JP2011123483A - Toner and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner having a core-shell structure, achieving both of fixability and heat resistance and having excellent charging uniformity and environmental stability. <P>SOLUTION: The toner comprises a main portion containing at least a resin, a release agent and a colorant, and protruding portions formed of resin fine particles on the surface of the main portion, and is characterized in that: the toner has a sea-island structure comprising the main portion as a sea portion and protruding portions as island portions; the resin contains at least a first resin and a second resin; the resin fine particles comprises a third resin; and the first resin is a crystalline resin and the second and third resins are non-crystalline resins. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a toner for developing an electrostatic latent image formed in an electrophotographic method, an electrostatic recording method, and an electrostatic printing method.

  Conventionally, research and development on electrophotography has been carried out by various creative ideas and technical approaches. In electrophotography, an electrostatic latent image formed by charging and exposing the surface of a photoconductor is developed with a colored toner to form a toner image, and the toner image is transferred to a transfer material such as transfer paper. The image is formed by fixing with a heat roll or the like.

As a toner fixing method, a contact heating fixing method such as a hot roll fixing method is widely adopted. A fixing device used for a heat roll fixing system includes a heating roll and a pressure roll, and passes a recording sheet carrying a toner image through a pressure contact portion (nip portion) between the heating roll and the pressure roll. As a result, the toner image is melted and fixed on the recording sheet.
In recent years, many fixing systems using belts have been adopted.

  Examples of the resin used in the toner include a vinyl polymer resin and a resin having a polyester skeleton. These resins have advantages and disadvantages with respect to fluidity, mobility, chargeability, fixability, image characteristics, etc., which are functional properties of the toner, and recently, both resins are used in combination. So-called hybrid type resins having both skeletons are also used. In addition to the so-called kneading and pulverization methods that exist conventionally, toner production methods include suspension methods and emulsification methods using organic solvents and aqueous solvents, and suspensions in which polymerized monomer droplets are controlled to obtain toner particles directly. A so-called wet granulation or chemical toner method such as a polymerization method or an aggregation method in which emulsified fine particles are produced and then aggregated to obtain toner particles is known.

  For example, a coating layer composed of resin particles prepared by an emulsion polymerization method using a surfactant or an emulsion dispersion method using a surfactant is formed on the surface of the colored resin particles prepared by an emulsion dispersion method, and the core is formed. An electrostatic charge image developing toner which is a polyester resin and whose coating layer is a vinyl resin is disclosed (for example, see Patent Document 1). Further, a dispersion obtained by aggregating resin particles in an aqueous medium and dispersing a resin solution obtained by dissolving a polyester resin and a styrene acrylic resin in an organic solvent in an aqueous medium is prepared. A toner obtained by removing an organic solvent from the dispersion and then aggregating resin particles in an aqueous medium is disclosed (for example, see Patent Document 2).

  Further, 1 μm resin fine particles are obtained from a polyester resin and carnauba wax by a polyaddition reaction or polycondensation reaction, and the resin fine particles are dispersed in an aqueous medium to prepare a dispersion, and the resin fine particles in the dispersion are obtained. Discloses a toner for developing an electrostatic image obtained by salting out / fusion in a water-based medium (see, for example, Patent Document 3). Also disclosed is a toner for developing an electrostatic image obtained by preparing 0.9 μm resin fine particles from a polyester-based resin and oxidized polypropylene and aggregating them (for example, see Patent Document 4). In addition, a mixed solution prepared by dissolving or dispersing a toner material containing a binder resin using a plurality of polyester resins having different acid values or glass transition temperatures and a colorant in an organic solvent is introduced into an aqueous medium. Patent Document 5 discloses a toner for developing an electrostatic image obtained by preparing 0.4 to 0.7 μm resin fine particles from a polyester-based resin and paraffin wax by suspension granulation and aggregating them. reference).

  In the above-mentioned contact heating fixing method, energy is saved by lowering the heating temperature as much as possible. Therefore, the toner resin is preferably one that melts at a low temperature. However, in the electrophotographic process, there is a process in which mechanical or thermal stress is applied to the toner. Therefore, in order not to cause a problem such as so-called blocking, a thermal characteristic restriction such as a glass transition point or a toner crack is generated. There are restrictions on molecular weight so as not to occur, and the resin is required to satisfy these characteristics. Therefore, the above two points are in a so-called trade-off relationship, and it is important to balance them. From this point of view, a so-called core / shell type toner is known in which a resin advantageous for heat fixing is used inside the toner and the outside is covered with a resin advantageous for blocking or the like.

  As a resin material, a core / shell type toner using a polyester resin advantageous for toughness, heat resistance, and fixability is known. For example, a core particle is produced by agglomerating / salting out a polyester resin fine particle dispersion using an agglomerated salt, and then a polyester resin fine particle dispersion is further added to form a shell layer by agglomerating / salting out in the same manner. A method of forming and then fusing is known (see Patent Document 6). Similarly, a method of forming a core / shell layer is also known, in which a polyester resin is dissolved in an organic solvent, resin fine particles are prepared by phase inversion emulsification, and an electrolyte is added to cause aggregation (Patent Document 7). reference).

In recent years, an electrophotographic apparatus with reduced power consumption has been developed due to increasing environmental awareness.
As a toner, a toner that can be fixed on paper even at a low fixing temperature has been researched and developed, and as one of the methods, a toner using crystalline polyester is already known.
In recent years, toners having a function-separated structure such as melting characteristics at the core, prevention of bleeding of member contaminants at the shell, and charge control have been developed.
Researches and developments have been made to fix images on paper even at a low fixing temperature and eliminate image defects due to contamination of members. As one of the methods, toner using a core-shell structure is already known.
It is already known that a crystalline polyester is used to give this core a low-temperature fixability. However, the existing crystalline polyester is more effective for low-temperature fixability than it is present inside the toner, but if it is exposed to the surface, it fuses at the photoconductor cleaning section, causing medaka. There was a problem that caused image defects. The medaka is a colored deposit called a photoreceptor adhering material as shown in FIG. 7, for example, and this is caused by a crater-like scratch serving as a trigger on the surface of the photoreceptor. That is, the additive, which is a component of the toner (developer), accumulates on the scratch while agglomerating to become a nucleus, and the aggregate of the additive grows upstream from the nucleus in the rotation direction of the photoreceptor. When this additive does not transmit the exposure light, the “medaka” portion is charged on the photosensitive member and then blocks the exposure light, so that a latent image is not formed and white spots are formed.
In addition, the conventional core-shell structure hinders the leaching of WAX and has a problem in releasability at fixing.

However, a core-shell toner that sufficiently expresses the function as a shell layer and does not inhibit, for example, the core fixing function has not been obtained.
Patent Document 8 discloses a structure containing a crystalline resin and silicon oxide particles surface-treated with oil for the purpose of exhibiting long-term stable cleaning characteristics while maintaining low-temperature fixability and chargeability. .
The present invention is similar to the present invention in that it is fixed at a low temperature with a crystalline resin and the cleaning property is improved with oil. However, the problem of contamination of crystalline resin members has not been solved.

Patent Document 9 discloses a toner for developing an electrostatic charge image that can be fixed at a low temperature, has sufficient hardness and chargeability, and satisfies toner flowability, transferability, and cleaning properties for a long time, and a method for producing the same. For the purpose of providing, a configuration is disclosed in which a crystalline resin is contained in the core and a modified silicone oil is contained in the shell.
The present invention is certainly similar in that it is fixed at a low temperature with a crystalline resin and improved in cleaning properties with silicone oil. However, since the silicone oil is contained in the toner, there is not enough silicone oil in the cleaning portion, so that the problem of suppressing medaka cannot be solved.

  In recent years, color image forming apparatuses using an electrophotographic method have become widespread, and in addition to the fact that digitized images can be easily obtained, the resolution of printed images has become higher. It is requested. As higher resolution and gradation of images are being studied, as a toner-side improvement that visualizes latent images, further spheroidization and smaller particle size have been studied in order to form high-definition images. ing. The toner produced by the pulverization method has limitations in these characteristics, so the so-called polymerized toner produced by suspension polymerization method, emulsion polymerization method, dispersion polymerization method, etc. that can be spheroidized or reduced in particle size is adopted. It is being done.

  In the case of the polymerized toner, there are problems of deterioration in transfer efficiency and filming due to an increase in adhesion to the member due to the small particle size, and deterioration in cleaning properties due to the spherical shape. In addition, since a relatively low-resistance toner component is unevenly distributed in the vicinity of the surface of the toner base in the production method of the polymerized toner, background contamination due to low chargeability is a problem.

  Therefore, attempts have been made to solve these problems by subjecting the toner base particles to surface modification. As a surface modification method, for example, Patent Document 10 discloses a method in which part or all of the surface of a toner base composed of first resin particles and a colorant is coated with second resin particles. However, in the method disclosed herein, the second resin particles to be coated are too sparse and non-uniform, and the cleaning property is improved, but it is insufficient for improving the background stain and the storage property. In addition, transferability is deteriorated.

  In the present invention, in a toner having a core-shell structure, the shell layer sufficiently exhibits the function as a shell layer, and does not hinder the fixing function of the core so that both the fixing property and the heat resistance are satisfied. An object is to provide a toner excellent in uniformity and environmental stability.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a toner structure composed of a main portion containing at least a resin, a release agent, and a colorant, and resin fine particles formed on the surface of the main portion. The toner has a sea-island structure in which the main part is the sea and the convex part is the island, the resin includes at least the first resin and the second resin, and the resin fine particles are the third. The first resin is a crystalline resin, and the second resin and the third resin are non-crystalline resins. As a result, the present invention has been completed. That is, the present invention for solving the above problems is as follows.

