JP4873734B2 - Toner and method for producing the same - Google Patents

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, a toner jet recording method or the like.

  More specifically, the present invention relates to a printing machine and a copying machine that form a toner image on an electrostatic latent image carrier and then transfer the toner image onto a transfer material to form a toner image and fix it under thermal pressure to obtain a fixed image. The present invention relates to toner used for printers and fax machines.

  Today, demands for electrophotographic devices are (1) faster printing, (2) so-called high image quality for high resolution and high definition images, (3) high color reproducibility, and (4) stable over a long period of time. The stability required for images and (5) energy saving such as low power consumption are increasing.

  Desired (1) From the viewpoint of speeding up, not only the request for shortening the first print time and the increase in the number of output sheets per minute in the electrophotographic apparatus, but also the startup in a shorter time from the power-off state, immediately after the power is turned on There is a demand for improvement in color stability. Therefore, a developer and a toner that are excellent in rising of charge are desired.

  Therefore, Patent Document 1 discloses a toner that performs a fixing process for fixing a charge control agent and inorganic fine particles on the surface of toner base particles in order to improve the charge rising property. However, when printing is performed for a long time, the member is contaminated and there is a problem in the durability of the toner, and it is difficult to meet the demand (4) stability.

  In addition, from the viewpoints of (2) higher image quality and (3) improved color reproducibility, the toner has excellent developability, that is, the particle size distribution is sharp, and the absolute value of the charge amount is easy to control. There is a demand for a toner having excellent tribocharging properties such as a sharpness. In order to be a toner having excellent triboelectric charging properties such as environmental stability of charging and start-up property, it is preferable that the triboelectric charging properties of the toner particles are excellent even without external addition treatment. Therefore, Patent Document 2 discloses toner particles containing acrylamidomethylpropane sulfonic acid as a charge control agent, but the compatibility with the binder resin is improved with the aim of uniformly present in the toner particles. There is a problem that the triboelectric charge amount is low.

  In addition, from the viewpoint of (5) low power consumption, a toner that can be fixed at a low temperature is desired. Therefore, Patent Document 3 discloses a capsule toner having a core-shell structure in which a coating layer made of a resin having a glass transition temperature higher than that of the binder resin is formed. In this invention, the low-temperature fixability is good, but the core layer contains a charge control agent, and the triboelectric charging performance may be insufficient. Further, Patent Document 4 discloses a toner containing a sulfoalkyl (meth) acrylic acid monomer as a charge control agent. However, the charge control agent is copolymerized with a binder resin, and the binder resin used is vinyl-based. There was a problem in improving the low-temperature fixability.

  When fixing start temperature is low and gloss at low temperature is increased (improvement of low temperature fixability), means such as lowering the softening point / glass transition temperature of the resin, specifically controlling the molecular weight and the number of crosslinking points It is used. As the softening point / glass transition temperature of the resin is lowered, there is a problem that the heat resistant storage stability is lowered.

  Therefore, for the toner particles of the pulverization method, it is necessary to select a resin giving priority to heat-resistant storage, and there is a problem that low-temperature fixability is sacrificed.

  Further, since the pulverized toner has an indefinite particle shape, when used in a high-speed and high-productivity apparatus, the toner is more easily pulverized due to stirring in the developing device, contact stress, or the like. For this reason, image quality may be deteriorated due to generation of fine powder of sub-μm order, exposure of wax, embedding of a fluidizing agent on the toner surface, and the like.

  On the other hand, the particle size of toner particles has been reduced for the purpose of high resolution and high definition, and spherical toner particles have been suitably used for the purpose of improving transfer efficiency and fluidity. As a method for efficiently preparing spherical toner particles having a small particle size, a wet method has been preferably used.

  The conventional wet method is a method for preparing toner particles by a so-called polymerization method such as a suspension polymerization method or an emulsion polymerization method. On the other hand, conventionally, in order to enable fixing at a lower temperature, a method of making the binder resin sharper melt is known as one of the effective methods, but according to these polymerization methods described above, There has been a problem that the binder resin of toner particles is limited to vinyl resin.

  Therefore, in Patent Document 5 and Patent Document 6, as a wet method in which a sharp melt polyester resin can be used, a resin component is dissolved in an organic solvent that is immiscible with water, and this solution is dispersed in an aqueous phase. Thus, a so-called dissolution suspension method for producing spherical toner particles by forming oil droplets has been proposed. According to this method, spherical toner particles having a small particle diameter can be easily obtained using a polyester resin having excellent low-temperature fixability as a binder resin. However, in this method, the surface layer tends to be peeled off from the toner base particles, which may become a fine powder and cause the same problem as in the case of the pulverized toner as described above.

  The present inventors have taken into consideration that no toner having satisfactory performance that can overcome all of the above problems is currently provided, and as a result of investigation, a toner that can be fixed at low temperature and has excellent frictional charging stability. It came to invent.

JP 2006-091648 A JP 2002-351147 A JP 2004-004506 A Japanese Patent Registration No. 3637618 JP 2004-198692 A JP 2002-169336 A

An object of the present invention is to provide a capsule-type toner having a surface layer on the surface of toner base particles containing a binder resin, a colorant and a wax.
While having heat-resistant storage stability and offset resistance, it has excellent low-temperature fixability,
Excellent triboelectric chargeability such as charging rise, stability over time, environmental stability,
It is another object of the present invention to provide a toner capable of achieving high-quality image output while achieving both fine line reproducibility and solid image density uniformity.

  The toner particles of the present invention include a surface layer (B) containing resin (b1) and resin (b2) on the surface of toner base particles (A) containing at least a binder resin (a), a colorant and a wax. The binder resin (a) is a resin mainly composed of polyester, and the resin (b1) is a reaction product of at least a diol component and a diisocyanate component, Good results can be obtained with toner particles satisfying that the resin (b2) contains a vinyl unit represented by the general formula (1).

Superior results by the toner particles obtained by satisfying the pre Symbol resin (b1) to further a urethane-modified polyester resin is obtained.

  A feature of the toner of the present invention is that it has a capsule-type structure having a surface layer containing a charge control resin on the surface of toner base particles containing a binder resin, a colorant and a wax. Due to the uneven distribution of the charge control resin in the surface layer, excellent triboelectric chargeability is exhibited with a small amount. Furthermore, the surface layer is easy to adhere to the binder resin and exhibits excellent durability.

  Furthermore, the binder resin has the property of being easily melted at low temperatures, while the resin forming the surface layer has the property of being difficult to melt in a normal storage environment, and exhibits excellent low-temperature fixability and heat-resistant storage stability. To do.

  The toner of the present invention must have a capsule-type structure having a relatively hard shell layer and a core layer that is soft against the shell layer.

  In the present invention, it is preferable that the resin (b1) mainly bears heat-resistant storage stability, durability and the like, and the resin (b2) mainly bears triboelectric chargeability and the like.

The toner of the present invention forms a capsule type structure,
(1) The charge control agent can be unevenly distributed in the vicinity of the toner surface and exhibits excellent tribocharging properties.
(2) The colorant is not easily exposed on the toner surface, and good triboelectric chargeability is exhibited even when a conductive colorant such as carbon black is used.
(3) A resin with a sharp melt and a low softening point / low glass transition temperature can be used, and is excellent in both heat resistant storage stability and low temperature fixability. As a result, fixing at a low temperature is possible as compared with conventional toners, and power during fixing can be reduced. In addition, since a resin excellent in sharp melt property can be used as a binder resin, it is excellent in color mixing, can provide a full-color image with vivid colors, and exhibits excellent fixing properties comprehensively.
(4) A large amount of low melting point wax can be encapsulated and the exposure of the wax can be prevented, thereby exhibiting excellent effects in releasability, fluidity and developability.

  In the present invention, it is essential to use a polyester resin as the binder resin. Polyester resins are easy to control properties related to fixing properties such as softening point, glass transition temperature, and molecular weight distribution, and are excellent in sharp melt properties. In addition, it is possible to provide a toner that is excellent in triboelectric chargeability, low-temperature fixability, and color developability.

  In the present invention, it is essential that the toner surface layer (B) contains the resin (b1) and the resin (b2). It is essential that the resin (b1) is a reaction product of at least a diol component and a diisocyanate component. When the resin (b1) is a reaction product of at least a diol component and a diisocyanate component, further excellent triboelectric chargeability can be exhibited. Although the reason is not certain, it is considered that the vinyl unit represented by the general formula (1) can be uniformly dispersed in the surface layer.

  Further, the resin (b1) is more preferably a reaction product of a diol component having an ester bond site and a diisocyanate component, and the surface layer (B) is formed from the toner base particles (A) even after continuous printing and long-term use. In an environment where stability is important, such as a POD device that is difficult to peel off, excellent stability, that is, durability and frictional charging properties can be exhibited at the same time. This is because the polyester resin as the binder resin, the reaction product of the diol component and the diisocyanate component, and the ester bond site exhibit an appropriate affinity for creating a capsule-type structure and have good adhesion to each other. it is conceivable that.

  Further, since the resin (b1) is a reaction product of at least a diol component and a diisocyanate component, it becomes easy to form a film-like shell layer having a uniform thickness. By forming a shell layer having a uniform thickness, the distribution of the vinyl units represented by the general formula (1) in the surface layer becomes uniform, and it is considered that excellent triboelectric chargeability is exhibited.

  In the present invention, the vinyl unit represented by the general formula (1) is preferably unevenly distributed in the vicinity of the toner surface. By doing so, better triboelectric chargeability is exhibited. The vinyl unit represented by the general formula (1) that can be suitably used in the present invention will be described below.

  The vinyl unit represented by the general formula (1) has an amide bond and a sulfonic acid ester in the polyethylene side chain, and exhibits excellent tribocharging properties. Further, the vinyl unit represented by the general formula (1) is preferably easily mixed with the resin (b1). The vinyl unit represented by the general formula (1) is preferably dispersible uniformly in the toner surface layer.

  In the present invention, for example, the following vinyl units can be used. The vinyl units listed below are examples, and the present invention is not limited to these.

The vinyl-based unit represented by the general formula (1) that can be used in the present invention has an R ¹ in the general formula (1) having an aliphatic hydrocarbon group having 1 to 8 carbon atoms and an aromatic hydrocarbon group. R ² is preferably a methyl group or an ethyl group in terms of charge imparting properties and compatibility. R ² may be a proton. When R ¹ has 8 or more carbon atoms, the charge imparting property is lowered, which is not preferable.

Even more preferably, R ¹ is preferably a lower hydrocarbon group such as o-, m-, p-phenylene group, methylene group, isopropylene group as mentioned above.

  More preferably, the following compounds are used.

  In the vinyl unit represented by the general formula (1) that can be used in the present invention, the method for synthesizing the sulfonic acid ester is not particularly limited. A known synthesis method can be used.

  That is, for example, when preparing a vinyl-based unit represented by the formula (3), 2-acrylamido-2-methylpropanesulfonic acid is copolymerized with styrene and (meth) acrylic acid ester as shown below (I ), A side chain sulfonic acid group may be esterified. On the other hand, after the side chain sulfonic acid group of 2-acrylamido-2-methylpropanesulfonic acid is methyl esterified to obtain (B), (B) and a vinyl monomer may be copolymerized.

  As a method for obtaining (b), a known method can be used.

  On the other hand, as a method for methyl esterifying the side chain of the copolymer (I), for example, the following method can be used. 10 parts by mass of copolymer (I) was placed in a reaction vessel, dissolved by adding 350 parts by mass of chloroform and 87.5 parts by mass of methanol, and cooled to 0 ° C. To this, 20 mL of a 2 mol / liter trimethylsilyldiazomethane-hexane solution (for example, manufactured by Aldrich) was added and stirred for 4 hours. Thereafter, distillation was performed to distill off the solvent.

  Furthermore, 350 parts by mass of toluene and 100 parts by mass of 2-butanone were added to redissolve the polymer, and the solvent was distilled off by distillation. This re-dissolution / distillation operation was repeated three times and dried at 50 ° C. under reduced pressure. The obtained solid was pulverized to obtain (3).

  In the scheme through (a), a large amount of solvent may be used to dissolve the copolymer. In order to reduce the amount of solvent used, the scheme through (b) is preferred.

  In order to comprehensively solve the above problems, the affinity between the surface layer (B) and the binder resin (a) is particularly important in the present invention. That is, it is essential to shield the core layer with a necessary amount of the surface layer to form a film-like capsule structure.

  Furthermore, in the present invention, the degree of affinity between the resin (b2) and the binder resin (a) is important. The resin (b2) is preferably not compatible with the binder resin, and is preferably present only in the surface layer. However, on the other hand, it is preferable that the resin (b2) is maintained on the surface layer without being detached from the toner. The resin (b2) having a vinyl-based unit represented by the general formula (1) exhibits excellent tribocharging properties due to uneven distribution in the surface layer.

  When the vinyl unit represented by the general formula (1) of the present invention has an amide bond as a polar group and a sulfonic acid ester in a side chain, it has an appropriate affinity with a polyester resin as a binder resin. Conceivable.

  In the present invention, the resin (b1) and the resin (b2) preferably have compatibility. When the compatibility is low, dispersion in the surface layer (B) of the vinyl-based unit represented by the general formula (1) may be non-uniform, and the triboelectric chargeability may be reduced. Further, when the compatibility is low, it is not preferable because, for example, in a high-speed and high-production electrophotographic apparatus, the surface layer is easily detached.

  In the present invention, the resin (b1) is a reaction product of at least a diol component and a diisocyanate component, and includes an amide bond site of the vinyl unit represented by the general formula (1) and a urethane bond site of the resin (b1). A relatively strong interaction is considered compatible. Moreover, it is thought that it has favorable compatibility also by interaction with the sulfonic acid ester site | part of the vinyl-type unit represented by General formula (1), and the sulfonic acid site | part of resin (b1).

  The resin (b2) is preferably a ternary copolymer containing at least styrene, a (meth) acrylic acid ester, and a vinyl unit represented by the general formula (1). (Meth) acrylic acid ester means alkyl 2-propenoate or alkyl 2-methyl-2-propenoate. More preferably, the (meth) acrylic acid ester is preferably butyl acrylate or hexyl acrylate.

  Furthermore, since resin (b2) can control glass transition temperature comparatively freely by changing the copolymerization ratio of styrene and (meth) acrylic acid ester, styrene and (meth) acrylic acid as vinyl monomers. It is preferred to use an ester. Furthermore, it is preferable to use a vinyl monomer copolymerizable at an arbitrary ratio as the ternary copolymer.

