JP2005266621A - Toner, its production method, developer, container storing toner, process cartridge, image forming apparatus and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner which is free from a releasing agent at least on the surface with at least either of supercritical fluid and subcritical fluid, has excellent low temperature fixing property, mold releasing property and anti-blocking property etc. and has high durability under high temperature and high humidity and to provide a production method of the toner which is efficient and applies a small load to the environment. <P>SOLUTION: The production method of the toner comprises at least a releasing agent removal process of removing the releasing agent on the surface of the toner by using at least either of the supercritical fluid and the subcritical fluid. It is preferable to include a particle formation process of forming toner prior to the releasing agent removal process. The embodiment that at least either of the supercritical fluid and the subcritical fluid contains carbon dioxide and an organic solvent, and the like are preferable. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a toner suitable as a toner used in electrophotography, electrostatic recording method, electrostatic printing method, and the like, an efficient production method thereof, a developer using the toner, a container containing the toner, and a process The present invention relates to a cartridge, an image forming apparatus, and an image forming method.

  A number of methods are known as electrophotographic methods (see Patent Documents 1 and 2). Generally, an electric latent image is formed on a photosensitive layer using a photoconductive substance by using various means. An electrostatic latent image forming process to be formed, a developing process in which toner is developed to form a toner image, a transfer process in which the toner image is transferred to a recording material such as paper, and the toner image transferred to the recording material is heated. , A fixing process for fixing to a recording material by pressure, thermal pressure, solvent vapor or the like, a cleaning process for removing toner remaining on the photoreceptor layer, and the like.

  The toner used in the electrophotographic method is required to be manufactured by a method that saves energy and has little influence on the environment. As a current toner production method, a melt kneading and pulverizing method has been conventionally known, but in recent years, a polymerization method (suspension method, emulsification method, dispersion method, etc.) in a liquid solvent is mainly used. It has become. The polymerized toner produced by such a polymerization method has a form capable of effectively expressing a desired function as expressed by names such as capsule toner and core-shell toner from the viewpoint of environmental issues in recent years. What you have is provided.

  As a method for producing the toner having the core-shell structure, a production method using a polymerization method or the like has been proposed (see Patent Documents 3 and 4). For example, in the suspension polymerization method, a polymerization monomer and a colorant (including a polymerization initiator, a cross-linking agent, a charge control agent, and other additives as necessary) are uniformly dissolved or dispersed in a single amount. After forming the composition, the monomer composition is dispersed using a stirrer in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer, and at the same time, a polymerization reaction is performed, and a desired composition is obtained. Toner particles having a particle size are prepared. In this suspension polymerization method, water having a large polarity is used as a dispersion medium, and the core of the monomer composition is generated in the dispersion medium. Since the non-polar component does not exist in the core surface layer portion which is easily present in the core surface layer portion which is an interface with the phase, a so-called core shell structure is formed. In recent years, it has become possible to incorporate a wax having a low melting point by utilizing such characteristics of the manufacturing method.

However, the toner produced by such a method has various drawbacks. That is, for example, the toner particles 500 having a core-shell structure obtained by the above method may not form an “ideal form” as shown in FIG. 6A. For example, as shown in FIG. When a “non-ideal form” is formed such that the release agent (wax or the like) 520 is not encapsulated in the toner particles 500, the toner particles 500 may have a reduced mechanical life or in a high temperature and high humidity environment. This causes the problem of decreased stability. That is, as shown in FIG. 6B, when the wax 520 is exposed on the surface of the outer shell resin 510 in the toner particles 500, the exposed wax 520 has a low softening point. Easily dissolves and flows out due to internal mechanical stress and heat generated by the peripheral friction between the photoconductor and toner carrier, causing problems such as filming on the photoconductor drum, toner carrier and carrier surface, resulting in product life Was significantly reduced. Further, there is a problem that the toner particles are blocked during storage of the toner particles or in the toner box to form an aggregate, resulting in poor storage stability.
As a method for solving such a problem, it is conceivable to reduce the probability of occurrence of “non-ideal form” toner particles by reducing the wax content. However, the reduction of the wax content causes a reduction in the allowable width with respect to the fixing offset, making the fixing control on the system side difficult, which is not preferable in terms of mechanical design. In recent years, low-temperature fixing to a heat fixing unit has been demanded from the viewpoint of reducing environmental load, but it is difficult to realize low-temperature fixing. For this reason, as shown in FIG. 6A, the toner particles 500 are sufficiently covered with the outer shell resin 510 in all the toner particles 500 while keeping the content of the wax 520 high. It is desirable to have an “ideal form” that is not exposed on the surface of 500.

  Therefore, it dissolves or removes only the wax adhering to the surface of the toner particles or exposed from the inside to the toner particles without affecting the outer shell strength of the toner particles produced by the conventional method. However, at present, no technology has been provided that can sufficiently solve the problems caused by these problems.

US Pat. No. 2,297,691 Japanese Patent Publication No.42-23910 International Publication No. 97/01131 Pamphlet Japanese Patent Publication No. 36-10231

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is such that at least one of the supercritical fluid and subcritical fluid removes at least the surface release agent, and is excellent in low temperature fixability, releasability, blocking resistance, etc., and high temperature and high humidity. Toner having high durability below, a manufacturing method thereof that is efficient and has a low environmental impact, and a developer, a container containing toner, a process cartridge, an image forming apparatus, and a toner capable of improving image quality using the toner An object is to provide an image forming method.

  As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, a toner having a release agent such as wax at least on its surface is treated with at least one of a supercritical fluid and a subcritical fluid for a certain period of time without adversely affecting the release agent contained in the toner. And the knowledge that only the release agent present on the surface can be removed without deteriorating the properties of the toner.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner production method including at least a release agent removing step of removing a release agent on the surface of the toner using at least one of a supercritical fluid and a subcritical fluid.
In the toner production method according to <1>, in the release agent removing step, the release agent on the surface of the toner is removed using at least one of the supercritical fluid and the subcritical fluid. Then, the release agent present on at least the surface of the toner is removed by at least one of the supercritical fluid and the subcritical fluid. As a result, a toner having excellent low-temperature fixability, releasability, blocking resistance and the like and high durability under high temperature and high humidity can be obtained.
<2> The method for producing a toner according to <1>, including a toner forming step of forming toner before the releasing agent removing step. In the toner production method according to <2>, the toner is formed in the toner forming step before the releasing agent removing step.
<3> The method for producing a toner according to any one of <1> to <2>, wherein at least one of the supercritical fluid and the subcritical fluid can dissolve the release agent without dissolving the toner. is there.
<4> The toner production method according to any one of <1> to <3>, wherein the removal is performed on a part or all of the toner surface. In the method for producing a toner according to <4>, since the removal is performed on at least part or all of the surface of the toner, the release agent is present on at least the surface of the toner. Depending on the case, selective removal is possible.
<5> The method for producing a toner according to any one of <1> to <4>, wherein at least one of the supercritical fluid and the subcritical fluid is either a simple substance or a mixture.
<6> The method for producing a toner according to any one of <1> to <5>, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide. In the method for producing a toner according to <6>, at least one of the supercritical fluid and the subcritical fluid contains carbon dioxide having a low critical temperature, and thus the handling property is excellent.
<7> The method for producing a toner according to any one of <1> to <6>, wherein at least one of the supercritical fluid and the subcritical fluid contains an organic solvent. In the method for producing a toner according to <7>, since at least one of the supercritical fluid and the subcritical fluid contains the organic solvent, it is preferable to remove the release agent on at least the surface of the toner. The release agent exposed to the surface from the inside is more efficiently removed.
<8> The method for producing a toner according to <9>, wherein the toner is selected from pulverized toner and chemical toner. In the method for producing a toner according to <8>, since the toner is selected from pulverized toner and chemical toner, for example, even when the toner is the chemical toner and has a core-shell structure, the outer shell shell is used. The release agent on the surface of the toner is removed without adversely affecting the toner.
<9> The above <1>, wherein the toner is obtained in the form of particles while producing an adhesive substrate in an aqueous medium by reacting at least the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. To <8>.
In the method for producing a toner according to <9>, the active hydrogen group-containing compound and a polymer having a site capable of reacting with the active hydrogen group-containing compound are reacted in the aqueous medium to form an adhesive group. The toner is obtained in the form of particles while the material is produced. As a result, the toner of the present invention is excellent in various properties such as aggregation resistance, fluidity and transferability, excellent in low-temperature fixability, releasability, blocking resistance and the like, and has high durability under high temperature and high humidity. Is efficiently manufactured.
<10> A toner produced by the toner production method according to any one of <1> to <9>. Since the toner according to <10> is produced by the toner production method of the present invention, it has excellent low-temperature fixability, releasability, blocking resistance, etc., and high durability even under high temperature and high humidity. Have
<11> The toner according to <10>, wherein the toner is selected from pulverized toner and chemical toner. Since the toner described in <11> is selected from pulverized toner and chemical toner, for example, even when the toner is the chemical toner and has a core-shell structure, the outer shell is adversely affected. And surface properties are good.
<12> A developer comprising the toner according to <10> to <11>. Since the developer according to <12> includes the toner of the present invention, when an image is formed by electrophotography using the developer, the developer has excellent low-temperature fixability and releasability, and high image density. A high-quality image with high sharpness can be obtained.
<13> A toner-containing container, wherein the toner according to <10> to <11> is accommodated in a container. In the toner-containing container according to <13>, the toner of the present invention is contained. Therefore, when image formation is performed by electrophotography using the toner contained in the toner-containing container, low-temperature fixability is achieved. In addition, a high quality image with high image density and high sharpness can be obtained.
<14> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <10> to <11> to be a visible image And a developing means for forming the process cartridge. The process cartridge according to <14> is detachable from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that it has excellent low-temperature fixability and releasability, and high image density. A high-quality image with high sharpness can be obtained.
<15> An electrostatic latent image carrier, an electrostatic latent image forming unit for forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to <10> to <11> Developing means for developing a visible image by developing using any of the toners, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium The image forming apparatus is characterized by having at least.
In the image forming apparatus according to <15>, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image with high image density and high sharpness can be obtained with excellent low-temperature fixability and releasability.
<16> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <10> to <11> An image comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium It is a forming method.
In the image forming method according to <16>, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, high-quality images with high image density and high sharpness can be obtained.

  According to the present invention, conventional problems can be solved, and at least one of the supercritical fluid and the subcritical fluid removes at least the surface release agent, thereby providing low-temperature fixability, releasability, Toner having excellent blocking properties and high durability under high temperature and high humidity, a production method thereof that is efficient and has a low environmental impact, and a developer and toner capable of improving image quality using the toner A container, a process cartridge, an image forming apparatus, and an image forming method can be provided.

(Toner and production method thereof)
The toner of the present invention is obtained by the toner production method of the present invention.
The toner production method of the present invention includes at least a releasing agent removing step, preferably includes a toner forming step before the releasing agent removing step, and further includes other steps appropriately selected as necessary.
Hereinafter, the details of the toner of the present invention will be clarified through the description of the toner production method of the present invention.

<Release agent removal process>
The releasing agent removing step is a step of removing the releasing agent on the surface of the toner using at least one of a supercritical fluid and a subcritical fluid.
There is no restriction | limiting in particular as said toner, Although it can select suitably according to the objective, For example, a toner, a carrier, etc. are mentioned suitably. These toners are preferably those obtained by a particle forming step described later, but commercially available products may also be used.
The release agent is not particularly limited as long as it is a low softening point substance, and can be appropriately selected according to the purpose. Examples thereof include wax and the like, and details thereof will be described in a particle forming step described later. . If the release agent is present on the surface of the toner, for example, the low-temperature fixability, releasability, blocking resistance, and durability under high temperature and high humidity of the toner are reduced.