(1) a main portion containing at least a resin, a release agent, and a colorant;
A toner comprising convex portions formed on the surface of the main portion by resin fine particles,
The toner has a sea-island structure in which the main part is the sea and the convex part is the island,
The resin includes at least a first resin and a second resin;
The resin fine particles are made of a third resin,
The toner according to claim 1, wherein the first resin is a crystalline resin, and the second resin and the third resin are non-crystalline resins.
(2) The toner according to (1), wherein the main portion has a state in which at least a first resin, a release agent, and a colorant are dispersed in a second resin.
(3) The toner according to (2), wherein the first resin, the second resin, and the third resin are incompatible with each other.
(4) The first resin is a crystalline polyester resin, the second resin is an amorphous polyester resin, and the third resin is a vinyl-based resin. The toner according to any one of the above.
(5) The third resin is a vinyl resin obtained by polymerizing a monomer mixture containing 80 to 100% by weight of an aromatic compound having a vinyl polymerizable functional group. Toner.
(6) The toner according to (4), wherein the third resin is a vinyl resin obtained by polymerizing a monomer mixture containing 100% by weight of an aromatic compound having a vinyl polymerizable functional group. .
(7) The toner according to (5) or (6), wherein the aromatic compound having a vinyl polymerizable functional group is styrene.
(8) 80 to 100% by weight of the component contained in the monomer mixture of the third resin is styrene, 0 to 20% by weight is acrylic, and the total amount of these two components is 90 to 100% by weight. (4) The toner according to (4).
(9) The toner according to any one of (4) to (8), wherein the main portion further contains a modified polyester resin having a urethane or / and urea group.
(10) The modified polyester resin is a modified polyester resin in which the polyester resin is chain-extended or / and cross-linked by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines (9) The toner described in 1.
(11) The average particle diameter of the resin fine particles is 50 to 300 nm, and the area of the island portion is 50 to 80% of the total surface area of the toner, (1) to (10) toner.
(12) The toner according to any one of (1) to (11), wherein an average height of the convex portions is 0.03 to 0.1 μm.
(13) The melting point Tw of the release agent and the melting point Tc of the crystalline resin are Tw <Tc
The toner according to any one of (1) to (12), wherein the relationship is satisfied.
(14) The toner according to (13), wherein the releasing agent has a melting point Tw of 80 ° C. or less.
(15) The toner according to (13) or (14), wherein the crystalline resin has a melting point Tc of 90 ° C. or less.
(16) The toner according to any one of (1) to (15), wherein the release agent is paraffin wax, Fischer-Tropsch wax, polyethylene wax, monoester wax, or diester wax.
(17) The toner for developing an electrostatic charge image according to any one of (1) to (16), wherein the toner contains an external additive, and the external additive is inorganic fine particles containing silicone oil.
(18) A toner container filled with the toner according to any one of (18).
(19) A developer containing the toner according to any one of (1) to (16).
(20) a developer carrying member that carries on the surface a developer to be supplied to the latent image carrying member;
A developer supply member for supplying the developer to the surface of the developer carrier;
A developer container for storing the developer;
A developing device comprising:
A developing device, wherein the developer according to (18) is stored in a developer container.
(21) In a process cartridge in which a latent image carrier and a developing device that develops at least a latent image on the latent image carrier with a developer are integrated and detachable from an image forming apparatus, 20) A process cartridge characterized by being a developing device.
(22) a latent image carrier that carries a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
Developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to make it visible;
Transfer means for transferring the visible image on the surface of the latent image carrier to the transfer target;
Fixing means for fixing a visible image on the transfer target;
An image forming apparatus comprising:
An image forming apparatus, wherein the developing means is the developing device according to (20).
(23) The image forming apparatus according to (22), wherein a roller or a belt is used as the fixing unit.
(24) The image forming apparatus according to (22) or (23), wherein no oil is applied to the fixing unit.
(25) a charging step for uniformly charging the surface of the latent image carrier,
An exposure process for exposing the surface of the charged latent image carrier based on the image data and writing an electrostatic latent image;
A developer layer having a predetermined layer thickness is formed on the developer carrier by a developer layer regulating member, and the electrostatic latent image formed on the surface of the latent image carrier is developed through the developer layer to be visualized. A development process to
A transfer step of transferring a visible image on the surface of the latent image carrier to the transfer target;
A fixing step of fixing a visible image on the transfer target,
An image forming method comprising using the developer described in (19) as a developer.
(26) The method for producing a toner according to (1), comprising at least the following steps (1) to (4).
(1) a step of dissolving or dispersing at least the first resin, the second resin, the release agent and the colorant in an organic solvent;
(2) A step of suspending the dissolved product or dispersion in an aqueous medium to produce a core particle dispersion that is the main part,
(3) adding a resin fine particle dispersion made of a third resin to the core particle dispersion to form convex portions made of resin fine particles on the core particles;
(4) The step of removing the organic solvent (27) The toner production method as described in (26), wherein the aqueous medium contains a surfactant.
(28) The resin fine particle dispersion comprising the third resin does not contain an organic solvent, and the fine particles are dispersed in a solid state. The toner according to (26) or (27), Production method.
(29) The method for producing a toner according to any one of (26) to (28), wherein the organic solvent is completely removed after the convex portion is formed.
(30) In the step of adding the resin fine particle dispersion liquid made of the third resin to form the convex parts made of resin fine particles on the core particles, the organic solvent is contained in the dispersed core particles in an amount of 10% by mass to 70% by mass. 30. The method for producing a toner according to claim 26, wherein the toner is contained in a percentage.

According to the present invention, it is possible to provide a toner having both fixing property and heat resistance, and having excellent charging uniformity and environmental stability. That is, since fine particles made of a resin that is incompatible with the toner main part are embedded in the toner surface, uniform chargeability can be obtained over a long period of time.
Further, since the fine particles are present on the toner surface with an appropriate gap, for example, elution of the release agent inside the toner can be controlled. Specifically, the toner main part is hardly rubbed due to the effect of fine particles having convex portions in the normal state, so that the transfer to other members due to the release agent or crystalline resin is suppressed, but the heat pressure fixing Sometimes the release agent elutes and performs its function. At that time, since the fine particle portion does not completely cover the main portion and has an appropriate gap, the release of the release agent is not hindered.

  In addition, by setting the melting point Tc of the crystalline resin dispersed in the toner lower than the softening temperature of the whole toner, it can be easily oozed at the time of fixing or the effect of plasticizing the main binder resin can be exhibited. Low temperature fixability is improved. At the same time, it is preferable to make Tc higher than the melting point Tw of the release agent because it does not hinder elution of the release agent. That is, it is preferable that the release agent quickly move to the outermost surface of the toner at the time of fixing, and for this reason, the melt viscosity of the release agent is preferably low.

Also, by forming the shell layer while swelling or dissolving the resin fine particles in the presence of an organic solvent when forming the shell layer, a toner surface layer having the shape as in the present invention can be obtained efficiently, and the charging uniformity In addition, it is possible to obtain a toner that has excellent heat resistance and suppresses adverse effects on fixing properties as much as possible.
Further, in order to realize the shape as in the present invention, it is very effective to prepare the core part by a dissolution suspension method and to introduce the shell resin fine particle dispersion in the presence of an organic solvent. It was found that a resin containing a relatively large amount of styrene and having a low compatibility with the core resin is suitable.

  Furthermore, in order to achieve low-temperature fixability, it is effective to disperse and contain a crystalline resin in the toner main part. For example, when crystalline polyester is used, a skeleton that exhibits crystallinity is not an aromatic monomer but a fatty acid. It must contain a lot of group monomers. As a result, the toner using crystalline polyester was inferior in chargeability and had a problem. However, as described above, according to the present invention, there are resin fine particles containing a large amount of styrene having excellent chargeability on the toner surface. In addition, since the surface has a large surface area due to the structure in which the convex portions are formed, a toner exhibiting extremely good charging performance is provided.

In addition, the main part including the toner resin, the release agent, and the colorant is made to contain crystalline polyester, and a granular shell (vinyl type) is adhered thereon, and the silicone oil-containing silica is further included. The effects described below can be obtained.
(1) Since it contains crystalline polyester, it has a high effect on low-temperature fixability.
(2) Since a granular shell having a high charging ability is adhered on the crystalline polyester, it is possible to prevent an adverse effect of charge reduction due to Cpes and to have high chargeability.
(3) Since the silicone oil-treated silica is contained, the crystalline polyester can be prevented from being fused at the cleaning portion.

3 is an SEM photograph showing the appearance of toner particles of the present invention. FIG. 3 is an explanatory diagram illustrating a main part of an embodiment of an image forming apparatus in which the electrostatic image developing toner of the present invention is used. FIG. 3 is an explanatory diagram illustrating a configuration of a fixing device used in an image forming apparatus in which the electrostatic charge image developing toner of the present invention is used. It is explanatory drawing which shows the other example of the image forming apparatus in which the toner for electrostatic image development of this invention is used. It is explanatory drawing which shows the other example of the image forming apparatus in which the toner for electrostatic image development of this invention is used. It is explanatory drawing which shows the process cartridge using the toner for electrostatic image development of this invention. It is a figure which shows the photoreceptor adhering called a medaka.

<About the sea-island structure>
The toner of the present invention has a sea-island structure including a main portion (sea portion) containing at least a resin, a release agent, and a colorant, and a convex portion (island portion) made of resin fine particles formed on the surface of the main portion.
The resin constituting the sea part includes at least a first resin made of a crystalline resin and a second resin made of an amorphous resin, and the resin fine particles are made of a third resin made of an amorphous resin. The first resin is incompatible with the second resin and exists in the sea island state in the toner.
From the viewpoint of the present invention, the melting point (Tc) of the crystalline resin is preferably 5 ° C. or more, more preferably 10 ° C. or more lower than the outflow start temperature (Tfb) of the toner. In consideration of the actual fixing temperature, Tc is preferably 90 ° C. or lower, and more preferably 80 ° C. or lower. The melting point Tw of the release agent is preferably 80 ° C. or lower, and more preferably 75 ° C. or lower.

The resin constituting the sea portion is not particularly limited, but it is preferable to use a resin having a polyester skeleton because good fixability can be obtained. Examples of the resin having a polyester skeleton include a polyester resin and a block polymer of a polyester and a resin having another skeleton, and the use of the polyester resin is preferable because the uniformity of the colored resin particles obtained is high.
In the present specification, for the sake of convenience, a convex portion made of resin fine particles is called a shell, and the other portion is called a core.

Examples of the polyester resin include ring-opening polymers of lactones, polycondensation products of hydroxycarboxylic acids, polycondensates of polyols and polycarboxylic acids, and the like. Polycondensates are preferred.
The peak molecular weight of the polyester resin is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. When it is 1000 or more, heat-resistant storage stability is good, and when it is 30000 or less, low-temperature fixability is good.
The glass transition temperature of the polyester resin is in the range of 35 to 80 ° C, preferably 40 to 70 ° C, more preferably 45 to 65 ° C. When the temperature is 35 ° C. or higher, the toner is not deformed when it is placed in a high temperature environment such as midsummer, and the toner particles do not adhere to each other and cannot behave as original particles. Further, the fixing property is improved when the temperature is 80 ° C. or lower.

  The toner of the present invention comprises a step of dissolving or dispersing a resin forming the main part, a colorant and a release agent in a solvent, a step of dispersing the dissolved or dispersed material in an aqueous medium and granulating core particles, Adding at least a resin fine particle dispersion in which resin fine particles forming convex portions are dispersed to the core particle dispersion to form convex portions made of resin fine particles on the surface of the core particles; It can be obtained through a step of removing the organic solvent from the dispersion.

<Polyester resin>
Examples of the polyester resin used in the present invention include the following polycondensates of polyol (1) and polycarboxylic acid (2), and any of them can be used. May be used.

(Polyol)
Examples of the polyol (1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Ethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyls such as bisphenol S, 3,3'-difluoro-4,4'-dihydroxybiphenyl, etc .; bis (3-fluoro-4-hydroxyphenyl) Nyl) methane, 1-phenyl-1,1-bis (3-fluoro-4-hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3 Bis (5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2,2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, etc. Hydroxyphenyl) alkanes; bis (4-hydroxyphenyl) ethers such as bis (3-fluoro-4-hydroxyphenyl) ether); alkylene oxides of the above alicyclic diols (ethylene oxide, propylene oxide, butylene oxide, etc.) Adducts; alkylene oxides of the above bisphenols (ethylene oxide) De, propylene oxide, and the like butylene oxide, etc.) adducts.

  Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.

In addition, trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.) ); Alkylene oxide adducts of the above trihydric or higher polyphenols.
In addition, the said polyol can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Polycarboxylic acid)
Examples of the polycarboxylic acid (2) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, Naphthalenedicarboxylic acid, 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid, 5- Trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane 2,2′-bis (trifluoromethyl) -4,4′- Phenyldicarboxylic acid, 3,3′-bis (trifluoromethyl) -4,4′-biphenyldicarboxylic acid, 2,2′-bis (trifluoromethyl) -3,3′-biphenyldicarboxylic acid, hexafluoroisopropylidene Dendiphthalic anhydride, etc.).

Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Further, polycarboxylic acids having 3 or more valences include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), and acid anhydrides or lower alkyl esters (methyl esters, ethyl esters) described above. , Isopropyl ester, etc.) may be used to react with polyol (1).
In addition, the said polycarboxylic acid can be used individually by 1 type or in combination of 2 or more types, It is not limited to the above.

(Ratio of polyol and polycarboxylic acid)
The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

(Molecular weight of polyester resin)
The peak molecular weight is usually 1000 to 30000, preferably 1500 to 10000, more preferably 2000 to 8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 30000, low-temperature fixability will deteriorate.

<Modified polyester resin>
The binder resin used in the present invention may contain a modified polyester resin having urethane or / and urea groups for adjusting viscoelasticity. The content of the modified polyester resin having a urethane or / and urea group is preferably 20% or less, more preferably 15% or less, and still more preferably 10% or less in the binder resin. When the content ratio exceeds 20%, the low-temperature fixability is deteriorated. The modified polyester resin having urethane or / and urea groups may be directly mixed with the binder resin, but from the viewpoint of manufacturability, a relatively low molecular weight modified polyester resin having an isocyanate group at the terminal (hereinafter referred to as “polyester resin”) And an amine that reacts with the binder resin is mixed with the binder resin, and during the granulation / after granulation, chain extension or / and cross-linking reaction is carried out to form the urethane or / and urea group. It is preferable to have a modified polyester resin. By doing so, it becomes easy to contain a relatively high molecular weight modified polyester resin for adjusting the viscoelasticity.

(Prepolymer)
Examples of the prepolymer having an isocyanate group include a polycondensate of the polyol (1) and the polycarboxylic acid (2) and a polyester having an active hydrogen group that is further reacted with a polyisocyanate (3). . Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

(Polyisocyanate)
Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

(Ratio of isocyanate group to hydroxyl group)
The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, more preferably 2 to 20% by mass. It is. If it is less than 0.5% by mass, the offset resistance deteriorates. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.

(Number of isocyanate groups in the prepolymer)
The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. When the number is less than 1 per molecule, the molecular weight of the modified polyester after chain extension and / or crosslinking becomes low, and offset resistance deteriorates.

(Chain extension and / or cross-linking agent)
In the present invention, amines can be used as chain extension and / or crosslinking agents. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned.

Examples of the diamine (B1) include the following.
Aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.);
Alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc.);
And aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylenediamine, etc.).

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.

Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

(Stopper)
Furthermore, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for the chain extension and / or crosslinking reaction, if necessary. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those blocked (ketimine compounds).

(Ratio of amino group to isocyanate group)
The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

<Crystalline polyester resin>
The toner of the present invention contains a crystalline polyester in order to improve low temperature fixability. Crystalline polyester can also be obtained as a polycondensation product of the aforementioned polyol and polycarboxylic acid, and the polyol is preferably an aliphatic diol, specifically, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,4-butenediol, etc. Of these, 1,4-butanediol, 1,6-hexanediol and 1,8-octanediol are preferable, and 1,6-hexanediol is more preferable. The polycarboxylic acid is preferably an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid, or an aliphatic carboxylic acid having 2 to 8 carbon atoms, but an aliphatic carboxylic acid is more preferable for increasing the crystallinity. .
A crystalline resin (crystalline polyester) and an amorphous resin are distinguished from each other by thermal characteristics. The crystalline resin refers to a resin having a clear endothermic peak such as wax in DSC measurement. On the other hand, a gentle curve based on the glass transition is observed in the amorphous resin.

(Vinyl resin fine particles)
A vinyl resin is suitably used as the third resin used in the present invention.
Resin fine particles made of a vinyl resin are obtained by polymerizing a monomer mixture mainly containing an aromatic compound having a vinyl polymerizable functional group as a monomer.
The content of the aromatic compound having a vinyl polymerizable functional group in the monomer mixture is 80 to 100% by mass, preferably 90 to 100% by mass, more preferably 95 to 100% by mass. When the aromatic compound having a vinyl polymerizable functional group is less than 80% by mass, the chargeability of the obtained toner becomes poor.

Examples of the polymerizable functional group in the aromatic compound having a vinyl polymerizable functional group include a vinyl group, an isopropenyl group, an allyl group, an acryloyl group, and a methacryloyl group.
Specific monomers include styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4-carboxystyrene or a metal salt thereof. 4-styrenesulfonic acid or its metal salt, 1-vinylnaphthalene, 2-vinylnaphthalene, allylbenzene, phenoxyalkylene glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, phenoxy polyalkylene glycol methacrylate, methoxydiethylene glycol methacrylate, etc. Can be mentioned.
Of these, it is preferable to mainly use styrene which is easily available, has excellent reactivity and high chargeability.

In addition, the vinyl resin used in the present invention may contain 0 to 7% by mass of a compound having a vinyl polymerizable functional group and an acid group (hereinafter also referred to as “acid monomer”) in the monomer mixture. The content of the acid monomer is preferably 0 to 4% by mass, and more preferably no acid monomer is used. When the acid monomer is used in excess of 7% by mass, the resulting vinyl resin fine particles have a high dispersion stability in itself, so that such a vinyl resin is contained in a dispersion in which oil droplets are dispersed in an aqueous phase. Even if resin fine particles are added, they are difficult to adhere at room temperature or are easily detached even if they are attached, and they are easily removed in the process of solvent removal, washing, drying, and external addition treatment. Furthermore, when the amount of the acid monomer used is 4% by mass or less, the change in chargeability can be reduced depending on the environment in which the obtained toner is used.

Examples of the acid group in the compound having a vinyl polymerizable functional group and an acid group include carboxylic acid, sulfonyl acid, and phosphonic acid.
Examples of the compound having a vinyl polymerizable functional group and an acid group include a carboxyl group-containing vinyl monomer and a salt thereof ((meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, Crotonic acid, itaconic acid, itaconic acid monoalkyl, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl, cinnamic acid, etc.), sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof, phosphoric acid Group-containing vinyl monomers and salts thereof. Among these, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, and monoalkyl fumarate are preferable.

If the compatibility of the core part with the resin is high, the desired toner surface state may not be obtained. If the polarity and structure of the monomer mixture used and the resin of the core part are controlled in the direction of low compatibility, Good.
The solubility in the organic solvent to be used should not be unnecessarily dissolved. In the case where the particles are so dissolved that the fine particle shape cannot be maintained, as a result, a desired toner surface state may not be obtained.

Although it does not specifically limit as a method to obtain vinyl resin fine particles, The following (a)-(f) is mentioned.
(A) The monomer mixture is reacted by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method or a dispersion polymerization method to produce a dispersion of vinyl resin fine particles.
(B) The monomer mixture is polymerized in advance, and the resin obtained is pulverized using a mechanical pulverizer or jet pulverizer and then classified to produce resin fine particles.
(C) A resin solution obtained by polymerizing a monomer mixture in advance and dissolving the obtained resin in a solvent,
The fine resin particles are produced by spraying in the form of a mist.
(D) polymerizing the monomer mixture in advance, adding a solvent to the resin solution obtained by dissolving the obtained resin in a solvent, or cooling the resin solution previously dissolved in a solvent to precipitate resin fine particles; Resin fine particles are produced by removing the solvent.
(E) A resin solution obtained by polymerizing a monomer mixture in advance and dissolving the obtained resin in a solvent,
Disperse it in an aqueous medium in the presence of a suitable dispersant, and remove the solvent by heating or reducing the pressure.
(F) A monomer mixture is polymerized in advance, an appropriate emulsifier is dissolved in a resin solution obtained by dissolving the obtained resin in a solvent, and water is added to perform phase inversion emulsification.
Among them, the method (a) is preferable because it is easy to produce and the resin fine particles can be obtained as a dispersion, and can be smoothly applied to the next step.

  In the method (a), when the polymerization reaction is performed, a dispersion stabilizer is added to the aqueous medium, or the dispersion stability of the resin fine particles obtained by polymerization can be imparted to the monomer that performs the polymerization reaction. It is preferable to add a stable monomer (so-called reactive emulsifier) or use these two means in combination to impart dispersion stability of the resulting vinyl resin fine particles. If a dispersion stabilizer or reactive emulsifier is not used, the dispersion state of the particles cannot be maintained, so the vinyl resin cannot be obtained as fine particles, or the dispersion stability of the obtained resin fine particles is low, so that the storage stability The toner particles are agglomerated during storage, or the dispersion stability of the particles in the resin fine particle adhesion process described later is reduced, so that the core particles easily aggregate and coalesce, resulting in toner particles finally obtained. Since uniformity of a diameter, a shape, a surface, etc. worsens, it is not preferable.

  Examples of the dispersion stabilizer include surfactants and inorganic dispersants. Examples of the surfactant include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters, and alkylamine salts. Amine salt types such as amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N Amphoteric surfactants such as N- dimethyl ammonium betaine and the like. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used.

In the case of producing the resin fine particles in the present invention, a generally used chain transfer agent can be used for the purpose of adjusting the molecular weight. The chain transfer agent is not particularly limited, but an alkyl mercaptan chain transfer agent having a hydrocarbon group having 3 or more carbon atoms is preferably used. The alkyl mercaptan-based hydrophobic chain transfer agent having a hydrocarbon group having 3 or more carbon atoms is not particularly limited, but butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl Mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-mercaptoethyl ester octanoate, 1,8-dimercapto-3,6- Dioxaoctane, decane trithiol, dodecyl mercaptan and the like can be mentioned. In this case, the hydrophobic chain transfer agent may be used alone or in the form of a mixture of two or more.

  At this time, the addition amount of the chain transfer agent is not particularly limited as long as the obtained copolymer can be adjusted so as to have a desired molecular weight, but is preferably 0 with respect to the total moles of the monomer components. 0.01 to 30 parts by mass, more preferably 0.1 to 25 parts by mass. At this time, if the added amount of the chain transfer agent is less than 0.01 parts by mass, the molecular weight of the resulting copolymer becomes too large, so that the fixability is lowered or gelation occurs during the polymerization reaction. there is a possibility. On the contrary, when the addition amount of the chain transfer agent exceeds 30 parts by mass, the chain transfer agent remains in an unreacted state, and the molecular weight of the obtained copolymer is small, causing member contamination.

  The weight average molecular weight of the vinyl resin is 3,000 to 300,000, preferably 4,000 to 100,000, more preferably 5,000 to 50,000. When the weight average molecular weight is less than 3,000, the mechanical strength of the vinyl resin is weak and fragile, and the toner surface easily changes depending on the use situation depending on the application of the finally obtained toner. This is not preferable because it causes a significant change in chargeability, contamination such as adhesion to peripheral agents, and the accompanying quality problems. On the other hand, if it exceeds 300,000, the molecular ends are reduced, so that the entanglement of the molecular chain with the core particle is reduced and the adhesion to the core particle is lowered, which is not preferable.

  The glass transition temperature (Tg) of the vinyl resin is 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher. A temperature lower than 40 ° C. is not preferable because the storage stability may be deteriorated such as blocking when the finally obtained toner is stored at a high temperature.

<Colorant>
As the coloring agent of the present invention, all known dyes and pigments can be used. 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, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing 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, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen 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, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

<Release agent>
As the release agent used in the present invention, known ones can be used, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, Fischer-Tropsch wax, sazol wax, etc.); carbonyl group Examples thereof include waxes. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitate, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); polyalkylamides (trimellitic acid tristearylamide, etc.) And dialkyl ketones (such as distearyl ketone), mono / diesters, and the like. Of these, polyolefin waxes and long-chain hydrocarbons are preferable because of their low polarity and low melt viscosity, and paraffin wax and Fischer-Tropsch wax are particularly preferable.