  In the present invention, the resin dispersion of the resin (b2) may be a known method in which a vinyl polymer is prepared using a monomer containing a water-soluble functional group, and then an aqueous dispersion is prepared with stirring in water. For example, the following method can be preferably used. In a solvent such as acetone or 2-butanone, a vinyl monomer having a sulfonic acid group, a carboxyl group and a salt thereof, styrene, and an acrylate ester are added to prepare a vinyl-based copolymer. An aqueous dispersion can be obtained by gradually dropping and stirring the combined solution.

  In order to exhibit the excellent triboelectric chargeability and low temperature fixability in the present invention, the amount of the surface layer is important.

  In order to exhibit excellent triboelectric charging properties, the vinyl unit represented by the formula (1) is preferably exposed or unevenly distributed on the toner surface. Therefore, it is preferable that the surface layer containing the vinyl unit is as thin as possible, that is, a small amount.

  In the present invention, when the surface layer is formed of resin fine particles, the amount of the surface layer with respect to the toner base particles will be described below.

  The preferred amount of the surface layer (B) depends on the average particle diameter of the resin fine particles, which are the main components of the surface layer (B), and the average particle diameter of the toner, but it is 2 mass relative to the amount of the toner base particles (A). % Or more and less than 15% by mass. By setting it in such a range, a toner particle size and a toner particle size distribution capable of improving image quality can be achieved. Furthermore, a surface layer having a uniform thickness is easily formed, and exhibits excellent triboelectric chargeability and durability.

  When the amount of the surface layer (B) relative to the toner base particles (A) is less than 2% by mass, the capsule structure tends to be insufficiently formed. As a result, the toner base particles (A) are exposed, and when a binder resin having a low viscosity and a low softening point is used, the heat-resistant storage stability tends to decrease. The tendency that the capsule structure is insufficiently formed becomes stronger as the average particle size of the resin fine particles becomes larger. Therefore, when the average particle size of the resin fine particles is large, 2% by mass tends to be insufficient.

  Even when the number average particle size of the resin fine particles is relatively small, such as about 20 nm, when the amount of the surface layer is less than 2% by mass, capsule-type structure formation tends to be insufficient. When the capsule-type structure is not sufficiently formed, the toner base particles (A) are exposed, and a soft binder resin is used, the heat-resistant storage stability tends to decrease. Furthermore, when the amount of resin fine particles is insufficient, it is difficult to form a surface layer with a uniform thickness, and durability may be reduced.

  On the other hand, when the amount of the surface layer (B) relative to the toner base particles (A) is more than 15% by mass, the triboelectric chargeability may be inferior. When the resin (b2) having a high vinyl unit content represented by the general formula (1) is used, the toner is likely to be charged up and the image density may be low. This is presumably because the content of the vinyl unit represented by the general formula (1) in the toner particles is high and the charge amount is too large. On the other hand, when the resin (b2) having a low vinyl unit content represented by the general formula (1) is used, image defects such as fog are likely to occur. This is considered to be because the vinyl unit content represented by the general formula (1) in the toner particles is the same, but is not unevenly distributed on the surface.

  In addition, the core shielding property is improved, but it tends to be a non-uniform thickness and a thick surface layer. A thick surface layer tends to be inferior in low-temperature fixability. For example, when resin fine particles having a number average particle size of about 40 nm used in the present invention are used and a toner with a volume average particle size of 5.5 μm is assumed, in order to achieve both heat-resistant storage stability and low-temperature fixability, the surface layer has toner base particles ( A range of 5% by mass or more and less than 10% by mass with respect to A) is more preferable.

  In the present invention, the resin (b2) is preferably contained in an amount of 0.1% by mass or more and less than 5.0% by mass with respect to the toner base particles (A). When the resin (b2) is less than 0.1% by mass with respect to the toner base particles (A), the charge amount may be insufficient and the charge rising property may be inferior. On the other hand, when the resin (b2) is 5.0% by mass or more based on the toner base particles (A), the durability under severe conditions may be inferior. This is considered to be because the interaction between the resin (b2) and the binder resin is weakened.

  More preferably, the resin (b2) is 0.2% by mass or more and less than 2.0% by mass with respect to the toner base particles (A).

  Next, the vinyl unit ratio represented by the general formula (1) in the resin (b2) will be described below.

  In this invention, it is preferable that the vinyl-type unit ratio represented by this general formula (1) in resin (b2) is 2 to 20 mass%. In the composition of the resin (b2), when the vinyl unit ratio represented by the general formula (1) is less than 2% by mass, the toner particles may be difficult to be charged. Moreover, since a relatively large number of surface layers are required to exhibit sufficient triboelectric chargeability, the low-temperature fixability may be lowered.

  On the other hand, when the vinyl-type unit ratio represented by General formula (1) in resin (b2) is 20 mass% or more, the vinyl-type unit represented by General formula (1) may become difficult to disperse | distribute. In addition, the electrical resistance value of the toner particles is lowered, the charge amount is stable over time, and the charge amount in a high-temperature and high-humidity environment is likely to decrease.

  It is more preferable that the vinyl-based unit ratio represented by the general formula (1) in the resin (b2) is 5% by mass or more and less than 15% by mass, which exhibits an excellent triboelectric charging property and is a capsule with a relatively small surface layer. Mold structure can be formed.

  The vinyl-based unit ratio represented by the general formula (1) in the toner particles is the ratio of the surface layer to the toner particles × the ratio of the resin (b2) in the surface layer × the general formula (1) in the resin (b2). It is calculated | required by the vinyl-type unit ratio represented. The unit ratio in the toner particles is important for making the units unevenly distributed on the toner surface layer in order to control the triboelectric chargeability of the toner particles.

  In the present invention, the vinyl unit ratio represented by the general formula (1) in the toner particles is preferably 0.01% by mass or more and less than 0.20% by mass. When the unit ratio in the toner particles is less than 0.01% by mass, even if it can be unevenly distributed on the surface layer, the amount of charge tends to be insufficient in a high-temperature and high-humidity environment, and fogging, blurring, etc. are likely to occur. It is easy to deteriorate. On the other hand, when the unit ratio in the toner particles is less than 0.20% by mass, the toner easily charges up in a low-temperature and low-humidity environment, that is, the charge amount becomes too high, resulting in a decrease in toner development amount and insufficient density. It may become. In addition, the toner stays on the carrier and the developing roller for a long time, and the toner remains unrefreshed, which may cause deterioration in image quality.

  In the present invention, the resin (b1) is preferably a polyester-containing urethane resin. That is, the resin (b1) is a reaction product of a diol component and a diisocyanate component, and the diol component is preferably a polyester prepolymer having both ends of the polyester resin having alcoholic hydroxyl groups. Furthermore, the polyester prepolymer preferably has a primary alcoholic hydroxyl group at both ends and has a linear structure.

  Further, the weight average molecular weight (Mw) of the polyester prepolymer is preferably 500 or more and less than 5,000. When the polyester prepolymer Mw is less than 500, the urethane bond density is increased and the fixability may be hindered. On the other hand, when the polyester prepolymer Mw is 5000 or more, durability and triboelectric chargeability may be inferior.

In the present invention, the vinyl unit represented by the general formula (1) preferably has the following structure. In the general formula (1), R ¹ can be an aromatic hydrocarbon. As already described, the monomer may be sulfonated, or the ternary copolymer may be sulfonated.

  Next, preferred resin fine particles in the present invention will be described.

In the present invention, the surface layer (B) is preferably formed from resin fine particles. By forming the surface layer (B) from resin fine particles,
(1) It is easy to obtain a surface layer having a uniform thickness and exhibits excellent triboelectric chargeability.
(2) The core layer can be shielded even with a small amount of resin (b1) and resin (b2), and a capsule-type structure is easily obtained.
(3) Toner particles can be easily produced.
(4) The particle size distribution is sharp and the particle size can be easily controlled.

  The resin fine particles do not mean external additives such as fine particles generally used for imparting toner fluidity, friction chargeability, and the like.

  The resin particles are preferably resin fine particles capable of forming the toner surface layer into a film by heating or swelling the toner particles with a solvent.

  Use a material that wants to avoid exposure to the toner surface, such as a low-melting / low-viscosity binder resin, low-melting-point wax, and conductive colorant by shielding the toner base particles (A) and taking a capsule-type structure. Will be able to.

  As a result, it is difficult to expose the binder resin and wax, and it is possible to suppress a decrease in heat-resistant storage stability, and it is possible to provide a toner having excellent developability without exposing the wax because the colorant is difficult to be exposed on the toner surface and has excellent charging stability. It is.

  The particle diameter of the resin fine particles forming the surface layer in the present invention is also important for forming a surface layer having a uniform thickness and exhibiting excellent triboelectric charging properties.

  The resin fine particles used in the present invention preferably have a number average particle size of 10 nm or more and less than 150 nm. When the average particle diameter of the resin fine particles is large, more resin fine particles are required to form a film-like surface layer. On the other hand, when the particle size of the resin fine particles is small, a film-like surface layer can be formed with a relatively small amount.

  When the number average particle size of the resin fine particles is smaller than 10 nm, the granulation stability is lowered when the toner particles of the present invention are produced in an aqueous system, as in the case where the coating amount of the resin fine particles is small. This makes it difficult to form a capsule structure, and the heat resistant storage stability tends to deteriorate.

  On the other hand, even when the number average particle size of the resin fine particles is relatively large as about 150 nm, it has been found that a capsule-type structure can be formed by increasing the amount of resin fine particles used. It is easy to become. If the surface layer is thick, the ratio of the second resin in the toner particles is high, and the low-temperature fixability may be inferior. Further, when the toner particles of the present invention are to be manufactured in an aqueous medium, the dispersibility in the aqueous medium is lowered, and the particles are easily united or irregularly shaped particles are likely to be generated.

  From the above viewpoint, a more preferable particle diameter of the resin fine particles is a number average particle diameter of 15 nm or more and less than 120 nm.

  Here, in order to use resin fine particles as a dispersant, the dispersibility of the resin fine particles themselves in an aqueous medium is also an important parameter in the preparation of toner particles. As a result of studying the improvement of the dispersibility of the resin fine particles in the aqueous medium, the dispersibility of the resin fine particles in the aqueous medium by having a functional group capable of taking a salt structure such as a carboxyl group and a sulfonic acid group in the side chain exists. Has been found to improve dramatically and improve the granulation properties (particle size, particle size distribution) of the toner particles.

  The resin (b1) preferably has a structure having a carboxyl group in the side chain. The carboxyl group can be easily introduced by giving a carboxyl group to the side chain of the monomer that forms a reaction product of the diol component and the diisocyanate component. Among the monomers, diols having a carboxyl group in the side chain can be suitably used as versatile monomers.

  Examples of the diol compound having a carboxyl group in the side chain described above include the following. Dihydroxylcarboxylic acids such as dimethylolacetic acid, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolpentanoic acid, and metal salts thereof.

  Similar to the monomer having a carboxyl group in the side chain described above, a monomer having a sulfonic acid group in the side chain is also effective in achieving the above purpose. Examples of the diol compound having a sulfonic acid group in the side chain include the following. Sulfoisophthalic acid, N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid and its metal salt.

  In the present invention, it is more preferable to use a carboxyl group-containing diol and a sulfonic acid group-containing diol in combination. The reason for this is not clear, but according to the study by the present inventors, in order to maintain dispersibility in water, insolubility in ethyl acetate, and proper affinity of the toner base particles (A) to the polyester, The combined use resulted in favorable results.

  In addition, since the carboxyl group-containing diol monomer is more versatile among the carboxyl group-containing diol and the sulfonic acid group diol, it is preferable to mainly use the carboxyl group-containing diol.

  The diol having a carboxyl group in the side chain or the diol having a sulfonic acid group is 10 mol% or more and less than 50 mol%, more preferably 20 mol% among monomers forming a reaction product of a diol component and a diisocyanate component. More than 30 mol% is preferably contained.

  When the diol is less than 10 mol%, the dispersibility of the fine particles is deteriorated and the granulation property may be remarkably impaired. When the amount is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may be dissolved in the aqueous medium depending on the case, so that a sufficient function as a dispersant may be achieved.

  Further, the presence of a polar group in the side chain of the reaction product of the diol component and the diisocyanate component also has an effect of lowering the solubility in ethyl acetate. When the monomer containing a carboxyl group in the side chain is less than the above, depending on the molecular weight and composition of the reaction product of the diol component and the diisocyanate component, it may be dissolved in ethyl acetate.

  In the present invention, the resin fine particles may contain the resin (b1) and the resin (b2) together, or may contain the resin (b1) and the resin (b2) separately.

  When one resin fine particle contains both the resin (b1) and the resin (b2), the vinyl unit represented by the general formula (1) is easily dispersed and the triboelectric charging property is improved. Furthermore, desorption from the surface layer of the resin (b2) is easily suppressed, and durability is improved. This is probably because the resin (b1) and the resin (b2) are compatible.

  The resin fine particles were prepared by preparing a resin (b1) solution and a resin (b2) solution, mixing them, adding a carboxyl group or a conjugated group of a sulfonic acid group, adding it to water, stirring, and mixing the resin fine particles. Any known method for preparing emulsions can be used. Furthermore, the resin (b1) solution and the resin (b2) solution can be prepared simultaneously.

  When the resin fine particles contain the resin (b1) and the resin (b2) separately, in order to impart water solubility to the resin fine particles made of the resin (b2), a vinyl-based unit represented by the general formula (1) Is preferably sulfonic acid. When the sulfonic acid ester is used here, the surface layer content of the resin (b2) may be lower than the charged content.

  In this case, the resin fine particles are prepared by separately preparing the resin (b1) solution and the resin (b2) solution, and then adding a base for the carboxyl group or sulfonic acid group, adding them to water, stirring, and stirring the resin fine particles. Known methods of preparing the emulsion separately can be used.

  The preparation of the resin fine particles used in the present invention is not particularly limited, and it is produced by dissolving the emulsion polymerization method or the resin in a solvent or liquefying it and suspending it in an aqueous medium. It can be prepared by granulating.

  At this time, known surfactants, dispersants and the like can be used, and the resin constituting the fine particles can be provided with self-emulsifying properties.

  The solvent that can be used when preparing the fine particles by dissolving the resin in a solvent is not particularly limited, but includes the following. Hydrocarbon solvents such as ethyl acetate, xylene and hexane. Halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane. Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate. Ether solvents such as diethyl ether. Ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane. Alcohol solvents such as methanol, ethanol, butanol.