-Supercritical fluid and subcritical fluid-
The supercritical fluid exists as a non-condensable high-density fluid in a temperature / pressure region that exceeds the limit (critical point) where gas and liquid can coexist, does not cause condensation even when compressed, and exceeds the critical temperature. And, as long as it is a fluid in a state of a critical pressure or higher, there is no particular limitation, and it can be appropriately selected according to the purpose, but those having a low critical temperature are preferred, and the subcritical fluid is the critical fluid. As long as it exists as a high-pressure liquid in the temperature / pressure region near the point, there is no particular limitation, and it can be appropriately selected according to the purpose. Examples of these fluids include carbon monoxide, carbon dioxide, ammonia, and nitrogen. , Water, methanol, ethanol, ethane, propane, 2,3-dimethylbutane, benzene, chlorotrifluoromethane, dimethyl ether and the like. Among these, carbon dioxide is particularly preferable in that the critical temperature is as low as about 31.3 ° C. and the handleability is excellent.
Various materials mentioned as the supercritical fluid can be preferably used as the subcritical fluid.
The supercritical fluid and the subcritical fluid may be used alone or as a mixture of two or more.

  The critical temperature and critical pressure of the supercritical fluid are not particularly limited and may be appropriately selected depending on the intended purpose. The critical temperature is preferably −273 to 300 ° C., particularly preferably 0 to 200 ° C. preferable. At this time, the critical pressure is preferably 1 to 60 MPa.

  In addition to the supercritical fluid and the subcritical fluid, other fluids can be used in combination. The other fluid is preferably one having a high affinity with the low softening point substance (release agent) to be removed. When the toner has a core-shell structure, one that does not dissolve the substance constituting the shell. preferable. Specifically, N20, ethane, propane, ethylene and the like are preferable. The mixing ratio of the other fluid and at least one of the supercritical fluid and the subcritical fluid is not particularly limited and may be appropriately selected depending on the purpose.

Furthermore, an organic solvent can be added in addition to the supercritical fluid and the subcritical fluid. By adding the organic solvent, the release agent described later can be removed more easily.
There is no restriction | limiting in particular as said organic solvent, According to the objective, it can select suitably, For example, methanol ammonia, a melamine, urea, thiodiethylene glycol etc. are mentioned. Specifically, a cleaning / removal aid such as chloroform having a high solubility of the polymerizable monomer is particularly preferable. Addition of the chloroform increases the effect of removing the release agent (wax component centered on a low molecular weight substance).

-Removal-
The removal is performed on the release agent present on at least the surface of the toner.

The part to be removed is not limited to the surface of the toner but preferably includes the inside thereof. When the removal is performed on the surface of the toner, the release agent present on the surface is removed, and when the removal is performed on the inside of the toner, the surface is exposed from the inside and is present It is possible to remove the releasing agent.
In addition, in order to change the site | part which performs the said removal, it can carry out by changing suitably types, such as temperature, a pressure, a supercritical fluid, etc., for example.

  When the removal is performed on the surface of the toner, it is preferably performed on a part or all of the surface. In this case, selective removal is possible depending on the position of the release agent on the surface of the toner.

The removal method is not particularly limited as long as at least one of the supercritical fluid and the subcritical fluid is brought into contact with the toner, and can be appropriately selected according to the purpose.
The apparatus used for the removal is not particularly limited and may be appropriately selected depending on the purpose. For example, a pressure vessel for removing the toner and a pressure for supplying the supercritical fluid A device including a pump and a separation tank having a pressure reducing valve for separating a gas containing the release agent removed from the toner into a release agent and a solvent is preferable. As a processing method using the apparatus, first, the toner is charged into the pressure-resistant container, the supercritical fluid is supplied into the pressure-resistant container by a pressure pump, and the supercritical fluid is brought into contact with the toner, The release agent is removed, and the supercritical fluid containing the release agent is discharged. When the supercritical fluid is returned to room temperature and normal pressure, the supercritical fluid becomes a gas, so that removal of the solvent is unnecessary and waste water generated by cleaning the toner surface, which has been conventionally required, is unnecessary. Thus, the burden on the environment is reduced. Further, at this time, in the separation tank, the pressure may be reduced by the pressure reducing valve, the release agent and the supercritical fluid may be separated, and the supercritical fluid may be reused.

The temperature at which the removal is performed is not particularly limited as long as it is equal to or higher than the critical temperature of the supercritical fluid or the subcritical fluid to be used, and can be appropriately selected according to the purpose. Is preferably below the melting point of the substance forming the toner, and more preferably at a temperature at which aggregation such as adhesion between the toners does not occur. The lower limit of the critical temperature is preferably a temperature at which the other fluid that can be added to the supercritical fluid can exist as a gas.
Specifically, the temperature for removing is preferably 0 to 100 ° C, more preferably 20 to 80 ° C, and particularly preferably 4 to 60 ° C. When the temperature is lower than 4 ° C., it is difficult to remove water adsorbed on the surface.

  Through the above process, the release agent on the surface of the toner is removed using at least one of the supercritical fluid and the subcritical fluid. Then, the release agent present on at least the surface of the toner is removed by at least one of the supercritical fluid and the subcritical fluid. For this reason, as shown in FIG. 1, the toner 450 of the present invention from which the release agent 470 exposed from the surface of the outer shell resin 460 is removed is obtained.

<Particle formation process>
The particle forming step is a step of forming the toner described above.

-Toner-
The toner is not particularly limited and may be appropriately selected from known ones according to the purpose. Examples thereof include pulverized toner and polymerized toner, and examples thereof include an active hydrogen group-containing compound and the active hydrogen group. It is obtained in the form of particles while producing an adhesive substrate in an aqueous medium by reacting at least a polymer capable of reacting with the contained compound, and if necessary, resin fine particles, colorant, release agent, non-reactive polyester Toners containing components such as resins and charge control agents are preferred.

Examples of the pulverized toner include toner produced by a known pulverization method.
Examples of the polymerized toner include a toner produced by a known polymerization method. There is no restriction | limiting in particular as this polymerization method, According to the objective, it can select suitably, For example, a suspension method, an emulsification method, a dispersion method etc. are mentioned.
The toner may be produced by a microencapsulation method (spray drying method, coacervation method, etc.), etc., in addition to the pulverization method and the polymerization method.

-Adhesive substrate-
The adhesive substrate is a polymer obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least other binders appropriately selected from known binder resins as required.