<External additive>
(Inorganic fine particles)
As the external additive for assisting the fluidity, developability and chargeability of the colored particles obtained in the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

(Polymer fine particles)
Other polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, polycondensation system such as silicon, benzoguanamine and nylon, and thermosetting resin Examples include polymer particles.

(Surface treatment of external additives)
Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .
In the case where crystalline polyester contaminates the surface of the photoreceptor and medaka or filming occurs, inorganic fine particles such as silica containing silicone oil can be mentioned as a preferred example of the surface-treated external additive. By adding this external additive, it is possible to provide a toner having good cleaning properties.
In addition, inorganic fine particles treated with silicone oil have high hydrophobicity, improve environmental stability of charging, and improve environmental resistance. The average particle size of primary particles of inorganic fine particles such as silica containing silicone oil is 30 to 100 nm is preferable and 30-80 nm is more preferable. If it is smaller than 30 nm, inorganic fine particles are likely to be present on the toner side, and silicone oil sufficient for cleaning is not supplied, and the medaka deteriorates. If it exceeds 100 nm, the toner tends to be separated from the toner, causing contamination of the developing member.
Moreover, 5.0-10.0 mass% is preferable and, as for the carbon content in this particle | grains originating in a silicone oil, 5.0-8.0 mass% is more preferable. If the amount of carbon is less than 5.0% by mass, silicone oil sufficient for cleaning is not supplied, and medaka deteriorates. It also affects the environmental resistance. When the content is more than 10% by mass, the developing member is contaminated by the free silicone oil.

(Cleaning aid)
Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, such as polymethyl methacrylate fine particles and polystyrene fine particles. And polymer fine particles produced by soap-free emulsion polymerization. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

<Toner production method>
The method for producing the toner of the present invention is exemplified below, but is not limited thereto.
<Core particle (main part) granulation process>
(Organic solvent)
The organic solvent used for granulation is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later. Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. Particularly preferred are ester solvents such as methyl acetate and ethyl acetate, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride. The polyester resin and the colorant may be dissolved or dispersed at the same time, but are usually dissolved or dispersed individually, and the organic solvents used at that time may be different or the same, but considering the subsequent solvent treatment The same is preferable. Moreover, when the solvent (single or mixed) which melt | dissolves a polyester-type resin suitably is selected, the mold release agent used preferably by this invention will hardly melt | dissolve from the difference in the solubility.

(Dissolution or dispersion of polyester resin)
The polyester resin is preferably dissolved or dispersed in a resin concentration of about 40% to 80%. If the concentration is too high, it becomes difficult to dissolve or disperse, and the viscosity is too high to handle. On the other hand, if the concentration is too low, the production amount of fine particles decreases, and the amount of solvent to be removed increases. When mixing the polyester resin with the modified polyester resin having an isocyanate group at the terminal, it may be mixed in the same solution or dispersion, or separately dissolved or dispersed, but the respective solubility In view of the viscosity, it is preferable to prepare separate solutions or dispersions.

(Aqueous medium)
As an aqueous medium to be used, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like. The usage-amount of the aqueous medium with respect to 100 mass parts of resin fine particles is 50-2000 mass parts normally, Preferably it is 100-1000 mass parts.

(Inorganic dispersant and organic resin fine particles)
When the dissolved or dispersed solution of the polyester resin and the release agent is dispersed in the aqueous medium, the particle size distribution is sharpened by dispersing the inorganic dispersant or the organic resin fine particles in the aqueous medium in advance. And is preferable in that the dispersion is stable. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. As the resin forming the organic resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Includes 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 and the like. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

(Surfactant)
Moreover, when manufacturing the said resin fine particle, surfactant etc. can also be used as needed. As surfactants, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, Quaternary ammonium salt type cationic surfactants such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, fatty acid amide derivative, polyhydric alcohol Nonionic surfactants such as derivatives, for example, amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine. It is.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms, and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (C6 -C11) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) ) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2-hydroxyethyl) par Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Can be mentioned. In addition, examples of the cationic surfactant include aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts. Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt and the like.

(Protective colloid)
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Of methyl alcohol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or compounds containing vinyl alcohol and carboxyl group Esters such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole , Homopolymers or copolymers such as those having a nitrogen atom such as ethyleneimine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used. In addition, when an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation. When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

(Distribution method)
The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. As temperature at the time of dispersion | distribution, it is 0-150 degreeC (under pressure) normally, Preferably it is 20-80 degreeC.

(Oil phase preparation process)
As a method of preparing an oil phase in which a resin, a colorant, a release agent, etc. are dissolved or dispersed in an organic solvent, the resin, colorant, etc. are gradually added to the organic solvent while stirring and dissolved. Alternatively, it may be dispersed. However, when using a pigment as a colorant or adding a release agent or charge control agent that is difficult to dissolve in an organic solvent, the particles should be made smaller prior to addition to the organic solvent. It is preferable.
As described above, the master batch of the colorant is one of the means, and the same method can be applied to the release agent and the charge control agent.

As another means, it is also possible to add a dispersion aid as necessary in an organic solvent and disperse the colorant, release agent, and charge control agent in a wet manner to obtain a wet master.
As another means, if a material that melts below the boiling point of the organic solvent is dispersed, a dispersion aid is added in the organic solvent as necessary, and the mixture is heated with stirring with the dispersoid. After dissolution, crystallization may be performed by cooling with stirring or shearing to produce dispersoid microcrystals.

  The colorant, release agent, and charge control agent dispersed using the above means may be further dispersed after being dissolved or dispersed together with the resin in the organic solvent. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

(Core particle production process)
The method of dispersing the oil phase obtained in the above-described step in an aqueous medium and preparing a dispersion liquid in which core particles composed of the oil phase are dispersed is not particularly limited. Known equipment such as a formula, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. If dispersion is performed for more than 5 minutes, particles with undesirable small diameters may remain, or dispersion may become overdispersed, resulting in instability of the system and generation of aggregates and coarse particles. It is not preferable. As temperature at the time of dispersion | distribution, it is 0-40 degreeC normally, Preferably it is 10-30 degreeC. If it exceeds 40 ° C., the molecular motion becomes active, so that the dispersion stability is lowered and aggregates and coarse particles are likely to be generated. On the other hand, when the temperature is less than 0 ° C., the viscosity of the dispersion increases and the shear energy required for dispersion increases, so that the production efficiency decreases.

  As the surfactant, the same surfactants as described in the description of the method for producing fine resin particles can be used. However, in order to efficiently disperse oil droplets containing a solvent, a disulfonate having a high HLB is used. preferable. The surfactant has a concentration in the aqueous medium of 1 to 10% by mass, preferably 2 to 8% by mass, more preferably 3 to 7% by mass. If it exceeds 10% by mass, the oil droplets will be too small, or a reverse micelle structure will be formed, and the dispersion stability will be lowered, resulting in the coarsening of the oil droplets. On the other hand, if it is less than 1% by mass, the oil droplets cannot be stably dispersed and the oil droplets become coarse, which is not preferable.

(Resin fine particle adhesion process)
The obtained core particle dispersion can keep the core particle droplets stably while stirring. In this state, the above-mentioned vinyl resin fine particle dispersion is introduced and adhered onto the core particles. The vinyl resin fine particle dispersion is preferably charged over 30 seconds. If the charging is performed in less than 30 seconds, it is not preferable because the dispersion system changes abruptly so that aggregated particles are generated and the adhesion of vinyl resin fine particles becomes uneven. On the other hand, it is not preferable to add to the dark cloud for a long time, for example, more than 60 minutes from the viewpoint of production efficiency.

The resin fine particle dispersion may be diluted or concentrated to adjust the concentration as appropriate before being added to the core particle dispersion. The concentration of the vinyl resin fine particle dispersion is preferably 5 to 30% by mass, and more preferably 8 to 20% by mass. If it is less than 5%, the change in the concentration of the organic solvent accompanying the introduction of the dispersion is large, and the adhesion of the resin fine particles becomes insufficient. Further, if it exceeds 30% by mass, the resin fine particles are likely to be unevenly distributed in the core particle dispersion, and as a result, the adhesion of the resin fine particles becomes non-uniform.

  The reason why the resin fine particles adhere to the core particles with sufficient strength by the method of the present invention is that when the resin fine particles adhere to the droplets of the core particles, the core particles can freely deform and come into contact with the resin fine particle interface. It seems that the surface is sufficiently formed and that the resin fine particles are swollen or dissolved by the organic solvent, and the resin fine particles and the resin in the core particles are likely to adhere to each other. Therefore, in this state, the organic solvent needs to be sufficiently present in the system. Specifically, in the state of the core particle dispersion, 10% by mass to 70% by mass, preferably 30% by mass with respect to the solid content (resin, colorant, and if necessary, release agent, charge control agent, etc.). % To 60% by mass, more preferably 40% to 55% by mass. If it exceeds 70% by mass, the colored resin particles obtained in a single production process are reduced and the production efficiency is low, and if there is a large amount of organic solvent, the dispersion stability is lowered and reagglomeration occurs. It is not preferable because it becomes difficult. Further, if it is less than 10% by mass, the resin fine particles cannot adhere to the core particles with sufficient strength as described above, which is not preferable. However, if the preferred concentration when attaching the resin particles is lower than the preferred organic solvent concentration when producing the core particles, the organic solvent concentration can be adjusted by partially removing the organic solvent after producing the core particles. Then, the resin particles may be adhered, and then the organic solvent may be completely removed. Here, the complete removal of the organic solvent means a level within a range that can be removed by a known method that is usually used in a demelting step described later.

  The temperature at which the vinyl resin fine particles adhere to the core particles is 10 to 60 ° C, preferably 20 to 45 ° C. If the temperature exceeds 60 ° C, the energy required for production increases and the environmental burden on the production increases. In addition, low acid value vinyl resin fine particles may be present on the droplet surface, making dispersion unstable. Since coarse particles may be generated, it is not preferable. On the other hand, when the temperature is lower than 10 ° C., the viscosity of the dispersion is increased, and adhesion of resin fine particles becomes insufficient, which is not preferable.

(Desolation)
In order to remove the organic solvent from the obtained colored resin dispersion, a known method can be used. For example, a method can be employed in which the entire system is gradually heated under normal pressure or reduced pressure to completely evaporate and remove the organic solvent in the droplets.

(Elongation or / and cross-linking reaction)
For the purpose of introducing a modified polyester resin having a urethane or / and urea group, when adding a modified polyester resin having an isocyanate group at the terminal and an amine capable of reacting with it, the toner composition is added to an aqueous medium. Before dispersing, amines may be mixed in the oil phase, or amines may be added to the aqueous medium. The time required for the above reaction is selected depending on the reactivity of the isocyanate group structure of the polyester prepolymer and the added amines, but is usually 1 minute to 40 hours, preferably 1 to 24 hours. The reaction temperature is usually 0 to 150 ° C, preferably 20 to 98 ° C.

