JP5853623B2 - Silicone material and photocurable ink using the silicone material - Google Patents

Description

  The present invention relates to a liquid toner used in an image forming apparatus using an electrophotographic method such as an electrophotographic method, an electrostatic recording method, and an electrostatic printing method, and a liquid ink used in a recording device using an ink jet method (in the present invention, Hereinafter, these may be collectively referred to as “liquid ink”), and a method for manufacturing the same.

Conventionally, printing presses using plates have been used to produce printed materials that require a certain number of copies, such as regional advertisements, in-house distribution materials, and large posters.
In recent years, on-demand printing presses capable of quickly responding to diversifying needs and capable of compressing inventory are being used in place of such conventional printing presses. As such an on-demand printing machine, an electrophotographic printing machine using dry toner or liquid toner and an inkjet printer capable of high-speed and high-quality printing are expected.

  It is known that an on-demand printer uses a solvent-based ink or a solvent-based liquid toner containing a pigment and an organic solvent, similarly to a printer using a plate. However, with this technique, when a certain number of copies are printed, a non-negligible amount of organic solvent volatilizes. Therefore, there is a problem of atmospheric pollution due to the volatilized organic solvent, and a disposal facility and a solvent recovery mechanism must be provided.

  In an ink jet printer, solvent-based ink can be handled in a closed system until it is discharged onto the printing surface. Therefore, by taking appropriate disposal measures, the problem of atmospheric contamination can be somewhat reduced. However, unlike ink used in a printing press using a plate, ink used in an ink jet printer needs to have fluidity necessary for ejection. Therefore, in the ink jet printer, the solvent concentration in the ink must be made sufficiently high. Therefore, even with this technique, it is essentially difficult to solve the problem of atmospheric contamination caused by the organic solvent.

  In addition, when solvent-based ink is used in an ink jet printer, the printing surface has a great influence on image quality. For example, bleeding tends to occur on a permeable printing surface, and fixing of an image is difficult on a non-permeable printing surface. Furthermore, it takes some time for the ink layer formed on the printing surface to dry. Therefore, when a dark image is formed on a wide printing surface, the image is liable to be crushed due to fluidity. That is, it is not always easy to obtain a high-quality printed material with this technique.

The liquid toner has a problem of atmospheric contamination caused by the organic solvent similar to the ink jet printer. As a solution to this problem, a solution in which colored resin particles are dispersed in a non-volatile liquid such as silicone oil is known.
However, in such a liquid toner, the presence of the non-volatile liquid may prevent the colored resin particles from being bonded to each other at the time of image fixing, and the toner may not be fixed to the recording medium. For this reason, it is necessary to remove the electrically insulating liquid (carrier liquid) in the liquid toner by using a plurality of removing rollers before image fixing, and the image forming apparatus using the liquid toner becomes complicated and demands for high speed are required. It has become difficult to meet.

As an effective technique for the above-described problems, photosensitive ink and a printer system using the same have begun to attract attention. This technique quickly cures the photosensitive ink discharged on the printing surface.
The photosensitive ink used here contains a polymerizable monomer or oligomer, a photopolymerization initiator, and a pigment. By irradiating the photosensitive ink with light such as ultraviolet rays, a polymerization reaction is caused to cure. It can be used at high speed. Furthermore, according to this technique, since the ink layer can be made non-fluidized by light irradiation, a relatively high quality printed matter can be obtained.

For example, as a photosensitive liquid ink for an ink jet system, in Patent Document 1 (Japanese Patent Laid-Open No. 2008-24881), as an ethylenically unsaturated compound having a specific structure, a lot of mainly a (meth) acrylic compound and a styrene compound are used. Cured compositions containing ethylenically unsaturated compounds are disclosed. Further, in Patent Document 2 (Japanese Patent No. 3998559), as a curable liquid, a compound having two or more acrylate bonds as a compound containing two or more ethylenic double bonds and one ethylenic double bond. An active energy ray-curable inkjet ink containing 2-phenoxyethyl acrylate as a compound to be contained is disclosed.
However, the (meth) acrylic compounds used in these inks can satisfy basic performances such as viscosity and photocuring speed when they have a relatively low molecular weight, but they are easy to handle such as odor and skin sensitization. Has a big problem. Thus, it is difficult to achieve both the basic performance of photocuring and the handling performance.

Further, as a liquid ink for electrophotography, Patent Document 3 (Japanese Patent No. 3442406) discloses a curable liquid vehicle having a specific viscosity range and a specific resistance value range as a curable liquid. Acrylic modified silicone is illustrated. More specifically, the silicone portion is described as having an aliphatic or aromatic siloxane chain or ring having a specific dimethylsiloxane unit.

Further, Patent Document 4 (Japanese Patent No. 4150118) discloses that a reactive silicone compound is contained in a molecule as a curable body. As the reactive silicone compound, an isocyanate group, Si— Silicone compounds having a functional group such as H group, vinyl group, amino group, hydroxyl group, epoxy group, methacryl group in the molecule, particularly silicone compounds having a methacryl group are described in the examples.
However, the (meth) acrylic compounds used in these inks have high photocurability, but have a large safety problem. Vinyl monomers such as styrene and (meth) acrylic are generally highly reactive, have a strong and unpleasant odor, are irritating to the skin and eyes and cause allergies. It has a possibility of becoming a product) and has a potential danger, so its use is restricted or its use is prohibited.
In addition, the (meth) acrylic compound used in these inks has a silicone part in the molecule, thereby reducing the concentration of the reactive part (reducing the number of collisions), resulting in insufficient photocuring speed, It is a difficult situation to meet the demand for higher speed.

The present invention has been made in view of the above circumstances, and the object thereof is to have basic performance such as low viscosity and photocuring speed, and handling performance such as low odor and low skin sensitization. It is also possible to provide both a photocurable liquid ink having sufficient fixability and a method for producing the same, as well as being able to achieve both compatibility and further suppressing background stains and image blurring.

As a result of intensive studies by the present inventors, the silicone material represented by the following general formula (1) can be reduced in viscosity even when polymerized, and a conventional functional group such as a (meth) acryloxy group is present in the molecule. It has been found that the photocuring speed is higher than that of the silicone material, and that the basic performance such as low viscosity and photocuring speed can be highly compatible with the handling performance. The present invention has been completed based on such knowledge.
That is, the said subject is solved by following (1)-(9) of this invention.
(1) “silicone material represented by the following general formula (1);

However, in the general formula (1), R1 independently represents a methyl group or a phenyl group, Y represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and l, m, and n are 0 to 0. Represents an integer of 100, X1, X2, and X3 independently represent a methyl group, a phenyl group, or a substituent A having a crotonic ester structure represented by the following general formula (A), and X1, X2, X3 At least one of them is the substituent A.

However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1. "
(2) “A photocurable ink containing at least a colorant and a curable liquid that is cured by light, wherein the curable liquid is represented by the general formula (1) described in the above (1). A photocurable liquid ink characterized by containing a silicone material ",
(3) “The photocurable liquid ink according to (2) above, wherein the silicone material represented by the general formula (1) is a silicone material represented by the following general formula (2);

However, in said general formula (2), Y represents a substituted or unsubstituted C1-C18 alkyl group, l, m, and n represent the integer of 0-100, A is general formula (A). The substituent A having the crotonic ester structure shown is represented.

However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1. "
(4) The photocurable liquid ink according to (2), wherein the silicone material represented by the general formula (1) is a silicone material represented by the following general formula (3);

However, in said general formula (3), l represents the integer of 0-100, A represents the substituent A which has the crotonic acid ester structure shown by general formula (A).

However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1. "
(5) “The colorant is a colored resin particle containing a colorant and a binder resin, and the binder resin has an acidic group. The acidic group, a silicone compound having an epoxy group, and an epoxy The surface of the colored resin particles is chemically modified by reaction with at least one compound selected from an aromatic compound having a group and a long-chain alkyl compound having an epoxy group (2) ) To (4), a photocurable liquid ink according to any one of the above],
(6) The method for producing a photocurable liquid ink according to any one of (2) to (5) above, which contains at least a colorant and a curable liquid that is cured by light.
The colorant is a colored resin particle containing a coloring material and a binder resin having an acidic group,
The colored resin particles and at least one compound selected from a silicone compound having an epoxy group, an aromatic compound having an epoxy group, and a long chain alkyl compound having an epoxy group are dispersed in a curable liquid and colored. A method for producing a photocurable liquid ink, wherein the resin particle surface is chemically modified.
(7) “A resin having an acidic group obtained by neutralizing and dissolving a dispersion of a colorant and a resin having an acidic group obtained by neutralizing and dissolving the colored resin particles in an aqueous solution on a colorant surface by a salting-out method. The method for producing a photocurable liquid ink as described in (6) above, wherein
(8) “An ink containing portion for containing a photocurable liquid ink, and a photocurable liquid ink drawn from the ink containing portion into the electrostatic latent image formed on the image carrier. A developing device including a liquid ink supply unit that supplies ink, wherein the photocurable liquid ink is the photocurable liquid ink according to any one of (2) to (5). Development device featuring ",
(9) “An image carrier on which an electrostatic latent image is formed, a developing device that supplies a photocurable liquid ink to the electrostatic latent image formed on the image carrier and develops the liquid ink image; A transfer device for transferring the liquid ink image formed by the developing device from the image carrier onto a recording medium, and irradiating the liquid ink image transferred by the transfer device with light to cure the photocurable liquid ink. An image forming apparatus comprising: a fixing device that fixes the liquid ink image on the recording medium, wherein the photocurable liquid ink is any one of (2) to (5). An image forming apparatus characterized by being a photocurable liquid ink.

As will be understood from the following detailed and specific description, according to the present invention, it is possible to reduce the viscosity even when polymerized, and a functional group such as a conventional (meth) acryloxy group in the molecule. A silicone material represented by the general formula (1) can be provided which has a high photocuring speed as compared with the silicone material and has a high level of both basic performance such as low viscosity and photocuring speed and handling performance.
In addition, the photocurable liquid ink containing silicone represented by the general formula (1) can achieve both high levels of basic performance such as low viscosity and photocuring speed and handling performance, and further suppress background stains and image blurring. In addition, it is possible to provide a photocurable liquid ink having sufficient fixability and a method for producing the same.

1 is a diagram illustrating a schematic configuration of an image forming apparatus according to an embodiment of the present invention. It is a figure which shows schematic structure of the image forming apparatus which concerns on other embodiment by this invention. It is an infrared absorption spectrum figure of a substituent A-1 alkenyl body. It is an infrared absorption spectrum figure of a substituent A-2 alkenyl body. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-1. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-2. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-3. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-4. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-5. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-8. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-9. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-10. It is an infrared absorption spectrum figure of the silicone material of the synthesis example IV-11.

  Hereinafter, preferred embodiments of the photocurable liquid ink and the method for producing the same of the present invention will be described in detail. The photocurable liquid ink of the present invention contains at least a colorant and a curable liquid that is cured by light.

(Curable liquid)
The curable liquid of the present invention contains a silicone material represented by the following general formula (1).

However, in the general formula (1), R1 independently represents a methyl group or a phenyl group, Y represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and l, m, and n are 0 to 0. Represents an integer of 100, X1, X2, and X3 independently represent a methyl group, a phenyl group, or a substituent A having a crotonic ester structure represented by the following general formula (A), and X1, X2, X3 At least one of them is the substituent A.

However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1.

Examples of the C1 to C4 alkylene group represented by R2 and R3 in the general formula (A) include a methylene group, an ethylene group, a propylene group, a butylene group, and positional isomers thereof.

In the general formula (1), the substituted or unsubstituted alkyl group having 1 to 18 carbon atoms of Y provides the reaction field of the substituent A, and the viscosity, resistance value, dielectric constant, etc. of the general formula (1) Examples of the substituted or unsubstituted alkyl group having 1 to 18 carbon atoms used for adjusting the liquid physical properties include alkyl compounds (substituent C) represented by the following general formula (C).
(Substituent C)

(However, in the general formula of the substituent C, Z1 represents a C1-C16 alkyl group.)

