JP2009145535A - Wet developer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wet developer containing toner particles, an insulating solvent and a dispersant, the developer having characteristics of not blcoking fixing properties, while keeping storage stability as a wet developer. <P>SOLUTION: The wet developer contains a combination of a toner essentially comprising a polyester resin, a basic polymer dispersant, as a dispersant, having high dispersibility and having an N-vinylpyrrolidone group contributing to storage stability, and a polyimine compound easily inducing toner aggregation and advantageous for fixing. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a wet developer in which toner is dispersed in an insulating solvent using a dispersant.

  2. Description of the Related Art An electrophotographic image forming apparatus that forms an electrostatic latent image on a photoconductor (photosensitive drum), adheres toner to the image, and transfers and fixes the image on paper or the like is widely used. In particular, in an image forming apparatus that requires higher image quality and higher resolution, such as an office printer for large-scale printing and an on-demand printing apparatus, a wet developer that uses a wet developer that has a small toner particle diameter and that does not easily disturb the toner image. Development methods are being used.

  In recent years, high-viscosity and high-concentration wet development, consisting of a high-concentration dispersion of toner as a solid component consisting of resin and pigment in an insulating solvent (carrier liquid) such as liquid paraffin and silicone oil Image forming apparatuses using an agent have been proposed.

  When developing using this wet developer, a thin layer of developer is formed on a developer carrier such as a developing roller, and the thinned developer is brought into contact with the photoreceptor. It is common to develop.

  The latent image on the surface of the photoreceptor is developed with a thin layer of a wet developer, and a toner image is formed on the surface of the photoreceptor. This toner image is transferred to a recording material. Alternatively, the toner image is first temporarily transferred to an intermediate transfer member or the like and then secondarily transferred to a recording material.

  The toner image transferred to the recording material is fixed on the recording material, which is usually paper, by being pressurized and heated by a fixing device. However, the toner image is originally developed using a wet developer in which the toner is dispersed in the carrier liquid, and the carrier liquid is contained not only between the toner but also between the toners and between the toner papers. Moreover, it has a fairly high viscosity.

  It is known that the presence of a high-viscosity carrier liquid hinders fixability during toner image fixing. For example, since the toner image and the recording material are wet with the carrier liquid, the fixability of the toner image may be lowered, and the image may be crushed or disturbed during pressure fixing.

  On the other hand, a technique for removing a solvent (carrier liquid) from an unfixed toner image before fixing has been developed.

  For example, a heat source is prepared in front of the fixing device, and the solvent on the recording material is removed by volatilization. Alternatively, the solvent in the toner image is deposited on the surface by heating and removed by a removing means such as squeeze. Further, the adhesion between the toner and the recording material is increased by applying an electric field. Etc. have been proposed.

  However, there are problems such as the safety of volatilized solvent and the increased energy to supply heat of vaporization, the risk of damaging the recording material in the squeeze process, and the occurrence of image distortion and roughness. Was difficult.

  The factor that the high-viscosity solvent hinders the fixability is related to the fact that high dispersibility is required from the viewpoint of storage stability as a wet developer. If the wet developer itself maintains high dispersibility, contact and coalescence of the toner particles do not proceed at the time of fixing, and the toner layer cannot form a condensed state of toner particles and cannot be fixed. become weak.

  On the other hand, if the dispersibility is lowered, there is a risk that toner aggregation occurs during storage of the wet developer and storage stability cannot be maintained. That is, the storage stability and the fixing property are incompatible characteristics.

  Therefore, it is desirable if the solvent can be removed from the toner layer at the time of fixing. However, in consideration of the above-mentioned difficulties, as a wet developer including a solvent, the storage stability is maintained and the fixing property is not hindered. In order to bring about such dispersibility, the type and amount of the dispersant have also been studied (see, for example, Patent Documents 1 and 2).

  In Patent Document 1, an N-vinyl-2-pyrrolidone / lauryl methacrylate copolymer basic dispersion resin or the like is used as a dispersant. This contributes to the uniform dispersion of the toner, but it is difficult to ensure high-speed fixability.

  Patent Document 2 proposes a positively charged polymer dispersant that is mainly made of polyester resin and adheres to the surface of toner particles such as a polyimine compound. Fixing property is good, but toner aggregation tends to occur during storage.

In addition, techniques using various dispersants have been proposed in various known documents. However, if either the storage stability or the fixing property is good, there is a problem, and there remains a problem of sufficiently satisfying both.
JP-A-8-220812 JP 2007-41163 A

  As described above, in the wet development, the toner image before fixing transferred to the recording material contains a carrier liquid (solvent) having a considerably high viscosity between the toner and the toner recording material as well as the toner. Therefore, the fixing property at the time of fixing the toner image is hindered. However, there are many problems in removing the carrier liquid.