<Washing and drying process>
A known technique is used for the step of washing and drying the toner particles dispersed in the aqueous medium.
That is, after solid-liquid separation with a centrifuge, a filter press, etc., the obtained toner cake is redispersed in ion-exchanged water at room temperature to about 40 ° C., and after adjusting the pH with acid or alkali as necessary, After removing the impurities and surfactants by repeating the process of solid-liquid separation again and again, the toner powder is obtained by drying with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. . At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

<External processing>
The obtained dried toner powder is mixed with different particles such as the charge control fine particles and fluidizing agent fine particles, or fixed and fused on the surface by applying mechanical impact force to the mixed powder. It is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle. Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

[Image Forming Method, Image Forming Apparatus, Process Cartridge]
<Image forming apparatus, process cartridge>
The image forming apparatus of the present invention forms an image using the toner of the present invention. The toner of the present invention can be used as either a one-component developer or a two-component developer, but is preferably used as a one-component developer. The image forming apparatus of the present invention preferably has an endless intermediate transfer unit. Furthermore, the image forming apparatus of the present invention preferably includes a photosensitive member and a cleaning unit that cleans the toner remaining on the photosensitive member and / or the intermediate transfer unit. At this time, the cleaning means may or may not have a cleaning blade. The image forming apparatus of the present invention preferably includes a fixing unit that fixes an image using a roller having a heating device or a belt having a heating device. Further, the image forming apparatus of the present invention preferably has a fixing unit that does not require oil application to the fixing member. Furthermore, it is preferable to include other means appropriately selected as necessary, for example, static elimination means, recycling means, control means, and the like.

  In the image forming apparatus of the present invention, the photosensitive member and the constituent elements such as the developing unit and the cleaning unit may be configured as a process cartridge, and the process cartridge may be configured to be detachable from the main body of the image forming apparatus. Further, at least one of a charging unit, an exposure unit, a developing unit, a transfer unit, a separating unit, and a cleaning unit is supported together with a photosensitive member to form a process cartridge, and a single unit that is detachable from the main body of the image forming apparatus. It is good also as a structure which can be attached or detached using guide means, such as a rail of a forming apparatus main body.

  FIG. 2 shows an example of the image forming apparatus of the present invention. In this image forming apparatus, a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 2 is housed in a main body housing (not shown), and around the latent image carrier (1). In addition, a charging device (2), an exposure device (3), a developing device (4) having the toner (T) of the present invention, a cleaning unit (5), an intermediate transfer member (6), a support roller (7), a transfer roller (8) A neutralizing means (not shown) is provided.

  The image forming apparatus includes a paper feed cassette (not shown) that stores a plurality of recording papers (P) as an example of a recording medium, and the recording paper (P) in the paper feed cassette is a paper feed (not shown). The timing is adjusted by a pair of registration rollers (not shown) one by one by a roller, and then sent out between a transfer roller (8) as a transfer means and an intermediate transfer body (6).

  In this image forming apparatus, the latent image carrier (1) is rotated clockwise in FIG. 2 to uniformly charge the latent image carrier (1) with the charging device (2), and then the exposure device ( 3) to irradiate the laser modulated with the image data to form an electrostatic latent image on the latent image carrier (1), and to the developing device (4) on the latent image carrier (1) on which the electrostatic latent image is formed. ) To attach toner and develop. Next, a transfer bias is applied from the latent image carrier (1) on which the toner image is formed by the developing device (4) to the intermediate transfer member (6) to transfer the toner image onto the intermediate transfer member (6). By transferring the recording paper (P) between the intermediate transfer body (6) and the transfer roller (8), the toner image is transferred to the recording paper (P). Further, the recording paper (P) on which the toner image is transferred is conveyed to a fixing means (not shown).

  The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats the recording paper conveyed from the transfer roller (8). After pressurizing and fixing the toner image on the recording paper on the recording paper, it is discharged onto a paper discharge tray (not shown).

  On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred onto the recording paper by the transfer roller (8), and the cleaning unit (5) applies the surface to the surface of the latent image carrier (1). After the remaining toner is scraped off and removed, the charge is removed by a charge removal device (not shown). The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the static eliminator with the charging device (2), and then performs the next image formation in the same manner as described above.

Hereinafter, each member suitably used for the image forming apparatus of the present invention will be described in detail.
The material, shape, structure, size and the like of the latent image carrier (1) are not particularly limited and may be appropriately selected from known ones. The shape may be a drum shape or a belt shape. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon and organic photoreceptors are preferable from the viewpoint of long life.

The electrostatic latent image can be formed on the latent image carrier (1) by, for example, charging the surface of the latent image carrier (1) and then exposing it like an image. It can be performed by latent image forming means. The electrostatic latent image forming means includes, for example, a charging device (2) for charging the surface of the latent image carrier (1) and an exposure device (3) for exposing the surface of the latent image carrier (1) imagewise. At least.
The charging can be performed, for example, by applying a voltage to the surface of the latent image carrier (1) using the charging device (2).

  The charging device (2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the charging device (2) includes a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotron and scorotron.

The shape of the charging device (2) may be a magnetic brush, a fur brush, or the like in addition to the roller, and can be selected according to the specifications and form of the electrophotographic apparatus. In the case of using a magnetic brush, the magnetic brush is composed of, for example, various ferrite particles such as Zn-Cu ferrite as a charging member, and a non-magnetic conductive sleeve for supporting the ferrite member, and a magnet roll included in the non-magnetic conductive sleeve. . Further, when using a brush, for example, as a material of the fur brush, a fur treated with carbon, copper sulfide, metal or metal oxide is used, and this is wound around a metal or other conductive core metal. It is configured by pasting.
Although the charging device (2) is not limited to the contact type charger as described above, an image forming apparatus in which ozone generated from the charger is reduced can be obtained. Therefore, a contact type charger is used. It is preferable.

  The exposure can be performed, for example, by exposing the surface of the photoreceptor imagewise using the exposure apparatus (3). The exposure device (3) is not particularly limited as long as the surface of the latent image carrier (1) charged by the charging device (2) can be exposed like an image to be formed. 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.

The development can be performed, for example, by developing the electrostatic latent image using the toner of the present invention, and can be performed by the developing device (4). The developing device (4) is not particularly limited as long as it can be developed using the toner of the present invention, for example, and can be appropriately selected from known ones. For example, the developing device (4) contains the toner of the present invention, Preferable examples include those having at least a developing unit that can apply toner to the electrostatic latent image in a contact or non-contact manner.

  The developing device (4) carries toner on its peripheral surface, rotates in contact with the latent image carrier (1), and supplies toner to the electrostatic latent image formed on the latent image carrier (1). The developing roller (40) that performs development and a thin layer forming member (41) that contacts the peripheral surface of the developing roller (40) and thins the toner on the developing roller (40) are preferable.

  As the developing roller (40), either a metal roller or an elastic roller is preferably used. There is no restriction | limiting in particular as a metal roller, Although it can select suitably according to the objective, For example, an aluminum roller etc. are mentioned. By performing a blasting process on the metal roller, it is possible to produce the developing roller (40) having an arbitrary surface friction coefficient relatively easily. Specifically, by treating the aluminum roller with glass bead blasting, the roller surface can be roughened, and an appropriate toner adhesion amount can be obtained on the developing roller.

As the elastic roller, a roller coated with an elastic rubber layer is used, and a surface coat layer made of a material that is easily charged to a polarity opposite to that of the toner is provided on the surface. The elastic rubber layer is set to a hardness of 60 degrees or less according to JIS-A in order to prevent toner deterioration due to pressure concentration at the contact portion with the thin layer forming member (41). The surface roughness (Ra) is set to 0.3 to 2.0 μm, and a necessary amount of toner is held on the surface. Further, since the developing roller (40) is applied with a developing bias for forming an electric field with the latent image carrier (1), the elastic rubber layer has a resistance value of 10 ³ to 10 ¹⁰ Ω. Is set. The developing roller (40) rotates in the clockwise direction, and conveys the toner held on the surface to a position facing the thin layer forming member (41) and the latent image carrier (1).

  The thin layer forming member (41) is provided at a position lower than the contact position between the supply roller (42) and the developing roller (40). The thin layer forming member (41) is made of a metal leaf spring material such as stainless steel (SUS) or phosphor bronze, and the free end is brought into contact with the surface of the developing roller (40) with a pressing force of 10 to 40 N / m. Therefore, the toner that has passed under the pressure is thinned and charged by frictional charging. Further, a regulating bias having a value offset in the same direction as the charging polarity of the toner with respect to the developing bias is applied to the thin layer forming member (41) in order to assist frictional charging.

There is no restriction | limiting in particular as a rubber elastic body which comprises the surface of a developing roller (40), Although it can select suitably according to the objective, For example, a styrene-butadiene-type copolymer rubber, an acrylonitrile-butadiene-type copolymer weight Examples thereof include coalesced rubber, acrylic rubber, epichlorohydrin rubber, urethane rubber, silicone rubber, or a blend of two or more thereof. Among these, a blend rubber of epichlorohydrin rubber and acrylonitrile-butadiene copolymer rubber is particularly preferable.
The developing roller (40) is manufactured, for example, by covering the outer periphery of the conductive shaft with a rubber elastic body. The conductive shaft is made of a metal such as stainless steel (SUS), for example.

The transfer can be performed, for example, by charging the latent image carrier (1), and can be performed by a transfer roller. The transfer roller includes a primary transfer unit that transfers a toner image onto an intermediate transfer member (6) to form a transfer image, and a secondary transfer unit (transfer) that transfers the transfer image onto a recording paper (P). An embodiment having a roller (8) is preferred. At this time, two or more colors, preferably full color toners are used as toners, and a primary transfer means for forming a composite transfer image by transferring the toner image onto the intermediate transfer member (6), and recording the composite transfer image An embodiment having secondary transfer means for transferring onto the paper (P) is more preferable.
The intermediate transfer member (6) is not particularly limited, and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (primary transfer means, secondary transfer means) preferably has at least a transfer device that peels and charges the toner image formed on the latent image carrier (1) to the recording paper (P) side. . There may be one transfer means, or two or more transfer means. Examples of the transfer means 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 paper (P) is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. It is also possible to use a PET base for OHP.

For example, the fixing can be performed on the toner image transferred to the recording paper (P) by using a fixing unit, and is performed each time the toner image of each color is transferred to the recording paper (P). Alternatively, it may be performed at the same time in a state where toner images of respective colors are laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the purpose. However, a known heating and pressing unit is preferable. 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. In addition, as for the heating temperature by a heating-pressing means, 80-200 degreeC is preferable.

It may be a soft roller type fixing device having a fluorine surface layer composition as shown in FIG. This is because the heating roller (9) has an elastic body layer (11) made of silicone rubber and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer (12) on an aluminum core bar (10). The heater (13) is provided inside the aluminum cored bar. The pressure roller (14) has an elastic layer (16) made of silicone rubber and a PFA surface layer (17) on an aluminum cored bar (15). The recording paper (P) on which the unfixed image (18) is printed is passed as shown.
In the present invention, for example, a known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization can be performed, for example, by applying a neutralization bias to the latent image carrier, and can be suitably performed by a neutralization unit. The neutralizing means is not particularly limited as long as it can apply a neutralizing bias to the latent image carrier, and can be appropriately selected from known static eliminators. For example, a neutralizing lamp is preferable. It is done.

  Cleaning can be suitably performed, for example, by removing the toner remaining on the photoreceptor by a cleaning means. The cleaning means is not particularly limited and may be any one selected from known cleaners as long as it can remove the toner remaining on the photosensitive member. For example, a magnetic brush cleaner, an electrostatic brush cleaner, or a magnetic roller can be selected. A cleaner, a blade cleaner, a brush cleaner, a web cleaner and the like are preferable.