Examples of the C1-C16 alkyl group of Z1 include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, Examples thereof include a tetradecyl group, a hexadecyl group, and positional isomers thereof.

Moreover, as a substituent of Y, hydrocarbon groups, such as a cyclopentyl group, a cyclohexyl group, a phenyl group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a peptyloxy group, an octyloxy group And an alkoxy group having an aromatic group such as phenyloxy group, benzyloxy group and phenethyloxy group, and a low molecular alkylene group such as methylene group, ethylene group and propylene group. And an alkoxy group having an aromatic group via a low-molecular alkylene group such as a methylene group, an ethylene group or a propylene group, or a siloxane compound (substituent D) represented by the following general formula (D) Can be mentioned.
(Substituent D)

(However, in the above general formula (D), Z2 is a single bond or a C1-C4 alkylene group, R is independently a methyl group or a phenyl group, and n is an integer of 0-10.)
Examples of the alkylene group having 1 to 4 carbon atoms of Z2 include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and positional isomers thereof.

Of the silicone materials represented by the general formula (1), silicone materials represented by the following general formula (2) or the following general formula (3) can be preferably used.

However, in said general formula (2), Y represents a substituted or unsubstituted C1-C18 alkyl group, l, m, and n represent the integer of 0-100, A is said general formula (A). The substituent A which has a crotonic ester structure shown by these is represented.

However, in said general formula (3), l represents the integer of 0-100, A represents the substituent A which has the crotonic acid ester structure shown by the said general formula (A).

  Although the silicone material represented by the general formula (1) has a low viscosity, a low odor, and a low skin sensitization compared with a material having a functional group such as a conventional (meth) acryloxy group in the molecule. Regardless, the reason for the excellent high photocurability is not clear, but the silicone material produces a weak repulsion in the interaction between the silicone backbone and the crotonic ester segment, resulting in the molecules of the silicone material, or It is presumed that an intermolecular “microphase separation” state was formed, a partial concentration effect of the aromatic ester segment portion was generated, and high photocurability was achieved. In this case, it is presumed that the crotonic acid ester segment portion is deeply involved in the interaction.

  The silicone material represented by the general formula (1) of the present invention can be produced by hydrosilylating a methyl hydrogen silicone material having a hydrogen atom and the following alkenyl compound corresponding to the substituent A.

A commercially available product can be used as the methyl hydrogen silicone material having a hydrogen atom.
For example, 423785 (average molecular weight: ~ 580, manufactured by Aldrich), 482064 (average molecular weight: ~ 17500, manufactured by Aldrich), DMS-H03 (molecular weight: 400-500, manufactured by Gelest) DMS-H11 (molecular weight) : 1000-1100, manufactured by Gelest), and 482196 (average molecular weight: 950, manufactured by Aldrich), 482374 (average molecular weight: -13000, manufactured by Aldrich), HMS-501 (molecular weight: 900-1200, Gelest) Manufactured), HMS-031 (molecular weight: 1900-2000, manufactured by Gelest), HMS-071 (molecular weight: 1900-2000, manufactured by Gelest), HMS-151 (molecular weight: 1900-2000, manufactured by Gelest), HMS-301 (molecular weight) : 1900 2000, manufactured by Gelest) HMS-991 (molecular weight: 1400-1800, manufactured by Gelest) SH1107 (viscosity: 20 mm ² / s, manufactured by Toray Dow Corning), KF-99 (viscosity: 20 mm ² / s, Shin-Etsu Chemical) And KF-9901 (viscosity: 20 mm ² / s, manufactured by Shin-Etsu Chemical Co., Ltd.).

(Alkenyl compound corresponding to Substituent A)

In the above formula, R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1.

  The alkenyl body corresponding to the substituent A can be produced from the corresponding alcohol body and carboxylic acid body or carboxylic acid anhydride body by an esterification reaction (condensation reaction). The reaction can be used. For example, a carboxylic acid anhydride (1 mol) is added to a toluene solution of the corresponding alcohol (1 mol), triethylamine (1 mol), and N, N-dimethylaminopyridine catalyst amount (0.1 mol). Thus, an alkenyl compound corresponding to the target substituent A can be produced almost quantitatively.

As for Y in the general formula (1), similarly to the alkenyl compound corresponding to the substituent A, the following alkenyl compound corresponding to the substituent C or the substituent D can be hydrosilylated.

(Alkenyl compound corresponding to substituent C)

In the above formula, Z1 represents a C1-C16 alkyl group.

(Alkenyl compound corresponding to Substituent D)

In the above formula, Z2 is a single bond or a C1-C4 alkylene group, R is independently a methyl group or a phenyl group, and n is an integer of 0-10.

In the hydrosilylation reaction, the desired compound can be obtained by heating at room temperature or in the presence of a solvent or in the absence of a solvent, but it is preferably in the presence of a catalyst.
A platinum catalyst can be used as the catalyst. As reaction conditions, it can synthesize | combine by the heat processing of room temperature-150 degreeC in presence of a solvent and a catalyst, for example. Furthermore, it is preferable to distill off the low molecular weight product and the unreacted raw material under reduced pressure after completion of the reaction (stripping treatment). Furthermore, it is preferable to purify by distillation.

Examples of the platinum catalyst include platinum alone, alumina, silica, carbon black and other solid carriers supported on platinum, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, platinum-phosphine complexes, platinum -Phosphite complexes, dicarbonyldichloroplatinum, Karlstedt catalyst and the like. Among these, chloroplatinic acid, platinum-olefin complexes, platinum-vinylsiloxane complexes, and the like are preferable from the viewpoint of catalytic activity.
These catalysts can be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular in the usage-amount of a catalyst, Usually, a platinum catalyst is used in 10 ^{< -1} > ^-10 <^-8> mol with respect to 1 mol of alkenyl groups, and it is used in the range of 10 ^{< -3} > ^-10 <^-6> mol. It is preferable to do. If the amount of catalyst is less than 10 ⁻⁸ mol, the hydrosilylation reaction may not proceed sufficiently. If the amount of catalyst is too large, the cost of raw materials will increase or the transparency of the target product will decrease due to the incorporation of catalyst residues. Problems occur.

As the solvent used in the hydrosilylation reaction, usually hydrocarbons, halogenated hydrocarbons, ethers, esters can be used, but heptane, hexane, benzene, toluene, xylene, etc. are preferably used. .

Furthermore, the hydrosilylation reaction can be performed in the presence of an antioxidant.
As the antioxidant, a phenolic antioxidant having a function of a radical chain inhibitor, for example, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, or the like is used. Can do. As a similar radical chain inhibitor, amine-based antioxidants such as N-phenyl-β-naphthylamine, N, N′-di-sec-butyl-p-phenylenediamine, phenothiazine and the like can be used.

(Coloring agent)
Next, the colorant that is an essential component of the photocurable liquid ink of the present invention will be described.
The colorant is used by forming colored resin particles with a coloring material and a binder resin and dispersing in a curable liquid.
It is preferable to disperse the colorant using an additive such as a dispersant / dispersion stabilizer because the uniformity of the photocurable liquid ink is excellent.
Further, the colorant can further contain additives such as a charge control agent and wax, if necessary.

Examples of the color material include various pigments and dyes.
Conventionally known pigments can be used as the organic pigment, and any pigment can be used. Examples of suitable organic pigments include aniline blue, calcoil blue, chrome yellow, ultramarine blue, and DuPont. Oil red, quinoline yellow, methylene blue chloride, copper phthalocyanine, malachite green oxalate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 184, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Solvent Yellow 162, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment blue 15: 1, C.I. I. And CI Pigment Blue 15: 3.

  A conventionally well-known pigment can be used as an inorganic pigment. Although any pigment can be used, examples of suitable inorganic pigments include carbon black, titanium oxide, bengara, ferrite, and magnetite. These color materials can be used alone or in combination as desired.

These color materials are used as colored resin particles coated with a binder resin.
Colored resin particles include what are called color chips (made by Taihei Chemical Co., Ltd., Taisei Kagaku Co., Ltd.) or microliths (Ciba Specialty Chemicals Co., Ltd.), which are a mixture of pigment and binder resin heated with two rolls. Commercially available processing colorants such as
Further, as the processing colorant, those obtained by any known method such as a coacervation method in which a pigment is dispersed in a resin solution and a poor solvent is added thereto to precipitate the resin on the pigment surface can be used. .

The amount of the coloring material used is 10 to 80% by weight, preferably 30 to 60% by weight, based on the colored resin particles (including the colored resin particles having acidic groups on the surface).

The glass transition point (Tg) of the resin constituting the colored resin particles according to the present invention is not particularly limited, but is preferably in the range of 50 to 120 ° C. The molecular weight of the resin particles according to the present invention is not particularly limited, but is preferably 2000 to 50000 in terms of mass average molecular weight.

As said binder resin, if it is resin which has acidic groups, such as a carboxyl group and a sulfonic acid group, or those groups into which those salts were introduce | transduced, it can be used.
For example, in addition to (meth) acrylic resin, natural resins such as styrene resin, epoxy resin, urethane resin, vinyl resin, phenol resin, polyester resin, polyamide resin, melamine resin, gelatin, casein, cellulose starch, etc. A copolymer resin such as a resin can be used.

Further, these binder resins may have a crosslinked structure formed according to the purpose of use. The binder resin having an acidic group is more preferably blended so that the acid value is in the range of 10 to 300 (mgKOH / g). When the acid value is 10 (mgKOH / g) or less, the solubility in an aqueous solvent is deteriorated, and as a result, the homogenization of particles is impaired, and the relative standard deviation value (CV value) may exceed 50%. . On the other hand, when the acid value is 300 (mgKOH / g) or more, the characteristics are hardly improved, and the cost for neutralization only increases.
Therefore, when the acid value is within a range of 10 to 300 (mgKOH / g), the dispersion stability during the production of colored resin particles can be improved, and the amount of the dispersant or the dispersion stabilizer can be reduced (self (Dispersion type), as a result, particles having high monodispersibility can be produced, and further, it is advantageous in terms of operation and environment such as reduction in the number of washings. Therefore, the monomer having an acidic group is more preferably blended so that the acid value is in the range of 10 to 300.

The colored resin particles can be produced by a conventionally known method according to the type of resin component and the desired particle size or shape.
Examples include suspension production methods, emulsion polymerization methods, dispersion polymerization methods, emulsion dispersion granulation methods, coacervation methods, seed polymerization methods and other wet production methods, pulverization methods, spray drying methods and other dry production methods. In terms of obtaining uniform spherical colored resin particles in a high yield, it is preferable to produce them by a wet production method.

Furthermore, the production of colored resin particles having acidic groups on the surface is a wet production method, and by using an aqueous solvent for the continuous phase, acidic groups that are polar groups in the production of colored resin particles are specifically particles. It is advantageous in that it is formed on the surface, and the acidic group formed on the surface is preferable because it can greatly contribute to the stabilization of the dispersion of the generated colored resin particles (self-dispersing type).

Furthermore, among the wet production methods, colored resin particles can be obtained by the emulsion dispersion granulation method or the coacervation method because of the variety of usable resins, the ease of molecular weight adjustment, the sharpness of the particle size distribution, etc. Is desirable.

The emulsification dispersion granulation method or the coacervation method is a method of granulating using the difference in solubility of the binder resin to be used in the solvent, and a conventionally known method can be appropriately used.
For example, in the emulsion dispersion granulation method, a resin solution obtained by dissolving a resin in a water-insoluble organic solvent is emulsified and dispersed in an aqueous continuous phase to form an O / W emulsion, and the O / W emulsion is stirred while stirring. This is a method of further removing the organic solvent and precipitating the resin particles.
The coacervation method is a method in which a binder resin is dissolved in a water-soluble solvent, and this resin solution is dropped into a poor solvent (aqueous continuous phase) with stirring with respect to the binder resin. In this case, in the resin or in the dispersion containing the resin, various additives such as a dispersant, a heat stabilizer, an antioxidant, and an ultraviolet absorber are uniformly dissolved in addition to the colorant, if necessary. You may make it disperse | distribute.
According to these methods, the process is simplified, and colored resin particles can be obtained by a relatively simple operation. Therefore, production efficiency can be improved and costs can be reduced.