The weight average molecular weight of the adhesive substrate is not particularly limited and may be appropriately selected depending on the purpose. For example, 1,000 or more is preferable, and 2,000 to 10,000,000 is more preferable. 3,000 to 1,000,000 is particularly preferred.
When the weight average molecular weight is less than 1,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, According to the objective, it can select suitably, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

There is no restriction | limiting in particular as a specific example of the said adhesive base material, According to the objective, it can select suitably, A polyester-type resin etc. are mentioned especially suitably.
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably, For example, a urea modified polyester resin etc. are mentioned especially suitably.
The urea-modified polyester resin comprises an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond, and in this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, and aliphatic diamines. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimines obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), or those obtained by blocking these (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes low. The hot offset resistance may be deteriorated.

--- Polymer capable of reacting with active hydrogen group-containing compound ---
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. It can be appropriately selected from known resins and the like, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) because it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond-forming group in the urea bond-forming group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And those obtained by reacting the active hydrogen group-containing polyester resin with polyisocyanate (PIC).

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol And a mixture with (TO). These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycol, alkylene ether glycol, alicyclic diol, alkylene oxide adduct of alicyclic diol, bisphenol, alkylene oxide adduct of bisphenol, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenols.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tricarboxylic or higher polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably 3 to 8 or higher, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

There is no restriction | limiting in particular as said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurate And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate, diphenyl ether-4,4′-diisocyanate and the like. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate and triisocyanatocycloalkyl-isocyanurate.
These can be used alone or in combination of two or more.

As a mixing ratio when reacting the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin), the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

The average number of isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A) is preferably 1 or more, more preferably 1.2 to 5, and more preferably 1.5 to 4.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

---- Aqueous medium ---
There is no restriction | limiting in particular as said aqueous medium, It can select suitably from well-known things, For example, water, a solvent miscible with this water, a mixture thereof, etc. are mentioned.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the cell solves include methyl cell solve. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

  The component that can be contained in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a colorant, a release agent, inorganic fine particles, resin fine particles, a charge control agent, and an unmodified polyester resin. , Polymer polymer particles, fluidity improver, cleaning property improver, magnetic material and the like.

The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include degreen lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed. When the content exceeds 15% by mass, poor pigment dispersion in the toner occurs, the coloring power decreases, The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes etc. are mentioned suitably.
Examples of the waxes include low molecular weight polyolefin waxes, synthetic hydrocarbon waxes, natural waxes, petroleum waxes, higher fatty acids and metal salts thereof, higher fatty acid amides, and various modified waxes thereof. These may be used individually by 1 type and may use 2 or more types together.
Examples of the low molecular weight polyolefin wax include low molecular weight polyethylene wax and low molecular weight polypropylene wax.
Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax.
Examples of the natural waxes include beeswax, carnauba wax, candelilla wax, rice wax, and montan wax.
Examples of the petroleum waxes include paraffin wax and microcrystalline wax.
Examples of the higher fatty acid include stearic acid, palmitic acid, myristic acid, and the like.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 40-160 degreeC is preferable, 50-120 degreeC is more preferable, 60-90 degreeC is especially preferable.
If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability. If the melting point exceeds 160 ° C., it may easily cause a cold offset when fixing at a low temperature. May occur.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass parts is preferable and 3-30 mass parts is more preferable.
When the content exceeds 40 parts by mass, the low-temperature fixability may be hindered or the image quality may be deteriorated (glossiness is too high).

The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples thereof include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.
The inorganic fine particles can be suitably used as an external additive for the toner.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, it is preferably formed of at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin in that an aqueous dispersion of fine spherical resin resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

The volume average particle size of the resin fine particles is preferably 20 to 400 nm, and more preferably 30 to 350 nm. When the volume average particle size is less than 20 nm, the resin fine particles remaining on the surface of the toner may be formed into a film or may cover the entire surface of the toner densely. As a result, the resin fine particles May hinder the adhesion between the toner inside the binder resin and the fixing paper as a transfer material, and the minimum fixing temperature may increase. If the particle diameter exceeds 400 nm, the resin fine particles will exude the wax component. Inhibiting, sufficient releasability may not be obtained, and offset may occur.
The resin coverage of the resin fine particles is preferably 75 to 100%, more preferably 80 to 100%. If the toner coverage is less than 75%, the storage stability of the toner is deteriorated, and blocking may occur during storage or use.
The content of the resin fine particles in the toner is preferably 0.5 to 8.0% by mass, and more preferably 0.6 to 7.0% by mass. When the content is less than 0.5% by mass, the storability of the toner deteriorates, and blocking may be observed during storage or use. When the content exceeds 8.0% by mass, The resin fine particles hinder the seepage of the wax, so that sufficient releasability cannot be obtained and offset may occur.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, a colorless or nearly white material may be used. Preferred examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides And a simple substance of phosphorus or a compound thereof, a simple substance of tungsten or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. Among these, salicylic acid metal salts and metal salts of salicylic acid derivatives are preferred. These may be used individually by 1 type and may use 2 or more types together. There is no restriction | limiting in particular as said metal, According to the objective, it can select suitably, For example, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, and salicylic acid metal complex. E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), fourth Copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR which is a boron complex -147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups, carbo Sill group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.
The charge control agent may be melted and kneaded with the master batch and then dissolved or dispersed, or may be added together with each component of the toner when directly dissolving or dispersing in the organic solvent, or The toner particles may be fixed on the toner surface after production.

  The content of the charge control agent in the toner varies depending on the type of binder resin, the presence or absence of an additive, a dispersion method, and the like, and cannot be generally specified. For example, for 100 parts by mass of the binder resin, 0.1-10 mass parts is preferable and 1-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charging characteristics of the toner may be deteriorated. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is increased. , And the electrostatic attraction force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

The unmodified polyester resin can be contained in the toner for the purpose of improving low temperature fixability, glossiness and the like.
The unmodified polyester resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, the same polyester resin as the urea bond-forming group-containing polyester resin, that is, polyol (PO) And polycondensates with polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure compatible with each other. It is preferable in terms of hot offset.

There is no restriction | limiting in particular as a weight average molecular weight of the said unmodified polyester resin, According to the objective, it can select suitably, For example, it is 1,000-30,000 by the measured value by GPC (gel permeation chromatography). Is preferable, 1,500 to 10,000 is more preferable, and 2,000 to 8,000 is particularly preferable.
When the weight average molecular weight is less than 1,000, the heat-resistant storage stability may be deteriorated, and when it exceeds 10,000, the low-temperature fixability may be deteriorated.

The hydroxyl value of the unmodified polyester resin is preferably 5 or more, more preferably 10 to 120, and still more preferably 20 to 80.
If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is preferably 1 to 40, and more preferably 4 to 30. Generally, it becomes easy to be negatively charged by giving the toner an acid value.

When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. ~ 50/50 is preferred.
When the mixing mass ratio of the unmodified polyester resin (PE) is less than 95, the hot offset resistance may be deteriorated, and it may be difficult to achieve both heat resistant storage stability and low temperature fixability, and is 50 or more. Deterioration of low-temperature fixing may be observed.

  The polymer polymer particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, polystyrene, methacrylic acid obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, etc. Examples thereof include particles formed of esters, acrylic acid ester copolymers, silicone resins, polycondensation resins such as benzoguanamine, nylon, and thermosetting resins.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having a fluoroalkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.

  The shape, size, etc. of the toner are not particularly limited and can be appropriately selected according to the purpose. However, the following penetration, low temperature fixability, thermal characteristics, image density, average It preferably has a circularity, a volume average particle diameter, a ratio of volume average particle diameter to number average particle diameter (volume average particle diameter / number average particle diameter), and the like.

As said penetration, the penetration measured by the penetration test (JIS K2235-1991) needs to be 15 mm or more, for example, and 20-30 mm is more preferable.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that the said heat-resistant storage property is excellent, so that the said penetration value is large.

As the low-temperature fixability, from the viewpoint of achieving both a reduction in fixing temperature and no occurrence of offset, the lower fixing minimum temperature is preferably lower, and the higher the offset non-reaction temperature is, the lower the fixing temperature and no occurrence of offset. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the temperature at which no offset occurs is 200 ° C.
The fixing minimum temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The fixing roll temperature is the lower limit fixing temperature.
The offset non-occurrence temperature is set by, for example, using an image forming apparatus, setting a transfer paper, and each color of solid images of red, blue, and green as single colors of yellow, magenta, cyan, and black, and solid colors of each color. It can be determined by adjusting the toner image to be developed, adjusting the temperature of the fixing belt to be variable, and measuring the temperature at which no offset occurs.

The thermal characteristics are also called flow tester characteristics, and are evaluated as, for example, a softening temperature (Ts), an outflow start temperature (Tfb), a 1/2 method softening point (T1 / 2), and the like.
These thermal characteristics can be measured by an appropriately selected method. For example, the thermal characteristics can be obtained from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
There is no restriction | limiting in particular as said softening temperature (Ts), According to the objective, it can select suitably, For example, 50 degreeC or more is preferable and 80-120 degreeC is more preferable. When the softening temperature (Ts) is less than 50 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
There is no restriction | limiting in particular as said outflow start temperature (Tfb), According to the objective, it can select suitably, For example, 60 degreeC or more is preferable and 70-150 degreeC is more preferable. If the outflow start temperature (Tfb) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may deteriorate.
The 1/2 method softening point (T1 / 2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 60 ° C. or higher is preferable, and 80 to 170 ° C. is more preferable. If the 1/2 method softening point (T1 / 2) is less than 60 ° C., at least one of heat resistant storage stability and low temperature storage stability may be deteriorated.

The image density is preferably 1.90 or more, more preferably 2.00 or more, and particularly preferably 2.10 or more, as measured by a spectrometer (X-Light, 938 Spectrodensitometer). preferable.
If the image density is less than 1.90, the image density may be low and high image quality may not be obtained.
The image density is determined by using, for example, imagio Neo 450 (manufactured by Ricoh Co., Ltd.) and copying paper (TYPE).
6000 <70W> (manufactured by Ricoh Co., Ltd.), a solid image having a developer adhesion amount of 1.00 ± 0.05 mg / cm ² was formed at a fixing roller surface temperature of 160 ± 2 ° C., and the resulting solid image It is possible to measure the image density at arbitrary six locations in the above by measuring using a spectrometer (X-Light, 938 Spectrodensitometer) and calculating the average value.

The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected shape as the toner shape by the perimeter of the actual particles, and is preferably 0.900 to 0.980, for example, 0.950 to 0 .975 is more preferred. In addition, it is preferable that the particles having an average circularity of less than 0.94 are 15% or less.
If the average circularity is less than 0.900, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and the transfer belt, and in the case of image formation with a high image area ratio such as a photographic image, an untransferred image is formed due to defective paper feeding, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.
The average circularity is measured by, for example, an optical detection band method in which a suspension containing toner particles is passed through an imaging unit detection band on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. For example, it can be measured using a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).

There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3-8 micrometers is preferable.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, more preferably 1.10 to 1.25.
When the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) exceeds 1.25, the two-component developer causes the surface of the carrier to be agitated for a long period of time in the developing device. The toner may be fused to reduce the charging ability of the carrier. In the case of a one-component developer, the toner filming on the developing roller or the toner is thinned so that the toner is fused to a member such as a blade. May occur easily, and it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase. is there.

  The volume average particle size and the ratio of the volume average particle size to the number average particle size (volume average particle size / number average particle size) are, for example, a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics. Can be measured.

  The method for producing the toner includes a step of obtaining a particulate toner while producing an adhesive substrate in an aqueous medium by reacting at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. It includes at least other processes that are appropriately selected as necessary.

  In the step, for example, preparation of an aqueous medium phase, preparation of an organic solvent phase, emulsification / dispersion, and others (synthesis of a polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound, the active hydrogen group-containing compound) Etc.).

The aqueous medium phase can be prepared, for example, by dispersing the resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.
The organic solvent phase is prepared by mixing the active hydrogen group-containing compound, the polymer capable of reacting with the active hydrogen group-containing compound, the colorant, the mold release agent, the charge control agent, The toner raw material such as a modified polyester resin can be dissolved or dispersed.
It should be noted that components other than the polymer (prepolymer) capable of reacting with the active hydrogen group-containing compound in the toner raw material are added when the resin fine particles are dispersed in the aqueous medium in the aqueous medium phase preparation. You may add and mix in an aqueous medium, or when adding the said organic solvent phase to the said aqueous medium phase, you may add to the said aqueous medium phase with this organic solvent phase.

The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner raw material, and can be appropriately selected according to the purpose, and has a boiling point of less than 150 ° C. in terms of ease of removal. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner raw materials, and 60-140 mass parts is. More preferably, 80-120 mass parts is still more preferable.

The emulsification / dispersion can be performed by emulsifying / dispersing the previously prepared organic solvent phase in the previously prepared aqueous medium phase. In the emulsification / dispersion, when the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction, the adhesive base material is generated.
The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). The organic solvent phase is emulsified and dispersed in the aqueous medium phase together with the active hydrogen group-containing compound (for example, the amines (B)) to form a dispersion, and both are extended in the aqueous medium phase. Or (2) the organic solvent phase is emulsified and dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance to form a dispersion, and the aqueous medium It may be produced by extending or cross-linking both in the phase, or (3) the organic solvent phase is added and mixed in the aqueous medium and then the active hydrogen group-containing The compound was added to form a dispersion, it may be generated by elongation reaction or crosslinking reaction from particle interfaces in the aqueous medium phase. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification / dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours, and the reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

In the aqueous medium phase, as a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), for example, Polymer capable of reacting with the active hydrogen group-containing compound dissolved or dispersed in the organic solvent in the aqueous medium phase (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, and the release agent And a method of adding the toner raw materials such as the charge control agent and the non-modified polyester resin and dispersing them by shearing force.
The dispersion is not particularly limited as a method thereof, and can be appropriately selected using a known disperser. Examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, and a friction type. Examples thereof include a disperser, a high-pressure jet disperser, and an ultrasonic disperser. Among these, a high-speed shearing disperser is preferable in that the particle size of the dispersion can be controlled to 2 to 20 μm.
When the high-speed shearing disperser is used, conditions such as the rotation speed, dispersion time, and dispersion temperature are not particularly limited and can be appropriately selected according to the purpose. For example, the rotation speed is 1000 -30000 rpm is preferable, 5000-20000 rpm is more preferable, the dispersion time is preferably 0.1-5 minutes in the case of a batch system, and the dispersion temperature is preferably 0-150 ° C. under pressure, -98 degreeC is more preferable. The dispersion temperature is generally easier when the temperature is higher.

In the emulsification / dispersion, the usage amount of the aqueous medium is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner raw material.
When the amount used is less than 50 parts by mass, the toner raw material is poorly dispersed, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, the production cost is high. May be.

In the emulsification / dispersion, it is preferable to use a dispersant as necessary from the viewpoint of sharpening the particle size distribution and performing stable dispersion.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a poorly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products); Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M Co.); Unidyne DS-202 (manufactured by Daikin Industries Ltd.), MegaFuck F-150 F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing a hydroxyl group, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and a compound containing a carboxyl group, amides Examples thereof include homopolymers or copolymers such as compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, and celluloses.
Examples of the acids include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like. Examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In the emulsification / dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate salts.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the emulsification / dispersion, a catalyst for the elongation reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

  The organic solvent is removed from the emulsified slurry obtained in the emulsification / dispersion. The organic solvent is removed by (1) a method in which the entire reaction system is gradually heated to completely evaporate and remove the organic solvent in the droplets, and (2) the emulsion dispersion is sprayed in a dry atmosphere. And a method in which the water-insoluble organic solvent in the droplets is completely removed to form toner fine particles, and the aqueous dispersant is removed by evaporation.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure is lowered, and a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

  Through the above steps, the toner is formed.

  In the toner manufacturing method of the present invention, in the release agent removing step, the release agent on the surface of the toner is removed using at least one of the supercritical fluid and the subcritical fluid. Then, the release agent present on at least the surface of the toner is removed by at least one of the supercritical fluid and subcritical fluid. As a result, the toner of the present invention, which has excellent low-temperature fixability, releasability, blocking resistance, and the like and high durability under high temperature and high humidity, is produced with high efficiency without causing a load on the environment.

(Developer)
The developer of the present invention contains at least the toner of the present invention and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner as the toner of the present invention, there is little fluctuation in the toner particle diameter even if the balance of the toner is performed, and the toner filming on the developing roller or the toner is thinned. The toner is not fused to a member such as a blade for layering, and good and stable developability and an image can be obtained even in the long-term use (stirring) of the developing device. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

-Career-
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

  There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality Is preferred. These may be used alone or in combination of two or more.

The core material has a volume average particle size of preferably 10 to 150 μm, and more preferably 40 to 100 μm.
If the average particle size (volume average particle size (D ₅₀ )) is less than 10 μm, the carrier particle distribution may increase the number of fine powders, lowering the magnetization per particle and causing carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner, it has excellent low-temperature fixability and releasability during image formation, and can stably form a high-quality image.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention contains the toner or the developer as the toner of the present invention in a container.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.
The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.
The developing means includes a toner container as a toner of the present invention or a developer container that stores the developer, and a developer carrier that supports and conveys the toner or developer stored in the developer container. And a layer thickness regulating member or the like for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the electrophotographic apparatus of the present invention described later.
Includes other steps.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and further other steps appropriately selected as necessary, for example, a static elimination step, a cleaning step, Includes recycling and control processes.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon or the like is preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferred examples include a developer containing at least a developer, and at least a developing device capable of contacting or non-contacting the toner or the developer with the electrostatic latent image. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.
There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.
The heating in the heating and pressing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 2 includes a photosensitive drum 10 as the electrostatic latent image carrier (hereinafter referred to as “photosensitive member 10”), a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 58 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 2, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 3 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 2, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is arranged directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 3, the same components as those in FIG. 2 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 120 shown in FIG. 4 is a tandem color image forming apparatus. The tandem image forming apparatus 120 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 120, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image-corresponding image (L in FIG. 5), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image with each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the surface, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta image) based on image information of each color. And cyan images) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

  In the image forming apparatus and the image forming method of the present invention, since the toner of the present invention having excellent low-temperature fixability and releasability is used, high image quality can be obtained efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Example 1)
-Manufacture of toner-
<Particle formation process>
-Preparation of polymerizable monomer for core-
Polymeric monomer for core consisting of 80 parts by mass of styrene and 20 parts by mass of n-butyl acrylate (the glass transition temperature (Tg) of the copolymer obtained (calculated value) = 55 ° C.) and carbon black (Mitsubishi Chemical Corporation) Manufactured, trade name: # 25B), 7 parts by weight, 1 part by weight of a charge control agent (trade name: Spiron Black TRH, manufactured by Hodogaya Chemical Co., Ltd.), 0.3 parts by weight of divinylbenzene, and tert-dodecyl mercaptan. 8 parts by mass, 10 parts by mass of pentaerythritol tetrastearate (stearic acid: about 60% purity), natural gas Fischer-Tropsch wax (D Shell MS, trade name: FT &#8722; 100, melting point 92 ° C. ) 2 parts by mass with a homomixer that can be mixed with high shear force (manufactured by Tokki Kako Co., Ltd., TK type) The core polymerizable monomer composition (mixed solution) was prepared.

-Preparation of polymerizable monomer for shell-
Finely disperse 5 parts by mass of methyl methacrylate (glass transition temperature (Tg) (calculated value) = 105 ° C.) and 100 parts by mass of water using an ultrasonic emulsifier (manufactured by Tokushu Kika Co., Ltd., TK homomixer). Treatment was performed to prepare an aqueous dispersion of a polymerizable monomer for shell.

-Preparation of magnesium hydroxide colloid dispersion-
In an aqueous solution obtained by dissolving 9.8 parts by mass of magnesium chloride (water-soluble polyvalent metal salt) in 250 parts by mass of ion-exchanged water, sodium hydroxide (alkali metal hydroxide) is added to 50 parts by mass of ion-exchanged water. An aqueous solution obtained by dissolving 9 parts by mass was gradually added with stirring to prepare a magnesium hydroxide colloid (colloid of a hardly water-soluble metal compound) dispersion.

To the obtained magnesium hydroxide colloidal dispersion, the above polymerizable monomer composition for the core was added and mixed, and then 4 parts by mass of t &#8722; butyl peroxy &#8722; 2 &#8722; ethylhexanoate were added. Then, using a TK homomixer, high shear stirring was performed at a rotational speed of 11000 rpm to granulate droplets of the polymerizable monomer composition for the core. The aqueous dispersion of the granulated monomer composition was placed in a polymerization reactor equipped with a stirring blade, the polymerization reaction was started at 90 ° C., and when the polymerization conversion reached almost 100%, An aqueous dispersion of a polymerizable monomer for shell and 1 part by mass of a 1% aqueous potassium persulfate solution were added and the reaction was continued for 5 hours. Then, the reaction was stopped, and an aqueous dispersion of core / shell polymer particles. Was prepared.
While stirring the aqueous dispersion of the obtained core-shell type polymer particles, the pH of the system is adjusted to 4 or less with sulfuric acid and acid washing (25 ° C., 10 minutes) is performed. 500 parts by mass of ion-exchanged water was added to form a slurry again and washed with water. Thereafter, again, dehydration and water washing were repeated several times, and the solid content was separated by filtration, followed by drying at 45 ° C. for 24 hours with a dryer to obtain polymer particles (toner).

<Release agent removal process>
-Production of toner particles-
The obtained toner is put in a pressure-resistant container, carbon dioxide is selected as a supercritical fluid, and the flow rate is 5.0 L / min (standard state conversion value), 70 ° C., 40.52 MPa (400 atm), treatment for 5 hours. The natural gas-based Fischer-Tropsch wax as a release agent was removed from the toner particles, and toner particles were prepared by removing the natural gas-based Fischer-Tropsch wax from at least the surface of the toner particles.
The resulting toner particles have a softening temperature (Ts) of ° C, an outflow start temperature (Tfb) of ° C, a 1/2 method softening point (T1 / 2) of ° C, an average circularity, a volume average particle diameter of μm, ( The volume average particle diameter / number average particle diameter) is
The toner particles obtained in this way do not require drying treatment, washing treatment, etc., and after the release agent removing step, the reaction vessel containing the supercritical fluid is decompressed to obtain carbon dioxide. Simply deaerate to complete the process. For this reason, toner particles can be produced efficiently in an extremely short time, waste liquid processing is unnecessary, and the burden on the environment is reduced.

-Production of developer-
To 100 parts by mass of the obtained polymer (toner particles), 0.8 part by mass of a silica having an average particle diameter of 12 nm (trade name “RX200” manufactured by Nippon Aerosil Co., Ltd.) that has been subjected to a hydrophobic treatment is added, and a Henschel mixer is added. Was subjected to surface treatment, and a developer was prepared by a conventional method.

(Example 2)
In Example 1, natural gas-based Fischer-Tropsch wax as a release agent was replaced with polyolefin wax (trade name: high wax, melting point 109 ° C., manufactured by Mitsui Chemicals, Inc.), and was the same as Example 1. By the method, a toner was produced and a developer was produced.

(Example 3)
In Example 1, the same method as in Example 1 except that the natural gas Fischer-Tropsch wax as a release agent was replaced with another natural gas Fischer-Tropsch wax (manufactured by Shell MDS, melting point 88 ° C.). Thus, a toner was produced and a developer was produced.

(Comparative Example 1)
In Example 1, a toner was produced and a developer was produced in the same manner as in Example 1 except that the release agent removing step using a supercritical fluid was not performed.

(Comparative Example 2)
In Example 2, a toner was produced and a developer was produced by the same method as in Example 2 except that the release agent removing step using a supercritical fluid was not performed.

(Comparative Example 3)
In Example 3, a toner was produced and a developer was produced in the same manner as in Example 3 except that the release agent removing step using a supercritical fluid was not performed.

  About the obtained developers of Examples 1 to 3 and Comparative Examples 1 to 3, the low-temperature fixability, blocking resistance, and durability were evaluated as follows. The results are shown in Table 1.

<< Low-temperature fixability >>
About each obtained developer, the adhesion amount of each developer is 1 on copy paper (TYPE6000 <70W>, manufactured by Ricoh Co., Ltd.) using a tandem type color electrophotographic apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.). A solid image of 0.000 ± 0.05 mg / cm ² was formed. The solid image was repeatedly formed on 8000 copy sheets. The obtained solid image was fixed using a fixing device, and the fixing temperature at which an offset occurred (offset generation temperature) was measured. Based on the offset generation temperature, low-temperature fixability was evaluated based on the following criteria. This evaluation corresponds to an embodiment of the container with toner, the process cartridge, the image forming apparatus, and the image forming method of the present invention.
〔Evaluation criteria〕
5: Less than 120 ° C 4: 120-130 ° C
3: 130-140 degreeC
2: 140-150 degreeC
1: 150 ° C. or higher Here, the conventional developer (toner) having a low temperature fixability is Evaluation Criteria 2, and if the evaluation criteria are 3 to 5, it is recognized that the low temperature fixability is good.

<< Blocking resistance >>
About 20 g of the obtained developer (toner) was placed in a 20 ml glass bottle and tapped 50 times to tightly solidify the toner. Subsequently, after putting it in a 50 degreeC thermostat and leaving it to stand for 24 hours, the penetration (%) was measured by the penetration test (JIS K2235-1991). The blocking resistance was evaluated based on the following criteria from the penetration (%) with respect to the toner after being solidified.
〔Evaluation criteria〕
5: 90-100%
4: 75-90%
3: 60-75%
2: 30-60%
1-30% or less Here, if the evaluation criteria is 3 to 5, it is recognized that there is no problem in blocking resistance.

<< Durability >>
Each developer (toner) obtained was copied to copy paper (TYPE6000 <70W>, manufactured by Ricoh Co., Ltd.) using a tandem type color electrophotographic apparatus (image Neo 450, manufactured by Ricoh Co., Ltd.) at a temperature of% and at%. Printing was performed. The printing was repeated for 8000 copies of the copy paper. The printed image was compared between the initial image and the image after 8000 sheets, and the number of images recognized as having deteriorated was evaluated. The printing speed was set to.

表１の結果より、超臨界流体により離型剤の除去が行われたトナーを用いた実施例１〜３の現像剤は、超臨界流体による離型剤の除去が行われていないトナーを用いた比較例１〜３の現像剤に比べ、低温定着性及び耐ブロッキング性に優れ、また、高温高湿下における耐久性が高いことが確認された。
なお、実施例１〜３の現像剤は、高速印字速度の画像形成装置にも十分対応可能であることが認められた。

From the results shown in Table 1, the developers of Examples 1 to 3 using the toner from which the release agent has been removed by the supercritical fluid use toner that has not been removed by the supercritical fluid. Compared to the developers of Comparative Examples 1 to 3, it was confirmed that the developer was excellent in low-temperature fixability and blocking resistance and high in durability under high temperature and high humidity.
In addition, it was recognized that the developers of Examples 1 to 3 can sufficiently cope with an image forming apparatus having a high printing speed.

  The toner of the present invention produced by the toner production method of the present invention is excellent in low temperature fixability, releasability, blocking resistance, etc., and has high durability under high temperature and high humidity, so that high quality image formation is possible. Preferably used. The developer, toner-containing container, process cartridge, image forming apparatus and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a cross-sectional view of an image forming material of the present invention from which a release agent has been removed with a supercritical fluid or the like. FIG. 2 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 4 is a schematic explanatory view showing an example of carrying out the image forming method of the present invention by the image forming apparatus (tandem color image forming apparatus) of the present invention. FIG. 5 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG. FIG. 6A is a cross-sectional view of an ideal form of toner particles, and FIG. 6B is a cross-sectional view of a non-ideal form of toner particles.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 21 exposure device 22 secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure belt 28 Sheet reversing device 30 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Developing roller 45K Black developing unit 45Y Yellow developing unit 45M Magenta developing unit 45C Cyan developing unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Separating roller 53 Constant current source 55 Switching claw 56 Discharging roller 57 Discharging tray 58 Corona charger 60 Cleaning device 61 Developer 62 Transfer charger 63 Photoconductor cleaning device 64 Charger 70 Charger lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 110 Belt type fixing device 120 Tandem type developer 121 Heating roller DESCRIPTION OF SYMBOLS 122 Fixing roller 123 Fixing belt 124 Pressure roller 125 Heat source 126 Cleaning roller 127 Temperature sensor 130 Document stand 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 14 Separation roller 146 feed path 147 transport rollers 148 feed path 150 copier main body 200 feeder table 300 Scanner 400 automatic document feeder (ADF)
450 Toner of the present invention 460 Outer shell resin 470 Release agent (wax, etc.)
500 Toner particles 510 Outer shell resin 520 Release agent (wax, etc.)

Claims (13)

  A toner production method comprising at least a release agent removing step of removing a release agent on the surface of a toner using at least one of a supercritical fluid and a subcritical fluid.   The toner production method according to claim 1, further comprising a toner forming step of forming toner before the releasing agent removing step.   The method for producing a toner according to claim 1, wherein at least one of the supercritical fluid and the subcritical fluid can dissolve the release agent without dissolving the toner.   The method for producing a toner according to claim 1, wherein the removal is performed on a part or all of the toner surface.   The method for producing a toner according to claim 1, wherein at least one of the supercritical fluid and the subcritical fluid is either a simple substance or a mixture.   The method for producing a toner according to claim 1, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide.   The method for producing a toner according to claim 1, wherein at least one of the supercritical fluid and the subcritical fluid contains an organic solvent.   The method for producing a toner according to claim 1, wherein the toner is selected from pulverized toner and chemical toner.   9. The toner according to claim 1, wherein the toner is obtained in the form of particles while producing an adhesive substrate in an aqueous medium by reacting at least the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. A method for producing the toner according to claim 1.   A toner produced by the toner production method according to claim 1.   The toner according to claim 10, selected from pulverized toner and chemical toner.   A developer comprising the toner according to claim 10. A toner container, wherein the toner according to claim 10 is contained in a container.

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