The recycling can be suitably performed, for example, by transporting the toner removed by the cleaning unit to the developing unit by the recycling unit. There is no restriction | limiting in particular as a recycling means, A well-known conveyance means etc. are mentioned.
Control can be suitably performed by controlling each means by a control means, for example. The control means is not particularly limited as long as 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.

  According to the image forming apparatus, the image forming method, and the process cartridge of the present invention, an excellent image can be obtained by using the electrostatic latent image developing toner that has excellent fixability and does not deteriorate due to stress in the developing process. Can be provided.

<Multicolor image forming apparatus>
FIG. 4 is a schematic view showing an example of a multicolor image forming apparatus to which the present invention is applied. FIG. 4 shows a tandem type full-color image forming apparatus.
In FIG. 4, the image forming apparatus has a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 4 in a main body housing (not shown), around the latent image carrier (1). A charging device (2), an exposure device (3), a developing device (4), an intermediate transfer member (6), a support roller (7), a transfer roller (8) and the like are arranged. Although not shown, the image forming apparatus includes a paper feeding cassette that stores a plurality of recording papers. The recording paper (P) in the paper feeding cassette is fed to a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the timing adjustment, the sheet is fed between the intermediate transfer member (6) and the transfer roller (8) and fixed by the fixing means (19).

  The image forming apparatus rotates the latent image carrier (1) clockwise in FIG. 4 to uniformly charge the latent image carrier (1) with the charging device (2), and then exposes the exposure device (3). The electrostatic image is formed on the latent image carrier (1) by irradiating the laser modulated with the image data, and the developing device (4) forms the latent image carrier (1) on which the electrostatic latent image is formed. Develop with toner attached. The image forming apparatus transfers the toner image formed by attaching the toner to the latent image carrier with the developing device (4) from the latent image carrier (1) to the intermediate transfer member. This is performed for each of the four colors of cyan (C), magenta (M), yellow (Y), and black (K) to form a full-color toner image.

  Next, FIG. 5 is a schematic diagram illustrating an example of a revolver type full-color image forming apparatus. In this image forming apparatus, a plurality of color toners are sequentially developed on one latent image carrier (1) by switching the operation of the developing device. Then, the color toner image on the intermediate transfer body (6) is transferred to the recording paper (P) by the transfer roller (8), the recording paper (P) to which the toner image is transferred is conveyed to the fixing unit, and the fixed image is transferred. obtain.

On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred to the recording paper (P) by the intermediate transfer member (6), and the latent image carrier (1) by the cleaning unit (5). ) The toner remaining on the surface is removed by scraping with a blade, and then the charge is removed by the charge removing unit. The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the neutralization unit with the charging device (2), and then performs the next image formation as described above. The cleaning unit (5) is not limited to scraping off the residual toner on the latent image carrier (1) with a blade. For example, the cleaning unit (5) scrapes off the residual toner on the latent image carrier (1) with a fur brush. It may be a thing.
In the image forming method and the image forming apparatus of the present invention, since the toner of the present invention is used as the developer, a good image can be obtained.

<Process cartridge>
The process cartridge of the present invention can develop an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using the toner of the present invention. A developing means for forming a visual image, and further comprising other means such as a charging means, a developing means, a transfer means, a cleaning means, and a static elimination means, which are appropriately selected as necessary. The image forming apparatus main body is detachable.

  The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member 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, facsimiles, and printers, and is preferably detachably provided in the image forming apparatus of the present invention described later.

  For example, as shown in FIG. 6, the process cartridge includes a latent image carrier (1), and includes a charging device (2), a developing device (4), a transfer roller (8), and a cleaning unit (5). In addition, other means are provided as necessary. In FIG. 6, (L) shows exposure from the exposure apparatus, and (P) shows recording paper. As the latent image carrier (1), the same one as the image forming apparatus can be used. An arbitrary charging member is used for the charging device (2).

  Next, the image forming process using the process cartridge shown in the figure will be described. The latent image carrier (1) is charged by the charging device (2) while being rotated in the direction of the arrow, and exposure by the exposure means (not shown) ( L), an electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed with toner by the developing device (4), and the toner development is transferred onto the recording paper (P) by the transfer roller (8) and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit (5), further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited by these Examples.
Hereinafter, “parts” and “%” indicate parts by mass and mass% unless otherwise specified.
First, analysis and evaluation methods for the toners obtained in Examples and Comparative Examples will be described.
In the following, the case of using the toner of the present invention as a one-component developer was evaluated. However, the toner of the present invention can be used as a two-component developer by using a suitable external addition treatment and a suitable carrier. Can be used.

<Measurement method>
(Average particle size)
Next, a method for measuring the particle size distribution of toner particles will be described.
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measuring method is as follows.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of the measurement sample is further added as a solid content. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be obtained.
The channel is, for example, less than 2.00 to 2.52 μm; less than 2.52 to 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Less than .40 μm; 25.40 to less than 32.00 μm; 13 channels less than 32.00 to less than 40.30 μm are used, and particles having a particle size of 2.00 μm to less than 40.30 μm can be targeted.

(Average circularity)
As a method for measuring the shape, an optical detection band method is suitable in which a suspension containing 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. The value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle is the average circularity.
This value is a value measured as an average circularity by a flow type particle image analyzer FPIA-2000. As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is obtained by performing dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser and measuring the shape and distribution of the toner with the above apparatus at a dispersion concentration of 3000 to 10,000 / μl. .

(Volume average particle diameter of resin fine particles)
As a measuring method of the volume average particle diameter of the resin fine particles, it can be measured with a nanotrack particle size distribution measuring apparatus UPA-EX150 (manufactured by Nikkiso, dynamic light scattering method / laser Doppler method). As a specific measuring method, the dispersion in which resin fine particles are dispersed is adjusted to a measurement concentration range for measurement. At that time, the background measurement is performed in advance using only the dispersion solvent of the dispersion. By this measurement method, it is possible to measure several tens of nm to several μm, which is the volume average particle size range of the resin fine particles used in the present invention.

(Molecular weight)
The molecular weights of the polyester resin and vinyl copolymer resin used were measured under the following conditions by ordinary GPC (gel permeation chromatography).
・ Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-M x 3
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 0.35 ml / min ・ Sample: 0.01 ml injection of a sample having a concentration of 0.05 to 0.6% Molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from the molecular weight distribution of the toner resin measured under the above conditions Was used to calculate the weight average molecular weight Mw. As monodisperse polystyrene standard samples, 5.8 × 100, 1.085 × 10000, 5.95 × 10000, 3.2 × 100,000, 2.56 × 1000000, 2.93 × 1000, 2.85 × 10000, Ten points of 1.48 × 100,000, 8.417 × 100,000, 7.5 × 1000000 were used.

(Glass transition point and endotherm)
For measuring the glass transition point of the polyester resin or vinyl copolymer resin to be used, for example, using a differential scanning calorimeter (for example, DSC-6220R: Seiko Instruments Inc.) After heating at 150 ° C. for 10 minutes, let stand at 150 ° C. for 10 minutes, cool the sample to room temperature, leave it for 10 minutes, and again heat to 150 ° C. at a heating rate of 10 ° C./min. The height of the baseline above the glass transition point can be obtained from a curved portion corresponding to ½.
Moreover, the endothermic quantity and melting | fusing point of a mold release agent, crystalline resin, etc. can be measured similarly. The endothermic amount is obtained by calculating the peak area of the measured endothermic peak. Generally, the release agent used in the toner melts at a temperature lower than the fixing temperature of the toner, and the heat of fusion at that time appears as an endothermic peak. Some releasing agents are accompanied by heat of fusion due to phase transition in the solid phase in addition to the heat of fusion. In the present invention, the total is the endothermic amount of heat of fusion.

<Toner softening point measurement method>
For the measurement, a toner conditioned for 24 hours or more at a temperature of 24 ° C. and a humidity of 50% RH is prepared in advance, and 1.5 g is weighed and molded by pressurizing with a load of 4 kN for 30 seconds using a molding machine. Using a flow tester (CFT-500 / manufactured by Shimadzu Corporation), using a die of H1.0 mm × φ1.0 mm, heating rate 3.0 ° / min, preheating time 180 seconds, load 30 kg, measurement temperature range 80 The measurement was performed under a condition of ˜140 ° C., and the temperature at which the above sample flowed out 1/2 was taken as the softening point.
The outflow start temperature was Tfb.

<Evaluation method>
(Toner surface and cross-sectional observation)
The state of the fine particles was evaluated by observing the toner surface with an SEM.
State of presence of fine particles on toner surface ○: Fine particles exist as particles and form convex portions to form islands of sea islands, and are present in 50-80% of the toner surface with appropriate gaps.
(Triangle | delta): The microparticles | fine-particles have adhered without being buried. Or the existence density is biased.
X: The fine particles are adhered without maintaining the shape of the particles, and the sea-island structure is not formed. Or the sea part is formed.

(Stress resistance)
The toner (developer) subjected to the external addition treatment was continuously printed in a N / N environment (23 ° C., 45%) with a predetermined print pattern having a B / W ratio of 6% using Ricoh ipsio CX2500. After 2000 continuous printing in N / N environment (after endurance), the toner on the developing roller during blank paper pattern printing is sucked, the charge amount is measured with an electrometer, and the charge amount after 50 sheets and 2000 sheets The difference was evaluated.
A: Absolute value of charge amount difference is 5 μC / g or less ○: Absolute value of charge amount difference is in the range of 5 μC / g to 10 μC / g Δ: Absolute value of charge amount difference is in the range of 10 μC / g to 15 μC / g Inner x: The absolute value of the charge amount difference is 15 μC / g or more

(Environment resistance)
The toner (developer) subjected to the external addition treatment was continuously printed in a N / N environment (23 ° C., 45%) with a predetermined print pattern having a B / W ratio of 6% using Ricoh ipsio CX2500. After 2000 continuous printing in N / N environment (after endurance), change to H / H environment (temperature / humidity, 27 ° C., 80%), suck the toner on the developing roller during blank pattern printing, The amount of charge was measured with an electrometer, and the difference in charge amount under the H / H environment after 50 sheets under the N / N environment and after 2000 sheets was evaluated.
○: The absolute value of the charge amount difference is 10 μC / g or less Δ: The absolute value of the charge amount difference is within the range of 10 μC / g to 15 μC / g ×: The absolute value of the charge amount difference is 15 μC / g or more

(Fixability)
Using an externally added toner (developer) with Ricoh's ipsio CX2500, an unfixed image in which a solid band image (adhesion amount 11 g / m ² ) with a width of 3 mm is printed on the tip 3 mm with A4 longitudinal paper is produced. did. This unfixed image was fixed at a fixing temperature in increments of 10 ° C. in the range of 115 ° C. to 175 ° C. using the following fixing device, and the separable / non-offset temperature range was determined. The temperature range is a fixing temperature range in which the paper is satisfactorily separated from the heating roller and no offset phenomenon occurs. The paper used and the direction of paper passing were 45 g / m ² paper of Y-th vertical paper that is unfavorable for separability. The peripheral speed of the fixing device was set to 200 mm / sec.
The fixing device is of a soft roller type having a fluorine surface layer composition as shown in FIG. Specifically, the heating roller 9 has an outer diameter of 40 mm, an aluminum core 10 and a 1.5 mm-thick elastic body layer 11 made of silicone rubber and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer. 12 and a heater 13 is provided inside the aluminum cored bar. The pressure roller 14 has an outer diameter of 40 mm, and an elastic body layer 16 and a PFA surface layer 17 made of silicone rubber and having a thickness of 1.5 mm on an aluminum core 15. The paper P on which the unfixed image 18 is printed is passed as shown in the figure.
A: Separable / non-offset in the entire range of 110 to 170 ° C., and the fixed image resistance was sufficient.
○: Separable / non-offset in the entire range of 110 to 170 ° C., but the fixed image in the low temperature range was easily peeled or scratched by scratching or rubbing.
(Triangle | delta): The separable / non-offset temperature range was 30 degreeC or more and less than 50 degreeC.
X: The separable / non-offset temperature range was less than 30 ° C.