  Even in the presence of a carrier liquid between toners and between toner recording materials, it is effective to reduce dispersibility as a wet developer in order to promote contact and coalescence of toner particles and improve fixability. It is. However, on the other hand, there is a problem in that the storage stability of the wet developer is impaired due to a decrease in dispersibility.

  An object of the present invention is to solve these problems, and to provide a wet developer having characteristics that maintain storage stability as a wet developer and does not impair fixing properties.

  In order to solve the above problems, the present invention has the following features.

  1. A wet developer containing toner particles, an insulating solvent, and a dispersant, wherein the toner particles include a polyester resin, and the dispersant is a basic polymer dispersant having an N-vinylpyrrolidone group. And a polyimine compound.

  2. 2. The wet developer according to 1, wherein the polyester resin has an acid value of 20 mgKOH / g or more and 80 mgKOH / g or less.

  3. 3. The wet developer according to 1 or 2, wherein the polyester resin has a glass transition temperature Tg of 60 ° C. or higher and 85 ° C. or lower.

  4). The total content of the basic polymer dispersant having the N-vinylpyrrolidone group and the polyimine compound is 1% by mass or more and 20% by mass or less based on the content of the polyester resin. 4. The wet developer according to any one of 1 to 3.

  In a wet developer containing toner particles, an insulating solvent, and a dispersant, the toner is mainly a polyester resin, and the dispersant has a base having an N-vinylpyrrolidone group that is highly dispersible and contributes to storage stability. And a polyimine compound that easily aggregates toner and is advantageous for fixing properties.

  Thereby, it is possible to provide a wet developer having characteristics that maintain storage stability as a wet developer and that do not impair fixing properties.

  Wet development using a wet developer is used in image forming apparatuses such as copiers, simple printers, and printers. In general, an electrophotographic image forming process is commonly used for these. First, the electrophotographic wet-type image forming unit will be described with reference to FIG. 1, and further, the fixing property of the toner image developed with the wet developer and transferred to the recording material and the storage stability of the wet developer will be described. The constitution of the wet developer relating to the property, particularly the dispersant will be described.

(Configuration of image forming unit and functional operation)
A configuration example of an image forming unit in an image forming apparatus using a wet developer according to the present embodiment will be described with reference to FIG. FIG. 1 is a cross-sectional view illustrating a schematic configuration example of an image forming unit in a wet image forming apparatus.

  In FIG. 1, reference numeral 1 denotes a photosensitive drum, which functions as an image carrier. The image forming unit 10 is centered on the photosensitive drum 1 and has a charging device 2 for uniformly charging the surface of the photosensitive drum 1, and an LED or laser beam on the charged photosensitive drum 1. , An exposure device 3 for forming an electrostatic latent image, a wet developing device 4 for developing the electrostatic latent image using a wet developer, a transfer device 5 for transferring the developed toner image to a transfer material 7, A cleaning device 6 for removing the wet developer remaining on the surface of the photosensitive drum after transfer is provided.

  In some cases, before and after the wet developing device 4, a device for applying or collecting a part of the wet developer in advance is provided. Here, a squeeze device 91 for removing excess wet developer from the developed toner image is provided after the wet developing device 4.

  The transfer material 7 may be a recording material such as recording paper as it is, or may be configured such that the transfer material 7 is transferred again to the recording material using an intermediate transfer belt or the like. In the present embodiment, the transfer material 7 is described as a recording material, that is, a recording paper (hereinafter referred to as recording material 7).

  In general, the wet developing device 4 bears a thin layer of a wet developer on the surface and abuts against a developing roller 41 and a developing roller 41 that develop a latent image on the photosensitive drum 1 as an image carrier. A transport roller 42 for transferring the wet developer whose liquid amount has been adjusted to the surface thereof, and a supply roller 43 that contacts the transport roller 42 and supplies the wet developer 8 in the developer tank 44 to the surface. .

  In FIG. 1, only one wet developing device 4 is disposed, but a plurality of wet developing devices 4 may be disposed for color image formation. The color development method, the presence / absence of intermediate transfer, and the like may be set arbitrarily, and an arbitrary arrangement according to it can be taken.