  Moreover, in this invention, it is one of the preferable forms to use the resin fine particle containing the reaction material of a diol component and a diisocyanate component as a dispersing agent. As this production method, a method can be preferably used in which a prepolymer having an isocyanate group is produced, this is rapidly dispersed in water, and subsequently an amine compound is added to prepare a chain extension or crosslinking.

  That is, in the present invention, a prepolymer having an isocyanate group and other necessary components as necessary are dissolved or dispersed in a solvent having high solubility in water such as acetone or alcohol among the above-mentioned solvents. A method of preparing a reaction product of a diol component and a diisocyanate component having desired physical properties by rapidly dispersing the prepolymer having an isocyanate group by adding this to water and subsequently adding an amine compound. It can be used suitably.

  Furthermore, in the present invention, the following method can be suitably used as a method for easily preparing the toner particles described above.

  That is, the preparation method includes dispersing both resin fine particles containing both resin (b1) and resin (b2), or resin fine particles containing resin (b1) and resin fine particles containing resin (b2). At least a binder resin and a colorant are dissolved or dispersed in an organic medium in an aqueous medium. A toner particle is obtained by dispersing the obtained dissolved or dispersed material, removing the solvent from the obtained dispersion and drying.

  In the above system, the resin fine particles are intended to function as a dispersant when suspending the toner composition. By preparing in such a system, the capsule toner of the present invention can be prepared by a simpler method without requiring an aggregation step on the surface of the toner particles.

  In the present invention, it is preferable that the resin (b1) and the resin (b2) are used in the form of resin fine particles, function as a dispersing agent during toner particle granulation, and change into a toner surface layer after granulation. That is, after the toner base particles (A) are produced, the surface layer can be formed by fixing resin fine particles by spray drying or applying the resin (b1) and resin (b2) solutions. As described above, it is preferable to prepare toner particles by a method in which resin fine particles also serve as a dispersion stabilizer in water.

  Further, the present inventors can form the surface layer by forming the surface layer by the above-described method, because the toner base particles and the resin fine particles forming the surface layer have an appropriate affinity. I believe. That is, if the affinity between the toner base particles and the surface layer is too weak, the resin fine particles as the surface layer are difficult to adsorb on the surface of the toner base particles, and conversely if the affinity is too strong, the fine particles are embedded in the toner base particles. It is thought that it becomes difficult to form a surface layer.

  In the above meaning, in the present invention, toner fine particles containing resin (b1) and resin (b2) together with toner base particles (A) having a polyester resin as a binder resin, or a resin containing resin (b1). It is important to form the surface layer using both the fine particles and the resin fine particles containing the resin (b2).

  Generally, the method for producing a capsule-type toner as in the present invention is roughly divided into a process for preparing toner base particles containing at least a polyester resin as a binder resin and a process for forming a surface layer.

  The method for preparing toner base particles using a polyester resin as a binder resin is not limited at all. For example, a binder resin, a pigment, and other toner compositions used as needed are melt-kneaded and then pulverized, spheroidized as necessary, and a so-called pulverization method in which classification steps are added, or target toner particles in an aqueous medium Emulsion aggregation method in which polyester fine particles smaller than the diameter are aggregated to a desired particle size by controlling the water-soluble salt, pH, temperature, stirring speed, etc., and then fused or aged, binder resin, pigment, and other necessary toner compositions For example, a suspension method in which a composition in which an organic solvent is dissolved and dispersed in an aqueous medium is suspended in a toner particle diameter in an aqueous medium, and then the organic solvent is removed.

  Further, the step of forming the surface layer of the present invention is not limited at all. For example, when the step of preparing the surface layer after preparation of the toner base particles is provided, the toner base particles and the toner base particles in the aqueous medium are provided. The substance that forms the surface layer is dispersed in the form of fine particles, and then wet external addition is performed to aggregate and adsorb the fine particles that form the surface layer on the surface of the toner base particles, or the powder form of the substance that forms the toner base particles and the surface layer. Examples include dry external addition in which the surface layer is mechanically fixed on the surface of the toner base particles by stirring the product dryly.

  As another method for forming the toner surface layer, a reactive monomer is mixed in the inside of the toner particles and in the aqueous medium, and the toner surface layer is formed by causing a reaction at the interface between the toner particles and the aqueous medium. A method called interfacial polymerization is also possible. However, in this method, it takes a long time to accompany the reaction, and it may be necessary to examine the reaction conditions in detail when preparing a surface layer exhibiting desired properties.

  Therefore, in the present invention, it is a simple method capable of preparing the capsule toner of the present invention in one step, and from the viewpoint of high image quality, toner particles having a spherical shape, a small particle size, and a sharp particle size distribution can be easily obtained. As a method for obtaining the surface layer, toner base particles are prepared by a dissolution suspension method, and a resin fine particle containing a reaction product of a diol component and a diisocyanate component is used as a dispersant as the dispersant. The method can be preferably used.

  The dissolution suspension method and fine particle dispersant in the present invention will be described below.

  Examples of the organic solvent for dissolving the binder resin and the like include the following. Hydrocarbon solvents such as ethyl acetate, xylene and hexane. Halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane. Ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isopropyl acetate. Ether solvents such as diethyl ether. Ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

  The aqueous medium used in the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include the following. Alcohols such as methanol, isopropyl alcohol, and ethylene glycol; lower ketones such as dimethylformamide, tetrahydrofuran, cellosolves, acetone, and methyl ethyl ketone.

  The amount of the aqueous medium used relative to 100 parts by mass of the toner composition is usually 50 to 2000 parts by mass, preferably 100 to 1000 parts by mass. If the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor and it is difficult to obtain toner particles having a predetermined particle size. If it exceeds 2000 parts by mass, it is not economical.

  In the present invention, it is preferable to mix an appropriate amount of an organic solvent used in the oil phase in the aqueous medium. By doing so, the stability of oil droplets during granulation can be improved, toner particles having a sharp particle size distribution can be granulated, and the surface of the toner particles can be easily smoothed. This is thought to be because when the oil phase is suspended in the aqueous phase, the solvent can be prevented from moving rapidly from the oil droplets to the aqueous phase.

  From the above viewpoint, the amount of the organic solvent added to the aqueous medium is more preferably a saturated amount.

  Moreover, a well-known surfactant, water-soluble polymer, etc. can also be used as a dispersing agent.

  Main surfactants include anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, etc., which can be arbitrarily selected in accordance with the polarity when forming toner particles. Is.

  Examples include the following. 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, alkyltrimethylammonium salts, Nonionic interfaces such as dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, quaternary ammonium salt type cationic surfactants such as benzethonium chloride, fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Activators, such as amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

  On the other hand, examples of the cationic surfactant include the following. Aliphatic primary, secondary or secondary amino acids having fluoroalkyl groups, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts , Imidazolinium salt.

  Moreover, you may use a polymer dispersing agent, for example, the following are mentioned. (Meth) acrylic monomers containing acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride, or hydroxyl groups For example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloroacrylate 2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylo Allyl acrylamide, N-methylol methacrylamide, etc., vinyl alcohol, or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and a carboxyl group 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, pinylviridine, vinylpyrrolidone, vinylimidazole, ethylene Homopolymers or copolymers such as those having a nitrogen atom such as imine or its heterocyclic ring, polyoxyethylene, polyoxypropylene, polyoxyethylene alcohol Luamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc. Celluloses such as polyoxyethylene, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like.

  When a dispersant is used, the dispersant can remain on the surface of the toner particles, but it is preferably dissolved and removed.

  In the present invention, in addition to the above-described surfactant, or in combination, it is also preferable to dissociate the carboxyl residue of the polyester, which is a binder resin, to develop a surfactant effect. Specifically, by allowing amines to be present in the oil phase or water phase, the carboxyl group of the polyester can be dissociated to impart water dispersibility.

  As amines that can be used at this time, amines of relatively low molecular weight such as aqueous ammonia, triethylamine, and triethanolamine are preferable.

  In the present invention, a solid dispersion stabilizer may be used in combination for maintaining a more preferable dispersion state.

  In the present invention, the dispersion stabilizer is used for the following reason. That is, the organic medium in which the binder resin, which is the main component of the toner particles, is dissolved, has a high viscosity, and the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with high shearing force. This is to prevent the oil droplets from re-aggregating and stabilize.

  As the dispersion stabilizer, an inorganic dispersion stabilizer or an organic dispersion stabilizer can be used. In the case of an inorganic dispersion stabilizer, toner particles are granulated in a state of adhering to the particle surface after dispersion, and thus have an affinity for a solvent. Those that can be removed by acids such as hydrochloric acid are preferred. For example, calcium carbonate, calcium chloride, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, calcium triphosphate and the like can be used.

  The dispersion method is not particularly limited, and general-purpose devices 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 used. A shearing type is preferred.

  There is no restriction | limiting in particular as a stirring apparatus which has a rotary blade, If it is a general thing as an emulsifier and a disperser, it can be used.

  For example, the following are mentioned. Ultra Thalax (manufactured by IKA), Polytron (manufactured by Kinematica), TK Auto Homo Mixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK Homomic Line Flow (special Kika Kogyo Co., Ltd.), colloid mill (Shinko Pantech Co., Ltd.), thrasher, trigonal wet milling machine (Mitsui Miike Kako Co., Ltd.), Cavitron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Ocean) Continuous type emulsifier such as Kiko Co., Ltd., batch type such as Claremix (M Technique Co., Ltd.), Fillmix (made by Tokushu Kika Kogyo Co., Ltd.), etc.

  When a high-speed shearing disperser is used, the rotation speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.

  In the case of a batch system, the dispersion time is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

  In order to remove the organic solvent from the emulsified dispersion obtained in this manner, a method in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely removed by evaporation can be employed.

  Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner particles, and the aqueous dispersant can be removed by evaporation together.

  In that case, the dry atmosphere in which the emulsified dispersion is sprayed is generally a gas heated with air, nitrogen, carbon dioxide gas, combustion gas, etc., particularly various air streams heated to a temperature higher than the boiling point of the highest boiling solvent used. Used.

  Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

  When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.

  The dispersant used is preferably removed from the obtained dispersion as much as possible, but more preferably it is performed simultaneously with the classification operation.

  Mix the obtained powder of toner particles after drying with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or give mechanical impact force to the mixed powder. By fixing and fusing on the surface, it is possible to prevent the dissociation of the foreign particles from the surface of the resulting composite particle.

  In the production method, it is possible to further provide a heating step after removing the organic solvent. By providing the heating step, the toner particle surface can be smoothed or the spheroidization degree can be adjusted.

  In the present invention, it is essential to use a polyester resin as the binder resin from the viewpoint of controlling the triboelectric chargeability. In some cases, the triboelectric chargeability can be controlled by controlling the acid value of the polyester resin. The acid value of the binder resin used is preferably 5.0 mgKOH / g or more and less than 20.0 mgKOH / g.

  In addition, when using several resin together, it is the whole acid value calculated | required by calculation from each ratio. For example, when 80% of the resin having an acid value of 12.0 mgKOH / g is used and 20% of the resin having an acid value of 6.0 mgKOH / g is used, 12.0 × 0.8 + 6.0 × 0.2 = 10.8. 10.8 mgKOH / g.

  When the acid value of the binder resin is less than 5.0 mgKOH / g, the charge rising may be inferior. On the other hand, when the acid value of the binder resin is 20.0 mgKOH / g or more, the environmental stability such as charging stability under high humidity may be inferior.

  Examples of the binder resin monomer that can be used in the present invention include the following.

  The alcohol component is preferably an aliphatic alcohol having 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms. Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butenediol, 1 , 7-heptanediol, 1,8-octanediol and other linear diols, hydrogenated bisphenol A, bisphenol derivatives represented by the following (formula 10), and diols represented by the following (formula 11).

  Further, it is preferable that the polyester skeleton of the polyester oligomer described above and the polyester skeleton of the binder resin described later are the same in view of the affinity between the resin (b1) and the toner base particles.

  Furthermore, in order to improve durability, the content is 30 mol% or more in the alcohol component, preferably 50 mol% or more.

  On the other hand, examples of the carboxylic acid component include the following. Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid, octenyl succinic acid, etc. Aliphatic polycarboxylic acids such as succinic acid substituted with an alkyl group or an alkenyl group having 2 to 20 carbon atoms, anhydrides of these acids and alkyls of these acids (esters having 1 to 8 carbon atoms).

  The raw material monomer may contain a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound.

  Next, the resin (b1) that can be used in the present invention will be described.

  In the present invention, examples of the substance containing an isocyanate group include the following. C6-C20 aromatic isocyanate, C2-C18 aliphatic isocyanate, C4-C15 alicyclic isocyanate, C8-C15 aromatic Aliphatic isocyanates and modified products of these isocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products) and two or more of these Mixture of.

  The following are mentioned as said aromatic isocyanate. 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde and aromatic amine (aniline) or a mixture thereof; a mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine] ] Phosgenates: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- and p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic isocyanate include the following. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl carbonate Aliphatic isocyanates such as proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate;

  Examples of the alicyclic isocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Examples of the aromatic aliphatic isocyanate include the following. m- and / or p-xylylene diisocyanate (XDI), α, α, α ', α'-tetramethylxylylene diisocyanate (TMXDI) and the like. Examples of the modified polyisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product.

  Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), a modified product of isocyanate such as urethane-modified TDI, and a mixture of two or more of these [for example, modified MDI and urethane-modified TDI ( In combination with an isocyanate-containing prepolymer). Of these, preferred are 6 to 15 aromatic isocyanates, C4 to C12 aliphatic polyisocyanates, and C4 to C15 alicyclic isocyanates, and particularly preferred are TDI, MDI, HDI, Hydrogenated MDI and IPDI.

  Moreover, as a hydroxyl-containing compound which can be used for the isocyanate type compound of this invention, diol is preferable, for example, the following are mentioned.

  Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.); the alkyl moiety of the above-described alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.

Alkylene ether glycol (diethylene glycol, triethylene 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, bisphenol S, etc.);
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above bisphenols;
In addition, polylactone diol (such as poly ε-caprolactone diol), polybutadiene diol.

  In the present invention, in addition to the diols described above, polyester oligomers having a terminal hydroxyl group can also be used as suitable diols.

  At this time, the molecular weight of the terminal diol polyester oligomer is preferably less than 3000, more preferably less than 2000.

  In addition, the above-described oligomer is preferably contained in the monomer constituting the isocyanate compound in an amount of 1 mol% or more and less than 10 mol%, more preferably 3 mol% or more and less than 6 mol%.

  The polyester skeleton of the polyester oligomer described above and the polyester skeleton of the binder resin described later are preferably the same in view of the affinity between the surface layer mainly composed of the second resin and the toner base particles.

  Moreover, the polyester oligomer mentioned above may have an ether bond modified with ethylene oxide, propylene oxide or the like.

  In the isocyanate compound of the present invention, an amino group can also be used in combination as a highly reactive hydrogen group that reacts with an isocyanate group. In particular, when the reaction with an isocyanate group is carried out in water, it is particularly important to use an amine. This is because amines generally react with isocyanates faster than alcohols or water.

  Examples of amines that can be used in the present invention include diamines such as diaminoethane, diaminopropane, diaminobutane, diaminohexane, piperazine, 2,5-dimethylpiperazine, amino-3-aminomethyl-3,5,5-trimethyl. Cyclohexane (isophoronediamine, IPDA), 4,4′-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, aminoethylethanolamine, hydrazine, hydrazine hydrate, or triamines such as triethylamine, diethylenetriamine and 1,8-diamino- 4-aminomethyloctane.

  In the present invention, it is essential to use wax in the toner particles in order to improve the releasability from the fixing member or to improve the fixability. Known waxes can be used for the present invention. Examples of the wax that can be used in the present invention include the following. Polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol-bis-stearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); Etc.); and dialkyl ketones (distearyl ketones).

  In the present invention, the melting point of the wax is in the range of preferably 40 ° C. or higher and lower than 160 ° C., more preferably 50 ° C. or higher and lower than 120 ° C. If the melting point is less than 40 ° C., the wax is likely to be exposed on the toner surface, and the heat resistant storage stability may be reduced. On the other hand, if the melting point is 160 ° C. or higher, the wax may not be melted properly at the time of fixing, and a release effect may not be exhibited.

  In the present invention, the wax content in the toner is preferably 2.0 or more and less than 20.0% by mass, more preferably 2.5 or more and less than 15.0% by mass.

  If it is less than 2.0% by mass, the releasability of the toner cannot be maintained, and if it is 20.0% by mass or more, wax is easily exposed on the surface of the toner, and the fluidity of the toner is likely to be lowered, resulting in deterioration of image quality. Or the heat resistant storage stability may be reduced.

  In the case of using the dissolution suspension method in the present invention, the wax is introduced in advance by melting and dissolving the wax in an organic solvent, then precipitating the wax in the solvent, and mechanically dispersing the wax as necessary. Introduce into the toner by preparing a dispersion in an organic solvent or by melting and dissolving wax in an oil phase containing at least an organic solvent, a binder resin and a colorant and then cooling. In addition, the wax powder can be mechanically pulverized and used.

  In the toner of the present invention, it is one of preferable modes to use a wax dispersant in order to disperse the wax more uniformly in the toner. The wax dispersant is not particularly limited, and any known wax dispersant can be used.

  The following are used as the colorant used in the toner of the present invention.

  As a colorant suitable for the yellow color, a pigment or a dye can be used. Specifically, the following are mentioned as a pigment. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Bat yellow 1,3,20. Examples of the dye include the following. C. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162. These are used alone or in combination of two or more.

  As a colorant suitable for magenta, a pigment or a dye can be used. Specific examples include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254; I. Pigment violet 19; C.I. I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35. Examples of the magenta dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as basic violet 1,3,7,10,14,15,21,25,26,27,28. These are used alone or in combination of two or more.

  As a colorant suitable for cyan, a pigment or a dye can be used. Specific examples include the following. C. I. CI pigment blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Acid Blue 45. Examples of the dye include the following. C. I. Solvent Blue 25, 36, 60, 70, 93, 95. These are used alone or in combination of two or more.

  The following are mentioned as a black pigment. Carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black. Magnetic powders such as magnetite and ferrite are also used.

  In the present invention, it is not preferable to use a dye or pigment having extremely high solubility in water as the colorant. When the above-mentioned dyes / pigments are used, they may dissolve in water during the production process, and granulation may be disturbed or desired coloration may not be obtained.

  As the external additive for assisting the fluidity, developability and triboelectric charging property of the toner 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 or more and less than 2 μm, particularly preferably 5 nm or more and less than 500 nm. The specific surface area by the BET method is preferably 20 m ² / g or more 500m less than ² / g.

  The proportion of the inorganic fine particles used is preferably 0.01 to 5% by mass of the toner particles, and more preferably 0.01% by mass or more and less than 2.0% by mass.

  These inorganic fine particles may be used alone or in combination of plural kinds.

  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, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  In addition, polymer fine particles such as polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, methacrylic acid ester and acrylic acid ester copolymer, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting Examples thereof include polymer particles made of a resin.

  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 a fluoroalkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include, for example, fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, such as polymethyl methacrylate fine particles, polystyrene fine particles, etc. 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.

  When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier. The carrier to toner content ratio in the developer is 1 part by mass or more of toner with respect to 100 parts by mass of the carrier. Less than 10 parts by mass is preferred.

  As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of 20 μm or more and less than 200 μm can be used.

  In the present invention, the weight average particle diameter (D4) of the toner is preferably 3.0 μm or more and less than 10.0 μm.

  When D4 is less than 3.0 μm, there is a problem that the toner is charged up after a long period of use, and the density is lowered. Further, when D4 is larger than 10.0 μm, in the case of outputting a line image or the like, it is easy to cause scattering and a drop of a button, which may be inferior in fine line reproducibility.

  In the present invention, the molecular weight of the toner is preferably a peak molecular weight of less than 10,000, more preferably less than 5000. The proportion of molecular weight of 100,000 or more is less than 5%, more preferably less than 1%. As a result, excellent low-temperature fixability and offset resistance can be exhibited at the same time.

  In order to achieve these molecular weight distributions, it is preferable to use a plurality of resins having different molecular weight distributions during toner production.

  The toner of the present invention can easily control the sphericity and surface properties. In the production method, it is possible to further provide a heating step after removing the organic solvent. By providing the heating step, the toner surface can be smoothed and the degree of spheroidization can be adjusted.

  In the present invention, the sphericity SF-1 of the toner is preferably in the range of 100 or more and less than 140, more preferably 100 or more and less than 130.

  When the SF-1 value is 140 or more, the transfer characteristics tend to particularly deteriorate, and image quality may be deteriorated. That is, when the SF-1 value is 100, a shape close to a true sphere is shown, and a toner shape close to 100 is more preferable.

-Measurement method-
Hereinafter, the measurement method and the evaluation method according to the present invention will be described.

<Tg measurement>
The Tg measurement method in the present invention was measured under the following conditions using DSC Q1000 (manufactured by TA Instruments), and the onset value shown in FIG.

Measurement conditions Modulation mode / Temperature increase rate: 0.1 ° C / min
Modulation temperature amplitude: ± 1.0 ° C / min
-Measurement start temperature: 25 ° C
-Measurement end temperature: 130 ° C

  The temperature was raised only once and the DSC curve was obtained by taking “Reversing Heat Flow” on the vertical axis, and the onset value shown in FIG. 1 was defined as Tg of the present invention.

<Measurement of acid value of resin>
2-10 g of sample is weighed into a 200-300 ml Erlenmeyer flask and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% by weight bromthymol blue and phenol red, titration was performed with a pre-standardized N / 10 caustic potash-alcohol solution, and the acid value was determined from the consumption amount of the alcohol potash liquid by the following formula. .
Acid value = KOH (mL) x N x 56.1 / sample weight (where N is a factor of N / 10: KOH)

<Measurement of resin particle size>
Using a Microtrac particle size distribution measuring apparatus HRA (X-100) (manufactured by Nikkiso Co., Ltd.), measurement was performed with a range setting of 0.001 μm to 10 μm, and the number average particle diameter was defined as the particle diameter of the resin fine particles of the present invention.

<Measurement of solid content ratio of resin fine particles>
Using a moisture meter FD240 manufactured by Kett Science Laboratory, the temperature was set to 120 ° C., and the weight loss was determined by evaporating moisture until no mass change was observed for 1 minute, and the solid content ratio was measured.

<Measurement of Number Average Particle Size (D1) and Volume Average Particle Size (D4) of Toner>
As a measuring device, Multisizer II (manufactured by Beckman Coulter, Inc.) is used. As the electrolyte, first grade sodium chloride is used to prepare an approximately 1% NaCl aqueous solution. For example, ISTON R-II (manufactured by Coulter Scientific Japan) can be used.

  As a measuring method, 0.5 mL of a surfactant (Contaminone, trade name, manufactured by Wako Pure Chemical Industries, Ltd.) is added as a dispersant to 20 mL of the electrolytic aqueous solution, and 5 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 minute, and the volume and number of toner particles having a particle diameter of 2.00 μm or more and less than 40.30 μm are measured using the 100 μm aperture. Measurement is performed for each channel, and the volume average particle diameter (D4) and the number average particle diameter (D1) are calculated from the volume distribution and number distribution of the toner, respectively. Channels are 2.00 to 2.52 μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm; 4.00 to 5.04 μm; 5.04 to 6.35 μm; 6.35 to 8. 00μm; 8.00 to 10.08 μm; 10.08 to 12.70 μm; 12.70 to 16.00 μm; 16.00 to 20.20 μm; 20.20 to 25.40 μm; 25.40 to 32.00 μm; 13 channels of 32.00 to 40.30 μm are used.

<Measurement of charge amount of toner particles>
The method for measuring the triboelectric charge amount of toner particles in the present invention will be described below.
First, a predetermined carrier and toner particles were allowed to stand for 1 day in a normal temperature and normal humidity environment (23 ° C., 65% RH).

Put a predetermined carrier and toner particles in a plastic bottle with a lid, shake with a shaker (YS-LD, manufactured by Yayoi Co., Ltd.) at a speed of 4 reciprocations per second for 1 minute, and then toner particles and carrier The developer consisting of is charged. Next, the charge amount is measured by the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 2, about 0.5 to 1.5 g of the developer described above is put in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is placed. The total mass of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction device 1 (at least the part in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted so that the pressure gauge 5 is 250 mmAq. In this state, the toner particles are sucked and removed sufficiently, preferably for 1 minute. The potential of the electrometer 9 at this time is set to E (V). Here, 8 is a capacitor, and the capacity is C (mF). Moreover, the mass of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge Q _O (μC / g) of this sample is calculated as follows.
Triboelectric charge quantity Q _O sample (μC / g) = C × E / (W1-W2)

<Environmental stability of charge amount>
Prepare toner particles and a carrier that were allowed to stand in a high temperature and high humidity environment (30 ° C., 80% RH) and a low temperature and low humidity environment (10 ° C., 15% RH) for one day. The charge amount of the toner particles was measured under the above environment.

When the charge amount in a high temperature and high humidity environment is Q _H (μC / g) and the charge amount in a low temperature and high humidity environment is Q _L (μC / g), the difference between Q _H and Q _O Q1, Q _O And Q _L are defined as Q2 and Q1 + Q2 (μC / g) is defined as the environmental stability of charging. The smaller Q1 + Q2 (μC / g), the higher the environmental stability of charging and the better.
A: Charge amount difference Q1 + Q2 is less than 4 μC / g (excellent environmental stability)
B: Charge amount difference Q1 + Q2 is 4 μC / g or more and less than 8 μC / g (good environmental stability)
C: Charge amount difference Q1 + Q2 is 8 μC / g or more and less than 16 μC / g (environmental stability with no practical problem)
D: Charge amount difference Q1 + Q2 is 16 μC / g or more (inferior in environmental stability)

<Rise of charge amount under normal temperature and humidity>
In the method for measuring the charge amount, the triboelectric charge amount after 5 seconds from the start of shaking with a shaker is measured in a room temperature and humidity environment, and this is defined as Q _I (μC / g). A ratio with the charge amount Q _O (μC / g) after 1 minute of shaking is taken, and Q _I / Q _O is defined as an index of charge rising property.
A: Q _I / Q _O is 0.8 or more (excellent charge rising property)
B: Q _I / Q _O is 0.5 or more and less than 0.8 (good charge rising property)
C: Q _I / Q _O is 0.2 or more and less than 0.5 (charge rising property having no practical problem)
D: Q _I / Q _O is less than 0.2 (inferior charge rising property)

<Evaluation of heat-resistant storage stability of toner>
The method for evaluating heat-resistant storage stability in the present invention will be described below. 3 g of toner was placed in a 100 mL polycup and allowed to stand in a constant temperature bath at 50 ° C. (within ± 0.5 ° C.) for 3 days, and then evaluated visually and touched with a finger.

(Evaluation criteria)
A: No change is observed, and very good heat resistant storage stability is exhibited.
B: Although fluidity | liquidity falls a little, it shows the outstanding heat-resistant storage property.
C: Aggregates are generated, but the heat-resistant storage stability is not a problem in practical use.
D: Aggregates can be pinched and do not collapse easily. Inferior to heat-resistant storage.

<Evaluation of fixing start temperature>
A fixing test was performed in a state where the fixing unit of the color laser copying machine CLC5000 (manufactured by Canon Inc.) was modified so that the fixing temperature could be manually set.

An image for evaluation of the fixing start temperature is CLC5000 (manufactured by Canon Inc.) using A4 paper (TKCLA4, 81.4 g / m ² Canon) in a single color mode in a normal temperature and humidity environment (23 ° C. and 65% RH). The development contrast is adjusted so that the amount of toner on the paper is 1.2 mg / cm ^2, and a solid unfixed image having a leading edge margin of 5 mm, a width of 100 mm, and a length of 280 mm is produced.

  In a room temperature and normal humidity environment, the temperature was increased from 90 ° C. in 10 ° C. increments and passed through a fixing device. A portion 5 cm from the rear end of the fixed image is rubbed 5 times with a soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd. can be used) while applying a load of 4.9 KPa. The image density before and after rubbing was measured, respectively, and the reduction rate ΔD (%) of the image density was calculated by the following equation. The image density was measured with an X-Rite color reflection densitometer (Color reflection densitometer X-Rite 404A).

The temperature at which ΔD (%) was less than 1% was determined as the fixing start temperature.
ΔD (%) = (Image density before rubbing−Image density after rubbing) × 100 / Image density before rubbing

<Evaluation of gloss (image gloss)>
An image is formed on an A4 sheet (TKCLA4 which is a CLC recommended sheet) with an image area ratio of 25%. Under normal temperature and humidity conditions, the temperature was gradually increased from 90 ° C. by 10 ° C., a fixing test was conducted to a temperature range where no offset or wrapping occurred, and glossiness was measured by the following means.

  The glossiness of the image was measured using a gloss meter PG-3G (manufactured by Nippon Denshoku Industries Co., Ltd.) for five solid image portions of the fixed image. The incident angle was 75 degrees.

The average value of the five measured values was calculated, and the maximum glossiness in the fixing temperature region was evaluated as follows.
A: Glossiness: 40 or more B: Glossiness: 30 or more and less than 40 C: Glossiness: 20 or more and less than 30 D: Glossiness: 15 or more and less than 20

<Evaluation of offset resistance>
In a room temperature and normal humidity environment, the temperature was increased by 10 ° C. sequentially from 90 ° C. to 180 ° C. Of the temperatures at which offset (peeling) and winding occurred, a temperature higher than the temperature at which the gross value showed the maximum value was defined as the offset generation temperature. The higher the offset generation temperature, the better. It is more preferable that no offset occurs.

<Durability evaluation>
For durability evaluation, CLC5000 (manufactured by Canon) with a modified process speed of 400 mm / sec was used, and up to 50,000 images (print area ratio 4%) with a 2 pixel line width grid printed on the entire surface of A4 paper were printed. The determination was made based on the number of images at the time when the smudge occurred on the image.
A: When 50,000 sheets are printed, no stains are generated and excellent durability is exhibited. B: When 40,000 sheets are printed, stains are generated and good durability is exhibited. C: When 20,000 sheets are printed. Despite the occurrence of smudges, it shows durability that is not a problem for practical use. D: Stain is generated when 5,000 sheets are printed, and the durability is poor.

<Evaluation of fine line reproducibility>
From the viewpoint of high image quality, fine line reproducibility was evaluated for the 5000th image out of the images output in the durability evaluation by the modified machine. The output resolution of the CLC5000 is 400 dpi, and the line width of 2 pixels is theoretically 127 μm. The line width of an actual image is measured, and when this is d, D is defined as the fine line reproducibility index.
D (%) = 100 × d / 127
A: D is 100 or more and less than 110 and shows excellent reproducibility of fine lines. B: D is 110 or more and less than 130, and slight fine line width variation is observed, but good fine line reproducibility C: D Is 130 or more and less than 160, and thin lines and splattering are conspicuous, but D: D is 160 or more to the extent that there is no practical problem.

  Hereinafter, the present invention will be described with reference to examples.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all.

  First, a method for preparing the toner raw material used in the present invention will be described.

<Preparation of binder resin 1>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
・ 928 parts by mass (10.3 mol) of 1,4-butanediol
-776 parts by mass of dimethyl terephthalate (4.0 mol)
・ 292 parts by mass of 1,6-hexanedioic acid (2.0 mol)
・ Tetrabutoxy titanate (condensation catalyst) 3 parts by mass

  The reaction was carried out for 8 hours at 160 ° C. while distilling off the produced methanol under a nitrogen stream. Next, while gradually raising the temperature to 210 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Subsequently, the mixture was cooled to 160 ° C., 173 parts by mass (0.9 mol) of trimellitic anhydride and 125 parts by mass (1.2 mol) of 1,3-propanedioic acid were added, and after reaction for 2 hours under atmospheric pressure sealing, The reaction was carried out at normal pressure, and the sample was taken out when the softening point reached 170 ° C. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a binder resin 1 which is a non-linear polyester resin. Table 1 shows the Tg and acid value of the binder resin 1.

<Preparation of binder resin 2>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
・ 799 parts by mass of 1,2-propanediol (10.5 mol)
-815 parts by mass of dimethyl terephthalate (4.2 mol)
-1,5-pentanedioic acid 238 parts by mass (1.8 mol)
・ Tetrabutoxy titanate (condensation catalyst) 3 parts by mass

  The reaction was carried out for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Then, while gradually raising the temperature to 230 ° C., the reaction was carried out for 4 hours while distilling off the produced propylene glycol and water under a nitrogen stream, and the reaction was further carried out for 1 hour under a reduced pressure of 20 mmHg. Next, the mixture was cooled to 180 ° C., 173 parts by weight (0.9 mol) of trimellitic anhydride was added, reacted for 2 hours under sealed atmospheric pressure, reacted at 220 ° C. and normal pressure, and when the softening point reached 180 ° C. I took it out. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a binder resin 2 which is a nonlinear polyester resin. Table 1 shows Tg and acid value of the binder resin 2.

<Preparation of binder resin 3>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,3-butanediol 1036 parts by mass (11.5 mol)
・ 892 parts by mass of dimethyl terephthalate (4.6 mol)
・ 205 parts by mass of 1,6-hexanedioic acid (1.4 mol)
・ Tetrabutoxy titanate (condensation catalyst) 3 parts by mass

  The reaction was carried out for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a binder resin 3 which is a linear polyester resin. The Tg and acid value of the binder resin 3 are shown in Table 1.

<Preparation of binder resin 4>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
・ 858 parts by mass of 1,2 propanediol (11.3 mol)
・ Dimethyl terephthalate 873 parts by mass (4.5 mol)
・ 219 parts by mass of 1,6-hexanedioic acid (1.5 mol)
・ Tetrabutoxy titanate (condensation catalyst) 3 parts by mass

  The reaction was carried out for 8 hours at 180 ° C. while distilling off the methanol produced under a nitrogen stream. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off the produced propylene glycol and water in a nitrogen stream, and further the reaction was performed under a reduced pressure of 20 mmHg, and the softening point was 150 ° C. Removed at the time. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a binder resin 4 which is a linear polyester resin. Table 1 shows Tg and acid value of the binder resin 4.

<Preparation of binder resin 5>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
・ 229 parts by mass of styrene (2.2 mol)
・ 231 parts by mass of n-butyl acrylate (1.8 mol)
・ Acrylic acid 14 parts by mass (0.2 mol)
・ 50 parts by mass of 2-butanone (solvent)

  As a polymerization initiator, 8 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. Polymerization was performed at 60 ° C. for 8 hours, the temperature was raised to 150 ° C., the solvent was removed under reduced pressure, and the product was taken out from the reaction vessel. After cooling to room temperature, it was pulverized and granulated to obtain a binder resin 5 which is a linear vinyl resin. Table 1 shows Tg and acid value of the binder resin 5.

<Preparation of resin (b1) solution>
-Number average molecular weight obtained from an equimolar mixture of terephthalic acid and isophthalic acid with a mixture of 50 mol%, 40 mol% and 10 mol% of 1,3-propanediol, ethylene glycol and 1,4-butanediol, respectively. 2000 polyester resin (acid value 2 mgKOH / g, hydroxyl value 19 mgKOH / g) 95 parts by mass, 1,4-butanediol 20 parts by mass (0.22 mol)
・ 85 parts by mass (0.63 mol) of dimethylolpropanoic acid
3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
5 parts by mass (0.02 mol)
The above material was dissolved in 150 parts by mass of sufficiently dehydrated and dried acetone, and then 250 parts by mass (1.12 mol) of isophorone diisocyanate was added and reacted at 60 ° C. for 4 hours. In order to neutralize the carboxyl group of dimethylolpropanoic acid in the reaction product, 64 parts by mass (0.63 mol) of triethylamine was added and stirred. Subsequently, it diluted with acetone so that solid content ratio might be set to 70%, and the acetone solution of resin (b1) which is a urethane-modified polyester resin was obtained.

<Preparation of Resin (b2) -1 to -15 Solution>
Into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer, the number of charged units shown in Table 2 for the monomer of the vinyl-based unit represented by the general formula (1), styrene, and acrylate is added. A mass part was added as a solvent, and 2 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved as a polymerization initiator to prepare a polymerizable monomer composition. Polymerization was performed at 60 ° C. for 8 hours, and the temperature was raised to 150 ° C. After cooling to room temperature, it was diluted with acetone to a solid content ratio of 76% to obtain acetone solutions from resin (b2) -1 to resin (b2) -15, respectively.

<Preparation of dispersion of resin fine particles 1>
128 parts by mass of an acetone solution (solid content ratio 70%) of the resin (b1) and 11 parts by mass of an acetone solution (solid content ratio 76%) of the resin (b2) -1 are mixed and stirred into 320 parts by mass of ion-exchanged water. While dropping, the mixture was emulsified. Then, 50 parts by mass of water, 3.6 parts by mass (0.06 mol) of ethylenediamine and 2.4 parts by mass (0.03 mol) of n-butylamine were added and reacted at 50 ° C. for 4 hours. Subsequently, acetone was removed under a reduced pressure of 100 mmHg by a rotary evaporator. The solid content ratio was measured to be 19%. Dilution with ion-exchanged water so as to have a solid content ratio of 15% yielded a dispersion of resin fine particles 1 containing resin (b1) and resin (b2).

  As a result of measuring the particle size of the dispersion of resin fine particles 1, it was 36 nm. After the dispersion of resin fine particles 1 was dried at room temperature, Tg was 60 ° C. The results are shown in Table 4.

<Preparation of dispersion of resin fine particles 2 to 15>
Resin fine particles 1 were prepared in the same manner as in the dispersion of resin fine particles 1 except that resins (b2) -2 to (b2) -15 were used in the formulations shown in Table 3 instead of resin (b2) -1. 2 to 15 dispersions were prepared. Table 4 shows the physical properties of the dispersions of resin fine particles 2 to 15.

  The dispersion of the resin fine particles 3 is a dispersion containing the resin (b1) and not containing the resin (b2), and the dispersion of the resin fine particles 15 is a dispersion containing no resin (b1) and containing the resin (b2).

<Preparation of wax dispersion 1>
In a reaction vessel equipped with a thermometer and a stirring blade, 50 parts by mass of purified No. 1 carnauba wax (manufactured by Nippon Wax Co., Ltd., melting point 72 ° C.), 30 parts by mass of a wax dispersant (manufactured by Toyo Petrolite Co., Ceramer 1608), acetic acid 420 parts by mass of ethyl was added, heated to 78 ° C. to dissolve sufficiently, cooled to 30 ° C. over 1 hour to crystallize the wax into fine particles, and then wet-pulverized with a bead mill to obtain a wax dispersion 1 (Solid content ratio 16%).

<Preparation of Colorant Dispersion 1>
In a heat-resistant glass bottle, C.I. I. Pigment Blue 15: 3 50 parts by mass, Azisper PB-822 (manufactured by Ajinomoto Co., Inc.) 3 parts by mass, ethyl acetate 300 parts by mass, and glass beads 50 parts by mass with a diameter of 1 mm are charged for 10 hours while maintaining normal temperature. After shaking, it was separated from the glass beads with nylon mesh to obtain a pigment dispersion 1 (solid content ratio 15%).

<Preparation of Toner Composition 1>
Binder resin 1 (PES type) 20 parts by mass Binder resin 3 (PES type) 80 parts by mass Wax dispersion 1 62 parts by mass Pigment dispersion 1 37 parts by mass Ethyl acetate 89 parts by mass Triethylamine 0. 55 parts by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper (manufactured by Tokushu Kika Co., Ltd.), sufficiently dissolved, and toner composition 1 was prepared. The solid content ratio of the toner composition 1 was 69%.

<Preparation of Toner Composition 2>
Binder resin 5 (vinyl) 100 parts by mass Wax dispersion 1 62 parts by mass Pigment dispersion 1 37 parts by mass Ethyl acetate 89 parts by mass Triethylamine 0.55 parts by mass The toner composition 2 was prepared by stirring at 2000 rpm for 3 minutes using a special machine company) and sufficiently dissolving. The solid content ratio of the toner composition 2 was 69%.

<Preparation of Toner Composition 3>
-Binder resin 5 (vinyl type) 100 parts by mass-Wax dispersion 1 62 parts by mass-Pigment dispersion 1 37 parts by mass-2-acrylamido-2-methylpropanesulfonic acid 2 parts by mass-Ethyl acetate 89 parts by mass-Triethylamine 0.55 parts by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper (manufactured by Tokushu Kika Co., Ltd.), and dissolved sufficiently to prepare toner composition 3. The solid content ratio of the toner composition 3 was 69%.

<Preparation of Toner Composition 4>
Binder resin 2 (PES system) 20 parts by weight Binder resin 4 (PES system) 80 parts by weight Wax dispersion 1 62 parts by weight Pigment dispersion 1 37 parts by weight Ethyl acetate 89 parts by weight Triethylamine 0. 55 parts by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper (manufactured by Tokushu Kika Co., Ltd.) and sufficiently dissolved to prepare toner composition 4. The solid content ratio of the toner composition 4 was 69%.

<Preparation of Toner Composition 5>
-Binder resin 1 (PES system) 30 parts by mass-Binder resin 4 (PES system) 70 parts by mass-Wax dispersion 1 62 parts by mass-Pigment dispersion 1 37 parts by mass-Ethyl acetate 89 parts by mass-Triethylamine 0. 51 parts by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper (manufactured by Tokushu Kika Co., Ltd.), and sufficiently dissolved to prepare toner composition 5. The solid content ratio of the toner composition 5 was 69%.

<Preparation of Toner Composition 6>
Binder resin 1 (PES system) 30 parts by mass Binder resin 3 (PES system) 70 parts by mass Wax dispersion 1 62 parts by mass Pigment dispersion 1 37 parts by mass Ethyl acetate 89 parts by mass Triethylamine 0. 51 parts by mass The above was put into a beaker, stirred at 2000 rpm for 3 minutes with a disper (manufactured by Tokushu Kika Co., Ltd.) and sufficiently dissolved to prepare toner composition 6. The solid content ratio of the toner composition 6 was 70%.

  A toner production method using the above toner raw materials and toner evaluation will be described below.

[Example 1]
[Production of Toner 1]
<Emulsification and desolvation process>
-170 parts by mass of ion exchange water-Dispersion liquid of resin fine particles 1 (solid content ratio 15%) 37 parts by mass (preparing 5 parts by mass of resin fine particles to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 24 parts by mass-19 parts by weight of ethyl acetate Stir for 1 minute to prepare an aqueous phase. The rotation number of the TK homomixer was increased to 8000 rpm, 160 parts by mass of the toner composition 1 (solid content ratio 69%) was added, and stirring was continued for 1 minute to suspend the toner composition 1.

  A stirring blade was set in a beaker, the mixture was stirred at 100 rpm for 15 minutes, transferred to an eggplant type flask, and rotated using a rotary evaporator, and the solvent was removed at normal pressure for 10 hours to obtain a toner aqueous dispersion.

<Washing and drying process>
The toner aqueous dispersion was filtered and charged into 500 parts by mass of ion exchange water to form a reslurry. Then, the system was stirred and hydrochloric acid was added until the system reached pH 4, followed by stirring for 5 minutes. The slurry was filtered again, and the operation of adding 200 parts by mass of ion-exchanged water and stirring for 5 minutes was repeated three times to remove the triethylamine remaining in the slurry and the toner, and a filter cake of toner particles was obtained. .

The filter cake was dried at room temperature for 3 days with a vacuum dryer, and sieved with a mesh having a mesh size of 75 μm, whereby toner particles 1 were obtained. When the charge amount of the toner particles 1 was measured, they were Q _O = −24 μC / g, Q _H = −22 μC / g, Q _L = −25 μC / g, and Q _I = −20 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 3 μC / g, indicating excellent environmental stability, and Q _I / Q _O was 0.83, indicating excellent charge rising property.

<Toner preparation and evaluation>
Next, 0.40 g of hydrophobic silica having an average diameter of 20 nm and 0.60 g of monodispersed silica having an average diameter of 120 nm are mixed and stirred with 40 μg of toner particles by Miller IFM-600DG (trade name, manufactured by Iwatani Corporation). As a result, Toner 1 was obtained.

  The physical properties of Toner 1 are shown below. The Tg of toner 1 was 45 ° C. Toner 1 had a volume average particle diameter (D4) of 5.5 μm and a number average particle diameter (D1) of 4.9 μm. When the heat-resistant storage stability of Toner 1 was evaluated, the fluidity was A as before the heat-resistant storage. It is considered that a surface layer having a Tg higher than the heat-resistant storage temperature, that is, a surface layer having a Tg of 55 ° C. shields the toner base particles. Furthermore, the resin fine particles are charged at 5%, which is almost the same amount as the required amount of resin fine particles obtained by calculation. Therefore, it can be considered that most of the resin fine particles are unevenly distributed in the toner surface layer to form a capsule-type structure.

  Furthermore, the performance evaluation results of toner 1 as toner are shown below. A developer comprising toner 1 (8 parts by mass) and 92 parts by mass of a silicone carrier-coated ferrite carrier having an average particle diameter of 35 μm was prepared. Using this developer, CLC5000 (manufactured by Canon Inc.) modified so that the electrophotographic process conditions can be changed was used to evaluate the performance as a toner.

  The fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited. The gloss value was 48 at a maximum value of 160 ° C. No offset was generated and excellent offset resistance was exhibited. Durability did not occur even when 50,000 images were output, and the durability was excellent. The fine line reproducibility was A.

[Comparative Example 1]
A toner having no shell layer related to charging and heat-resistant storage stability was prepared and evaluated. Details are given below.

[Preparation of Toner 2] <Preparation of Inorganic Aqueous Dispersant>
After adding 451 parts by mass of a 0.1 mol / L Na ₃ PO ₄ aqueous solution to 709 parts by mass of ion-exchanged water and heating to 60 ° C., the mixture was stirred at 12,000 rpm with a TK homomixer (manufactured by Special Machine Industries). An inorganic aqueous dispersion medium containing Ca ₃ (PO ₄ ) ₂ was obtained by gradually adding 67.7 parts by mass of a 0.0 mol / L CaCl ₂ aqueous solution.

<Emulsification and desolvation process>
-200 parts by weight of the above inorganic aqueous dispersion-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 4 parts by weight-21 parts by weight of ethyl acetate The mixture was stirred at 5000 rpm for 1 minute to prepare an aqueous phase. The rotation number of the TK homomixer was increased to 8000 rpm, the toner composition 1 (170 parts by mass) was added, and stirring was continued for 3 minutes to suspend the toner composition 1. A stirring blade was set in a beaker, the system was heated to 50 ° C. while stirring at 200 rpm, and the solvent was removed in a draft chamber for 10 hours to obtain an aqueous toner particle dispersion.

<Washing and drying process>
The toner particle aqueous dispersion is filtered and charged into 500 parts by mass of ion exchange water to form a reslurry. Then, the system is stirred and hydrochloric acid is added until the system reaches pH 1.5 to add Ca ₃ (PO ₄ ). ₂ was dissolved and stirred for 5 minutes.

  The slurry was filtered again, and the operation of adding 200 parts by mass of ion-exchanged water and stirring for 5 minutes was repeated three times to remove triethylamine remaining in the system and obtain a filter cake of toner particles.

  The above filter cake was dried with a hot air dryer at 45 ° C. for 3 days, and sieved with a mesh opening of 75 μm to obtain toner particles 2.

When the charge amount of the toner particles 2 was measured, Q _O = −6 μC / g, Q _H = −1 μC / g, Q _L = −10 μC / g, and Q _I = −1 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 9 μC / g, indicating environmental stability with no practical problems. Q _I / Q _O was 0.17, indicating that the charge rising property was inferior.

  The reason why the toner particles 2 have a significantly inferior frictional charging property compared to the toner particles 1 is considered to be because the vinyl resin represented by the general formula (1) is not present on the surface of the toner particles 2.

  Subsequently, the same external addition treatment as in Example 1 was performed to obtain toner 2.

  The Tg of toner 2 was 45 ° C., D4 = 5.8 μm, and D1 = 5.1 μm. Toner 2 produced lumps after heat-resistant storage, and the heat-resistant storage stability was D. This result is considered to be because the toner 2 does not have a surface layer, and heat-unstable binder resin, wax, and the like are exposed on the toner surface. The fixing start temperature was 90 ° C., which showed very excellent low-temperature fixability. The gloss value showed a maximum value of 46 at 160 ° C., and the glossiness was as excellent as that of the toner 1. Offset occurred at 170 ° C. As a result of evaluating durability, dirt was generated at the time when 40,000 images were output, and the durability was excellent. The fine line reproducibility of Toner 2 was B.

[Comparative Example 2]
Another example of the preparation of a toner that does not have a capsule-type configuration, an examination of trial production by a pulverization method, and evaluation results are described below.

[Preparation of Toner 3]
Binder resin 2 (PES resin) 800 parts by mass Binder resin 4 (PES resin) 200 parts by mass I. Pigment Blue 15: 3 50 parts by mass / ester wax (melting point 65 ° C.) 50 parts by mass The above materials were mixed with a Henschel mixer and melt kneaded at 140 ° C. with a biaxial extruder. The melt-kneaded product was cooled to room temperature and roughly crushed with a hammer mill to obtain a 1 mm mesh-pass crushed product. Further, after finely pulverizing with a jet mill, a classification operation using a wind multi-segment classifier utilizing the Coanda effect was performed to obtain toner particles 3.

When the charge amount of the toner particles 3 was measured, Q _O = −11 μC / g, Q _H = −5 μC / g, Q _L = −14 μC / g, and Q _I = −5 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 9 μC / g, indicating environmental stability with no practical problems. Further, Q _I / Q _O was 0.45, indicating a charge rising property having no practical problem.

  Subsequently, an external addition process was performed in the same manner as in Example 1 to obtain Toner 3. Tg of toner 3 was 49 ° C., D4 = 6.8 μm, and D1 = 5.3 μm. Toner 3 formed lumps after heat-resistant storage, and the heat-resistant storage stability was inferior D. The result of inferior heat-resistant storage stability is considered to be because there is no surface layer as in Comparative Example 1, and a thermally unstable material is exposed. As a result of image evaluation of the toner 3 by the same method as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited. The gross value was 41 at a maximum of 170 degrees. As a result of the durability evaluation, dirt was generated when 40,000 images were output, and there was practically no problem. Fine line reproducibility was B.

[Comparative Example 3]
In order to confirm the advantage of using a polyester resin as a binder resin, a toner using only a vinyl resin as a binder resin was prepared and examined.

[Preparation of Toner 4]
In Example 1, toner composition 2 was replaced with toner composition 1 in the same manner except that a dispersion of resin fine particles 1 (42 parts by mass, ie, 6 parts by mass with respect to toner base particles) was used. Toner particles 4 were produced.

When the charge amount of the toner particles 4 was measured, Q _O = −16 μC / g, Q _H = −15 μC / g, Q _L = −18 μC / g, and Q _I = −12 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 3 μC / g, which showed environmental stability with no practical problems. Further, Q _I / Q _O was 0.75, indicating excellent charge rising property.

  Subsequently, the toner particles 4 were subjected to the same external addition treatment as in Example 1 to obtain toner 4. The toner 4 was evaluated in the same manner as in Example 1.

  The Tg of toner 4 was 46 ° C., D4 = 5.6 μm, and D1 = 4.8 μm.

  The heat resistant storage stability of Toner 4 was evaluated as C. As a result of image evaluation of the toner 4 by the same method as in Example 1, the fixing start temperature was 140 ° C., which showed low-temperature fixability with no practical problems. The gross value was 36 at 180 ° C., the maximum value. No offset occurred. In the durability evaluation, dirt was generated at the time when 5,000 images were output, and inferior durability (Evaluation D) was shown. The fine line reproducibility was A.

  The reason why the durability was inferior is considered to be that the adhesion between the binder resin and the surface layer was low.

[Comparative Example 4]
A toner in which the resin fine particles do not contain the resin (b1) was prepared and examined.

[Preparation of Toner 5]
<Emulsification and desolvation process>
・ Ion-exchanged water 170 parts by mass ・ Dispersion liquid of resin fine particles 2 (solid content ratio 15%) 42 parts by mass (preparing 6 parts by mass of resin fine particles to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 24 parts by mass-19 parts by weight of ethyl acetate Stir for 1 minute to prepare an aqueous phase. The rotation number of the TK homomixer was increased to 8000 rpm, 160 parts by mass of the toner composition 1 (solid content ratio 69%) was added, and stirring was continued for 1 minute to suspend the toner composition 1.

  A stirring blade was set in a beaker, the mixture was stirred at 100 rpm for 15 minutes, transferred to an eggplant type flask, and rotated using a rotary evaporator, and the solvent was removed at normal pressure for 10 hours to obtain a toner aqueous dispersion.

The washing and drying steps were performed in the same manner as in Example 1 to obtain toner particles 5. When the charge amount of the toner particles 5 was measured, Q _O = −19 μC / g, Q _H = −13 μC / g, Q _L = −20 μC / g, and Q _I = −13 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 7 μC / g, indicating good environmental stability, and Q _I / Q _O was 0.68, indicating a good charge rising property.

<Toner preparation and evaluation>
Next, the same external addition as in Example 1 was performed on 40 g of toner particles 5 and the same evaluation was performed.

  The physical properties of Toner 5 are shown below. The Tg of Toner 5 was 46 ° C. Toner 5 had a volume average particle diameter (D4) of 5.6 μm and a number average particle diameter (D1) of 4.9 μm. When the heat resistant storage stability of Toner 5 was evaluated, it was B.

  The results of performance evaluation as a toner will be described below. The fixing start temperature was 110 ° C., and excellent low-temperature fixability was exhibited. The gloss value was 48 at a maximum value of 160 ° C. No offset was generated and excellent offset resistance was exhibited. Durability was inferior when 5,000 images were output, indicating poor durability (Evaluation D). Fine line reproducibility was B.

  The reason why the durability was inferior is considered to be that the polyurethane compound was not used for the resin (b1) and the adhesion between the surface layer and the binder resin was low.

[Comparative Example 5]
A toner was prepared by using a vinyl resin represented by the general formula (1) for the toner base particles without using the vinyl unit represented by the general formula (1) in the surface layer, and examined.

[Preparation of Toner 6]
<Emulsification and desolvation process>
・ Ion-exchanged water 170 parts by mass ・ Dispersion liquid of resin fine particles 4 (solid content ratio 15%) 42 parts by mass (preparing 6 parts by mass of resin fine particles to 100 parts by mass of toner particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 24 parts by mass-19 parts by weight of ethyl acetate Stir for 1 minute to prepare an aqueous phase. The number of revolutions of the TK homomixer was increased to 8000 rpm, 160 parts by mass of the toner composition 3 (solid content ratio 69%) was added, and stirring was continued for 1 minute to suspend the toner composition 1.

  A stirring blade was set in a beaker, the mixture was stirred at 100 rpm for 15 minutes, transferred to an eggplant type flask, and rotated using a rotary evaporator, and the solvent was removed at normal pressure for 10 hours to obtain a toner aqueous dispersion.

The washing and drying steps were performed in the same manner as in Example 1 to obtain toner particles 5. When the charge amount of the toner particles 5 was measured, Q _O = −8 μC / g, Q _H = −2 μC / g, Q _L = −12 μC / g, and Q _I = −1 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 10 μC / g, indicating environmental stability with no practical problems, and Q _I / Q _O was 0.13, indicating poor charge rise. This resulted in inferior frictional chargeability in the configuration of the present invention even when the surface layer did not have a material having a charge control function and matched with the toner base particles.

<Toner preparation and evaluation>
Next, the same external addition as in Example 1 was performed on 40 g of toner particles 6, and the same evaluation was performed.

  The physical properties of Toner 6 are shown below. The Tg of Toner 6 was 46 ° C. Toner 6 had a volume average particle diameter (D4) of 6.1 μm and a number average particle diameter (D1) of 5.0 μm. When the heat resistant storage stability of Toner 6 was evaluated, it was A.

  The results of performance evaluation as a toner will be described below. The fixing start temperature was 110 ° C., and excellent low-temperature fixability was exhibited. The gross value was 38 at 160 ° C., which was the maximum value. No offset was generated and excellent offset resistance was exhibited. Durability was observed even when 40,000 images were output, indicating good durability. Fine line reproducibility was B.

[Comparative Example 6]
A toner was prepared using resin fine particles not containing a vinyl-based unit represented by the general formula (1) and toner base particles and examined. That is, a toner containing no vinyl unit represented by the general formula (1) was prepared and evaluated.

[Preparation of Toner 7]
Toner particles 7 were produced in the same manner as in Comparative Example 5 except that Toner Composition 1 (160 parts by mass) was used instead of Toner Composition 3 (160 parts by mass) in Comparative Example 5. When the charge amount of the toner particles 7 was measured, Q _O = −5 μC / g, Q _H = −1 μC / g, Q _L = −10 μC / g, and Q _I = 0 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 9 μC / g, indicating environmental stability with no practical problems. Q _I / Q _O was 0, indicating a result inferior in charge rising property. However, when stirring was continued for 2 minutes, the charge amount became -5 μC / g, which resulted in a charge amount that could be developed. Furthermore, after the external addition treatment for toner performance evaluation described below, the charge amount was measured by stirring in the same manner for 1 minute, and it was -23 μC / g.

  Subsequently, toner particles 7 were externally added in the same manner as in Example 1 to obtain toner 7, and the same evaluation was performed.

  The physical properties of the toner 7 are shown below. The Tg of Toner 7 was 46 ° C. Toner 7 had a volume average particle diameter (D4) of 5.7 μm and a number average particle diameter (D1) of 4.9 μm. The heat resistant storage stability of Toner 7 was evaluated and was A.

  The results of performance evaluation as a toner will be described below. The fixing start temperature was 110 ° C., and excellent low-temperature fixability was exhibited. The gross value was 38 at 160 ° C., which was the maximum value. No offset was generated and excellent offset resistance was exhibited. As for durability, dirt was generated at the time when 40,000 images were output, and good durability was exhibited. Fine line reproducibility was B.

[Example 2]
[Preparation of Toner 8]
In Example 1, instead of the dispersion 1 of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 4 (43 parts by mass, ie, 6 parts by mass with respect to the toner base particles). Toner particles 8 were produced in the same manner except that part preparation was used.

When the charge amount of the toner particles 8 was measured, Q _O = −22 μC / g, Q _H = −20 μC / g, Q _L = −24 μC / g, and Q _I = −16 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 4 μC / g, indicating excellent environmental stability. Further, Q _I / Q _O was 0.73, indicating a good charge rising property.

  Next, the toner particles 8 were subjected to the same external addition treatment as in Example 1 to obtain toner 8. The toner 8 was evaluated in the same manner as in Example 1.

  The Tg of Toner 8 was 47 ° C., D4 = 5.5 μm, and D1 = 4.8 μm.

  The heat resistant storage stability of Toner 8 was A. As a result of image evaluation of the toner 8 in the same manner as in Example 1, the fixing start temperature was 130 ° C., which showed low-temperature fixability with no practical problems. The gross value was 38 at a maximum of 170 ° C. No offset occurred. In the durability evaluation, dirt was generated at the time when 20,000 images were output, but the durability showed no problem in practical use. Fine line reproducibility was B.

  When the resin (b2) contains styrene and a vinyl unit represented by the general formula (1) and does not contain an acrylate monomer, the low-temperature fixability is slightly inferior. This is probably because the Tg of the resin fine particles has increased.

Example 3
[Preparation of Toner 9]
In Example 1, instead of the dispersion 1 of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 5 (72 parts by mass, ie, 10 parts by mass with respect to the toner base particles). Toner particles 9 were produced in the same manner except that part preparation was used.

When the charge amount of the toner particles 9 was measured, Q _O = −18 μC / g, Q _H = −15 μC / g, Q _L = −20 μC / g, and Q _I = −5 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 5 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.28, indicating a charge rising property having no practical problem.

  Next, the toner particles 9 were subjected to the same external addition treatment as in Example 1 to obtain toner 9. The toner 9 was evaluated in the same manner as in Example 1.

  The Tg of Toner 9 was 46 ° C., D4 = 5.6 μm, and D1 = 4.8 μm.

  The heat resistant storage stability of Toner 9 was rated C. As a result of image evaluation of the toner 9 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited. The gross value was 35, showing a maximum value at 170 ° C. No offset occurred. In the durability evaluation, dirt was generated at the time when 40,000 images were output, and the durability was good. Fine line reproducibility was B.

  When the resin (b2) did not contain styrene, excellent low-temperature fixability was exhibited. In addition, although the charge rising characteristics were not problematic in practice, the results were slightly inferior. This is considered that the interaction of π electrons is involved in the tribocharging property in the resin (b2).

Example 4
[Production of Toner 10]
In Example 1, instead of the dispersion 1 of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 6 (72 parts by mass, ie, 10 parts by mass with respect to the toner base particles). Toner particles 10 were prepared in the same manner except that part preparation was used.

When the charge amount of the toner particles 10 was measured, Q _O = −23 μC / g, Q _H = −20 μC / g, Q _L = −24 μC / g, and Q _I = −6 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 4 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.26, indicating a charge rising property having no practical problem.

  Subsequently, the toner particles 10 were subjected to the same external addition treatment as in Example 1 to obtain toner 10. The toner 10 was evaluated in the same manner as in Example 1.

  The Tg of Toner 10 was 46 ° C., D4 = 5.5 μm, and D1 = 4.7 μm.

  The heat-resistant storage stability of the toner 10 was C evaluation. As a result of image evaluation of the toner 10 by the same method as in Example 1, the fixing start temperature was 100 ° C., and low-temperature fixability with no practical problem was exhibited. The gross value was 35, showing a maximum value at 170 ° C. No offset occurred. In the durability evaluation, dirt was generated at the time when 40,000 images were output, and the durability was good. Fine line reproducibility was B.

  As in Example 3, when the resin (b2) did not contain styrene, the charge rise characteristic was slightly inferior although there was no practical problem.

Example 5
[Production of Toner 11]
<Emulsification and desolvation process>
・ Ion-exchanged water 170 parts by mass ・ Resin fine particle 1 dispersion (solid content ratio 15%) 11 parts by mass (preparing 1.5 parts by mass with respect to toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 24 parts by weight-Ethyl acetate 19 parts by weight Stir for 1 minute to prepare an aqueous phase. The rotation number of the TK homomixer was increased to 8000 rpm, 160 parts by mass of the toner composition 1 (solid content ratio 69%) was added, and stirring was continued for 1 minute to suspend the toner composition 1.

  A stirring blade was set in a beaker, the mixture was stirred at 100 rpm for 15 minutes, transferred to an eggplant type flask, and rotated using a rotary evaporator, and the solvent was removed at normal pressure for 10 hours to obtain a toner aqueous dispersion. The toner dispersion was heated with stirring at a temperature 2 ° C. higher than the Tg 55 ° C. of the resin fine particles 1 for 1 hour to level (smooth) the toner surface.

<Washing and drying process>
The toner aqueous dispersion was filtered and charged into 500 parts by mass of ion exchange water to form a reslurry. Then, the system was stirred and hydrochloric acid was added until the system reached pH 4, followed by stirring for 5 minutes. The slurry was filtered again, and the operation of adding 200 parts by mass of ion-exchanged water and stirring for 5 minutes was repeated three times to remove the triethylamine remaining in the slurry and the toner, and a filter cake of toner particles was obtained. .

The filter cake was dried at room temperature for 3 days with a vacuum dryer, and sieved with a mesh having a mesh size of 75 μm, whereby toner particles 1 were obtained. When the charge amount of the toner particles 11 was measured, Q _O = −7 μC / g, Q _H = −3 μC / g, Q _L = −10 μC / g, and Q _I = −5 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 7 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.71, indicating a good charge rising property.

  From the viewpoint of triboelectric charging, it is preferable that the resin (b2) is unevenly distributed in the surface layer even in a small amount. Good triboelectric chargeability can be exhibited even in a small amount.

<Toner preparation and evaluation>
Next, 0.40 g of hydrophobic silica having an average diameter of 20 nm and 0.60 g of monodispersed silica having an average diameter of 120 nm are mixed and stirred with 1400 g of toner particles by Miller IFM-600DG (trade name, manufactured by Iwatani Corporation). As a result, toner 11 was obtained.

  Subsequently, the toner particles 11 were subjected to the same external addition treatment as in Example 1 to obtain toner 11. The toner 11 was evaluated in the same manner as in Example 1.

  The toner 11 had a Tg of 45 ° C., D4 = 6.0 μm, and D1 = 5.1 μm. When the amount of resin fine particles was small, the toner particle size was slightly increased.

  The heat resistant storage stability of the toner 11 was evaluated as C, and there was no problem in practical use. The average particle size of the dispersion of the resin fine particles 1 is 36 nm, and when the toner particle size is assumed to be 6 μm of monodispersion, the required amount of resin fine particles obtained by calculation is 3%. Even when the surface layer was insufficient, the toner surface was leveled by heating the toner slurry at Tg + 2 ° C. of resin fine particles. Although not perfect, it is presumed to be a good capsule type structure.

  As a result of image evaluation of the toner 11 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and low temperature fixability with no practical problem was exhibited. The gross value was 43, which was the maximum at 160 ° C. The offset was 180 ° C. In the durability evaluation, dirt was generated at the time when 40,000 images were output, and the durability was good. Fine line reproducibility was B.

Example 6
[Production of Toner 12]
In Example 1, instead of dispersion 1 of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to toner base particles), dispersion of resin fine particles 1 (129 parts by mass, ie, 18 parts by mass with respect to toner base particles) Toner particles 12 were produced in the same manner except that the partial charge was used.

When the charge amount of the toner particles 12 was measured, Q _O = −25 μC / g, Q _H = −21 μC / g, Q _L = −25 μC / g, and Q _I = −13 μC / g. The charging ratio of the vinyl unit represented by the formula (3) in the toner is as high as 0.086%. There was no significant difference in the charge amount.

The charge amount difference Q1 + Q2 was 4 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.52, indicating good charge rising property.

  Next, the toner particles 12 were subjected to the same external addition treatment as in Example 1 to obtain toner 12. The toner 12 was evaluated in the same manner as in Example 1.

  The Tg of Toner 12 was 46 ° C., D4 = 5.3 μm, and D1 = 4.6 μm.

  The heat-resistant storage stability of the toner 12 was A. As a result of image evaluation of the toner 12 in the same manner as in Example 1, the fixing start temperature was 120 ° C. and good low-temperature fixability was exhibited. Having a large amount of a surface layer harder than the toner base particles showed a slightly disadvantageous result in terms of low-temperature fixability.

  The gross value was 34, showing a maximum value at 170 ° C. No offset occurred. In the durability evaluation, dirt was generated at the time when 40,000 images were output, and the durability was good. Fine line reproducibility was B.

Example 7
[Preparation of Toner 13]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 7 (58 parts by mass, ie, 8 parts by mass with respect to the toner base particles). The toner particles 13 were prepared in the same manner except that the toner composition 4 (160 parts by mass) was used instead of the toner composition 1 (160 parts by mass).

When the charge amount of the toner particles 13 was measured, Q _O = −9 μC / g, Q _H = −7 μC / g, Q _L = −13 μC / g, and Q _I = −2 μC / g.

The charge amount difference Q1 + Q2 was 6 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.22, indicating a charge rising property having no practical problem.

  The charge rising property was not so good because the charging ratio of the vinyl unit represented by the formula (3) in the toner is 0.024%, but the amount of the resin (b2) in the resin fine particles is small, This is probably because the dispersibility is not good.

  Subsequently, the toner particles 13 were subjected to the same external addition treatment as in Example 1 to obtain toner 13. The toner 13 was evaluated in the same manner as in Example 1.

  The Tg of toner 13 was 52 ° C., D4 = 5.7 μm, and D1 = 4.7 μm.

  The heat resistant storage stability of Toner 13 was A. As a result of image evaluation of the toner 13 in the same manner as in Example 1, the fixing start temperature was 110 ° C., and good low-temperature fixability was exhibited.

  The gloss value was 42 at a maximum value of 170 ° C. No offset occurred. In the durability evaluation, no stain was generated at the time when 50,000 images were output, and the durability was excellent. Fine line reproducibility was C.

  In the prescription with the resin (b2) content in the resin fine particles as low as 1%, there is a possibility that the toner charge amount distribution is broad.

Example 8
[Preparation of Toner 14]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 8 (57 parts by mass, ie, 8 parts by mass with respect to the toner base particles). The toner particles 14 were prepared in the same manner except that the toner composition 4 (160 parts by mass) was used instead of the toner composition 1 (160 parts by mass).

When the charge amount of the toner particles 14 was measured, they were Q _O = −11 μC / g, Q _H = −7 μC / g, Q _L = −13 μC / g, and Q _I = −7 μC / g.

The charge amount difference Q1 + Q2 was 6 μC / g, indicating good environmental stability. In addition, Q _I / Q _O was 0.64, indicating a good charge rising property.

  In Example 8, the charge rising property was improved from Example 7. This is because the charging ratio of the vinyl unit represented by the formula (3) in the toner is only slightly increased from 0.024% (Example 7) to 0.026% (Example 8). This is probably because the amount of the resin (b2) in the fine particles increased (1% → 2%) and the dispersibility improved.

  Subsequently, the toner particles 14 were subjected to the same external addition treatment as in Example 1 to obtain the toner 14. The toner 14 was evaluated in the same manner as in Example 1.

  The Tg of toner 14 was 53 ° C., D4 = 5.5 μm, and D1 = 4.6 μm.

  The heat-resistant storage stability of Toner 14 was A. As a result of image evaluation of the toner 14 by the same method as in Example 1, the fixing start temperature was 110 ° C., and good low-temperature fixability was exhibited.

  The gross value was 43, which was the maximum at 160 ° C. No offset occurred. In the durability evaluation, no stain was generated at the time when 50,000 images were output, and the durability was excellent. Fine line reproducibility was B.

Example 9
[Preparation of Toner 15]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 9 (42 parts by mass, ie, 6 parts by mass with respect to the toner base particles). The toner particles 15 were prepared in the same manner except that the toner composition 5 (160 parts by mass) was used instead of the toner composition 1 (160 parts by mass).

When the charge amount of the toner particles 15 was measured, Q _O = −19 μC / g, Q _H = −16 μC / g, Q _L = −21 μC / g, and Q _I = −13 μC / g.

The charge amount difference Q1 + Q2 was 5 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.68, indicating a good charge rising property.

  Subsequently, the toner particles 15 were subjected to the same external addition treatment as in Example 1 to obtain toner 15. The toner 15 was evaluated in the same manner as in Example 1.

  The Tg of toner 15 was 53 ° C., D4 = 5.5 μm, and D1 = 4.7 μm.

  The heat resistant storage stability of Toner 15 was evaluated as B. As a result of image evaluation of the toner 15 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited.

  The gross value was 36 at 160 ° C., the maximum value. No offset occurred. Durability evaluation showed good durability although dirt was generated when 40,000 images were output. Fine line reproducibility was B.

Example 10
[Production of Toner 16]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 10 (29 parts by mass, ie, 4 parts by mass with respect to the toner base particles). Toner particles 16 were prepared in the same manner except that the toner composition 6 (160 parts by mass) was used instead of the toner composition 1 (160 parts by mass).

When the charge amount of the toner particles 16 was measured, Q _O = −27 μC / g, Q _H = −25 μC / g, Q _L = −29 μC / g, and Q _I = −16 μC / g.

The charge amount difference Q1 + Q2 was 4 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.69, indicating a good charge rising property.

  Next, the toner particles 16 were subjected to the same external addition process as in Example 1 to obtain the toner 16. The toner 16 was evaluated in the same manner as in Example 1.

  The Tg of toner 16 was 53 ° C., D4 = 5.6 μm, and D1 = 4.7 μm.

  The heat resistant storage stability of Toner 16 was C evaluation. As a result of image evaluation of the toner 16 by the same method as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited.

  The gross value was 36 at 160 ° C., the maximum value. No offset occurred. In the durability evaluation, dirt was generated at the time when 40,000 images were output, and the durability was good. Fine line reproducibility was C.

  The charging rate of the vinyl unit represented by the formula (3) of toner 16 was 0.080%, and the developability was slightly lowered.

Example 11
[Preparation of Toner 17]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 11 (42 parts by mass, ie, 6 parts by mass with respect to the toner base particles). Toner particles 17 were produced in the same manner except that the partial charge was used.

When the charge amount of the toner particles 17 was measured, Q _O = −35 μC / g, Q _H = −33 μC / g, Q _L = −35 μC / g, and Q _I = −29 μC / g.

The charge amount difference Q1 + Q2 was 2 μC / g, indicating excellent environmental stability. Further, Q _I / Q _O was 0.83, indicating an excellent charge rising property.

  Subsequently, the toner particles 17 were subjected to the same external addition process as in Example 1 to obtain toners 17. The toner 17 was evaluated in the same manner as in Example 1.

  The Tg of toner 17 was 48 ° C., D4 = 5.9 μm, and D1 = 4.8 μm.

  The heat resistant storage stability of Toner 17 was evaluated as A. As a result of image evaluation of the toner 17 in the same manner as in Example 1, the fixing start temperature was 110 ° C., and excellent low-temperature fixability was exhibited.

  The gloss value was 45 at a maximum of 160 ° C. No offset occurred. In the durability evaluation, dirt was generated when 40,000 images were output, and the durability was excellent. The fine line reproducibility was A.

Example 12
[Preparation of Toner 18]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 12 (42 parts by mass, ie, 6 parts by mass with respect to the toner base particles). The toner particles 18 were prepared in the same manner except that the toner composition 4 (160 parts by mass) was used instead of the toner composition 1 (160 parts by mass).

When the charge amount of the toner particles 18 was measured, Q _O = −39 μC / g, Q _H = −38 μC / g, Q _L = −40 μC / g, and Q _I = −23 μC / g.

The charge amount difference Q1 + Q2 was 2 μC / g, indicating excellent environmental stability. Further, Q _I / Q _O was 0.59, indicating a good charge rising property.

  Next, the toner particles 18 were subjected to the same external addition process as in Example 1 to obtain the toner 18. The toner 18 was evaluated in the same manner as in Example 1.

  The Tg of toner 18 was 53 ° C., D4 = 5.8 μm, and D1 = 4.5 μm.

  The heat resistant storage stability of Toner 18 was A. As a result of image evaluation of the toner 18 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited.

  The gross value was 41 which was the maximum value at 160 ° C. No offset occurred. Durability evaluation showed excellent durability with no stain on the 50,000th sheet. The fine line reproducibility was A.

Example 13
[Preparation of Toner 19]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 13 (51 parts by mass, ie, 7 parts by mass with respect to the toner base particles). The toner particles 19 were prepared in the same manner except that the toner composition 5 (160 parts by mass) was used instead of the toner composition 1 (160 parts by mass).

When the charge amount of the toner particles 19 was measured, Q _O = −29 μC / g, Q _H = −27 μC / g, Q _L = −30 μC / g, and Q _I = −24 μC / g.

The charge amount difference Q1 + Q2 was 3 μC / g, indicating excellent environmental stability. Further, Q _I / Q _O was 0.83, indicating an excellent charge rising property.

  Next, the toner particles 19 were subjected to the same external addition treatment as in Example 1 to obtain toner 19. The toner 19 was evaluated in the same manner as in Example 1.

  The Tg of toner 19 was 47 ° C., D4 = 5.7 μm, and D1 = 4.5 μm.

  The heat resistant storage stability of Toner 19 was B. As a result of image evaluation of the toner 19 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited.

  The gross value was 40, which was the maximum value at 150 ° C. No offset occurred. Durability evaluation showed excellent durability with no stain on the 50,000th sheet. The fine line reproducibility was A.

Example 14
[Preparation of Toner 20]
In Example 1, instead of the dispersion of resin fine particles 1 (37 parts by mass, charging 5 parts by mass with respect to the toner base particles), the dispersion of resin fine particles 14 (51 parts by mass, ie, 7 parts by mass with respect to the toner base particles). The toner particles 20 were prepared in the same manner except that the toner composition 6 (160 parts by mass) was used instead of the toner composition 1 (160 parts by mass).

When the charge amount of the toner particles 20 was measured, Q _O = −13 μC / g, Q _H = −12 μC / g, Q _L = −16 μC / g, and Q _I = −3 μC / g.

The charge amount difference Q1 + Q2 was 4 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.23, indicating a charge rising property having no practical problem.

  Subsequently, the toner particles 20 were subjected to the same external addition treatment as in Example 1 to obtain toner 20. The toner 20 was evaluated in the same manner as in Example 1.

  The Tg of toner 20 was 54 ° C., D4 = 5.5 μm, and D1 = 4.3 μm.

  The heat resistant storage stability of Toner 20 was A. As a result of image evaluation of the toner 20 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited.

  The gross value was 36 at a maximum of 170 ° C. No offset occurred. Durability evaluation showed excellent durability with no stain on the 50,000th sheet. Fine line reproducibility was B.

Example 15
[Preparation of Toner 21]
-Number average molecular weight obtained from a mixture of 1,2-propanediol, ethylene glycol, and 1,4-butanediol of 50 mol%, 40 mol%, and 10 mol%, and an equimolar mixture of terephthalic acid and isophthalic acid, respectively. 2000 polyester resin (acid value 2 mgKOH / g, hydroxyl value 19 mgKOH / g) 95 parts by mass, 1,4-butanediol 20 parts by mass (0.22 mol)
・ 85 parts by mass (0.63 mol) of dimethylolpropanoic acid
3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
5 parts by mass (0.02 mol)
The above materials are dissolved in 500 parts by mass of acetone, and then 250 parts by mass of isophorone diisocyanate (1.12 mol)
And reacted at 60 ° C. for 4 hours. In order to neutralize the carboxyl group of dimethylolpropanoic acid, 64 parts by mass (0.63 mol) of triethylamine was added to the reaction product and stirred. Further, 3 parts by mass of an acetone solution of resin (b2) -1 (solid content ratio: 76%) was added and stirred. An acetone solution (solid content ratio 51%) containing a polyester resin having both ends of an isocyanate group and resin (b2) -1 was obtained.

<Emulsification and desolvation process>
Ion-exchanged water 170 parts by weight Resin fine particle 1 dispersion 38 parts by weight (5 parts by weight charged to toner base particles)
50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 24 parts by weight ethyl acetate 19 parts by weight 10% ammonia water 30 parts by weight 1,4-butanediamine 17 parts by weight The mixture was stirred for 1 minute at 2000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase.

  Next, the number of revolutions of the TK homomixer was increased to 8000 rpm, 160 parts by mass of the toner composition 1 was added, and stirring was continued for 1 minute to suspend the toner composition 1. Next, a stirring blade was set in a separable flask with a lid and stirred at 100 rpm, and a shell layer was formed on the toner surface by reaction of isocyanate and amine over 50 ° C. for 8 hours. After the reaction, the mixture was cooled to room temperature to obtain a toner dispersion.

<Washing and drying process>
Next, the above toner dispersion was filtered, put into 500 parts by mass of ion exchange water to form a reslurry, and the system was stirred until hydrochloric acid was added to pH 4 and stirred for 5 minutes. The above slurry was filtered again, and 200 parts by mass of ion exchange water was added and the operation of stirring for 5 minutes was repeated three times to remove ammonia, 1,4-butanediamine, and triethylamine remaining in the slurry and toner. A toner particle filter cake was obtained.

Subsequently, the above filter cake was dried at room temperature for 3 days with a vacuum dryer, and sieved with a mesh having a mesh size of 75 μm, whereby toner particles 21 were obtained. When the charge amount of the toner particles 21 was measured, Q _O = −18 μC / g, Q _H = −16 μC / g, Q _L = −21 μC / g, and Q _I = −15 μC / g.

The charge amount difference Q1 + Q2 was 5 μC / g, indicating good environmental stability. Further, Q _I / Q _O was 0.83, indicating a charge rising property having no practical problem.

  Next, the toner particles 21 were subjected to the same external addition process as in Example 1 to obtain toner 21. The toner 21 was evaluated in the same manner as in Example 1.

  The Tg of toner 21 was 54 ° C., D4 = 5.5 μm, and D1 = 4.3 μm.

  The heat resistant storage stability of Toner 21 was A. As a result of image evaluation of the toner 20 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited.

  The gross value was 33, showing the maximum value at 170 ° C. No offset occurred. In the durability evaluation, dirt was generated when 20,000 images were output, but the durability showed no problem in practical use. Fine line reproducibility was B.

  Compared with the case where resin fine particles were used as a shelling agent and a dispersant stabilizer as in Example 1, the surface layer was formed by interfacial polymerization, resulting in poor durability.

Example 16
[Production of Toner 22]
<Emulsification and desolvation process>
・ Ion-exchanged water 170 parts by mass ・ Dispersion liquid of resin fine particles 1 (solid content ratio 15%) 42 parts by mass (preparing 6 parts by mass of resin fine particles to 100 parts by mass of toner base particles)
-Dispersion liquid of resin fine particles 15 (solid content ratio 15%) 5 parts by mass (preparing 0.5 parts by mass of resin fine particles to 100 parts by mass of toner base particles)
-50% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 24 parts by mass-19 parts by weight of ethyl acetate Stir for 1 minute to prepare an aqueous phase. The rotation number of the TK homomixer was increased to 8000 rpm, 160 parts by mass of the toner composition 1 (solid content ratio 69%) was added, and stirring was continued for 1 minute to suspend the toner composition 1.

  A stirring blade was set in a beaker, the mixture was stirred at 100 rpm for 15 minutes, transferred to an eggplant type flask, and rotated using a rotary evaporator, and the solvent was removed at normal pressure for 10 hours to obtain a toner aqueous dispersion.

The washing and drying steps were performed in the same manner as in Example 1 to obtain toner particles 22. When the charge amount of the toner particles 22 was measured, Q _O = −21 μC / g, Q _H = −18 μC / g, Q _L = −25 μC / g, and Q _I = −14 μC / g.

Therefore, the charge amount difference Q1 + Q2 was 7 μC / g, indicating a good environmental stability, and Q _I / Q _O was 0.67, indicating a good charge rising property.

  Subsequently, the toner particles 22 were subjected to the same external addition process as in Example 1 to obtain the toner 22. The toner 22 was evaluated in the same manner as in Example 1.

  The Tg of toner 22 was 47 ° C., D4 = 5.6 μm, and D1 = 4.3 μm.

  The heat resistant storage stability of the toner 22 was evaluated as A. As a result of image evaluation of the toner 222 in the same manner as in Example 1, the fixing start temperature was 100 ° C., and excellent low-temperature fixability was exhibited.

  The gross value was 33, which was the maximum value at 160 ° C. No offset occurred. In the durability evaluation, dirt was generated at the time when 20,000 images were output, but the durability showed no problem in practical use. The developer at the time of the occurrence of the stain was removed, and the toner was observed with an SEM. This detached resin fine particle seems to have deteriorated developability. Fine line reproducibility was B.

It is a figure of the calculation method of Tg in this invention. It is the schematic of the charge amount measuring apparatus in this invention.

Explanation of symbols

1 Suction machine (at least the part in contact with the measurement container 2 is an insulator)
2 Metal measuring container 3 500 mesh screen 4 Metal lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (9)

Capsule type toner particles having a surface layer (B) containing resin (b1) and resin (b2) on the surface of toner base particles (A) containing at least binder resin (a), colorant and wax A toner having
The binder resin (a) is a resin mainly composed of polyester, the resin (b1) is a reaction product of at least a diol component and a diisocyanate component, and the resin (b2) is represented by the general formula (1). A toner comprising: a vinyl unit represented by:

  2. The toner according to claim 1, wherein the resin (b2) is a ternary copolymer containing at least styrene, (meth) acrylic acid ester, and the vinyl-based unit. The toner according to claim 1 or 2 wherein the resin (b1) is characterized by a polyester-containing urethane resin. The toner according to any one of claims 1 to 3 vinyl unit represented by the general formula (1) is characterized in that it is a formula (2-1).

The toner according to any one of claims 1 to 3 , wherein the vinyl unit represented by the general formula (1) is represented by the formula (2-2).

The toner according to any one of claims 1 to 3 , wherein the vinyl unit represented by the general formula (1) is represented by the formula (2-3).

The toner according to any one of claims 1 to 3 vinyl unit represented by the general formula (1) is characterized in that it is a formula (6-2).

Capsule type toner particles having a surface layer (B) containing resin (b1) and resin (b2) on the surface of toner base particles (A) containing at least binder resin (a), colorant and wax A method for producing a toner comprising:
The binder resin (a) is a resin mainly composed of polyester, the resin (b1) is a reaction product of at least a diol component and a diisocyanate component, and the resin (b2) is represented by the general formula (1). Containing the vinyl-based unit represented,

Obtained by dissolving or dispersing the binder resin (a), colorant and wax in an organic medium in an aqueous medium in which resin fine particles containing the resin (b1) and the resin (b2) are dispersed. A method for producing a toner, comprising: dispersing a solution or a dispersion; removing the solvent from the obtained dispersion; and drying to obtain toner particles. Capsule type toner particles having a surface layer (B) containing resin (b1) and resin (b2) on the surface of toner base particles (A) containing at least binder resin (a), colorant and wax A method for producing a toner comprising:
The binder resin (a) is a resin mainly composed of polyester, the resin (b1) is a reaction product of at least a diol component and a diisocyanate component, and the resin (b2) is represented by the general formula (1). Containing the vinyl-based unit represented,

The binder resin (a), the colorant and the wax are dissolved in an organic medium in an aqueous medium in which both the resin fine particles containing the resin (b1) and the resin fine particles containing the resin (b2) are dispersed. Alternatively, a toner production method comprising dispersing a solution or dispersion obtained by dispersing, removing the solvent from the obtained dispersion and drying to obtain toner particles.

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