(Heat resistant storage stability)
After the toner was stored at 55 ° C. for 8 hours, it was sieved with a 42 mesh screen for 2 minutes, and the residual rate on the wire mesh was used as an index for heat resistant storage stability. The heat resistant storage stability was evaluated in the following four stages.
A: Less than 10% B: 10-20%
Δ: 20-30%
×: 30% or more (cleanability)
Using a color electrophotographic apparatus (IPSIO SP C220), after outputting 2000 image charts having a 1% image area, the photoreceptor medaka was evaluated in four stages by visual inspection and a black solid image.
◎ ・ ・ ・ No medaka, very good level.
○ ・ ・ ・ Level that has medaka but does not affect image △ ・ ・ ・ Level that has medaka and affects image × ・ ・ ・ Level that medaka is conspicuous and greatly affects image

Next, a method for preparing a toner raw material used in Examples and the like will be described.
<Synthesis of non-crystalline polyester>
(Polyester 1)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 2765 parts of bisphenol A ethylene oxide 2-mole adduct, 480 parts of bisphenol A propylene oxide 2-mole adduct, 1100 parts of terephthalic acid, 225 parts of adipic acid and dibutyl After putting 10 parts of tin oxide and reacting at 230 ° C. under normal pressure for 8 hours, and further reacting at 10-15 mmHg under reduced pressure for 5 hours, 130 parts of trimellitic anhydride was put into the reaction vessel, and 180 ° C. under normal pressure. Reaction was performed for a time to obtain [Polyester 1]. [Polyester 1] had a number average molecular weight of 2200, a weight average molecular weight of 5600, a Tg of 43 ° C., and an acid value of 24.

(Polyester 2)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 1195 parts of bisphenol A ethylene oxide 2-mole adduct, 2765 parts of bisphenol A propylene oxide 3-mole adduct, 900 parts of terephthalic acid, 200 parts of adipic acid and dibutyl After putting 10 parts of tin oxide and reacting at 230 ° C. under normal pressure for 8 hours and further reacting for 5 hours under reduced pressure of 10 to 15 mmHg, 220 parts of trimellitic anhydride was put into the reaction vessel, and 2 parts at 180 ° C. and normal pressure. Reaction was performed for a time to obtain [Polyester 2]. [Polyester 2] had a number average molecular weight of 2500, a weight average molecular weight of 6500, a Tg of 47 ° C., and an acid value of 18.

(Polyester 3)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 264 parts of bisphenol A ethylene oxide 2-mole adduct, 523 parts of bisphenol A propylene oxide 2-mole adduct, 123 parts terephthalic acid, 173 parts adipic acid and dibutyl 1 part of tin oxide was added and reacted for 8 hours at 230 ° C. under normal pressure, and further reacted for 8 hours under reduced pressure of 10 to 15 mmHg. Thereafter, 26 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Polyester 3]. [Polyester 3] had a number average molecular weight of 4000, a weight average molecular weight of 47000, Tg of 65 ° C., and an acid value of 12.

<Synthesis of crystalline polyester>
(Polyester 4)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 500 parts of 1,6-hexanediol, 500 parts of succinic acid, and 2.5 parts of dibutyltin oxide were placed and reacted at 200 ° C. for 8 hours. Further, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Polyester 4]. [Polyester 4] showed an endothermic peak at 65 ° C. by DSC measurement.

(Polyester 5)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 500 parts of 1,6-hexanediol, 590 parts of fumaric acid, 90 parts of terephthalic acid, and 2.5 parts of dibutyltin oxide were placed at a normal pressure of 200 ° C. Was reacted for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Polyester 5]. [Polyester 5] showed an endothermic peak at 110 ° C. by DSC measurement.

(Polyester 6)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 500 parts of 1,6-hexanediol, 360 parts of terephthalic acid, 330 parts of adipic acid, and 2.5 parts of dibutyltin oxide were placed at a normal pressure of 200 ° C. For 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Polyester 6]. [Polyester 6] showed an endothermic peak at 89 ° C. by DSC measurement.

(Polyester 7)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 500 parts of 1,6-hexanediol, 480 parts of fumaric acid, and 2.5 parts of dibutyltin oxide were placed and reacted at 200 ° C. under normal pressure for 8 hours. Further, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 1 hour to obtain [Polyester 7]. [Polyester 7] showed an endothermic peak at 78 ° C. by DSC measurement.

<Synthesis of prepolymer>
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction pipe, 366 parts of 1,2-propylene glycol, 566 parts of terephthalic acid, 44 parts of trimellitic anhydride and 6 parts of titanium tetrabutoxide are placed at a normal pressure of 230 The mixture was reacted at 0 ° C. for 8 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate polyester 1] had a number average molecular weight of 3200, a weight average molecular weight of 12000, and a Tg of 55 ° C.
Next, 420 parts of [Intermediate polyester 1], 80 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer] was obtained. [Prepolymer] had a free isocyanate mass% of 1.34%.

<Preparation of resin fine particle dispersion>
(Vinyl copolymer resin fine particles V-1)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1.6 parts of sodium dodecyl sulfate and 492 parts of ion exchange water are heated to 80 ° C., and then 2.5 parts of potassium persulfate is ion exchanged. What was dissolved in 100 parts of water was added, and 15 minutes later, a mixture of 200 parts of styrene monomer and 3.5 parts of n-octyl mercaptan was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes. Thereafter, the mixture was cooled to obtain a dispersion of [vinyl copolymer resin fine particles V-1]. The solid content concentration of this dispersion was measured and found to be 25%. The volume average particle diameter of the fine particles was 130 nm. The dispersion was taken in a small petri dish, and the solid obtained by evaporating the dispersion medium was measured. The number average molecular weight was 11,000, the weight average molecular weight was 18000, and Tg was 83 ° C.

(Vinyl copolymer resin fine particles V-2 to V-4)
The monomer composition was changed as shown in the table, and each was prepared in the same manner as the vinyl copolymer resin fine particles V-1. The physical properties are shown in Table 1.

<Synthesis of master batch>
Carbon black (Cabot Corp. Regal 400R): 40 parts, Binder resin: Polyester resin (Sanyo Kasei RS-801, acid value 10, Mw 20000, Tg 64 ° C.): 60 parts, water: 30 parts are mixed in a Henschel mixer, A mixture in which water was soaked into the pigment aggregate was obtained. This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mmφ with a pulverizer to obtain [Masterbatch 1].

[Example 1]
<Production of oil phase>
A container equipped with a stir bar and thermometer is charged with 4 parts of [Polyester 1], 20 parts of [Polyester 4], 8 parts of paraffin wax (melting point 72 ° C.) and 96 parts of ethyl acetate, and the temperature is raised to 80 ° C. with stirring. The sample was kept at 80 ° C. for 5 hours and then cooled to 30 ° C. in 1 hour. Next, after adding 35 parts of [Masterbatch 1] and mixing for 1 hour, the container was transferred, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / second Then, 80% by volume of 0.5 mm zirconia beads were filled and dispersed under the condition of 3 passes to obtain [Material Solution 1]. Next, 74.1 parts of a 70% ethyl acetate solution of [Polyester 1], 21.6 parts of [Polyester 3] and 21.5 parts of ethyl acetate were added to 81.3 parts of [Raw Material Solution 1], and 2 for 3 One Motor. The mixture was stirred for a time to obtain [Oil Phase 1]. Ethyl acetate was added and adjusted so that the solid content concentration of [Oil Phase 1] (measured at 130 ° C. for 30 minutes) was 49%.

<Preparation of aqueous phase>
472 parts of ion-exchanged water, 81 parts of 50% aqueous solution of dodecyl diphenyl ether disulfonate (ELEMINOL MON-7: manufactured by Sanyo Chemical Industries), 67 parts of 1% aqueous solution of carboxymethyl cellulose as a thickener, and 54 parts of ethyl acetate are mixed and stirred. A milky white liquid was obtained. This is designated as [Aqueous Phase 1].

<Emulsification process>
After mixing the total amount of [Oil Phase 1] with a TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, add 321 parts of [Aqueous Phase 1], and with a TK homomixer, rotating at 8,000 to While adjusting at 13,000 rpm, mixing for 20 minutes gave [core particle slurry 1].

<Shell process (resin fine particle adhesion process to core particles)>
While stirring [Core Particle Slurry 1] at 200 rpm using a three-one motor, 21.4 parts of [Vinyl Copolymer Resin Fine Particle V-1] was added dropwise over 5 minutes, and stirring was continued for 30 minutes. Thereafter, a small amount of the slurry sample was collected, diluted with 10 times water, and centrifuged using a centrifugal separator. As a result, toner base particles settled on the bottom of the test tube, and the supernatant liquid was almost transparent. [Slurry 1 after shell] was obtained as described above.

<Desolvent>
[Slurry after shell 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [dispersed slurry 1].

<Washing->Drying>
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μS / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry liquid of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μS / cm or less to obtain [Filter Cake 1]. The remaining [Dispersion Slurry 1] was washed in the same manner and further mixed as [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier and sieved with a mesh of 75 μm to obtain [Toner Base 1]. 50 parts of the base toner is mixed with 1 part of hydrophobic silica having a primary particle diameter of about 30 nm and 0.5 part of hydrophobic silica having a primary particle diameter of about 10 nm using a Henschel mixer, and [Developer 1 of the present invention]. ] Was obtained.
FIG. 1 shows an SEM photograph of the toner base 1 obtained. The toner surface has a sea-island structure, and the island part protrudes from the sea part and exists as a convex part. This island portion is resin fine particles made of the third resin.

[Example 2]
[Toner base 1] 50 parts of hydrophobic silica treated with a silicone oil with a primary particle size of about 30 nm and 0.5 part of hydrophobic silica with a primary particle size of about 10 nm are mixed in a Henschel mixer, [Developer 2] of the invention was obtained.
[Example 3]
[Developer 3] was obtained by changing [Polyester 4] in Example 1 to [Polyester 5].
[Example 4]
[Developer 4] was obtained by changing [vinyl copolymer resin fine particles V-1] in the shell process of Example 1 to [vinyl copolymer resin fine particles V-2].

[Example 5]
A container equipped with a stir bar and thermometer is charged with 4 parts of [Polyester 1], 20 parts of [Polyester 4], 8 parts of paraffin wax (melting point 72 ° C.) and 96 parts of ethyl acetate, and the temperature is raised to 80 ° C. with stirring. The sample was kept at 80 ° C. for 5 hours and then cooled to 30 ° C. in 1 hour. Next, after adding 35 parts of [Masterbatch 1] and mixing for 1 hour, the container was transferred, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), liquid feeding speed 1 kg / hr, disk peripheral speed 6 m / second Then, 80% by volume of 0.5 mm zirconia beads were filled and dispersed under the condition of 3 passes to obtain [Material Solution 1]. Next, 84.4 parts of a 70% ethyl acetate solution of [Polyester 1] was added to 81.3 parts of [Raw Material Solution 1] and stirred with a three-one motor for 2 hours to obtain [Oil Phase 4]. Ethyl acetate was added and adjusted so that the solid content concentration of [Oil Phase 4] (measured at 130 ° C. for 30 minutes) was 50%.