  The photosensitive drum 1 rotates in the direction of arrow A shown in FIG. 1, and the charging device 2 charges the surface of the rotating photosensitive drum 1 to about several hundred volts by corona discharge or the like. On the downstream side of the charging device 2 in the rotation direction of the photosensitive drum, an electrostatic latent image whose surface potential is lowered to about 100 V or less is formed by the laser beam emitted from the exposure device 3.

  A wet developing device 4 is disposed further downstream of the exposure device 3, and the electrostatic latent image formed on the photosensitive drum 1 is developed using the wet developer 8.

  In the wet developing device 4, a wet developer 8 in which toner is dispersed in an insulating solvent (hereinafter also referred to as a carrier liquid) is accommodated in a developer tank 44, and the surface of the conveying roller 42 is supplied by a supply roller 43. A wet developer 8 is supplied.

  The conveying roller 42 conveys a thin layer of the wet developer 8 and transfers it to the developing roller 41. A thin layer of the wet developer 8 is carried on the developing roller 41. Further, due to the potential difference between the developing roller 41 and the electrostatic latent image on the photosensitive drum 1, the toner particles in the thin layer of the wet developer 8 carried on the developing roller 41 become an electrostatic latent image on the photosensitive drum 1. Moving, the electrostatic latent image is developed.

  The developed toner image on the photosensitive drum 1 contains toner and carrier liquid. The squeeze device 91 is, for example, a squeeze roller, and removes excess carrier liquid from the developed toner image. The carrier liquid on the squeeze roller is removed by the blade 92.

  In the transfer device 5 (for example, a transfer roller), the recording material 7 conveyed at the same speed as the peripheral speed of the photosensitive drum 1 is charged, or a voltage is applied to develop the development on the photosensitive drum 1. The toner image is transferred onto the recording material 7.

  A cleaning device 6 (for example, a cleaner blade) that removes the wet developer 8 remaining on the surface of the photosensitive drum 1 is disposed on the downstream side of the transfer device 5. The cleaning device 6 removes the wet developer 8 remaining on the photosensitive drum 1.

  The recording material 7 onto which the toner image has been transferred by the transfer device 5 is conveyed to a fixing device including a pair of fixing rollers 9a and 9b, and is discharged after being heated and fixed.

(Storage stability and fixability)
The wet developer contains a carrier liquid having a high viscosity, and the dispersibility of the toner particles in the carrier liquid affects the occurrence of aggregation between the toner particles, and the trade-off between storage stability and fixability is caused. Explain that this is connected to the relationship.

  In the image forming apparatus, the toner image developed by the wet developer 8 and transferred to the recording material 7 is fixed to the recording material 7 which is usually paper by being pressurized and heated by a fixing device. The

  However, a toner image is originally developed using a wet developer in which toner is dispersed in a carrier liquid, and not only toner particles but also a carrier liquid is contained between toners and between toner papers. . In addition, the carrier liquid has a considerably high viscosity.

  The presence of the high-viscosity carrier liquid hinders fixability during toner image fixing. For example, since the toner image and the recording material are wet with the carrier liquid, the fixability of the toner image is lowered, and the image may be crushed or disturbed during pressure fixing.

  The factor that the high-viscosity solvent hinders the fixability is related to the fact that high dispersibility is required from the viewpoint of storage stability as a wet developer. The dispersant adsorbs on the surface of the toner particles, prevents contact and aggregation between the toner particles, and maintains high dispersibility. As a result, toner aggregation and sedimentation hardly occur during storage, and good storage stability can be obtained.

  However, if the wet developer itself maintains high dispersibility in this way, contact and coalescence of the toner particles do not proceed during fixing, and the toner layer cannot form a condensed state where the toner particles are dense. , The fixability becomes weak. However, if the dispersibility is lowered in order to secure the fixing property, there is a risk that the storage stability cannot be maintained due to the aggregation of toner during storage of the wet developer. That is, from the viewpoint of dispersibility, storage stability and fixability are incompatible characteristics.

(Structure of wet developer)
The configuration of the wet developer according to the embodiment of the present invention will be described.

  In the wet developer according to the present embodiment, both the storage stability and the fixability are achieved by configuring the dispersant in a specific combination.

  First, the configuration of a general wet developer will be described, and then the configuration of the wet developer according to the present embodiment will be described.

<General wet developer composition>
A general wet developer will be described. In a wet developer, colored toner particles are dispersed at a high concentration in a carrier liquid which is a solvent. In addition, additives such as a dispersant and a charge control agent may be appropriately selected and added to the wet developer.

  As the carrier liquid, an insulating, non-volatile solvent at room temperature is used. As the non-volatile solvent, insulating oil, for example, general liquid paraffin such as Moresco White or Isopar, silicon oil, or the like is used.

