roller)
25A Heating roll 25B Pressurizing roll 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 62 Hole 64 Coupling portion 66 Connecting portion 68 Agitator 100 Ink-receiving particles 101 Base particles 101A Hydrophilic organic particles 101B Hydrophilic organic resin 101C Water-repellent organic material 101D Water-repellent particles 101E Inorganic particles 102A constituting the base particles Hydrophobic organic particles 102B Inorganic particles to be attached

Claims (15)

A hydrophilic organic resin having a ratio of polar monomers to all monomer components of 10 mol% or more and 90 mol% or less;
And at least one of a first organic material having water repellency that is solid at room temperature and having a melting point of 150 ° C. or lower and a second organic material having water repellency that is liquid at normal temperature,
Ink-receiving particles that receive ink.   2. The ink receiving particle according to claim 1, wherein the hydrophilic organic resin has a ratio of a polar monomer to a total monomer component of 30 mol% to 80 mol%.   The ink receiving particles according to claim 1, wherein the melting point of the first organic material is 50 ° C. or higher and 110 ° C. or lower. The hydrophilic organic resin has a ratio of polar monomers to all monomer components of 30 mol% or more and 80 mol% or less,
The second organic material includes at least one selected from silicone oil, fluorine oil, and an organic compound having a solubility parameter (SP value) of 11 or less.
The ink receiving particles according to claim 1.   2. The ink receiving particle according to claim 1, wherein a ratio of a total amount of the first organic material and the second organic material is 1% or more and 15% or less by mass ratio with respect to the whole ink receiving particle. .   2. The ink receiving particle according to claim 1, wherein a ratio of a total amount of the first organic material and the second organic material is 2% or more and 5% or less by mass ratio with respect to the entire ink receiving particle. .   2. The ink receiving particle according to claim 1, wherein a ratio of the hydrophilic organic resin to the whole ink receiving particle is 50% or more and 99% or less by mass ratio.   The ink receptive particles are composite particles having first particles containing the hydrophilic organic resin and second particles containing at least one of the first organic material and the second organic material. The ink receptive particles according to claim 1.   The ink receiving particles according to claim 8, wherein the ink components are captured in a gap between the particles of the composite particles.   The ink receiving particles according to claim 9, wherein the ink includes a recording material, and the recording material is captured in a gap between the particles of the composite particles.   A recording material comprising ink and the ink receiving particles according to claim 1. An intermediate transfer member;
Supply means for supplying the ink receiving particles according to any one of claims 1 to 7 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,
The ink receptive particles are supplied onto the intermediate transfer body and receive the ink ejected from the ink ejection means,
The recording apparatus according to claim 1, wherein the fixing unit includes a release layer formed of at least one of the first organic material and the second organic material included in the ink receiving particles. An intermediate transfer member;
Supply means for supplying the ink receiving particles according to claim 8 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,
The ink receptive particles are supplied onto the intermediate transfer body and receive the ink ejected from the ink ejection means,
The recording apparatus according to claim 1, wherein the fixing unit includes a release layer formed of at least one of the first organic material and the second organic material included in the ink receiving particles. An intermediate transfer member;
Supply means for supplying the ink receiving particles according to claim 10 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,
The ink receptive particles are supplied onto the intermediate transfer body and receive the ink ejected from the ink ejection means,
The recording apparatus according to claim 1, wherein the fixing unit includes a release layer formed of at least one of the first organic material and the second organic material included in the ink receiving particles.   An ink receptive particle storage member that is detachable from the recording apparatus and stores the ink receptive particles according to claim 1.