In addition, as in the emulsion dispersion granulation method or the coacervation method, there is a salting out method as a further devised method for granulating using the difference in solubility for the binder resin to be used.
In the salting-out method, a coloring material is dispersed at a predetermined temperature in a solution obtained by solubilizing a binder resin having an acidic group in an aqueous solvent by neutralization. This dispersion is stably dispersed in an aqueous solvent by the action of the electric double layer in a form in which a color material is taken in with an acid group salt. Next, the binder resin neutralized on the colorant is destabilized by adding an electrolyte that destroys or reduces the electric double layer to the dispersion solution, thereby destabilizing the neutralized binder resin. To form colored resin particles (salting out), and then the binder resin neutralized with acid is returned to the acid form (fixed), separated by filtration or the like, and washed with water. By performing and drying, colored resin particles having an acidic group on the surface can be produced.
In this salting-out method, the resin is precipitated in a uniform system from the resin solution, so that very uniform and homogeneous colored resin particles can be obtained. Further, it is simple and minimizes the use of a dispersant or a dispersion stabilizer. This is a production method that is unnecessary or unnecessary, and has few dispersants or dispersion stabilizers attached to the colored resin particles, and can be suitably used.

The temperature at the time of salting out may be any temperature as long as it is not higher than the glass transition point (Tg) of the binder resin, but is more preferably [Tg-50] ° C. or lower. In the range of Tg to [Tg-50] ° C., although depending on the salting-out conditions, coalescence is likely to occur during granulation, resulting in a lump.

For neutralizing the binder resin having an acidic group, a basic compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, or ammonia is used.

The aqueous solvent means a hydrophilic organic solvent having a solubility in water at 20 ° C. of 2% or more. Examples of the hydrophilic organic solvent include methyl alcohol, ethyl alcohol, modified ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, 3-pentanol, Alcohols such as benzyl alcohol, cyclohexanol, ethylene glycol, glycerin and diethylene glycol, ether alcohols such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve (registered trademark), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, tetrahydrofuran, ethylene glycol Ethers such as dimethyl ether and dioxane, pyridine, dimethylform Such as a nitrogen atom-containing organic solvents amides. These hydrophilic organic solvents can be used singly or as a mixture of two or more. Of these, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol are more preferable.
The dispersion stability of the resin solution can be controlled by a mixed solvent of these hydrophilic organic solvent and water.
The ratio of the hydrophilic organic solvent in adjusting the aqueous solvent is preferably 50% by weight or less with respect to the aqueous solvent. If the ratio of the hydrophilic organic solvent exceeds 50% by weight, the resulting colored resin particles may coalesce and the particle size and particle size distribution may not be controlled.

Examples of the electrolyte include acidic substances such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, and oxalic acid, organic substances such as sodium sulfate, ammonium sulfate, potassium sulfate, magnesium sulfate, sodium phosphate, sodium chloride, potassium chloride, and sodium acetate. Examples thereof include inorganic water-soluble salts. These electrolytes may be used alone or in combination of two or more substances. Among these, monovalent cation sulfates such as sodium sulfate, ammonium sulfate, and potassium sulfate are preferable for promoting uniform precipitation. These electrolytes may be added in the form of powder while stirring the dispersion solution. However, in order to ensure more uniformity, it is preferable to drop the aqueous electrolyte solution while stirring the dispersion solution. In this case, various additives such as a dispersant, a heat stabilizer, an antioxidant, and an ultraviolet absorber may be uniformly dissolved and dispersed in the resin or the resin solution as necessary.

In this case, the particle size and particle size distribution can be controlled by the precipitation rate of the neutralized resin during salting out.
That is, it was recognized that when the deposition rate is high, colored resin particles having a small particle size are formed, and when the deposition rate is low, colored resin particles having a large particle size are formed. In particular, when producing colored resin particles having a relatively large particle size, a low stirring speed and a low electrolyte addition speed are required, and the possibility that the resulting colored resin particles coalesce increases. In some cases, auxiliary means such as a mixed solvent (aqueous solvent) or an additive such as a dispersion stabilizer may be necessary.
The colored resin particles having an acidic group are preferably particles having an average particle diameter of 0.01 to 5 μm.

Since the particle size distribution of the colored resin particles is reflected in the particle size distribution of the colored resin particles whose surface in the photocurable liquid ink to be produced is modified, those having high monodispersity are preferable, and relative standards The deviation (CV value) is preferably 50% or less.
When the relative standard deviation (CV value) exceeds 50%, the particle size distribution of the colored resin particles whose surface is modified in the photocurable liquid ink produced from the colored resin particles is widened, and the particle size is not uniform. The properties of the resulting particles are remarkably impaired. For example, the dispersibility and dispersion stability of the photocurable liquid ink are impaired, which causes a problem.

The relative standard deviation (CV value) is calculated by the following formula (1).
Relative standard deviation (CV value (%)) = (sd / m) × 100 (1)
(In the above formula, sd represents the standard deviation of the particle diameter, and m represents the average diameter.)
The above sd and m are numerical values obtained by a dynamic light scattering method using a particle size analyzer (FPAR-1000: manufactured by Otsuka Electronics Co., Ltd.).

  The acid value (mgKOH / g) of the produced colored resin particles is preferably within the range of 3 to 200. When the acid value is 3 or less, the reaction is restricted in the chemical modification with the silicone compound having an epoxy group and / or the long-chain alkyl compound having an epoxy group in the next step, and the silicone group on the surface of the colored resin particles, and / or Or, the function of the long chain alkyl group is not fully exhibited, good dispersibility / dispersion stability cannot be obtained, and when the acid value is 200 or more, almost no improvement in properties is observed, and the surface of the colored resin particles It appears that the function of the silicone group and / or the long chain alkyl group has reached saturation.

Next, the additive used for preparation of the particle | grains which have the said acidic group is demonstrated.
When producing colored resin particles having an acidic group, a surfactant may be added as necessary. The blending amount of the surfactant is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total monomers. The surfactant is not particularly limited, but the following ionic and nonionic surfactants are preferably used.

  Examples of the ionic surfactant include sodium dodecylbenzenesulfonate, sodium arylalkylpolyethersulfonate, sodium 3,3-disulfonediphenylurea-4,4-diazobis-amino-8-naphthol-6-sulfonate, Sulfates such as sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium dialkylsulfosuccinate, etc., sodium oleate, sodium laurate, sodium caprate, sodium caproate, potassium stearate, etc. Examples include fatty acid salts.

  Nonionic surfactants include polyethylene oxide, polypropylene oxide, a combination of polyethylene oxide and polypropylene oxide, higher fatty acid esters of polyethylene glycol, higher fatty acid esters of polypropylene oxide, alkylphenol polyethylene oxide, alkylphenol polypropylene oxide, polyethylene oxide alkyl. Examples include ether, polypropylene oxide alkyl ether glycol, sorbitan ester and the like.

  Furthermore, a dispersion stabilizer may be added to the particles having the acidic group as necessary. Examples of the dispersion stabilizer include partially saponified polyvinyl alcohol, poly (meth) acrylic acid, polystyrene-poly (meth) acrylic acid copolymer, poly (meth) acrylic acid-poly (meth) acrylic acid ester copolymer. Polymer, Polyvinyl pyrrolidone, Polyvinyl ether, Gelatin, Methyl cellulose, Ethyl cellulose, Hydroxyethyl cellulose, Polymer dispersion stabilizer such as sodium salt of carboxymethyl cellulose, Calcium phosphate, Magnesium phosphate, Aluminum phosphate, Calcium carbonate, Magnesium carbonate, Barium sulfate, Water Examples thereof include inorganic dispersion stabilizers such as magnesium oxide and bentonite.

The disperser used for the dispersion treatment of the colorant is not particularly limited, but preferably an ultrasonic disperser, a pressure disperser such as a mechanical homogenizer or a pressure homogenizer, a medium type dispersion such as a sand grinder, a diamond fine mill, or a bead mill. Machine.

Next, the surface-treated colored resin particles will be described.
The surface-treated colored resin particles are the above-described colored resin particles having acidic groups on the surface, at least one of a silicone compound having an epoxy group, an aromatic compound having an epoxy group, and a long-chain alkyl compound having an epoxy group. It is obtained by chemical modification with a seed. The chemical modification is mainly due to a chemical reaction between an acidic group and an epoxy group on the surface of the colored resin particle, and a silicone group, an aromatic group and / or a long-chain alkyl group are introduced to the surface of the colored resin particle via an ester group. By direct bonding, the silicone group, aromatic group and / or long-chain alkyl group coats the colored resin particles, and the colored resin particles are well dispersed without causing aggregation or fusion between the colored resin particles. Property, redispersibility, and dispersion stability over a long period of time can be achieved.

The surface-treated colored resin particles include colored resin particles having acidic groups on the surface, a silicone compound having an epoxy group, an aromatic compound having an epoxy group, and / or a long-chain alkyl compound having an epoxy group in an organic solvent. It can be produced by processing and chemical modification.

The organic solvent to be used dissolves or partially dissolves a silicone compound having an epoxy group, an aromatic compound having an epoxy group and / or a long-chain alkyl compound having an epoxy group without dissolving colored resin particles having an acidic group. Any organic solvent can be used as long as it can be dissolved, but a hydrocarbon-based solvent or a reaction inert organic solvent such as silicone oil can be preferably used.

The silicone compound having an epoxy group, the aromatic compound having an epoxy group and / or the long chain alkyl compound having an epoxy group will be described.
The silicone compound having an epoxy group has, for example, a molecular structure represented by the following general formula (4).

In the general formula (4), R ₁₁ is an epoxy group such as an epoxy group or an epoxy cyclohexane group, q is 0 or 1, R ₁₂ and R ₁₃ are independently a single bond, a methylene group or an ethylene group. , A propylene group, a butylene group and other alkylene groups having 1 to 4 carbon atoms, and their positional isomers, R ₁₄ has a dimethylpolysiloxane skeleton, and a lower alkyl having 1 to 6 carbon atoms as a terminal substituent. Those having a group are preferred.
The dimethylsiloxane unit (degree of polymerization) is 1 to 50, more preferably 1 to 16.

  The silicone compound having an epoxy is already commercially available, and a commercially available product can be used. Among them, preferable specific examples include (3-glycidoxypropyl) bis (trimethylsiloxy) methylsilane (manufactured by Tokyo Chemical Industry), (3-glycidoxypropyl) pentamethyldisiloxane (manufactured by Amax Co.), and the like. Molecular weight epoxy-modified silicone, MCR-E11 (manufactured by Amax), MCR-E21 (manufactured by Amax), X-22-173DX (manufactured by Shin-Etsu Chemical), FZ-3720 (manufactured by Toray Dow Corning), BY16-839 ( And high molecular weight epoxy-modified silicones such as SF8411 (manufactured by Toray Dow Corning).

Examples of the aromatic compound having an epoxy group include compounds such as benzyl glycidyl ether, glycidyl 4-tert-butylbenzoate, and phenol (EO) 5 glycidyl ether.

  Specific examples of the long-chain alkyl compound having an epoxy group include 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2- Alkyl glycidyl ethers such as epoxy dodecane, 1,2-epoxy tetradecane, 1,2-epoxy hexadecane, 1,2-epoxy octadecane, 1,2-epoxy eicosane, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, benzyl glycidyl ether Examples thereof include long-chain alkyl carboxylic acid ester compounds such as compounds, glycidyl butyrate ester, glycidyl stearate, and glycidyl neodecanoate.

Next, the production of the surface-treated colored resin particles basically has surface acidic groups in the colored resin particles, a silicone compound having an epoxy group, an aromatic compound having an epoxy group, and / or an epoxy group. The esterification (reaction) of the acidic group proceeds by collision with the epoxy group in the long-chain alkyl compound in the organic solvent, and the colored resin particles having the acidic group on the surface are in an aggregated state at the initial stage of the treatment (reaction). As the treatment (reaction) progresses, the compatibility with the organic solvent increases, and in the latter stage of the treatment (reaction), it is considered that most of the aggregated state proceeds to the primary particle dispersed state.
Therefore, the production of the surface-treated colored resin particles is preferably performed under stirring, and the stirring may be performed to such an extent that the entire reaction solution flows with a stirrer such as a three-one motor. As the stirring blade, a flat turbine blade, a propeller blade, an anchor blade, or the like can be used. Furthermore, pressure dispersers such as ultrasonic dispersers, mechanical homogenizers and pressure homogenizers, medium type dispersers such as sand grinders, diamond fine mills and bead mills, among which ultrasonic dispersers with excellent dispersion efficiency are preferably used. be able to.

Further, the surface-treated colored resin particles can be produced under heating as necessary, and the temperature is 80 ° C. from room temperature, preferably 50 ° C. from room temperature.

The silicone compound having an epoxy group, the aromatic compound having an epoxy group and / or the long chain alkyl compound having an epoxy group is added in an amount of 1 to 5 equivalents relative to the acid value of the colored resin particles having an acidic group on the surface. Thus, chemical modification is preferable.

The photocurable liquid ink of the present invention will be described.
The photocurable liquid ink contains at least a colorant and a curable liquid that is cured by light, and the curable liquid contains a silicone material represented by the general formula (1).
The production of the photocurable liquid ink according to the present invention comprises: (i) coloring resin particles having an acidic group on the surface, a silicone compound having an epoxy group, an aromatic compound having an epoxy group and / or an epoxy group in a curable liquid. (Ii) a colored resin particle having an acidic group on its surface in an organic solvent, a silicone compound having an epoxy group, an aromatic compound having an epoxy group, and / or an epoxy. After producing colored resin particles obtained by chemical modification using a long-chain alkyl compound having a group, the organic resin is removed or the colored resin particles which have been surface-treated by filtration are separated, and then re-converted into a curable liquid. In the production of the photocurable liquid ink of the present invention, the method (i) is “the surface-treated colored resin particles”. A method of producing a child in one step in a curable liquid is effective. This is because the silicone treatment (reaction) having an epoxy group of colored resin particles having acidic groups on the surface, the aromatic compound treatment (reaction) having an epoxy group, and / or the long chain alkyl treatment (reaction) having an epoxy group, As a result, only ester groups and alcoholic OH groups are generated, and there is no need for other additives (catalysts, etc.), and the effect on the liquid physical properties of the photocurable ink is very small. Yes.

The content of the surface-treated colored resin particles contained in the photocurable liquid ink of the present invention is preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight based on the total amount of the photocurable liquid ink. . When the content of the surface-treated colored resin particles is less than 0.5% by weight, the coloring power is poor and a sufficient image density may not be obtained in a printed image. On the other hand, if it exceeds 50% by weight, the viscosity of the liquid ink is increased, and the transportability, stretchability, and photocurability of the liquid ink in the printing apparatus are inferior, and a good printed image may not be obtained.
In addition, the average particle diameter (weight average particle diameter) of the surface-treated colored resin particles is preferably 0.01 to 5 μm. Colored resin particles larger than 5 μm not only cause a reduction in image quality, but also tend to settle if left standing, and may cause aggregation of the colored resin particles. On the other hand, if it is 0.01 μm or less, the cohesive force increases and handling becomes difficult.

Furthermore, in the photocurable liquid ink of the present invention, in the silicone material represented by the general formula (1), which is a curable liquid, as necessary for the purpose of adjusting liquid properties such as viscosity, resistance value, and dielectric constant. In addition, a non-reactive liquid such as high-purity petroleum or silicone oil can be added.

Specific commercial products of the high-purity petroleum include, for example, Isopar G, H, L, M (manufactured by Exxon Chemical) and Norper 12 (manufactured by Exxon Chemical).

Examples of the silicone oil include SH-200 series (manufactured by Dow Corning Toray), KF-96 series (manufactured by Shin-Etsu Chemical), L-45 series (manufactured by Nihon Unicar), and AK series (Asahi Kasei Wacker Silicone). Etc.). Furthermore, silicone oil can be preferably used in these non-reactive liquids.
The amount of these non-reactive liquids used is 0 to 20% by weight of the total electrical insulating liquid including the curable liquid contained in the photo-curable liquid ink. It is not preferable because there is a risk of incurring.

Examples of other components contained in the photocurable liquid ink of the present invention include a wax and a charge control agent.
The wax is not particularly limited and may be appropriately selected from known ones. Examples thereof include paraffin wax, polyethylene wax, polypropylene wax, polyester wax, alcohol wax, urethane wax and the like. These waxes may be used alone or in combination of two or more.

  The charge control agent is not particularly limited and may be appropriately selected from known ones. For example, metal sulfosulfosuccinates such as cobalt dialkylsulfosuccinate, manganese dialkylsulfosuccinate, zirconium dialkylsulfosuccinate and nickel dialkylsulfosuccinate; Naphthenic acid metal salts such as manganese naphthenate, calcium naphthenate, zirconium naphthenate, cobalt naphthenate, iron naphthenate, nickel naphthenate; manganese octylate, zirconium octylate, calcium octylate, iron octylate, cobalt octylate, etc. Metal salt of dodecyl acid such as calcium dodecylate, manganese dodecylate, zirconium dodecylate, manganese dodecylate, magnesium dodecylate, etc .; sodium dodecylbenzenesulfonate Alkylbenzene sulfonic acid metal salts such as calcium, calcium dodecylbenzene sulfonate, barium dodecylbenzene sulfonate; metal-containing dyes such as lecithin, fluorosurfactants, salicylic acid metal complexes, azo compounds, quaternary ammonium salts, nigrosine, etc. Examples include azine dyes. These may be used alone or in combination of two or more.

Moreover, you may add a well-known additive further to the photocurable liquid ink of this invention as needed. Examples thereof include a dispersant, a heat stabilizer, an antiseptic, a surface tension adjuster, a polymerization inhibitor, an antioxidant, a near infrared absorber, an ultraviolet absorber, a fluorescent agent, and a fluorescent brightening agent. In particular, the polymerization inhibitor is added so that a monomer or oligomer having a functional unsaturated group of the curable liquid does not react with heat. Examples of the polymerization inhibitor include 2,6-di-tert-butyl-4-cresol, anthraquinone, hydroquinone, hydroquinone monomethyl ether, etc. Among them, 2,6-di-tert-butyl-4-cresol is a photocurable type. It is preferably used because it has very little influence on the liquid physical properties of the liquid ink. These may be used alone or in combination of two or more.

(Developer)
Next, an electrophotographic developing apparatus and an image forming apparatus using the photocurable liquid ink according to the present invention will be described with reference to FIGS. FIG. 1 is a diagram showing a schematic configuration of an image forming apparatus according to an embodiment of the present invention. FIG. 2 is a diagram showing a schematic configuration of an image forming apparatus according to another embodiment of the present invention.

  FIG. 1 shows a schematic configuration of an image forming apparatus used in an image forming method as an embodiment of the present invention. In this image forming apparatus, a photosensitive drum (1) (for example, an organic photosensitive member: OPC), which is a latent image carrier, is disposed in the approximate center of a base frame (not shown), and the photosensitive drum (1) is rotated perpendicularly to the paper surface. Equipped to be rotatable around the axis. A document placement surface (not shown) for placing a document is provided above the photosensitive drum (1), and a document image on the document placement surface is read as an image signal by a known image reading element (not shown). The read image signal is digitized and subjected to image processing, and sent to a known optical writing unit (3). The optical writing unit (3) performs optical writing on the photosensitive drum (1).

  At this time, an electrostatic latent image is formed on the surface of the photosensitive drum (1) which has already been uniformly charged by the charging charger (2) and has reached the optical writing unit (3). The electrostatic latent image is removed from the latent image in a predetermined area by the erase lamp (4), and reaches the developing device (5) provided on the side of the photosensitive drum (1). The developing device (5) converts the electrostatic latent image into a visible toner image with a developing solution, and this toner image reaches the transfer device (6) and is a recording sheet sent from a paper feeding unit (not shown). The image is transferred to a certain transfer paper (P) by corona discharge of the transfer charger (8). Thereafter, the transfer paper (P) onto which the toner image has been transferred is separated from the surface of the photosensitive drum (1) by a separation charger (not shown), and after the toner image on the transfer paper is fixed by a fixing unit (not shown), The paper is discharged to a paper discharge tray (not shown). The developer remaining on the surface of the photosensitive drum (1) after the transfer is removed by the cleaning device (9), and the charge is uniformly removed by the charge removal lamp (10), and the process proceeds to the next image forming process.

  Next, the developing device (5), the transfer device (6), and the cleaning device (9) in FIG. 1 will be further described. The developing device (5) is a wet developing device using a liquid ink in which toner particles made of a colorant are dispersed in a carrier liquid containing a curable liquid. The developing device (5) is supported by a base frame and is also a photosensitive drum (1). A container (51) opening toward the outer peripheral surface of the container, a developing roller (52) as a developing electrode pivotally supported in the container (51), a squeeze roller (53) as surplus liquid removing means, and a container (51 ) And a squeeze roller scraper (55) which is supported by the inner wall of the container (51) and removes liquid ink on the outer peripheral surface of the squeeze roller (53). (57) and a supply nozzle (54) of the liquid ink supply pipe system (58). Here, both rotation axes of the developing roller (52) and the squeeze roller (53) are arranged in the direction perpendicular to the paper surface of FIG. 1, and the developing roller is located upstream along the rotational direction of the outer peripheral surface of the photosensitive drum (1). (52), squeeze rollers (53) are sequentially arranged in parallel on the downstream side.

The outer peripheral surface of the developing roller (52) is disposed on the outer peripheral surface of the photosensitive drum (1) with a gap A, and the outer peripheral surface is in the same direction b as the moving direction a of the outer peripheral surface of the photosensitive drum (1). It is driven by the rotational drive means (80) so as to move to the position. The squeeze roller (53) has its outer peripheral surface disposed on the outer peripheral surface of the photosensitive drum (1) with a gap B, and its outer peripheral surface is in a direction opposite to the moving direction a of the outer peripheral surface of the photosensitive drum (1). It is driven by the rotation drive means (81) so as to move to c. The rear end of the developing roller scraper (55) is supported by a sliding actuator (551), and the sliding actuator (551) is coupled to the control means (64) via a connection circuit (not shown). The developing roller scraper (55) is configured to be switched between a position where the lower end thereof is in sliding contact with the outer peripheral surface of the developing roller (52) and a retreat position (not shown) where the developing roller scraper (55) is separated from the outer peripheral surface. Each rotation drive means (80), (81) is connected to a motor side (not shown) which is a rotation source through each rotation transmission system, and the developing roller (52) and the squeeze roller (53) rotate at a predetermined rotation speed. As described above, the rotation driving means (80) and (81) are driven and controlled by the control means (64). The photosensitive drum (1) is also equipped with a rotation drive means (82), and this rotation drive means (82) is also driven and controlled by the control means (64).

  The lower end of the developing roller scraper (55) is in sliding contact with the outer peripheral surface of the developing roller (52) on the side surface opposite to the photosensitive drum (1), and a wedge-shaped portion (56) is formed therebetween. Above the wedge-shaped part (56), the supply nozzle (54) of the liquid ink supply pipe system (58) is arranged oppositely. The liquid ink supply pipe system (58) is connected to the liquid ink tank (583) through a pipe (581) equipped with a pump (582). The liquid ink tank (583) contains the liquid ink returning from the container (51), and is controlled so that the ratio between the carrier liquid and the toner is maintained within a certain allowable range by a toner concentration adjusting unit (not shown). A pump motor (68) for driving the pump (582) is connected to a power source (69) via a drive switch (70), and the drive switch (70) is ON / OFF controlled by the control means (64).

  The developing roller (52) also serves as a developing electrode. The developing roller (52) includes a conductor inside the skin surface of the dielectric, and the conductor is connected to the bias circuit (60). The bias circuit (60) is connected to the developing roller (52) via the bias voltage switch (63) to the first and second power sources (61) and (62). The first power source (61) applies a voltage for attracting the toner in the liquid ink toward the developing roller (52), and the second power source (62) generates a voltage for causing the toner in the developer to be separated from the developing roller (52). The bias voltage switch (63) is controlled to be switched by the control means (64). The power source here may be only the first power source (61), and the bias voltage switch (63) may be eliminated.

  The squeeze roller (53) rotates and moves in the direction opposite to the moving direction of the surface of the photosensitive drum (1) with the interval B maintained. This regulates the liquid film thickness of the liquid ink adhering to the photoreceptor surface, and the scraped liquid ink flows down to the lower part of the container (51) by the squeeze roller scraper (57). The squeeze roller (53) includes a conductor inside the dielectric skin, and the conductor is connected to a bias circuit (73). The bias circuit (73) switches and connects the squeeze roller (53) to the first and second power sources (65) and (66) via the bias voltage switch (67). The first power source (65) applies a voltage for sucking the toner in the liquid ink toward the squeeze roller (53), and the second power source (66) generates a voltage for causing the toner in the liquid ink to be released from the squeeze roller (53). The bias voltage switch (67) is controlled to be switched by the control means (64).

  A liquid ink replenishing means (90) is disposed opposite the outer peripheral surface of the photosensitive drum (1), downstream in the rotational direction a from the developing roller (52) facing portion, and upstream from the facing portion of the squeeze roller (53). The The liquid ink replenishing means (90) can directly supply liquid ink as a replenishing liquid to a replenishment position C where the squeeze roller (53) and the photoreceptor surface face each other. The liquid ink replenishing means (90) includes a replenishing liquid nozzle (91) provided on the surface of the photosensitive drum (1), and a replenishing liquid supply pipe system (92) capable of connecting the nozzle and the liquid ink tank (583). And a pump (83) on the replenisher supply pipe system (92). A pump motor (94) for driving the pump (83) is connected to a power source (69) via a drive switch (95), and the drive switch (95) is ON / OFF controlled by the control means (64).

  The transfer device (6) is formed in a belt shape, and a transfer member (12) whose surface is covered with a dielectric, and a transfer charger (8) disposed opposite to the photosensitive surface at the transfer position via the transfer member (12). ). When the transfer device is driven, the toner image on the photosensitive drum (1) is transferred onto the transfer paper (P) by corona discharge of the transfer charger (8). At this time, the belt-shaped transfer member (12) is moved and operated at the same speed as the outer peripheral surface of the photosensitive drum (1) by a driving means (not shown), and the supplied transfer paper (P) is transferred to the photosensitive drum (1). The toner image on the surface of the photosensitive member is transferred onto the transfer paper (P) by the electric force applied by the transfer charger (8). The cleaning device (9) removes the liquid ink remaining on the photosensitive drum (1) after the transfer process. The movable plate member (13) and the movable plate member (13) that can contact and separate from the photosensitive drum (1) are provided. 13) includes an actuator (71) that switches between a cleaning position indicated by a solid line and a retreat position indicated by a broken line. The actuator (71) is a solenoid, and its drive output is output from the drive circuit (72) that has received a command from the control means (64).

The color liquid ink image transferred onto the recording medium (P) is irradiated with ultraviolet rays by the fixing light irradiating means (120) to be photocured and fixed onto the recording medium P.
As described above, the colored image containing the colored resin particles is appropriately fixed on the recording medium P, and the colored image is reliably prevented from peeling off from the recording medium P.

Next, a case where a color image is formed on the recording medium P will be described with reference to FIG.
An electrophotographic image forming apparatus (200) for forming a color image shown in FIG. 2 includes a drum-shaped photoconductor (101) as an image carrier that rotates in the direction of arrow A, and yellow, magenta, cyan, and black. The developing device (5) having the liquid ink supply means (40Y, 40M, 40C, 40B) for supplying the photocurable liquid ink, the driving roller (115a), and the support rollers (115b, 115c) are stretched over the arrows And an endless intermediate transfer belt (112) transported in the F direction.

The developing device (5) includes an endless conveying belt (117) that is stretched around a driving roller (121) and a supporting roller (122) and is transferred in the direction of arrow D. Then, photocurable liquid inks of yellow, magenta, cyan, and black are supplied from the liquid ink supply means (40Y, 40M, 40C, and 40B) to the transport belt (117) and supplied by the corona discharge unit (113). The toner particles made of the colorant in the photocurable liquid ink are charged, and the photocurable liquid ink is supplied to the photoconductor (101) on the support roller (122). The ink supply means (40Y, 40M, 40C, 40B) are respectively yellow, magenta, cyan, and black photo-curing types containing toner particles and a curable liquid containing the silicone material represented by the general formula (1). Liquid ink containers (106Y, 106M, 106C, 106B) for storing liquid ink are provided. Then, a liquid ink supply roller (107Y, 107M, 107C, 107B) for pumping photocurable liquid ink while rotating in the direction of arrow C from these liquid ink containers (106Y, 106M, 106C, 106B), and a liquid ink supply roller Developing rollers (105Y, 105M, 105C, 105B) that supply photocurable liquid ink supplied from (107Y, 107M, 107C, 107B) to the surface of the transport belt (117) while rotating in the direction of arrow B. ).

In this case, the supply of yellow, magenta, cyan, and black photocurable liquid ink from the liquid ink supply means (40Y, 40M, 40C, and 40B) to the transport belt (117) is image information corresponding to each color. In response to the electrostatic latent image corresponding to each color on the photoconductor (101) formed by the writing exposure unit (104). That is, when a yellow electrostatic latent image is formed, only the yellow photocurable liquid ink is supplied from the yellow liquid ink supply means (40Y) to the transport supply belt (117) and is supplied to the photoconductor (101). ) To be developed into yellow curable liquid ink. The yellow curable liquid ink image thus formed is charged by the corona discharger (114) and transferred onto the intermediate transfer belt (112) by the primary transfer roller (123). Similarly, when forming a liquid ink image with respect to a magenta image, the magenta photocurable liquid ink is supplied from the curable liquid ink supply means (40M) to the photoconductor (101), and the magenta curable liquid is supplied. An ink image is formed. The magenta curable liquid ink image is transferred onto the yellow curable liquid ink image transferred onto the intermediate transfer belt (112). Similarly, cyan and black curable liquid ink images are superimposed and transferred onto the liquid ink image on the intermediate transfer belt (112) to form a color image.

The color curable liquid ink image on the intermediate transfer belt (112) formed in this way is partially cured by the pre-transfer light irradiation means (119) to impart surface tackiness. Is done. In this way, the curable liquid ink image to which surface tackiness is imparted is transferred onto the recording medium P such as transfer paper conveyed in the direction of the arrow E by the registration roller (109) on the secondary transfer roller (109). 124). The color liquid ink image transferred onto the recording medium (P) is irradiated with ultraviolet rays by the fixing light irradiating means (120) to be photocured and fixed onto the recording medium (P).

  In this image forming apparatus (200), the photocurable liquid ink remaining on the conveyance belt (117) and the photoconductor (101) is removed from the cleaning roller (118), the cleaning roller (110), and the cleaning blade, respectively. It is removed and cleaned by (111) to return to the initial state.

As described above, the colored image containing the colorant is appropriately fixed on the recording medium (P), and the colored image is reliably prevented from peeling off from the recording medium (P).

  Next, a case where the photocurable liquid ink according to the present invention is applied to an ink jet recording method in which printing is performed by flying a recording medium to form recording dots will be described.

Inkjet recording, which performs printing by flying ink onto a recording medium to form recording dots, is attracting interest as a non-impact recording method that can be easily colored and recorded directly on plain paper. Printers using this method are attracting attention. Various applications have been made. As an ink jet recording method, there are an on-demand (voluntary ejection) and a continuous (continuous ejection) system. Furthermore, a recording method called an electrostatic method (Sweet type, Hertz type) is known for the continuous type, and a piezo piezoelectric method, a shear mode piezo piezoelectric method, or a thermal ink jet method is known for the on-demand type. As one of on-demand type ink jet recording methods, for example, a method called electrostatic acceleration type ink jet or slit jet described in Non Patent Literature 1 and Non Patent Literature 2 is known.

The photocurable liquid ink using the curable liquid containing the silicone material represented by the general formula (1) according to the present invention can be suitably used for a piezoelectric mode and a shear mode piezoelectric mode.
However, the difference from the above-described photocurable liquid ink for electrophotography is that a restriction condition is added that the colored resin particle diameter must basically be smaller than the nozzle diameter of the inkjet head. Specifically, the surface-treated colored resin particles are preferably from 0.01 to 0.5 μm, and more preferably from 0.01 to 0.3 μm.

  As a further method, as described above, a curable liquid containing the silicone material represented by the general formula (1) according to the present invention without using colored resin particles having a small particle diameter produced by a salting-out method or the like. A method of dispersing a commercially available colorant or the processed colorant (colored resin particles) directly can be used. In this case, a dispersant or a dispersion stabilizer can be added as necessary.

As the dispersant and the dispersion stabilizer, polyether-modified silicone oil can be preferably used. Specific commercial products of polyether-modified silicone oil include KF-945, KF-6020, KF-352A, KF-353, KF-615A, X-22-4515, KF-6012, KF-6015, KF-6017. (Above, manufactured by Shin-Etsu Chemical Co., Ltd.), FZ-2154, FZ-2191, FZ-2130, SH-8400, FZ-2123 (above, manufactured by Toray Dow Corning), etc. 10 polyether-modified silicone oils can be suitably used, and polyether-modified silicone oils having an HLB value of 4 to 7 such as KF-945, KF-6020, FZ-2154, and FZ-2130 are preferably used. Can do.

  Furthermore, as a pigment dispersion method, the colored resin particles can be preferably used. That is, among the colored resin particles, a resin having an acidic group is used as a carrier resin, and the colored resin particles having an acidic group on the surface are cured by the silicone material represented by the general formula (1) of the present invention. Dispersion of colored resin particles and acidic group of carrier resin by chemical modification using a silicone compound having an epoxy group, an aromatic compound having an epoxy group and / or a long chain alkyl compound having an epoxy group in a liquid The effect of stabilizing the dispersion due to the reaction between the epoxy group and the epoxy group proceeds at the same time, whereby a very excellent photocurable liquid ink can be produced.

  In addition, since the electrostatic acceleration type ink jet basically has no nozzle of the ink jet head, there is no restriction on the diameter of the colored resin particle. Therefore, the photocurable ink for electrophotography, the piezoelectric method, and the shear mode piezoelectric method are used. Any liquid ink of a photocurable liquid ink can be used.

  Moreover, you may add a well-known additive further to the photocurable liquid ink for inkjets of this invention as needed. Examples thereof include a dispersant, a heat stabilizer, an antiseptic, a surface tension adjuster, a polymerization inhibitor, an antioxidant, a near infrared absorber, an ultraviolet absorber, a fluorescent agent, and a fluorescent brightening agent.

  In particular, the polymerization inhibitor is added so that a monomer or oligomer having a functional unsaturated group of a photo-curable electrical insulating liquid does not react with heat. Examples of the polymerization inhibitor include 2,6-di-tert-butyl-4-cresol, anthraquinone, hydroquinone, hydroquinone monomethyl ether, and the like. These may be used alone or in combination of two or more.

  Furthermore, for the purpose of dispersion stability caused by the zeta potential, a charge control agent exemplified for the photocurable ink for electrophotography may be added. A charge control agent may be used individually by 1 type, and may use 2 or more types together.

Next, the photocuring method of the photocurable liquid ink according to the present invention will be described.
After the image is formed with the photocurable liquid ink of the present invention, the formed liquid ink image is irradiated with light to solidify the curable liquid on the liquid ink image.

Photocuring can be performed before or after transfer to the recording medium. Pre-transfer light irradiation partially cures the formed liquid ink image before transfer, imparts surface tackiness to the formed liquid ink image, and promotes transfer to a recording medium (adhesive transfer method). Further, curing proceeds by light irradiation after transfer, and adhesion of the liquid ink image to the recording medium can be greatly promoted.

Photocuring can be carried out by a known appropriate method. When a photopolymerization initiator is used, curing is performed by irradiating the liquid ink image with active energy rays having a wavelength sensitive to the initiator by an active energy ray such as ultraviolet rays. , By exposing.

The active energy ray used here is preferably one of electron beam, ultraviolet ray, and visible ray, and the peak wavelength of the active energy ray depends on the absorption characteristics of the sensitizer, but is, for example, 300 nm to 450 nm. It is preferable that The active energy ray used in the curing system applied to the photocurable liquid ink of the present invention is appropriately irradiated with an illuminance on the exposed surface of preferably 10 to 2,000 mW / cm ² . As active energy ray sources, mercury lamps and gas / solid lasers are mainly used. In particular, mercury lamps and metal halide lamps are widely known as light sources used for curing UV-curable liquid inks. .

However, from the viewpoint of environmental protection, mercury-free is strongly desired, and replacement with a GaN-based semiconductor ultraviolet light device is very useful industrially and environmentally. Further, LEDs (light-emitting diodes) (UV-LEDs) and LDs (UV-LDs) are small, have a long life and are highly efficient, and are expected as light sources for photocurable liquid ink.

  Furthermore, the photocurable liquid ink of the present invention can also contain a photopolymerization initiator that initiates curing of the curable liquid made of the silicone material represented by the general formula (1). The photopolymerization initiator is not particularly limited and can be appropriately selected from known ones. Preferred examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin. -N-butyl ether, benzoin isobutyl ether, acetophenone, dimethylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1 -One, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 4- (2-hydroxyethoxy) phenyl-2-hydroxy-2- Propyl ketone Benzophenone, p-phenylbenzophenone, 4,4-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2 -Isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, benzyl, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 6-trimethylbenzoyl Diphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl phosphine oxide, and p- dimethylamino benzoate, and the like. These may be used alone or in combination of two or more. The amount of the photopolymerization initiator is usually 0.05 to 20% by weight, preferably 0.2 to 15% by weight, based on the total amount of the photocurable liquid ink. These photopolymerization initiators can be added before or after image development.

  In general, characteristics required for the photocurable liquid ink include the following.

(Curable)
When forming images of graphic arts, signs, displays, labels, etc. using liquid ink, naturally high productivity is required. Further, the liquid ink applied onto the recording medium moves on the recording medium due to its fluidity, and may cause problems in image quality such as flow, bleeding, and flipping. In order to reduce and prevent this, the property of being quickly cured by light irradiation and fixed on the recording medium is very important.

(Liquid characteristics)
In applying a liquid ink to a recording medium, liquid properties having a relatively low viscosity and excellent dispersibility and dispersion stability of a colorant or colored resin particles are preferred for driving at high speed. At the same time, it is desired to reduce the particle size of the colorant or colored resin particles with the recent improvement in image quality, and these conflicting properties such as low viscosity, high dispersibility, and small particle size are highly complex and complex. It is important to be satisfied.

(Cured film properties)
The properties required for the cured film can be roughly divided into three. One is the strength of the cured film. When used for a display, a label, or the like, the image may be damaged by rubbing, scratching, writing, sand dust or the like by the user, and the film strength for maintaining the image is indispensable. The other is the adhesion to the recording medium. The image must not be lifted or peeled off from the recording medium by being exposed to various environments, or subjected to a force such as rounding or bending, so that the cured film is strongly and uniformly applied to the recording medium. It is demanded to adhere to. The other is stickiness of the cured film. For example, if the film after curing has a sticky stickiness, the images may stick to each other, dirt may be adsorbed, and the value of the image may be significantly impaired. Therefore, it is also an important characteristic that the cured film has a less sticky film.

(Stability)
Like normal ink, liquid ink may be distributed and stored in the market, and may remain in the apparatus. Therefore, it must be avoided that the components are decomposed in a short period of time that is unacceptable due to social conventions, or that the viscosity is increased and the resin is hardened. Of course, it is one of the important characteristics that the curing characteristics are sufficiently sustained. In general, these liquid inks are often used by being mixed with various additives such as a charge control agent, but at that time, the original properties should not be impaired by reacting with the additives. .

The photocurable liquid ink comprising the silicone material represented by the general formula (1) according to the present invention can sufficiently satisfy the basic characteristics, and has low viscosity and excellent handling performance of conventional silicone materials. Furthermore, it is an excellent material having both high curability as compared with a conventional silicone material having a functional group such as methacryloxy group in the molecule. Further, the photocurable liquid ink can give a high-resolution image free from background stains and image blur.
By irradiating the photocurable liquid ink containing the curable liquid with light, the curable liquid together with the colorant can be fixed to the recording medium by the polymerization reaction of the crotonic acid ester segment in the substituent A. High-quality images without blurring or color change due to the recording medium can be achieved. Furthermore, in the inkjet method, the speed of the image forming apparatus and the strength of the printed part are increased compared to the conventional natural drying method. In addition, in the electrophotographic system, it is not necessary to melt and fix the toner with heat as in the conventional case, and the image forming apparatus can be speeded up and energy consumption can be reduced.

  The colorant preferably forms colored resin particles having an acidic group on the surface, and is further subjected to a reaction treatment with at least one of a silicone compound having an epoxy group and a long-chain alkyl compound having an epoxy group. When the surface is directly bonded / coated with an aromatic compound having a silicone group or an epoxy group and / or a long-chain alkyl group, it is excellent in dispersibility and redispersibility and can provide a higher quality image. In particular, in the electrophotographic liquid toner, the surface of the colored resin particles is directly bonded and coated with at least one of a silicone group having an epoxy group, an aromatic group having an epoxy group, and a long chain alkyl group having an epoxy group. Due to the structure, the influence on the physical properties such as the resistance value of the liquid toner is minimized by reacting with at least one of a silicone compound having a small amount of an epoxy group and a long-chain alkyl compound having an epoxy group. Can provide a higher quality image. Moreover, by producing colored resin particles having acidic groups on the surface by the salting-out method, homogeneous particles can be produced by a very simple method, and a further high-quality image can be given.

  Further, the photocurable liquid ink according to the present invention includes a colored resin particle having an acidic group on the surface, a silicone compound having an epoxy group, and an epoxy in a curable liquid containing a silicone material represented by the general formula (1). It can be produced by a very simple method in which at least one long-chain alkyl compound having a group is subjected to a reaction treatment under mild conditions.

Further, the colored resin particles according to the present invention can be produced by a salting-out method and homogeneous particles having relatively high monodispersibility can be produced by a simple method, and basic properties relating to liquid properties such as viscosity, resistance value, dielectric constant and the like. In addition, the siloxyl group and / or the long chain alkyl group on the surface of the colored resin particles can minimize the use of additives such as a dispersant or do not require any additives. The dispersibility and redispersibility are excellent, and as a comprehensive result, the photocurable liquid ink has very high resolution and high stability. In addition, since the photocurable liquid ink according to the present invention can be produced by a very simple method, the liquid ink characteristics are stable, and a printed image with good quality can be produced with high reliability.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples.
First, the method and apparatus used for evaluating liquid ink are shown below.

(Measurement of particle size and relative standard deviation (CV value))
Measurement apparatus: Particle size analyzer FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) Sample: Measurement was performed with a 1.0 wt% aqueous solution.

(Measurement of acid value)
・ Measured according to JIS K0070.

(Measurement of curing speed)
-Measuring device: Viscoelasticity measuring device VAR-200AD (manufactured by Reologica)
-Light source: LED light source LC-L1 (manufactured by Hamamatsu Photonics, 365 nm)
・ Measurement frequency: 1 Hz
・ Measurement Stress: 150Pa
・ Measuring plate: 20mmφ (gap: 10μm)

Under the above conditions, the exposure surface illuminance is set to 50 mW / cm ² in advance, the sample is injected into the measurement plate, and the curing energy is calculated by measuring the irradiation time required for curing. However, the criterion for curing was an elastic modulus of 1 × 10 ⁴ Pa.

(Synthesis Example I (Preparation of colored particles having acidic groups on the surface by salting out method))
In advance, 380.5 parts by weight of water, 249.5 parts by weight of 1N-potassium hydroxide, and a styrene / acrylic resin having a carboxyl group (Mw = 8,500, Tg = 85 ° C., acid value = 200 mgKOH / g: Toagosei Co., Ltd.) A UC-3910 aqueous solution consisting of 70 parts by weight of UC-3910), 150 parts by weight of a 10% by weight UC-3910 aqueous solution, and 15 parts by weight of carbon black (Mitsubishi Chemical # 5B) Ball milling was performed with 2 mmφ zirconia balls for 12 hours to prepare a ball mill colorant dispersion.

Subsequently, in a 1000 ml separable flask equipped with a stirrer, a thermometer, and a dropping funnel prepared in advance, a colorant dispersion obtained by removing zirconia balls from the ball mill colored dispersion, and water (666.5). Parts by weight) was added, and the mixture was cooled to 10 ° C. while stirring, and a saturated aqueous ammonium sulfate solution (283.7 parts by weight) was added dropwise over 1 hour under cooling.
The mixture was further stirred for 1 hour under the same conditions, then acidified with 0.4N—H ₂ SO ₄ , filtered, washed with water three times, and freeze-dried to give a color having a carboxyl group on the surface. 27.92 parts by weight of particles (A) were obtained.
When the particle size distribution of the particles was measured, the average particle size was 0.18 μm, and the relative standard deviation (CV value) was 25%. The acid value was 75 mgKOH / g.

(Comparative Synthesis Example I (Creation of toner particles by coacervation method))
A vessel equipped with a thermometer and a reflux condenser is charged with 800 parts by weight of a branched chain aliphatic hydrocarbon (Esso Petroleum Corporation: Isopar G), 480 parts by weight of toluene, and 300 parts by weight of ethanol, and further ethylene / vinyl acetate. Partial saponification product of copolymer (manufactured by Takeda Pharmaceutical Co., Ltd .: Dumiran C-2280), 13.3 parts by weight of carbon black (manufactured by Mitsubishi Chemical: # 5B), and phosphate surfactant (first 8 parts by weight of Kogyo Seiyaku Co., Ltd .: Prisurf AL) was added and stirred at 70 ° C. for 3 hours at high speed to prepare a carbon black dispersion.
This carbon black dispersion is slowly cooled to 30 ° C. under weak stirring, and further, toluene and ethanol are distilled off under reduced pressure to precipitate colored particles, which are further collected by filtration, and dried under reduced pressure. As a result, 76.4 parts by weight of colored particles (B) were obtained. When the particle size distribution of the particles was measured, the average particle size was 0.25 μm, and the relative standard deviation (CV value) was 320%.

(Synthesis Example II (Synthesis of Substituent A-1 Alkenyl Compound; Compound with R2 = CH ₂ , p = 0))
In a 500 ml container equipped with a stirrer, thermometer, and dropping funnel, 20.91 parts by weight of allyl alcohol (Tokyo Kasei), 36.43 parts by weight of triethylamine (Tokyo Kasei), dimethylaminopyridine (manufactured by Tokyo Chemical) 3 .42 parts by weight of crotonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) is added dropwise to .67 parts by weight and 303 parts by weight of toluene under stirring at room temperature over about 30 minutes. After dropping, stirring is continued at room temperature for 6 hours.
Next, the reaction product was concentrated to about ½ volume and subjected to silica gel chromatography using toluene as a developing solvent to obtain 31.03 parts by weight of allyl crotonic acid (Compound II).
An infrared absorption spectrum is shown in FIG.

(Synthesis Example III (Synthesis of Substituent A-2 Alkenyl Compound; Compound of R2 = CH ₂ , R3 = OC ₂ H ₄ , p = 1))
In a 500 ml container equipped with a stirrer, a thermometer, and a dropping funnel, 39.75 parts by weight of allyloxyethanol (manufactured by Tokyo Chemical Industry), 39.38 parts by weight of triethylamine (manufactured by Tokyo Chemical Industry), dimethylaminopyridine (manufactured by Tokyo Chemical Industry) 50 parts by weight of crotonic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) is added dropwise to 3.96 parts by weight and 367.85 parts by weight of toluene under stirring at room temperature over about 30 minutes. After dropping, stirring is continued at room temperature for 6 hours.
Next, the reaction product was concentrated to about ½ volume and subjected to silica gel chromatography using toluene as a developing solvent to obtain 42.32 parts by weight of allyloxyethyl crotonic acid (Compound III).
An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-1 (silicone material; R1 = CH ₃ , m = n = 0, 1≈6, X1 = X3 = A in the general formula (1): Crotonic acid ester structure A-1 (R2 = CH ₂ , p = 0))
4.57 parts by weight of allyl crotonate (compound II), which is an alkenyl compound that becomes the substituent A, and stabilizer (2,6-di-t-butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd .: BHT) 0.008 parts by weight 10 parts by weight of toluene and 0.066 part by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) with stirring A solution consisting of 10 parts by weight of a gen silicone material (polydimethylsiloxane both-end hydrogen atoms, molecular weight: ˜580, manufactured by Aldrich) and 10 parts by weight of toluene was added dropwise at room temperature over about 30 minutes, and overnight under the same conditions. Perform the reaction. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 14.03 parts by weight of the target silicone material (M1) was obtained.
An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-2 (silicone material; R1 = CH ₃ , m = n = 0, l≈4, X1 = X3 = A in general formula (1): Crotonic acid ester structure A-1 (R2 = CH ₂ , p = 0))
2.80 parts by weight of allyl crotonate (compound II), which is an alkenyl compound to be substituted A, 0.010 parts by weight of stabilizer (2,6-di-t-butyl-4-methylphenol Tokyo Chemical Industry: BHT) 10 parts by weight of toluene and 0.042 parts by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) with stirring A solution consisting of 5 parts by weight of a gen silicone material (polydimethylsiloxane both terminal hydrogen atoms, molecular weight: ~ 500, manufactured by AMAX) and 5 parts by weight of toluene was added dropwise at room temperature over about 30 minutes, and overnight under the same conditions. Perform the reaction. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 7.70 parts by weight of the desired silicone material (M2) was obtained.
An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-3 (silicone material; R1 = CH ₃ , m = n = 0, l = 1, X1 = X3 = A in general formula (1): Crotonic acid ester structure A-1 (R2 = CH ₂ , p = 0))
3.63 parts by weight of allyl crotonate (compound II) which is an alkenyl material to be substituted A, 0.013 parts by weight of stabilizer (2,6-di-t-butyl-4-methylphenol Tokyo Chemical Industry: BHT) 10 parts by weight of toluene and 0.055 part by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) with stirring A solution composed of 3 parts by weight of Gensilicone material (1,1,3,3,5,5-hexamethyltrisiloxane: manufactured by Tokyo Chemical Industry Co., Ltd.) and 3 parts by weight of toluene is dropped at room temperature over about 30 minutes. The reaction is performed overnight under the same conditions. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 5.48 parts by weight of the target silicone material (M3) was obtained.
An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-4 (silicone material; R1 = CH ₃ , l = m = n = 0, X1 = X3 = A in the general formula (1): Crotonic acid ester structure A-1 (R2 = CH ₂ , p = 0))
4.70 parts by weight of allyl crotonate (compound II), which is an alkenyl compound to become the substituent A, 0.016 parts by weight of stabilizer (2,6-di-t-butyl-4-methylphenol Tokyo Chemical Industry: BHT) 10 parts by weight of toluene and 0.071 part by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) with stirring A solution comprising 2.5 parts by weight of Gensilicone material (1,1,3,3-tetramethyldisiloxane: manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.5 parts by weight of toluene is dropped at room temperature over about 30 minutes. And react overnight under the same conditions. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 7.13 parts by weight of the desired silicone material (M4) was obtained.
An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-5 (silicone material; R1 = CH ₃ , X1 = X3 = CH ₃ , l = n = 0, m = 1, X2 = A in the general formula (1): Crotonic acid ester structure A- 1 (R2 = CH ₂ , p = 0))
5.95 parts by weight of allyl crotonate (compound II), which is an alkenyl compound to become the substituent A, and 0.010 parts by weight of stabilizer (2,6-di-t-butyl-4-methylphenol Tokyo Chemical Industry: BHT) 10 parts by weight of toluene, and 0.086 parts by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) with stirring A solution comprising 10 parts by weight of a silicone material (1,1,1,3,5,5,5-heptamethyltrisiloxane: manufactured by Tokyo Chemical Industry) and 10 parts by weight of toluene requires about 30 minutes at room temperature. Add dropwise and react overnight under the same conditions. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 15.59 parts by weight of the target silicone material (M5) was obtained.
An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-6 (silicone material; R1 = CH ₃ , X1 = X3 = CH ₃ , Y = C ₁₀ H ₂₁ in general formula (1), l = 5.87, m = n = 2.94, X2 = A: Crotonate structure A-1 (R2 = CH ₂ , p = 0))
3.89 parts by weight of allyl crotonate (compound II), which is an alkenyl compound to be the substituent A, 4.33 parts by weight of 1-decene, stabilizer (2,6-di-t-butyl-4-methylphenol Tokyo Kasei) Manufactured: BHT) 0.007 parts by weight, toluene 10 parts by weight, and 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene solution (manufactured by Aldrich) 0.118 10 parts by weight of methyl hydrogen silicone material (poly [dimethylsilicone / methylhydrosilicone (molar ratio 50%)] copolymer, molecular weight: ~ 950, manufactured by Aldrich) and 10 parts by weight of toluene while stirring The solution consisting of is dropped at room temperature over about 30 minutes, and the reaction is carried out overnight under the same conditions. Thereafter, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours to obtain 18.39 parts by weight of the desired silicone material (M6).

(Synthesis Example IV-7 (silicone material; R1 = CH ₃ , X1 = X3 = CH ₃ , Y = C ₂ H ₄ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₃ in general formula (1), l = 5 .87, m = n = 2.94, X2 = A: Crotonate structure A-1 (R2 = CH ₂ , p = 0))
1.36 parts by weight of allyl crotonate (compound II) which is an alkenyl compound to be substituted A, 1.24 g by weight of allyl phenyl ether, stabilizer (2,6-di-t-butyl-4-methylphenol Tokyo Chemical Industry Manufactured: BHT) 0.005 parts by weight, toluene 10 parts by weight, and 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex in xylene solution (manufactured by Aldrich) 0.041 parts by weight 3. parts by weight of methyl hydrogen silicone material (poly [dimethylsilicone / methylhydrosilicone (molar ratio 50%)] copolymer, molecular weight: 950, manufactured by Aldrich) with stirring, and toluene 3. A solution consisting of 5 parts by weight is dropped at room temperature over about 30 minutes, and the reaction is carried out overnight under the same conditions. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 6.76 parts by weight of the desired silicone material (M7) was obtained.

(Synthesis Example IV-8 (silicone material; R1 = CH ₃ , m = n = 0, l≈6, X1 = X3 = A in the general formula (1): Crotonic acid ester structure A-2 (R2 = CH ₂ , R3 = 0C ₂ H ₄ , p = 1))
2.48 parts by weight of allyloxyethyl crotonic acid (compound III), which is an alkenyl compound to become the substituent A, stabilizer (2,6-di-t-butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd .: BHT) 0.006 While stirring, 0.027 parts by weight of 10 parts by weight of toluene, 10 parts by weight of toluene, and 0.027 parts by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) A solution consisting of 4 parts by weight of methyl hydrogen silicone material (polydimethylsiloxane, hydrogen atoms at both ends, molecular weight: ˜580, manufactured by Aldrich) and 4 parts by weight of toluene is dropped at room temperature in about 30 minutes, The reaction is performed overnight under the same conditions. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 6.79 parts by weight of the target silicone material (M8) was obtained.
An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-9 (silicone material; R1 = CH ₃ , m = n = 0, l = 1, X1 = X3 = A in general formula (1): Crotonic acid ester structure A-2 (R2 = CH ₂ , R3 = 0C ₂ H ₄ , p = 1))
4.99 parts by weight of allyloxyethyl crotonic acid (compound III), which is an alkenyl compound to become the substituent A, stabilizer (2,6-di-tert-butyl-4-methylphenol, manufactured by Tokyo Chemical Industry: BHT) 0.013 While stirring, 0.055 parts by weight of 10 parts by weight of toluene, 10 parts by weight of toluene, and 0.055 parts by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) A solution consisting of 3 parts by weight of methyl hydrogen silicone material (1,1,3,3,5,5-hexamethyltrisiloxane: manufactured by Tokyo Chemical Industry) and 3 parts by weight of toluene requires about 30 minutes at room temperature. The reaction is carried out overnight under the same conditions. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. Thus, 7.33 parts by weight of the target silicone material (M9) was obtained. An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-10 (silicone compounds; in the general formula (1), R1 = CH3, l = m = n = 0, X1 = X3 = A: crotonic acid ester structure _{A-2 (R2 = CH 2} , R3 = 0C ₂ H ₄ , p = 1))
5.16 parts by weight of allyloxyethyl crotonic acid (compound III) which is an alkenyl compound of the substituent A, stabilizer (2,6-di-t-butyl-4-methylphenol manufactured by Tokyo Chemical Industry: BHT) 0.013 weight Parts of toluene, 10 parts by weight of toluene, and 0.057 parts by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) while stirring. A solution consisting of 2 parts by weight of Gensilicone material (1,1,3,3-tetramethyldisiloxane: manufactured by Tokyo Chemical Industry Co., Ltd.) and 2 parts by weight of toluene was added dropwise at room temperature over about 30 minutes. Do the reaction overnight. Then, the solvent was distilled off under reduced pressure, and further stripping treatment was performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours, and the disappearance of Si—H absorption (2155 cm ⁻¹ ) was confirmed by infrared absorption spectrum. 6.14 parts by weight of the target silicone material (M10) was obtained. An infrared absorption spectrum is shown in FIG.

(Synthesis Example IV-11 (silicone material; R1 = CH ₃ in general formula (1), X1 = X3 = CH ₃ , 1 = m = 5.87, n = 0, X2 = A: Crotonate structure A) _{-2 (R2 = CH 2, R3} = 0C 2 H 4, p = 1))
3.21 parts by weight of allyloxyethyl crotonic acid (compound III), which is an alkenyl compound to become the substituent A, stabilizer (2,6-di-t-butyl-4-methylphenol, manufactured by Tokyo Chemical Industry Co., Ltd .: BHT) 0.008 While stirring, 10 parts by weight of toluene, 10 parts by weight of toluene, and 0.035 parts by weight of a 2% platinum / 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution (manufactured by Aldrich) A solution comprising 3 parts by weight of a methyl hydrogen silicone material (poly [dimethylsilicone / methylhydrosilicone (molar ratio 50%)] copolymer, molecular weight: ~ 950, manufactured by Aldrich) and 3 parts by weight of toluene at room temperature, It takes about 30 minutes to drop and react overnight under the same conditions. Thereafter, the solvent was distilled off under reduced pressure, and stripping treatment was further performed at 40 ° C. under reduced pressure of 10 mmHg for 2 hours to obtain 6.46 parts by weight of the desired silicone material (M11). An infrared absorption spectrum is shown in FIG.

Example 1
In a 20 ml beaker, 1 part by weight of colored resin particles (A) having a carboxyl group on the surface obtained in Synthesis Example I, and a silicone material having a crotonic acid ester segment at both ends obtained in Synthesis Example IV-1 (M1 ) 8.55 parts by weight of an epoxy group-containing silicone oil compound ((3-glycidoxypropyl) bis (trimethylsiloxy) methylsilane: manufactured by Tokyo Chemical Industry Co., Ltd.) equivalent to the acid value of the colored resin particles (A) 0.45 parts by weight, and dispersion treatment for 2 hours with an ultrasonic disperser (output: 130 W, frequency: 20 kHz, pulsar method), and further 15 wt% zirconium octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 4 parts by weight were added to obtain a curable liquid ink (1).
This curable liquid ink (1) had an average particle diameter: 0.22 μm and a relative deviation value (CV value): 28%. Further, when this dispersion was subjected to a storage test for 20 days, the average particle size was 0.22 μm and no aggregation occurred, and the storage stability was very excellent. The viscosity was 11.8 (mPa · s).

(Example 2)
In a 20 ml beaker, 1 part by weight of colored resin particles (A) having a carboxyl group on the surface obtained in Synthesis Example I, and a silicone material having a crotonic acid ester segment at both ends obtained in Synthesis Example IV-3 (M3 ) 8.55 parts by weight of an epoxy group-containing silicone oil compound ((3-glycidoxypropyl) bis (trimethylsiloxy) methylsilane: manufactured by Tokyo Chemical Industry Co., Ltd.) with an equivalent value relative to the acid value of the colored resin particles (A) 0.45 part by weight is added, and dispersed for 2 hours with an ultrasonic disperser (output: 130 W, frequency: 20 kHz, pulsar method), and further 15 wt% zirconium octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 0.4 Part by weight was added to obtain a curable liquid ink (2).
This curable liquid ink (2) had an average particle size: 0.22 μm and a relative deviation value (CV value): 28%. Further, when this dispersion was subjected to a storage test for 20 days, the average particle size was 0.22 μm and no aggregation occurred, and the storage stability was very excellent. The viscosity was 5.4 (mPa · s).

(Example 3)
In a 20 ml beaker, 1 part by weight of colored resin particles (A) having a carboxyl group on the surface obtained in Synthesis Example I, and a silicone compound having a crotonic acid ester segment at both ends obtained in Synthesis Example IV-9 (M9) ) 8.55 parts by weight of an epoxy group-containing silicone oil compound ((3-glycidoxypropyl) bis (trimethylsiloxy) methylsilane: manufactured by Tokyo Chemical Industry Co., Ltd.) with an equivalent value relative to the acid value of the colored resin particles (A) 0.45 part by weight is added, and dispersed for 2 hours with an ultrasonic disperser (output: 130 W, frequency: 20 kHz, pulsar method), and further 15 wt% zirconium octylate (manufactured by Nippon Chemical Industry Co., Ltd.) 0.4 Part by weight was added to obtain a curable liquid ink (3).
This curable liquid ink (3) had an average particle diameter: 0.21 μm and a relative deviation value (CV value): 25%. When this dispersion was subjected to a storage test for 20 days, it showed an excellent storage stability with an average particle size of 0.21 μm and no aggregation. The viscosity was 3.4 (mPa · s).

Example 4
In Example 3, instead of 0.67 parts by weight of an epoxy group-containing silicone oil compound ((3-glycidoxypropyl) bis (trimethylsiloxy) methylsilane: manufactured by Tokyo Chemical Industry Co., Ltd.), a long-chain alkyl compound having an epoxy group ( A curable liquid in the same manner as in Example 1, except that 0.14 parts by weight of 2-ethylhexyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) was added in an amount equivalent to 1.2 times the acid value of the colored resin particles (A). Ink (4) was obtained. This curable liquid ink (4) had an average particle diameter: 0.20 μm and a relative deviation value (CV value): 28%. When this dispersion was subjected to a storage test for 20 days, it showed an excellent storage stability with an average particle size of 0.20 μm and no aggregation. The viscosity was 2.4 (mPa · s).

(Comparative Example 1)
(Creation of liquid ink using non-curing silicone oil compound)
In a 20 ml beaker, colored particles (B) obtained in Comparative Synthesis Example I (1 part by weight), non-cured dimethylsiloxane (viscosity: 20 mPa · s, SH200 manufactured by Toray Dow Corning Co., Ltd.) 9 parts by weight And processed with an ultrasonic disperser (output: 130 W, frequency: 20 kHz, pulsar method) for 2 hours, and further added 0.4 parts by weight of 15 wt% zirconium octylate (manufactured by Nippon Chemical Industry Co., Ltd.) Although liquid ink (5) was obtained, due to poor dispersion, polyether-modified silicone oil [Shin-Etsu Chemical Co., Ltd., KF-945] (1.0 part by weight) was further added, and ultrasonic dispersion was performed again. A liquid ink (6) was obtained.
This liquid ink (6) had an average particle size of 0.52 μm and a relative deviation value (CV value) of 280%. When this dispersion was subjected to a storage test for 20 days, it aggregated and redispersed. It was bad.

(Comparative Example 2)
(Creation of liquid ink using methacrylic modified curable silicone oil compound)
To a 20 ml beaker, 1 part by weight of the colored particles (B) obtained in Comparative Synthesis Example I and 9 parts by weight of a methacryl-modified curable silicone material (X-22-164, manufactured by Shin-Etsu Chemical Co., Ltd.) are added, and an ultrasonic disperser ( (Output: 130 W, frequency: 20 kHz, pulsar method) was treated for 2 hours, and 0.2 wt part of 15 wt% zirconium octylate (manufactured by Nippon Chemical Industry Co., Ltd.) was added to obtain a liquid ink (7). However, due to poor dispersion, 1.0 part by weight of polyether-modified silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd .: KF-945) was further added and ultrasonically dispersed again to obtain a liquid ink (8). .
This liquid ink (8) had an average particle diameter of 0.40 μm and a relative deviation value (CV value): 190%. When this dispersion was subjected to a storage test for 20 days, it aggregated and redispersed. It was bad.

[Evaluation Test 1]
<Evaluation of photocurability>
For each of the curable liquid inks obtained in Example 1, Example 2, Example 3, Example 4, and Comparative Example 2, a photopolymerization initiator (manufactured by Ciba Specialty Chemicals: Irgacure 907) 5.0 Part by weight was added, and the curability by viscoelasticity was evaluated by the curing energy. The smaller the curing energy, the faster the curing.

[Evaluation Test 2]
<Image evaluation by electrophotographic liquid developing device>
The liquid inks obtained in Example 3, Example 4, Comparative Example 1, and Comparative Example 2 were developed by the liquid developing device shown in the schematic diagram of FIG. 1, and the resolution of the developed image on the photoreceptor was visually evaluated. did. The evaluation results are shown in Table 2.

[Evaluation Test 3] <Image Evaluation by Inkjet Method>
The liquid inks obtained in Example 1, Example 2, Comparative Example 1, and Comparative Example 2 were imaged with an inkjet printer IPSIO GX5000 (manufactured by Ricoh), and the resolving power was visually evaluated. The evaluation results are shown in Table 3.

DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Charging charger 3 Optical writing device 4 Erase lamp 5 Developing device 6 Transfer device 8 Transfer charger 9 Cleaning device 12 Transfer member 13 Movable plate member 40Y, 40M, 40C, 40B Liquid ink supply means 51 Container 52 Developing roller 53 Squeeze roller 54 Supply nozzle 55 Developing roller scraper 551 Sliding actuator 56 Wedge-shaped portion 57 Squeeze roller scraper 58 Supply pipe system 581 Pipe 582 Pump 583 Liquid ink tank 60 Bias circuit 61 First power supply 62 Second power supply 63 Bias voltage switch 64 Control means 65 First power supply 66 Second power supply 67 Bias voltage switch 68 Pump motor 70 Drive switch 71 Actuator 72 Drive circuit 73 Bias circuit 80 Rotation drive means 81 Rotation drive Means 82 Rotation drive means 83 Pump 90 Liquid ink replenishment means 91 Replenishment liquid nozzle 92 Replenishment liquid supply pipe system 94 Pump motor 95 Drive switch 100, 200 Image forming apparatus 101 Photoconductor 102 Corona charger 104 Write exposure unit 105 Development roller 106 Liquid ink container 107 Liquid ink supply roller 108 Transfer roller 109 Registration roller 110 Cleaning roller 111 Cleaning blade 112 Intermediate transfer belt 113, 114 Corona charger 115a Drive roller 115b, 115c Support roller 117 Conveyor belt 118 Cleaning roller 119 Ultraviolet irradiation means 120 Fixing Ultraviolet irradiation means 121 Drive roller 122 Support roller 123 Primary transfer roller 124 Secondary transfer roller P Recording medium L Exposure

JP 2008-24881 A Japanese Patent No. 3985459 Japanese Patent No. 3442406 Japanese Patent No. 4150118

Susumu Ichinose, Yuji Ohba, IEICE Transactions Vol. J66-C (No. 1), P47 (1983) Tadayoshi Ohno, Mamoru Mizuguchi, Journal of the Institute of Image Electronics Engineers of Japan, Vol. 10 (no. 3), P157 (1981)

Claims (9)

A silicone material represented by the following general formula (2) or general formula (3) .
However, in said general formula (2), Y represents a substituted or unsubstituted C1-C18 alkyl group, l and m represent the integer of 0-100, A is following General formula (A). The substituent A having the crotonic ester structure shown is represented.
However, in said general formula (3), l represents the integer of 0-100, A represents the substituent A which has the crotonic acid ester structure shown by the following general formula (A).
However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1. And at least a colorant and a curable liquid which is cured by light, a photocurable ink containing the curable liquid, characterized in that it contains a silicone material represented by the following general formula (1) Light curable liquid ink.
However, in the general formula (1), R1 independently represents a methyl group or a phenyl group, Y represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, and l, m, and n are 0 to 0. Represents an integer of 100, X1, X2, and X3 independently represent a methyl group, a phenyl group, or a substituent A having a crotonic ester structure represented by the following general formula (A), and X1, X2, X3 At least one of them is the substituent A.
However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1. The photocurable liquid ink according to claim 2, wherein the silicone material represented by the general formula (1) is a silicone material represented by the following general formula (2).
However, in the above general formula (2), Y represents a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, l, and m represents an integer of 0 to 100, A is the following general formula (A) The substituent A having the crotonic ester structure shown is represented.
However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1. The photocurable liquid ink according to claim 2, wherein the silicone material represented by the general formula (1) is a silicone material represented by the following general formula (3).
However, in the general formula (3), l represents an integer of 0 to 100, A represents a substituent A with a crotonic acid ester structure represented by the following general formula (A).
However, in said general formula (A), R2 represents a single bond or a C1-C4 alkylene group, R3 represents a C1-C4 alkyleneoxy group, and p represents 0 or 1. The colorant is a colored resin particle containing a colorant and a binder resin, the binder resin having an acidic group, the acidic group, a silicone compound having an epoxy group, and an aromatic group having an epoxy group. 5. The surface of the colored resin particle has a chemical modification in which a group compound and at least one compound selected from a long-chain alkyl compound having an epoxy group are bonded to each other. The photocurable liquid ink described. The method for producing a photocurable liquid ink according to any one of claims 2 to 5, comprising at least a colorant and a curable liquid that is cured by light,
The colorant is a colored resin particle containing a coloring material and a binder resin having an acidic group,
The colored resin particles and at least one compound selected from a silicone compound having an epoxy group, an aromatic compound having an epoxy group, and a long chain alkyl compound having an epoxy group are dispersed in a curable liquid and colored. A method for producing a photocurable liquid ink, wherein the resin particle surface is chemically modified.   A dispersion of a resin having an acidic group obtained by neutralizing and dissolving the colored resin particles in an aqueous solution and a coloring material, and depositing a resin having an acidic group neutralized and dissolved on the surface of the coloring material by a salting-out method. The method for producing a photocurable liquid ink according to claim 6.   An ink storage unit that stores the photocurable liquid ink, and the photocurable liquid ink is drawn from the ink storage unit, and the photocurable image ink is supplied to the electrostatic latent image formed on the image carrier. A developing device comprising a liquid ink supply means, wherein the photocurable liquid ink is the photocurable liquid ink according to any one of claims 2 to 5.   An image carrier on which an electrostatic latent image is formed, a developing device that supplies photocurable liquid ink to the electrostatic latent image formed on the image carrier and develops the liquid ink image, and the developing device A transfer device for transferring the formed liquid ink image from the image carrier onto a recording medium, and irradiating the liquid ink image transferred by the transfer device with light to cure the photocurable liquid ink. An image forming apparatus comprising a fixing device for fixing an image on the recording medium, wherein the photocurable liquid ink is the photocurable liquid ink according to any one of claims 2 to 5. An image forming apparatus.