  The toner particles mainly contain a resin and a pigment or dye for coloring. The resin has a function of uniformly dispersing pigments and dyes in the resin and a function as a binder when being fixed to the recording material.

  Examples of the resin include thermoplastic resins such as polystyrene resin, styrene-acrylic resin, acrylic resin, polyester resin, epoxy resin, polyamide resin, polyimide resin, and polyurethane resin. A plurality of these resins may be used in combination.

  Commercially available pigments and dyes used for coloring the toner are also used. For example, carbon black, bengara, titanium oxide, silica, phthalocyanine blue, phthalocyanine green, sky blue, benzidine yellow, lake red D, etc. can be used as the pigment. Solvent red 27, acid blue 9, or the like is used as the dye.

  As the dispersant, a general oil-soluble dispersant is used.

  The wet developer is adjusted based on commonly used techniques. For example, the resin and the pigment are melt kneaded using a pressure kneader, a roll mill or the like at a predetermined blending ratio and uniformly dispersed, and the obtained dispersion is finely pulverized by, for example, a jet mill. Further, the obtained fine powder is classified by, for example, an air classifier to obtain a colored toner having a predetermined particle size.

  Subsequently, the obtained toner is mixed with an insulating oil as a carrier liquid at a predetermined blending ratio. This mixture is uniformly dispersed by a dispersing means such as a ball mill to obtain a wet developer.

  The volume average particle diameter of the toner is suitably in the range of 0.1 μm or more and 5 μm or less. When the average particle diameter of the toner is less than 0.1 μm, the developability is greatly lowered. On the other hand, when the average particle diameter exceeds 5 μm, the quality of the image is deteriorated.

  The ratio of the toner particle mass to the wet developer mass is suitably about 10 to 50%. If it is less than 10%, toner particles are liable to settle, and there is a problem with the stability over time during long-term storage. Further, in order to obtain a required image density, it is necessary to supply a large amount of developer, the carrier liquid adhering to the paper increases, and it must be dried at the time of fixing, and steam is generated, resulting in environmental problems. If it exceeds 50%, the viscosity of the wet developer becomes too high, making it difficult to manufacture and handle.

  The viscosity of the wet developer is preferably from 0.1 mPa · s to 10,000 mPa · s at 25 ° C. When it is 10,000 mPa · s or more, it becomes difficult to stir the carrier liquid and the toner, and the burden on the apparatus surface for obtaining a uniform wet developer is large.

<Configuration of Wet Developer According to this Embodiment>
The wet developer according to the present embodiment further has the following configuration as compared with the configuration of the conventional wet developer. The toner particles are mainly composed of a polyester resin. In addition, a basic polymer dispersant having an N-vinylpyrrolidone group and a polyimine compound are adsorbed on the surface of the toner particles as a dispersant. In this state, the toner particles are dispersed in an insulating solvent.

  The combination of the polyester resin as the binder resin and the two kinds of dispersants provides a wet developer having excellent fixing characteristics and storage stability. Details of these configurations will be described below.

(Binder resin for toner)
The binder resin of the toner is mainly composed of a polyester resin. The polyester resin has a high translucency, so that the resulting image has good color developability, and it is easy to obtain an appropriate color even when forming a color image. In addition, it is preferable that content of the polyester resin in resin is 50 mass% or more, and it is more preferable that it is 80 mass% or more.

  The acid value of the polyester resin is preferably 20 mgKOH / g or more and 80 mgKOH / g or less. When the acid value is lower than 20 mgKOH / g, it is difficult to improve the system speed. When the acid value is higher than 80 mgKOH / g, it becomes difficult to produce a polyester resin while maintaining a predetermined molecular weight. Various characteristics of the developer tend to be unstable. However, in this embodiment, since the basic polymer dispersant having an N-vinylpyrrolidone group and the polyimine compound are used, the wet developer can be made stable over time.

  The glass transition temperature (Tg) of the polyester resin is preferably 60 to 85 ° C. When the Tg is lower than 60 ° C., the storage stability is slightly deteriorated.

  The polyester resin is thermoplastic and can be obtained by polycondensation of a polyhydric alcohol and a polybasic acid (polycarboxylic acid).

  Examples of the polyhydric alcohol include, but are not limited to, propylene glycol such as ethylene glycol, diethylene glycol, triethylene glycol, and 1,2-propylene glycol, butanediol such as 1,4-butanediol, neo Pentyl glycol, alkylene glycols (aliphatic glycols) such as hexanediol such as 1,6-hexanediol and the like, and alkylene oxide adducts thereof, bisphenols such as bisphenol A and hydrogenated bisphenol, and phenolic systems of these alkylene oxide adducts Examples include glycols, alicyclics such as monocyclic or polycyclic diols, and aromatic diols, triols such as glycerin and trimethylolpropane. These can be used alone or in admixture of two or more. In particular, a bisphenol A alkylene oxide 2-3 mol adduct is preferable because it is suitable as a binder resin for a toner of a wet developer in terms of solubility and stability of the polyester resin as a product, and is also low in cost. . Examples of the alkylene oxide include ethylene oxide and propylene oxide.

  The polybasic acid (polyvalent carboxylic acid) is not limited to this, but malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, phthalic acid and its modification Saturated or unsaturated divalent basic acids such as acids (eg, hexahydrophthalic anhydride), isophthalic acid, terephthalic acid, etc., trifunctional or more saturated polyfunctional groups such as trimellitic acid, trimesic acid, pyromellitic acid, methyl nadic acid, etc. Examples thereof include monobasic acids, acid anhydrides thereof, and lower alkyl esters. These can be used alone or in admixture of two or more. In particular, isophthalic acid and terephthalic acid are preferable because they are suitable as a binder resin for a toner of a wet developer in terms of solubility and stability of the product polyester resin, and are low in cost. As the polycondensation method, generally known polycondensation methods can be used.

(Dispersant)
In order to stably disperse the toner particles and obtain good fixing properties, a basic polymer dispersant having an N-vinylpyrrolidone group and a polyimine compound are used as a dispersant.

  When a polyimine compound is used as a dispersant, it has a high adsorbing power with a polyester resin at room temperature and high dispersibility, but has a problem of poor heat stability. Therefore, dispersion stability is lowered even in an environment of about 50 ° C., and toner aggregation occurs. However, the property that toner aggregates at this high temperature works effectively at the time of fixing, and leads to securing the fixing property at high speed.

  On the other hand, when a basic polymer dispersant having an N-vinylpyrrolidone group is used, the storage stability is good even at about 50 ° C. because the dispersion stability with respect to the polyester resin is extremely high. However, the dispersion stability of the toner is maintained even when the temperature reaches the temperature at which the toner is to be fixed. Therefore, toner aggregation hardly occurs and a problem arises in the fixability.

  The wet developer containing both the basic polymer dispersant having an N vinylpyrrolidone group and the polyimine compound as a dispersant is superior in storage stability to the polyester resin as the binder resin of the toner described above. In addition, it is possible to obtain the effect of securing the fixing property at high speed.

  Examples of the basic polymer dispersant having an N-vinylpyrrolidone group include a random copolymer or a graft copolymer of N-vinyl-2-pyrrolidone and a methacrylic acid ester. In addition to methacrylic acid esters, acrylic acid esters and alkylene compounds may be used. As for the carbon number of the alkyl group of methacrylic acid ester and acrylic acid ester, about 10-20 are preferable. The alkyl group of the alkylene compound preferably has about 10 to 30 carbon atoms.

  Furthermore, a commercially available product can be used as the basic polymer dispersant having an N-vinylpyrrolidone group. Examples include “Antaron V-216”, “Antaron V-220” (both manufactured by GAF / ISP Chemicals).

  Examples of the polyimine compound include a condensed compound of a polyamine compound and a hydroxyalkyl, and commercially available products include “Solsperse 11200”, “Solsperse 13940”, and “Solsperse 17000” (all manufactured by Nippon Lubrizol).

  When these dispersants are included in the wet developer, the content thereof is preferably 1 to 20% by mass with respect to the polyester resin. More preferably, it is 2-10 mass%. If the amount is too small, toner aggregation easily occurs, and if the amount is too large, the chargeability of the toner may be adversely affected.

  In the present invention, since two types of a basic polymer dispersant having an N-vinylpyrrolidone group and a polyimine compound are added, the total amount of the two types of dispersant becomes the above-mentioned appropriate amount. In addition, the basic polymer dispersant having an N-vinylpyrrolidone group and the polyimine compound can be arbitrarily mixed at a ratio of 1: 9 to 9: 1. What is important here is the dispersion of these two types. All agents are included.

(Carrier liquid)
The carrier liquid is not particularly limited. Any solvent having a resistance value (approximately 10 ¹¹ to 10 ¹⁶ Ω · cm) that does not disturb the electrostatic latent image may be used. Furthermore, a solvent having no odor and toxicity and having a relatively high flash point is preferable. In general, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, polysiloxanes and the like can be mentioned. In particular, a normal paraffin solvent and an isoparaffin solvent are preferable in terms of odor, harmlessness, and cost. Specifically, Moresco White (manufactured by Matsumura Oil Research Co., Ltd.), Isopar (manufactured by Exxon Chemical), Shellsol 71 (manufactured by Shell Petrochemical), IP Solvent 1620, IP Solvent 2028 (all of which are Idemitsu Petrochemical) Etc.).

(Coloring agent)
The colorant is not particularly limited, and the following pigments can be used.

  A typical colorant for black is carbon black.

  Examples of colorants other than black include yellow pigments, magenta pigments, and cyan pigments. Color image formation is performed by subtractive color mixing based on these pigment colors.

  Examples of cyan pigments include copper phthalocyanine blue cyan pigments such as Color Index (CI) Pigment Blue 15: 1, 15: 3.

  Examples of magenta pigments include C.I. I. Pigment Red 48, 57 (Kermin 6B), 5, 23, 60, 114, 146, 186 and the like azo lake-based magenta pigments, insoluble azo-based magenta pigments, thioindigo-based magenta pigments, C.I. I. Examples thereof include quinacridone magenta pigments such as Pigment Red 122 and 209.

  Examples of yellow pigments include C.I. I. Examples thereof include disazo yellow pigments represented by Pigment Yellow 12, 13, 14, 17, 55, 81, 83, and the like.

  The amount of the colorant added to the binder resin is preferably about 5 to 30% by mass with respect to the resin.

  An example in which the above-described wet developer was prepared and the fixability and storage stability were actually evaluated by an image forming process is shown below.

  Each wet developer used in each Example and Comparative Example (see Table 2) to be described later was prepared as follows.

-Three kinds of polyester resins 1 to 3 are synthesized as a binder resin for the toner.
3 types of coarsely pulverized toners A to C are obtained using three types of polyester resins 1 to 3.
Each of the three types of coarsely pulverized toners A to C was mixed with two types of dispersants and a carrier liquid to prepare wet developers used in Examples and Comparative Examples described later.

<Synthesis of polyester resin>
In a round bottom flask equipped with a reflux condenser, water / alcohol separator, nitrogen gas inlet tube, thermometer and stirrer, 65 parts by mass of a propylene oxide adduct of bisphenol A (polyhydric alcohol) and 35 parts by mass of isophthalic acid Part (polybasic acid) was added, nitrogen gas was introduced with stirring, and dehydration polycondensation or dealcoholization polycondensation was performed at a temperature of 200 to 240 ° C.

  When the acid value of the produced polyester resin or the viscosity of the reaction solution reached a predetermined value, the temperature of the reaction system was lowered to 100 ° C. or less to stop polycondensation. Thus, a thermoplastic polyester resin (polyester resin 1) was obtained.

  Similarly to the polyester resin 1, polyester resins 2 and 3 were synthesized by adding a predetermined amount of polyhydric alcohol and polybasic acid (see Table 1).

  The obtained polyester resin 1 had Tg = 61.5 ° C. and acid value = 38.2 mgKOH / g. Polyester resin 2 had Tg = 55.7 ° C. and acid value = 14.1 mgKOH / g, and polyester resin 3 had Tg = 87.3 ° C. and acid value = 81.3 mgKOH / g.

(Measurement of Tg)
The glass transition temperature Tg was measured using a differential scanning calorimeter DSC-6200 (manufactured by Seiko Instruments Inc.) under the conditions of a sample amount of 20 mg and a heating rate of 10 ° C./min.

(Measurement of acid value)
The acid value was measured under the conditions of JIS K5400 method.

<Manufacture of toner>
100 parts by mass of polyester resin 1 and 10 parts by mass of carbon black “Mogal-L” (Cabot) are mixed thoroughly with a Henschel mixer, and then melt-kneaded using a co-rotating twin-screw extruder with a heating temperature in the roll of 100 ° C. The resulting mixture was cooled and coarsely pulverized to obtain coarsely pulverized toner A.

  A coarsely pulverized toner B was obtained using the polyester resin 2 in the same manner as the coarsely pulverized toner A, and a coarsely pulverized toner C was obtained using the polyester resin 3.

<Manufacture of dispersant>
As the dispersant 1, a polyimine compound (S13940) was used, and as the dispersant 2, an N-vinylpyrrolidone / lauryl methacrylate copolymer or an N-vinylpyrrolidone / alkylene copolymer (V220) was used.

  The N-vinylpyrrolidone / lauryl methacrylate copolymer was produced as follows.

  Moresco White P40 (manufactured by Matsumura Oil Research Co., Ltd.) 100 parts by mass, 45 parts by mass of lauryl methacrylate represented by chemical formula (1), 3 parts by mass of N-vinyl-2-pyrrolidone represented by chemical formula (2) which is a basic monomer, 0.2 parts by mass of azobisisobutyronitrile as a polymerization initiator was reacted at a reaction temperature of 60 to 70 ° C. for about 12 hours in a nitrogen atmosphere to obtain an N-vinylpyrrolidone / lauryl methacrylate copolymer. .

<Creation of wet developer>
With the composition shown in Table 2, a wet developer was prepared for each of Examples and Comparative Examples, and subjected to tests for fixability and storage stability.

Example 1
Moresco White P40 (manufactured by Matsumura Oil Research Co., Ltd.) 80 parts by mass, coarsely pulverized toner A 20 parts by mass, predetermined amounts of Dispersant 1 and Dispersant 2 shown in Example 1 of Table 2 are mixed, and wetted by a sand mill Crushed. Wet pulverization was stopped when the predetermined toner particle size was reached, and the wet developer of Example 1 was obtained.

(Example 2 or later)
Hereinafter, wet developing agents of Examples 2 to 5 and Comparative Examples 1 to 4 were obtained using the coarsely pulverized toner in Table 2 as well as Dispersant 1 and Dispersant 2 as in Example 1.

<Image forming process conditions>
A toner image for each wet developer was formed and fixed using the image forming apparatus having the configuration shown in FIG. The process conditions for image formation are as follows.

  The system speed was 400 mm / s, and negatively charged OPC was used as the photoreceptor. The charging potential of the photosensitive member was −700 v, the developing voltage was −450 v, and the transfer voltage was +600 v.

<Fixability evaluation method>
A fixability test was performed on a fixed sample on which a toner image was formed and fixed by the above process.

Samples were prepared by preparing a solid pattern (10 cm × 10 cm, adhesion amount 2 mg / m ² ) on high-quality paper / coated paper for each Example and Comparative Example, and heat roller fixing (180 ° C. × nip time 80 ms). .

  For each sample, select a part without offset, rub an eraser (made by Lion Corporation, sand eraser “LION 26111”) twice with a pressing load of 9.8 N, and set the residual ratio of image density to “X” manufactured by X-Rite. -Rite model 404 "and the following four ranks were evaluated. More than Δ is the allowable range.

A: Image density residual ratio is 90% or more,
○: Image density remaining rate is 80% or more and less than 90%,
Δ: Image density residual ratio is 70% or more and less than 80%,
X: Image density residual ratio is less than 70%.

  The results of the fixability test for each example and comparative example are shown in Table 2.

<Storage stability evaluation method>
A storage stability test was performed on the wet developer for each example and comparative example.

  About half of each developer is put in a sample bottle and stored in a thermostat set at 55 ° C. for 24 hours. After storage, the presence or absence of sedimentation is confirmed by visual evaluation.

  It was confirmed whether to re-disperse by shaking, or to re-disperse by stirring with a spatula. Evaluation is in the following four stages. ○ The above is the allowable range.

A: No sedimentation,
○: Stir with a spatula to redisperse,
X: Not redispersed.

  The results of the storage stability test for each example and comparative example are also shown in Table 2.

<Evaluation results>
Table 2 shows combinations of toner resins and dispersants of Examples 1 to 5 and Comparative Examples 1 to 4, and evaluation results for each.

  Example 1 is an example in which a toner using the polyester resin 1 is combined with a polyimine compound (S13940) as the dispersant 1 and an N-vinylpyrrolidone / alkylene copolymer (V220) as the dispersant 2. It is. As a result of the evaluation, the fixing property was good and the storage stability was good.

  Example 2 is an example in which a toner using the polyester resin 2 is combined with a polyimine compound (S13940) as the dispersant 1 and an N-vinylpyrrolidone / lauryl methacrylate copolymer as the dispersant 2. . Compared to Example 1, the acid value and Tg of the polyester resin are lower. As a result of the evaluation, the fixing property was good and the storage stability was good.

  Example 3 is an example in which a toner using the polyester resin 3 is combined with the same dispersant as in Example 2. Compared to Example 1, the acid value and Tg of the polyester resin are higher. Regarding the evaluation results, the fixing property was Δ and the storage stability was ◎.

  From the above, it can be seen that the combination of the polyester resin as the binder resin and the dispersant 1 and the dispersant 2 used provides good fixability and storage stability. The Tg of the polyester resin is preferably low for fixability and rather high for storage stability, but there is no problem in the range used in Examples 1 to 3.

  Example 4 is an example in which the same binder resin as in Example 1 and dispersant 1 and dispersant 2 are combined, but the added amount of dispersants 1 and 2 is 0.14 parts by mass. It has become. As a result of the evaluation, the fixing property was good and the storage stability was good.

  Example 5 is also an example in which a binder resin similar to Example 1 and a polyimine compound (S11200) are combined as the dispersant 1, and an N-vinylpyrrolidone / lauryl methacrylate copolymer is combined as the dispersant 2. However, the total amount of dispersants 1 and 2 added is 4.4 parts by mass. Regarding the evaluation results, the fixing property was Δ and the storage stability was ◎.

  From the above, Example 1 was 1.2 parts by mass of the added amounts of Dispersants 1 and 2, so that if the amount of dispersant is large (Example 4), the fixing property is lowered and the amount of dispersant is small. Although (Example 3) and storage stability tend to decrease, there is no particular problem in the range of Example 3 to Example 4.

  Comparative Example 1 is an example in which only the N-vinylpyrrolidone / lauryl methacrylate copolymer is combined as a dispersant with the toner using the polyester resin 1. A polyimine compound is not contained as a dispersant. As a result of the evaluation, there was a problem in the fixing property, in which the fixing property was x and the storage stability was ◎.

  Comparative Example 2 is an example in which only the polyimine compound (S13940) is combined with the toner using the polyester resin 1 as a dispersant. N-vinylpyrrolidone / lauryl methacrylate copolymer is not included as a dispersant. Regarding the evaluation results, there was a problem in storage stability with ◎ for fixability and x for storage stability.

  Comparative Example 3 is an example in which only the N-vinylpyrrolidone / alkylene copolymer (V220) is combined as a dispersant with the toner using the polyester resin 2. A polyimine compound is not contained as a dispersant. As a result of the evaluation, there was a problem in the fixing property, in which the fixing property was x and the storage stability was ◎.

  Comparative Example 4 is an example in which only the polyimine compound (S11200) is combined with the toner using the polyester resin 3 as a dispersant. N-vinylpyrrolidone / alkylene copolymer is not included as a dispersant. Regarding the evaluation results, there was a problem in storage stability with Δ for fixing property and x for storage stability.

  As described above, when only one of the dispersants is contained, there is a problem in either fixing property or storage stability. However, as shown in Examples 1 to 5, if two or more kinds of dispersants are used, it is not always possible to achieve both fixability and storage stability, and it is good to select and use the dispersant according to the present invention. Results.

  Thus, according to the present embodiment, in a wet developer containing toner particles, an insulating solvent, and a dispersant, a polyester resin is mainly used as a toner, and the dispersant is highly dispersible and storage stability. By maintaining a combination of a basic polymer dispersant having an N-vinyl pyrrolidone group that contributes to toner and a polyimine compound that is easy to agglomerate toner and is advantageous for fixing properties, while maintaining storage stability as a wet developer. In addition, it is possible to provide a wet developer having characteristics that do not impair fixing properties.

  In addition, the above-mentioned embodiment is an illustration and restrictive at no points. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

It is sectional drawing which shows the schematic structural example of the image formation part in a wet image forming apparatus.

Explanation of symbols

1 Photosensitive drum (image carrier)
2 Charging device 3 Exposure device 4 Wet development device 5 Transfer device (transfer roller)
6 Cleaning device (cleaner blade)
7 Transfer material (recording material)
8 Wet developer 9a, 9b Fixing device (fixing roller)
10 Image Forming Unit 41 Developing Roller (Developer Carrier)
42 Conveying roller 43 Supply roller 44 Developer tank 91 Squeeze device (roller)
92 blades

Claims (4)

A wet developer containing toner particles, an insulating solvent, and a dispersant,
The toner particles include a polyester resin,
The wet developer comprising a basic polymer dispersant having an N-vinylpyrrolidone group and a polyimine compound. The wet developer according to claim 1, wherein the polyester resin has an acid value of 20 mgKOH / g or more and 80 mgKOH / g or less. The wet developer according to claim 1, wherein the polyester resin has a glass transition temperature Tg of 60 ° C. or higher and 85 ° C. or lower. The total content of the basic polymer dispersant having the N-vinylpyrrolidone group and the polyimine compound is 1% by mass or more and 20% by mass or less based on the content of the polyester resin. The wet developer according to any one of claims 1 to 3.

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