<Emulsification process>
After adding 0.4 parts of isophoronediamine and 28.5 parts of [prepolymer] to the total amount of [Oil Phase 4], the mixture was mixed for 1 minute at 5,000 rpm with a TK homomixer (manufactured by Tokushu Kika), Phase 1] The whole amount was added and mixed for 20 minutes while adjusting at a rotation speed of 8,000 to 13,000 rpm with a TK homomixer to obtain [core particle slurry 4].

<Shell process>
While stirring [Core Particle Slurry 4] at 200 rpm using a three-one motor, 21.4 parts of [Vinyl Copolymer Resin Fine Particle V-1] was added dropwise over 5 minutes, and stirring was continued for 30 minutes. Thereafter, a small amount of the slurry sample was collected, diluted with 10 times water, and centrifuged using a centrifugal separator. As a result, toner base particles settled on the bottom of the test tube, and the supernatant liquid was almost transparent. [Slurry 4 after shell] was obtained as described above.
The subsequent steps were performed in the same manner as in Example 1 to obtain [Developer 5].

[Example 6]
[Developer 6] was obtained by changing [Polyester 4] in Example 1 to [Polyester 6].
[Example 7]
[Developer 7] was obtained by changing [Polyester 4] in Example 1 to [Polyester 7].
[Example 8]
8 parts of paraffin wax (melting point 72 ° C.) in Example 6 was changed to 8 parts of paraffin wax (melting point 68 ° C.) to obtain [Developer 8].
[Example 9]
8 parts of paraffin wax (melting point: 72 ° C.) in Example 7 was changed to 8 parts of paraffin wax (melting point: 68 ° C.) to obtain [Developer 9].

[Comparative Example 1]
[Developer 910] was obtained by changing [Vinyl copolymer resin fine particles V-1] in the shell process of Example 1 to [Vinyl copolymer resin fine particles V-3].
[Comparative Example 2]
[Developer 1011] was obtained by changing [Vinyl copolymer resin fine particles V-1] in the shell step of Example 5 to [Vinyl copolymer resin fine particles V-3].
[Comparative Example 3]
[Developer 12] was obtained by changing [Vinyl copolymer resin fine particles V-1] in the shell process of Example 1 to [Vinyl copolymer resin fine particles V-4].

[Comparative Example 4]
[Developer 13] was obtained by changing [Vinyl copolymer resin fine particles V-1] in the shell process of Example 5 to [Vinyl copolymer resin fine particles V-4].
[Comparative Example 5]
[Developer 14] was obtained by changing [Polyester 4] in Example 1 to [Polyester 1].
[Comparative Example 6]
The <emulsification step> in Example 1 was changed as follows, and the other steps were performed in the same manner as in Example 1 without passing through the <shell step> to obtain [Developer 15].

<Emulsification process>
After mixing the total amount of [Oil Phase 1] with a TK homomixer (made by Tokushu Kika) at 5,000 rpm for 1 minute, 321 parts of [Water Phase 1] [Vinyl Copolymer Resin Fine Particles V-1] 21. A mixture obtained by mixing and stirring 4 parts was added and mixed with a TK homomixer at a rotational speed of 8,000 to 13,000 rpm for 20 minutes to obtain [core particle slurry 8].
The vinyl copolymer resin fine particle dispersions are summarized in Table 1.

  Table 2 summarizes the physical properties and evaluation results of the developers obtained in the above Examples and Comparative Examples.

The example of the present invention gave good results. However, in Comparative Examples 1, 2, and 6, the fine particles maintained the shape of the particles, but were hardly buried and adhered to the toner surface, did not form a beautiful sea-island structure, and were resistant to stress. In the evaluation of the properties, peeling of the fine particles was observed, which was not preferable. Further, in Comparative Examples 3 and 4, the fine particles hardly maintained the shape of the particles and were not uniformly stretched and adhered to the toner surface, resulting in poor results.
The example of the present invention gave good results. However, in Comparative Examples 1, 2, and 6, the fine particles maintained the shape of the particles, but were hardly buried and adhered to the toner surface, did not form a beautiful sea-island structure, and were resistant to stress. In the evaluation of the properties, peeling of the fine particles was observed, which was not preferable. Further, in Comparative Examples 3 and 4, the fine particles hardly maintained the shape of the particles and were not uniformly stretched and adhered to the toner surface, resulting in poor results. Further, in Comparative Example 5 containing no crystalline resin, the fixability was particularly bad, and a favorable temperature range could not be secured.

  Since the toner of the present invention has both fixing properties and heat resistance, is excellent in charging uniformity and environmental stability, and can provide a high-quality image, the copying machine and printer based on the electrophotographic recording method It is suitable as a toner for electrophotography used in a fax machine and a multifunction machine thereof.

DESCRIPTION OF SYMBOLS 1 Latent image carrier 2 Charging apparatus 3 Exposure apparatus 4 Developing apparatus 5 Cleaning part 6 Intermediate transfer body 7 Support roller 8 Transfer roller 9 Heating roller 10 Aluminum core 11 Elastic body layer 12 PFA surface layer 13 Heater 14 Pressure roller 15 Aluminum core Gold 16 Elastic layer 17 PFA surface layer 18 Unfixed image 19 Fixing means 40 Developing roller 41 Thin layer forming member 42 Supply roller L Exposure P Recording paper T Electrostatic charge image developing toner

Japanese Patent Laying-Open No. 2005-084183 JP 2004-295105 A JP 2004-271686 A Japanese Patent No. 3577390 JP 11-007156 A Japanese Patent No. 4033096 JP 2008-089670 A JP 2009-025744 A JP 2007-086211 A JP 2008-090256 A

Claims (30)

A main portion containing at least a resin, a release agent, and a colorant;
A toner comprising convex portions formed on the surface of the main portion by resin fine particles,
The toner has a sea-island structure in which the main part is the sea and the convex part is the island,
The resin includes at least a first resin and a second resin;
The resin fine particles are made of a third resin,
The toner according to claim 1, wherein the first resin is a crystalline resin, and the second resin and the third resin are non-crystalline resins.   The toner according to claim 1, wherein the main part has a state in which at least a first resin, a release agent, and a colorant are dispersed in a second resin.   The toner according to claim 2, wherein the first resin, the second resin, and the third resin are incompatible with each other.   The first resin is a crystalline polyester resin, the second resin is an amorphous polyester resin, and the third resin is a vinyl resin. The toner described.   The toner according to claim 4, wherein the third resin is a vinyl resin obtained by polymerizing a monomer mixture containing 80 to 100 wt% of an aromatic compound having a vinyl polymerizable functional group.   The toner according to claim 4, wherein the third resin is a vinyl resin obtained by polymerizing a monomer mixture containing 100 wt% of an aromatic compound having a vinyl polymerizable functional group.   The toner according to claim 5, wherein the aromatic compound having a vinyl polymerizable functional group is styrene.   80 to 100% by weight of the component contained in the monomer mixture of the third resin is styrene, 0 to 20% by weight is acrylic, and the total amount of these two components is 90 to 100% by weight. The toner according to claim 4.   The toner according to claim 4, wherein the main portion further contains a modified polyester resin having a urethane or / and urea group.   10. The modified polyester resin according to claim 9, wherein the modified polyester resin is a modified polyester resin in which a polyester resin is chain-extended or / and cross-linked by a reaction between a modified polyester resin having an isocyanate group at a terminal and amines. toner.   11. The toner according to claim 1, wherein the resin fine particles have an average particle diameter of 50 to 300 nm, and the area of the island portion is 50 to 80% of the total surface area of the toner.   The toner according to claim 1, wherein an average height of the convex portions is 0.03 to 0.1 μm. The melting point Tw of the release agent and the melting point Tc of the crystalline resin are Tw <Tc
The toner according to claim 1, wherein the relationship is satisfied.   The toner according to claim 13, wherein the release agent has a melting point Tw of 80 ° C. or less.   The toner according to claim 13, wherein the crystalline resin has a melting point Tc of 90 ° C. or less.   The toner according to claim 1, wherein the release agent is paraffin wax, Fischer-Tropsch wax, polyethylene wax, monoester wax, or diester wax.   The electrostatic charge image developing toner according to claim 1, wherein the toner contains an external additive, and the external additive is inorganic fine particles containing silicone oil.   A toner container filled with the toner according to claim 1.   A developer comprising the toner according to claim 1. A developer carrier that carries on the surface a developer to be supplied to the latent image carrier;
A developer supply member for supplying the developer to the surface of the developer carrier;
A developer container for storing the developer;
A developing device comprising:
A developing device, wherein the developer according to claim 18 is stored in a developer container.   In the process cartridge in which the latent image carrier and the developing device for developing at least the latent image on the latent image carrier with the developer are integrated and configured to be detachable from the image forming apparatus, the developing device is claimed in claim 20. A process cartridge according to claim 1. A latent image carrier for carrying a latent image;
Charging means for uniformly charging the surface of the latent image carrier;
Exposure means for exposing the surface of the charged latent image carrier on the basis of image data and writing an electrostatic latent image;
Developing means for supplying toner to the electrostatic latent image formed on the surface of the latent image carrier to make it visible;
Transfer means for transferring the visible image on the surface of the latent image carrier to the transfer target;
Fixing means for fixing a visible image on the transfer target;
An image forming apparatus comprising:
21. An image forming apparatus, wherein the developing means is the developing device according to claim 20.   The image forming apparatus according to claim 22, wherein a roller or a belt is used as the fixing unit.   24. The image forming apparatus according to claim 22, wherein oil is not applied to the fixing unit. A charging step for uniformly charging the surface of the latent image carrier,
An exposure process for exposing the surface of the charged latent image carrier based on the image data and writing an electrostatic latent image;
A developer layer having a predetermined layer thickness is formed on the developer carrier by a developer layer regulating member, and the electrostatic latent image formed on the surface of the latent image carrier is developed through the developer layer to be visualized. A development process to
A transfer step of transferring a visible image on the surface of the latent image carrier to the transfer target;
A fixing step of fixing a visible image on the transfer target,
An image forming method using the developer according to claim 19 as the developer. The method for producing a toner according to claim 1, comprising at least the following steps (1) to (4).
(1) a step of dissolving or dispersing at least the first resin, the second resin, the release agent and the colorant in an organic solvent;
(2) A step of suspending the dissolved product or dispersion in an aqueous medium to produce a core particle dispersion that is the main part,
(3) adding a resin fine particle dispersion made of a third resin to the core particle dispersion to form convex portions made of resin fine particles on the core particles;
(4) Step of removing the organic solvent   27. The toner manufacturing method according to claim 26, wherein a surfactant is contained in the aqueous medium.   28. The toner production method according to claim 26 or 27, wherein the resin fine particle dispersion comprising the third resin does not contain an organic solvent, and the fine particles are dispersed in a solid state.   The toner production method according to any one of claims 26 to 28, wherein the organic solvent is completely removed after the protrusion is formed.   In the step of adding the resin fine particle dispersion liquid made of the third resin to form the convex parts made of the resin fine particles on the core particles, the dispersed core particles contain 10 mass% to 70 mass% of the organic solvent. The toner production method according to any one of claims 26 to 29, wherein: