JP2015219289A - Manufacturing method of toner particles and manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing toner particles each having a more particle and an outer shell, and have suppressed drop-out of the outer shell from the core particle while protrusion parts derived from resin fine particles on the outer shell are reduced.SOLUTION: A method of manufacturing toner particles includes a step of processing the surface of polymer particles A to be core particles to obtain a dispersion B containing polymer particles B having the surface free energy smaller than the surface free energy of the polymer particles A. When the value of the surface free energy of the polymer particles A is EA, the value of the surface free energy of the polymer particles B is EB, the value of the surface free energy of the resin fine particles C to be the outer shells is EC, and the value of the surface free energy of water is EW, EW>EA>EC, EA>EB, and EW>EC>EB are satisfied.

Description

  The present invention relates to a toner particle manufacturing method and a toner manufacturing method for developing an electrostatic image used in an image forming method such as an electrophotographic method and an electrostatic printing method.

  In recent years, high speed and low power consumption are required for printers and copiers. In order to satisfy the demand, there is a demand for a toner that can be fixed at a low temperature and has high durability. In order to realize a toner that can be fixed at a low temperature, it is necessary to soften the toner at a low temperature. However, a toner that is softened at a low temperature is likely to be deteriorated in heat-resistant storage stability and durability. Therefore, a toner having toner particles having a capsule structure (core-shell structure) composed of core particles excellent in low-temperature fixability and an outer shell formed by coating the surface of the core particles with resin fine particles has been proposed. Yes.

  However, in the case of toner having toner particles having a capsule structure, if the adhesion between the core particles and the outer shell is weak, the toner becomes less durable due to peeling of the outer shell. Therefore, efforts have been made to increase the adhesion between the core particles and the outer shell.

  Patent Document 1 discloses a method in which resin fine particles are added during the formation of core particles, and the resin fine particles are adhered to the surface of the core particles. In this method, the resin particles are slightly dissolved in the polymerizable monomer present in the core particles being formed, thereby improving the adhesion between the core particles and the resin particles, and the adhesion between the core particles and the outer shell. Is increasing.

  Further, Patent Document 2 discloses that amorphous polyester plasticized with crystalline polyester is segregated on the surface of the core particle, and only the surface of the core particle is softened, thereby improving the adhesion between the core particle and the resin fine particle. A method for improving the adhesion between the core particles and the outer shell is disclosed.

  Patent Document 3 discloses a technique for reducing the number of raised portions derived from resin fine particles in the outer shell by applying heat above the glass transition point of the core particles.

JP 2011-17864 A JP 2012-2833 A JP 2000-112174 A

  However, in the methods disclosed in Patent Documents 1 and 2, many protruding portions derived from resin fine particles tend to remain in the outer shell, and when the speed of the printer or copying machine is increased, a heavy load is applied to the protruding portion and the outer shell is the core. It was found that it was easy to fall off from the particles.

  Further, in the method disclosed in Patent Document 3, although the protruding portion of the outer shell is reduced, heat is applied to the core particles for a long time, so the compatibility between the core particles and the resin fine particles proceeds, and good heat resistance is achieved. It was difficult to obtain a toner having storage stability.

  An object of the present invention is to produce toner particles and toner having toner particles having a core particle and an outer shell, in which the protruding portion derived from the resin fine particles in the outer shell is reduced and the outer shell is prevented from falling off from the core particle. It is to provide a method.

The present invention
(I) adding a polymerizable monomer composition containing a polymerizable monomer and a colorant to an aqueous medium to form particles of the polymerizable monomer composition in the aqueous medium;
(Ii) polymerizing the polymerizable monomer contained in the particles to obtain a dispersion A containing polymer particles A;
(Iii) treating the surface of the polymer particles A contained in the dispersion A to obtain a dispersion B containing polymer particles B whose surface free energy is smaller than the surface free energy of the polymer particles A Obtaining a step;
(Iv) adding resin fine particles C to the dispersion B, and applying the resin fine particles C to the surface of the polymer particles B to obtain the dispersion C;
(V) heating the dispersion C to a glass transition temperature (Tg) or higher of the resin fine particles C to obtain toner particles in this order,
The surface free energy value of the polymer particles A is EA, the surface free energy value of the polymer particles B is EB, the surface free energy value of the resin fine particles C is EC, and the surface free energy of water is When the value is EW, the following formulas (1) to (3):
EW>EA> EC (1)
EA> EB (2)
EW>EC> EB (3)
The toner particle manufacturing method is characterized by satisfying the above relationship.

The present invention also provides a toner manufacturing method for manufacturing toner having toner particles and inorganic fine particles externally added to the toner particles,
A step of producing the toner particles by the method for producing toner particles of the invention;
And a step of externally adding the inorganic fine particles to the toner particles in this order.

  According to the present invention, toner particles and toner having core particles and an outer shell are manufactured in which the protruding portion derived from the resin fine particles in the outer shell is reduced and the outer shell is prevented from dropping from the core particles. be able to.

  Various methods for producing toner particles having a core particle and an outer shell, that is, toner particles having a capsule structure are known. Among them, a method of forming a capsule structure by using polymer particles as core particles in an aqueous medium and coating the surface of the core particles with resin fine particles is particularly excellent because a uniform outer shell can be formed.

  As a result of intensive studies by the present inventors, in the method for forming the capsule structure, the surface free energy of the surface of the core particle and the surface of the resin fine particle satisfies a specific relationship, so that there are few raised portions and high smoothness. It was found that an outer shell can be formed. The relationship is a relationship that satisfies the following two points.

  The first point is that the surface free energy of the resin fine particles is closer to the surface free energy of water than the surface free energy of the polymer particles. The second point is that both the surface free energy of the polymer particles and the resin fine particles are lower than the surface free energy of water. That is, it was found that the case where the surface free energy satisfies the relationship of water> resin fine particles> polymer particles is important for the formation of a highly smooth outer shell. When this relationship is satisfied, there is no need for excessive heating, so that a highly smooth outer shell can be formed while maintaining phase separation (hardness of compatibility between core particles and resin fine particles).

  The inventor considers this mechanism as follows.

  In the method of coating the surface of polymer particles with resin fine particles in an aqueous medium, the resin fine particles adhere to the surface of the polymer particles while maintaining the particle state, and then smoothing proceeds by heat. Here, it can be said that the state in which the fine resin particles are attached to the surface of the polymer particles is that the polymer particles and the fine resin particles each form an interface with water and the interfacial energy of the entire system is high. In particular, since many resin fine particles have a smaller particle size than the polymer particles, it can be said that the entire system is in a high energy state because of a large surface area. For this reason, in the subsequent smoothing step, it is considered that the resin fine particles are fused with each other to reduce the surface area, thereby reducing the energy. Here, it is considered that whether the resin fine particles alone form an agglomerate or covers the surface of the polymer particles depends on which energy of the entire system is lower. Therefore, in the aqueous dispersion, the system changes so as to generate a resin surface having a small surface free energy difference from water. That is, it is important that the surface free energy of the resin fine particles is closer to the surface free energy of water than the surface free energy of the polymer particles. Further, when the resin fine particles have a surface free energy higher than that of water, the surface free energy is lowered, so that water is easily adsorbed on the surface of the toner particles, and there is a concern about the influence on the chargeability. In addition, when the polymer particles have a surface free energy higher than that of water, problems are likely to occur on the production side of the polymer particles. Therefore, it is important that the surface free energy of both the polymer particles and the resin fine particles is lower than the surface free energy of water.

  However, when polymer particles are formed, a material satisfying this surface free energy relationship is not necessarily capable of forming toner particles having a desired particle diameter and having sufficient performance.

  Therefore, as a result of earnestly studying a method for satisfying smoothness by using a material with good manufacturability in particle formation, the surface of the polymer particle A is reduced to a low surface free energy and controlled to a specified energy range. The problem can be solved.

That is,
(I) adding a polymerizable monomer composition containing a polymerizable monomer and a colorant to an aqueous medium to form particles of the polymerizable monomer composition in the aqueous medium;
(Ii) polymerizing the polymerizable monomer contained in the particles to obtain a dispersion A containing polymer particles A;
(Iii) treating the surface of the polymer particles A contained in the dispersion A to obtain a dispersion B containing polymer particles B whose surface free energy is smaller than the surface free energy of the polymer particles A Obtaining a step;
(Iv) adding resin fine particles C to the dispersion B, and applying the resin fine particles C to the surface of the polymer particles B to obtain the dispersion C;
(V) heating the dispersion C to a glass transition temperature (Tg) or higher of the resin fine particles C to obtain toner particles in this order,
The surface free energy value of the polymer particles A is EA, the surface free energy value of the polymer particles B is EB, the surface free energy value of the resin fine particles C is EC, and the surface free energy of water is When the value is EW, the following formulas (1) to (3):
EW>EA> EC (1)
EA> EB (2)
EW>EC> EB (3)
It is achieved by a toner particle production method characterized by satisfying the following relationship.

  Hereinafter, (i)-(v) is demonstrated in order about this manufacturing method.

  In the step (i), a polymerizable monomer composition containing a polymerizable monomer and a colorant is added to an aqueous medium to form particles of the polymerizable monomer composition in the aqueous medium. To do. More specifically, first, a polymerizable monomer in which a colorant is added to a polymerizable monomer that is a main constituent material (binder resin) of toner particles, and these are uniformly dissolved or dispersed using a disperser. A body composition is prepared. Examples of the disperser include a homogenizer, a ball mill, a colloid mill, and an ultrasonic disperser. In the polymerizable monomer composition, additives such as a polyfunctional monomer, a chain transfer agent, a wax as a release agent, a charge control agent, a plasticizer, and a dispersing agent are added as necessary. be able to.

  Next, the polymerizable monomer composition is put into an aqueous medium containing a dispersion stabilizer prepared in advance, suspended using a disperser, and granulated (formation of particles). Examples of the disperser include a high-speed stirrer and an ultrasonic disperser.

  The polymerization initiator may be mixed together with other additives when preparing the polymerizable monomer composition, and the polymerization initiator is polymerizable immediately before the polymerizable monomer composition is added (suspended) in the aqueous medium. You may mix in a monomer composition. Moreover, it can also be added in the state melt | dissolved in the polymerizable monomer or other solvent as needed during granulation or after granulation completion, ie, just before starting a polymerization reaction.

  In this way, particles of the polymerizable monomer composition are formed in the aqueous medium.

  Next, in the step (ii), the suspension after the step (i) is heated to a temperature of 50 ° C. or higher and 90 ° C. or lower, and the particles of the polymerizable monomer composition in the suspension become particles. The polymerization reaction is carried out with stirring so as to maintain the state and prevent the particles from floating or settling.

  The said polymerization initiator decomposes | disassembles by heating and produces | generates a free radical (radical). The generated radical is added to the unsaturated bond of the polymerizable monomer to newly generate an adduct radical. The generated adduct radical is further added to the unsaturated bond of the polymerizable monomer. By repeating such an addition reaction in a chain manner, the polymerization reaction proceeds, and polymer particles A having a polymer of the polymerizable monomer as a main constituent material (binder resin) are formed. A dispersion A is obtained. If necessary, this may be followed by a distillation step to remove the remaining polymerizable monomer.

  Next, in the step (iii), the surface of the polymer particle A contained in the dispersion A is treated so that the surface free energy is smaller than the surface free energy of the polymer particle A. A dispersion B containing The surface treatment may be before the distillation step for removing the polymerizable monomer or after the distillation step. Any method may be used as long as the surface treatment can be performed so as to satisfy the above formulas (1) to (3), but a preferable method is as follows.

  In this method, the dispersion B containing the polymer particles B is obtained by applying a material having a surface free energy smaller than EC to the surface of the polymer particles A.

  More preferable surface treatment methods include the following three methods.

  The first method is to apply an organosilicon polymer which is a low surface free energy material. The alkoxysilane is added to the dispersion A, and then the dispersion A is heated and the organosilicon polymer derived from the alkoxysilane is applied to the surface of the polymer particle A, whereby the polymer particle B is obtained. This is a method for obtaining the above-mentioned dispersion B. The alkoxysilane is preferably a compound represented by the following formula (Z).

(In Formula (Z), R ¹ represents a methyl group, a vinyl group, an amino group, an epoxy group, a methacryloyl group, or a mercapto group. R ² , R ^3, and R ⁴ are each independently a halogen atom. Represents a hydroxy group or an alkoxy group, provided that one or more of R ² , R ³ and R ⁴ are alkoxy groups.)
When alkoxysilane is added to Dispersion B, R ² , R ³ and R ⁴ (hereinafter also referred to as “reactive group”) are hydrolyzed to produce silanol and alcohol. Thereafter, silanols are gradually condensed to form a siloxane bond, and an organosilicon polymer is produced. At this time, since the hydroxy group on the surface of the polymer particle A is condensed and a covalent bond is formed, an organosilicon polymer is provided on the surface of the polymer A, and the polymer particle B and a dispersion containing the same B can be obtained. In general, an organosilicon polymer is a material having a low surface free energy, but the value of the surface free energy differs depending on the progress of hydrolysis and condensation reaction. This reaction can be controlled by the reaction temperature, reaction time, pH, etc., and it is preferable to determine the conditions by confirming the surface free energy of the polymer particles B. The surface free energy can be measured by a method described later.

  The amount of alkoxysilane to be added is preferably 1.0 part by mass to 15.0 parts by mass with respect to 100 parts by mass of the polymer A. If it is 1.0 mass part, surface free energy can fully be reduced, and if it is 15.0 mass parts or less, alkoxysilane will become difficult to inhibit adhesion of the resin fine particle C.

Alkoxysilane is moderately hydrolyzable, and from the viewpoint of the coverage with respect to the surface of the polymer particle A, R ² , R ³ and R ⁴ in the above formula (Z) are preferably a methoxy group or an ethoxy group.

Below, the preferable specific example of the alkoxysilane shown by the said formula (Z) is shown. In the following specific examples, R ¹ in the above formula (Z) is a methyl group, but those in which R ¹ is a vinyl group, an amino group, an epoxy group, a methacryloyl group, or a mercapto group are also preferable.
Methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyl Triacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxy Hydroxysilane, methylethoxymethoxyhydroxysila , Methyl diethoxy hydroxy silane.
One type of alkoxysilane may be used, or two or more types may be used.

Moreover, as what may be used together with the alkoxysilane shown by the said Formula (Z), the following are mentioned, for example.
Dimethyldiethoxysilane, tetraethoxysilane, hexamethyldisilazane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-amino Propyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3-phenylaminopropyltrimethoxysilane 3-anilinopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, hexamethyldisilane, tetraisocyanatesilane, methyltriisocyanatesilane, vinyltriisocyanatesilane.

  The second method is to add the polymer particles B by adding resin fine particles B having a surface free energy smaller than EC to the dispersion A and applying the resin fine particles B to the surface of the polymer particles A. This is a method for obtaining the dispersion B.

  The resin constituting the resin fine particles B preferably has a surface free energy lower than EC and can be used as a binder resin for toner particles. Specific examples include vinyl resins, polyester resins, epoxy resins, and urethane resins. Considering the adhesion with the core particles, vinyl resins and polyester resins are more preferable.

  When the resin fine particles B are added to the dispersion A, they are electrostatically attached to the surface of the polymer particles A. Then, it can give to the surface of the polymer particle A by heating at the temperature more than the glass transition point of the polymer particle A. At this time, it is more preferable to apply by heating at a temperature equal to or higher than the glass transition point of the resin fine particles B. When the resin fine particles B are added, it is preferable to add them in a state of being dispersed in an aqueous medium from the viewpoint of adhesion uniformity. The concentration of the resin fine particles in the aqueous dispersion is preferably 10.0% by mass or more and 30.0% by mass or less.

  The resin fine particles B enter the gaps of the dispersing agent present on the surface of the polymer particles A and adhere to the surface of the polymer particles A. Therefore, it is preferable that the resin fine particle B has a particle size that can enter the gap, and the volume-based median diameter (D50) is preferably 10 nm or more and 100 nm or less. A method for measuring the volume-based median diameter (D50) of the resin fine particles will be described later.

  Moreover, in order to give the effect of a reduction | decrease in surface free energy, it is preferable that the usage-amount of the resin fine particle B is 0.3 mass part-2.5 mass parts with respect to 100 mass parts of polymer particles A.

  The manufacturing method of the resin fine particle B can be manufactured by the same manufacturing method as the resin fine particle C described later.

  The third method is a method for obtaining the dispersion B containing the polymer particles B by applying a water-soluble resin having a surface free energy smaller than EC to the surface of the polymer particles A.

  Examples of water-soluble resins include water-soluble polyester resins, water-soluble acrylic resins, water-soluble epoxy resins, water-soluble melamine resins, water-soluble rosin-modified resins, polyvinyl alcohol, polyvinyl pyrrolidone, polyethyleneimine, carboxymethyl cellulose, sodium alginate, and collagen. , Gelatin, starch, chitosan and the like. Among these, it is preferable to select and use them according to the surface free energy EC. Among these, those that are neutralized and solubilized by neutralization are preferable.

  The water-soluble resin is added to the dispersion A after the above step (ii). When adding a water-soluble resin, it is preferable to add at a pH at which the water-soluble resin is soluble. Thereafter, when the pH is adjusted to a value at which the water-soluble resin is precipitated, the water-soluble resin is precipitated and attached to the surface of the polymer particle A, and the polymer particle A contains polymer particles provided with the water-soluble resin. Dispersion B can be obtained. Since the soluble pH varies depending on the water-soluble resin, it is preferably adjusted as appropriate. However, in the present invention, a resin that is soluble at pH 8.0 or more is preferably used.

  The amount of the water-soluble resin used is 0.1 parts by mass or more and 2.0 parts by mass with respect to 100 parts by mass of the polymer particles A, considering the effect of reducing the surface free energy and the adhesion of the resin fine particles C in the subsequent process. The following is preferable.

  In the step (iv), the resin fine particles C are added to the dispersion B, and the resin fine particles C are applied to the surface of the polymer particles B to obtain the dispersion C.

  The polymer particles B obtained in the step (iii) are in a state where the dispersion stabilizer is adsorbed on the surface. While the dispersion B is being stirred, the resin fine particles C are added in a state where the resin fine particles C having the same polarity with respect to the dispersion stabilizer as the polymer particles B are dispersed in an aqueous medium. In this manner, the resin fine particles C can be densely and uniformly attached to the polymer particles B in which the dispersion stabilizer is adsorbed on the surface.

  It is preferable to slowly add the aqueous dispersion of the resin fine particles in order to suppress the single aggregation of the resin fine particles and allow the resin fine particles to adhere more uniformly. A suitable addition rate is 0.1 parts by mass or more and 5.0 parts by mass or less (as the solid content of the resin fine particles C) with respect to 100 parts by mass of the solid content of the dispersion of the core particles.

  The temperature at which the resin fine particles C are added to the dispersion B is preferably a temperature at which single aggregation of the resin fine particles C hardly occurs.

  In the present invention, the average particle diameter of the resin fine particles C is a median diameter value determined by particle size distribution measurement by a laser scattering method, and is preferably in the range of 10 nm to 200 nm. More preferably, it is the range of 30 nm or more and 130 nm or less.

  If the average particle diameter is 10 nm or more, sufficient heat resistance is easily obtained. Further, when the average particle size is 200 nm or less, non-uniform fixation is unlikely to occur.

  The ratio (D50 / D10) between the volume-based median diameter (D50) of the resin fine particles and the particle diameter (D10) at which the cumulative number of particles in the volume distribution is 10% is 1.0 to 3.0. Is preferred. Furthermore, the ratio (D90 / D50) between the volume-based median diameter (D50) of the resin fine particles and the particle diameter (D90) at which the cumulative number of particles in the volume distribution is 90% is 1.0 or more and 3.0 or less. Preferably there is. Being within these ranges means that the particle size distribution of the resin fine particles is uniform, and as a result, there is little variation between the toner particles of the outer shell formed, and stable performance as a toner can be obtained.

  The addition amount of the resin fine particles C is preferably an amount capable of uniformly covering the surface of the polymer particles B. The amount that can be uniformly coated changes when the particle size of the polymer particle B and the resin fine particle C changes, and the spreading method at the time of smoothing varies depending on the type of resin and the like. The optimum amount is preferably adjusted as appropriate while observing the coating state with an SEM or the like.

  Thereafter, in the step (v), the dispersion C is heated to a temperature equal to or higher than the glass transition temperature (Tg) of the resin fine particles C to obtain toner particles.

  When the dispersion C is heat-treated at a temperature equal to or higher than the glass transition temperature (Tg) of the resin fine particles C, the resin fine particles C enter between the polymer particles B and the dispersion stabilizer and come into contact with the surface of the polymer particles B. If the heating is continued as it is, smoothing proceeds, and the adhesion between the polymer particles B and the resin fine particles C and the adhesion between the adjacent resin fine particles are increased and fixed. By sufficiently increasing the smoothness and adhesion, good durability of the toner can be realized. In order to suppress the aggregation of the polymer particles B and the resin fine particles C and further increase the production stability, a dispersion stabilizer may be additionally added. A small amount of a surfactant can also be added.

  After the step (v), the dispersion stabilizer is removed at a temperature lower than the glass transition temperature (Tg) of the resin fine particles C. Then, it is filtered, washed and dried to obtain toner particles.

  The toner particles of the present invention have high smoothness. Smoothness can be evaluated by using SPM (scanning probe microscope) and converting the surface roughness into a numerical value. In the present invention, the surface roughness is evaluated based on an average surface roughness Ra value obtained by analyzing an image obtained by scanning the surface of toner particles with SPM. In the present invention, the average surface roughness Ra of the surface of the toner particles is preferably 20 nm or less. More preferably, it is 10 nm or less. If it is this range, smoothness is high and sufficient durability is exhibited. A method for measuring SPM will be described later.

The surface free energy in the present invention is when the value of the polymer particle A is EA, the value of the polymer particle B is EB, the value of the resin fine particle C is EC, and the value of the surface free energy of water is EW. The following formulas (1) to (3):
EW>EA> EC (1)
EA> EB (2)
EW>EC> EB (3)
Satisfy the relationship.

As the surface free energy in the present invention, the surface free energy determined by the extended Fowkes theory devised by Kitasaki, Hata et al. (Japan Adhesion Association Paper 8 (3), 131-141 (1972)) is used. According to the extended Fowkes theory, the surface free energy γ of each substance is given by the sum of a dispersion component γ ^d , a dipole component γ ^p and a hydrogen bond component γ ^h as shown in the following formula (4).
γ = γ ^d + γ ^p + γ ^h (4)
Furthermore, the relationship of following formula (5) is materialized between a contact angle and each component.

In the above formula (5), gamma _L represents the surface free energy of the liquid represented by ^{_{γ d L + γ p L +}} γ h L. γ ^d _L represents a dispersion component of the surface free energy of the liquid. γ ^p _L represents the dipole component of the surface free energy of the liquid. γ ^h _L represents a hydrogen bond component of the surface free energy of the liquid. γ ^d _S represents a dispersion component of the surface free energy of the solid. γ ^p _S represents the dipole component of the surface free energy of the solid. γ ^h _S represents a hydrogen bonding component of the surface free energy of the solid. θ represents the contact angle.

Here, the contact angle θ on the surface of the solid is measured using the liquid sample 1 satisfying the following formula (6), the liquid sample 2 satisfying the following formula (7), and the liquid sample 3 satisfying the following formula (8). Γ _S can be derived by solving Equation (5) as a ternary simultaneous equation.
γ ^d _L ≠ 0, γ ^p _L = γ ^h _L = 0 (6)
γ ^d _L ≠ 0, γ ^p _L ≠ 0, γ ^h _L = 0 (7)
γ ^d _L ≠ 0, γ ^p _L ≠ 0, γ ^h _L ≠ 0 (8)
Table 1 shows the liquid sample used in the present invention and its surface free energy.

The surface free energy EA of the polymer particles A in the present invention is subjected to an acid treatment to remove the dispersant adsorbed on the polymer particles A after the step (ii), and then filtered and dried. Measured using polymer particles A. For the measurement, it is preferable to use a pellet of the dried polymer particles A. Further, the surface free energy EB of the polymer particle B was subjected to an acid treatment to remove the dispersant adsorbed on the polymer particle B after the above step (iii), and then filtered and dried. Measurement is performed using Polymer B. For the measurement, it is preferable to use a pellet of the dried polymer particles B. Further, the surface free energy EC of the resin fine particles C is measured by dissolving the resin used for the resin fine particles C in an organic solvent, spin-coating it on a glass plate or the like, and drying it. Alternatively, an aqueous dispersion of resin fine particles C may be dried and pelletized. As the surface free energy EW of water, 72.8 mJ / m ² which is the value of the surface free energy of water shown in Table 1 is used. The preparation method and measurement method of the sample used for measuring the surface free energy will be described later.

  Next, materials that can be used in the present invention will be described.

Examples of the polymerizable monomer include the following.
Styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Styrenes such as butyl styrene, pn-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene Monomer,
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, Acrylic esters such as phenyl acrylate, 2-hydroxyethyl acrylate,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylic acid esters such as 2-hydroxyethyl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
Examples include acrylonitrile, methacrylonitrile, and acrylamide.

  Among these polymerizable monomers, it is preferable to use a mixture of a styrenic monomer and another polymerizable monomer from the viewpoint of development characteristics and durability of the toner. And it is preferable to select suitably the mixing ratio of these polymerizable monomers in consideration of the glass transition temperature (Tg) of the desired polymer particles.

  A polymerization initiator can be used for the production of the polymer particles. Examples of the polymerization initiator include a peroxide polymerization initiator and an azo polymerization initiator.

  The peroxide polymerization initiator includes an organic type and an inorganic type.

  Examples of organic peroxide polymerization initiators include peroxyesters, peroxydicarbonates, dialkyl peroxides, peroxyketals, ketone peroxides, hydroperoxides, and diacyl peroxides.

  Examples of inorganic peroxide polymerization initiators include persulfates and hydrogen peroxide.

More specifically,
t-butyl peroxyacetate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-hexyl peroxyacetate, t-hexyl peroxypivalate, t-hexyl peroxyisobutyrate, t- Peroxyesters such as butyl peroxyisopropyl monocarbonate and t-butylperoxy 2-ethylhexyl monocarbonate; diacyl peroxides such as benzoyl peroxide;
Peroxydicarbonates such as diisopropylperoxydicarbonate;
Peroxyketals such as 1,1-di-t-hexylperoxycyclohexane;
Dialkyl peroxides such as di-t-butyl peroxide;
Examples include t-butyl peroxyallyl monocarbonate.

Examples of the azo polymerization initiator include:
2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, dimethyl-2,2'-azobis (2-methylpropionate)
Etc.

  1 type may be used for a polymerization initiator and 2 or more types may be used for it. The amount of the polymerization initiator used is preferably 0.100 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

The toner of the present invention can also be used as a magnetic toner, in which case the following magnetic materials are preferably used.
Iron oxides including magnetite, maghemite, ferrite, and other metal oxides; metals such as Fe, Co, Ni, and these metals and Al, Co, Cu, Pb, Mg, Ni, Sn, Zn , Alloys with metals such as Sb, Ca, Mn, Se, and Ti, and mixtures thereof. More specifically, triiron tetroxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), copper iron oxide (CuFe ₂ O ₄ ), oxidation Iron neodymium (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ).

  Among these, particularly preferred magnetic materials are triiron tetroxide and γ-iron sesquioxide.

  1 type may be used for a magnetic body and 2 or more types may be used for it.

These magnetic materials preferably have an average particle size of 0.1 μm to 2 μm, and more preferably 0.1 μm to 0.3 μm. The magnetic characteristics when 795.8 kA / m (10 K Oersted) is applied are such that the coercive force (Hc) is 1.6 kA / m or more and 12 kA / m or less (20 Oersted or more and 150 Oersted or less), and the saturation magnetization (σs) is 5 Am ² / kg to 200 Am ² / kg. Preferably they are 50 Am < ² > / kg or more and 100 Am < ² > / kg or less. Residual magnetization (.sigma.r) is, ^2Am 2 / kg or more 20 Am ² / kg or less being preferred.

  The amount of the magnetic substance used is preferably 10.0 parts by mass or more and 200 parts by mass or less, and more preferably 20.0 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. .

  As the colorant used in the toner of the present invention, various colorants such as dyes and pigments can be used.

  Examples of the color pigment for yellow include C.I. I. Pigment yellow 1, 3, 12, 13, 14, 17, 55, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, 185, and the like. These may use 1 type and may use 2 or more types.

  Examples of magenta coloring pigments include C.I. I. Pigment red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 178, 179, 190, 202, C.I. I. Pigment violet 19, 23 and the like. These may use 1 type and may use 2 or more types.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 15, 15: 1, 15: 3 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton. These may use 1 type and may use 2 or more types.

  Examples of the black colorant include carbon black, aniline black, acetylene black, titanium black, and those that are toned to black using the yellow / magenta / cyan colorant. These may use 1 type and may use 2 or more types.

  Further, the toner of the present invention may contain a release agent.

As a mold release agent, for example,
Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax;
Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax;
Block copolymer of aliphatic hydrocarbon wax;
Waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanate wax;
Deoxidized part or all of fatty acid ester such as deacidified carnauba wax, partially esterified product of fatty acid such as behenic acid monoglyceride and polyhydric alcohol;
Examples include methyl ester compounds having a hydroxy group obtained by hydrogenating vegetable oils and fats.

  As for the molecular weight distribution of the release agent, the main peak is preferably in a region having a molecular weight of 400 or more and 2400 or less, and more preferably in a region of 430 or more and 2000 or less. Thereby, preferable thermal characteristics can be imparted to the toner. The amount of the release agent used is preferably 2.5 parts by mass or more and 40.0 parts by mass or less, and 3.0 parts by mass or more and 15.0 parts by mass with respect to 100 parts by mass of the polymerizable monomer. The following is more preferable.

  In the production of the polymer particles, a chain transfer agent can be used for the purpose of adjusting the molecular weight.

  Examples of the chain transfer agent include n-pentyl mercaptan, isopentyl mercaptan, 2-methylbutyl mercaptan, n-hexyl mercaptan, n-heptyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, t-nonyl mercaptan, n- Alkyl mercaptans such as dodecyl mercaptan, t-dodecyl mercaptan, n-tetradecyl mercaptan, t-tetradecyl mercaptan, n-pentadecyl mercaptan, n-hexadecyl mercaptan, t-hexadecyl mercaptan, stearyl mercaptan, thioglycolic acid Alkyl esters, alkyl esters of mercaptopropionic acid, halogenated hydrocarbons such as chloroform, carbon tetrachloride, ethylene bromide, carbon tetrabromide, α-methylstyrene Ndaima and the like.

  These chain transfer agents do not necessarily need to be used, but when used, the preferred use amount is 0.05 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

  In the production of the polymer particles, a small amount of a polyfunctional monomer can be used in combination for the purpose of improving the high temperature offset resistance.

  Here, the high temperature offset is a reduction in which the toner melted at the time of fixing adheres to the surface of the above-described heat roller or fixing film, which contaminates the subsequent fixing sheet.

  As the polyfunctional monomer, compounds having two or more polymerizable double bonds are mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, such as ethylene glycol diacrylate and ethylene glycol. Carboxylic acid esters having two double bonds such as dimethacrylate and 1,3-butanediol dimethacrylate, or divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone, and more than two vinyl groups The compound which has is mentioned.

  These polyfunctional monomers are not necessarily used, but when used, the preferred amount used is 0.01 parts by mass or more and 1.00 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. is there.

  Moreover, in this invention, you may superpose | polymerize by adding resin in the polymerizable monomer composition mentioned above. For example, a polyester resin is a relatively polar resin containing many ester bonds. When this polyester resin is dissolved in the polymerizable monomer composition and polymerized, the resin tends to move to the surface layer of the droplets in the aqueous medium, and is unevenly distributed on the surface of the particle as the polymerization proceeds. Therefore, the granulation property is improved, and the above-described release agent is easily included.

  As the polyester resin, for example, one synthesized using an alcohol component and an acid component can be used. Examples of the alcohol component include monovalent alcohols, divalent alcohols, and trivalent or higher alcohols that can be crosslinked. Examples of the acid component include a monovalent acid component, a divalent acid component, and a trivalent or higher acid component that can be crosslinked.

  Examples of the divalent alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, and diethylene glycol. Propylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, neopentyl glycol, 2,2,4-trimethylpentane-1,3-diol, polyethylene glycol, Polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (i),

(In formula (i), R ¹¹ and R ¹² each independently represents an ethylene group or a propylene group. X and y represent the number of repetitions of the structure in parentheses, and each independently represents 1 (The average value of x + y is 2 or more and 10 or less.)
Diols represented by the following formula (ii)

(In formula (ii), R ²¹ and R ²² are each independently an ethylene group, 1-methylethylene group, 2-methylethylene group, 1,1-dimethylethylene group, or 2,2-dimethylethylene. Group.)
Is mentioned.

  Examples of the trivalent or higher alcohol include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Can be mentioned.

  1 type may be used for these alcohol components, and 2 or more types may be used for them.

  Examples of the divalent acid component include dicarboxylic acids such as naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, succinic acid, adipic acid, sebacic acid, and azelaic acid. And dicarboxylic anhydrides such as phthalic anhydride and maleic anhydride, and lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate, and dimethyl adipate. Of these, lower alkyl esters of dicarboxylic acids such as dimethyl terephthalate, dimethyl maleate, and dimethyl adipate or derivatives thereof are preferred.

  Examples of the trivalent or higher acid component include trimellitic acid, tri-n-ethyl 1,2,4-tricarboxylate, tri-n-butyl 1,2,4-tricarboxylate, and 1,2,4-tricarboxylic acid tri Lower alkyl such as n-hexyl, triisobutyl 1,2,4-benzenetricarboxylate, tri n-octyl 1,2,4-benzenetricarboxylate, tri-2-ethylhexyl 1,2,4-benzenetricarboxylate, tricarboxylic acid Examples include esters.

  Examples of the monovalent acid component include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid. , Dodecanoic acid, stearic acid and the like.

  Examples of the monovalent alcohol component include n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, dodecyl alcohol, and the like. Is mentioned.

  It is preferable to use a monovalent acid component or a monovalent alcohol component to such an extent that the properties of the polyester resin are not impaired.

  It is preferable that the usage-amount of a polyester resin is 1 to 20 mass parts with respect to 100 mass parts of polymerizable monomers. If the amount is 1 part by mass or more, the effect of use can be sufficiently obtained, and if it is 20 parts by mass or less, various physical properties of the toner can be easily designed.

  The toner of the present invention can contain a charge control agent as necessary for the purpose of stabilizing the charge characteristics. As a method of inclusion, there are a method of adding the toner particles inside and a method of externally adding them. When added to the inside, a charge control agent that has a low inhibitory effect on the polymerization of the polymerizable monomer and does not substantially contain a solubilized product in an aqueous medium is preferable. Examples of the charge control agent include a negative charge control agent and a positive charge control agent.

  Examples of negative charge control agents include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, sulfo groups (sulfone And a polymer compound having a side chain having a carboxy group (also referred to as a carboxylic acid group), a boron compound, a urea compound, a silicon compound, and a calixarene.

  Examples of the positive charge control agent include quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in the side chain, guanidine compounds, nigrosine compounds, imidazole compounds, and the like.

  When the charge control agent is internally added to the toner particles, the use amount of the charge control agent is preferably 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. It is more preferable that the amount is not less than 5 parts by mass. Further, when externally added to the toner particles, the amount of the charge control agent used is preferably 0.005 parts by mass or more and 1.0 parts by mass or less, and 0.01 parts by mass or more with respect to 100 parts by mass of the toner particles. More preferably, it is 0.30 part by mass or less.

  In order to improve the image quality, it is preferable that a fluidity improver (external additive) is externally added to the toner particles. Examples of the fluidity improver include inorganic fine particles such as silica fine particles, titania fine particles, and alumina fine particles. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof.

  The toner of the present invention can be used as it is as a one-component developer, or can be mixed with a magnetic carrier and used as a two-component developer. When used as a two-component developer, the average particle size of the magnetic carrier to be mixed is preferably 10 μm or more and 100 μm or less. The amount of toner in the two-component developer is preferably 2% by mass or more and 15% by mass or less based on the total mass of the two-component developer.

  Examples of the resin used for the resin fine particles C and the resin fine particles B according to the present invention include vinyl resins, polyester resins, epoxy resins, and urethane resins. Among these, polyester resins are preferable from the viewpoints of sharp melt properties and solubility in polymerizable monomers used for core particles. Also, a combination of a plurality of the above resins, a crystallized one, or a hybridized one can be used. Further, a resin in which a part of the resin is modified can be used, and a resin having a function such as charging can also be used.

  D50, D10, and D90 of the resin fine particles C and the resin fine particles B can be controlled by the physical properties of the resin constituting the resin fine particles and the manufacturing conditions of the resin fine particles. The physical properties of the resin fine particles C and the resin fine particles B can be controlled by the acid value, the type of functional group, and the molecular weight of the resin constituting the resin fine particles.

  The resin constituting the resin fine particles preferably contains a hydrophilic functional group from the viewpoint of the water dispersion stability of the resin fine particles and the chargeability of the toner. The hydrophilic functional group is preferably a carboxy group or a sulfo group from the viewpoint of toner production stability. The acid value at this time is preferably 5.0 mgKOH / g or more and 50.0 mgKOH / g or less from the viewpoint of dispersion stability of the resin fine particles and charging stability of the toner. When it is 5.0 mgKOH / g or more, sufficient adhesion to the dispersion stabilizer is obtained, and sufficient coverage is obtained, so that deterioration of heat resistance is suppressed. In addition, when the amount is 50.0 mgKOH / g or less, a change in the toner charge amount in a high-humidity environment hardly occurs, and an environmental difference in chargeability is suppressed.

  For the types and acid values of the hydrophilic functional groups contained in the resin constituting the resin fine particles described above, a monomer containing a hydrophilic functional group or other constituent material is used for the resin constituting the resin fine particles. It is possible to control.

  The resin fine particles can be produced by a method such as an emulsion polymerization method, a soap-free emulsion polymerization method, or a phase inversion emulsification method. Among these production methods, the phase inversion emulsification method is preferable because it does not require an emulsifier or a dispersion stabilizer and resin particles having a smaller particle diameter can be easily obtained.

  In the phase inversion emulsification method, a resin having self-dispersibility or a resin capable of developing self-dispersibility by neutralization is used. Here, the resin having self-water dispersibility is a resin containing a functional group capable of self-dispersion in an aqueous medium in the molecule, for example, a carboxy group, a sulfo group, a phosphate group, or a salt thereof. It is resin containing. Further, a resin that can exhibit self-dispersibility by neutralization is a resin that contains a functional group in the molecule that can increase self-dispersibility in an aqueous medium by neutralization.

  When these resins are dissolved in an organic solvent, a neutralizing agent is added as necessary, and mixed with an aqueous medium while stirring, the resin solution causes phase inversion emulsification to produce fine particles. The organic solvent can be removed using a method such as heating or decompression after phase inversion emulsification.

  Thus, according to the phase inversion emulsification method, a stable aqueous dispersion of resin fine particles can be obtained without substantially using an emulsifier or a dispersion stabilizer.

  In addition, a method of adding a surfactant and performing phase inversion emulsification in the step of dissolving a resin having self-dispersibility or a resin capable of developing self-dispersibility by neutralization in an organic solvent is also preferable. When a surfactant is added at the time of phase inversion emulsification, the effect of suppressing aggregation in the fine particle fixing step described above increases, and the production stability increases.

  Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, nonionic surfactants and anionic surfactants are preferable. A nonionic surfactant and an anionic surfactant may be used in combination.

  As the surfactant, one type may be used, or two or more types may be used.

  The surfactant is preferably used in an amount of 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the resin having self-dispersibility, since a good aggregation suppressing effect and charging performance can be balanced.

  When preparing the core particles in the present invention, the dispersion stabilizer is a hardly water-soluble inorganic salt, and the hardly water-soluble inorganic salt contained in the obtained toner particles is 1.0% by mass or less. preferable. By using the poorly water-soluble inorganic salt as the dispersion stabilizer, the washing treatment becomes easy and the amount of the hardly water-soluble inorganic salt remaining in the toner particles can be reduced. Further, when the content is 1.0% by mass or less, it is possible to suppress the influence of the poorly water-soluble inorganic salt on the performance of the toner, and it is possible to obtain a toner having more excellent charging stability and low-temperature fixability. it can. The content of the hardly water-soluble inorganic salt can be controlled by sufficiently washing the toner particles under pH conditions where the hardly water-soluble inorganic salt is soluble.

  In the present invention, it is more preferable to add resin fine particles in the presence of a poorly water-soluble inorganic salt to form an outer shell. The presence of the hardly water-soluble inorganic salt improves the dispersion stability during the production of the toner particles and improves the production stability. In addition, there is an effect of suppressing the resin fine particles from being buried in the core particles, and excellent heat resistant storage stability can be obtained. A preferable poorly water-soluble inorganic salt is tricalcium phosphate. When tricalcium phosphate is used, the outer shell can be formed in the presence of tricalcium phosphate by keeping the pH of the aqueous medium at 3.0 or higher.

  The toner produced according to the present invention has a weight average particle diameter (D4) of 3.0 μm or more and 12.0 μm or less, and a ratio (D4 / D1) of D4 to the number average particle diameter (D1) of 1.40 or less. Preferably there is. By being in the above range, it is possible to obtain toner performance and excellent electrophotographic characteristics. If D4 is 3.0 μm or more, various characteristics in the electrophotographic system are unlikely to deteriorate, and electrophotographic photosensitive member cleaning defects and toner transfer defects are less likely to occur. If D4 is 12.0 μm or less, the durability of the toner is not easily lowered even with a soft toner aiming at low-temperature fixability. In some cases, the large particles include aggregates of resin fine particles alone or coalesced particles of toner particles. Large particles may deteriorate the low-temperature fixability of toner and various electrophotographic characteristics. If (D4 / D1) is 1.40 or less, variations in the outer shells of individual toner particles can be suppressed, and a decrease in toner durability can be suppressed. Note that (D4 / D1) is an index indicating the degree of particle size distribution, and is 1.00 in the case of complete monodispersion. A larger (D4 / D1) value than 1.00 indicates a wider particle size distribution.

  In the present invention, the content of particles of 2.0 μm or less in the toner number distribution is preferably 15% by number or less. When the content of the particles is 15% by number or less, the particles are hardly accumulated on the charging member or the like in the developing device, and a decrease in development stability can be suppressed. In the present invention, when the adhesion between the core particles and the resin fine particles is not sufficient, or when aggregation between the resin fine particles occurs, the aggregates of the resin fine particles and the resin fine particles are easily detected as particles of 2.0 μm or less. Problems such as component contamination are likely to occur. When many agglomerates of resin fine particles containing a hydrophilic group are present, the charge amount may be significantly reduced in a high humidity environment.

  The average circularity of the toner is preferably 0.945 or more and 0.995 or less, and preferably 0.960 or more and 0.990 or less from the viewpoint of transferability. If the average circularity is 0.945 or more, the toner can be prevented from cracking from the concave and convex portions of the toner in the developing device, and the deterioration of the development stability performance due to the accumulated toner on the charging member is suppressed. Is done. In the present invention, if the resin fine particles are not uniformly adhered to the surface of the toner particles, the average circularity of the toner tends to be small, and the resin fine particles may be peeled off from the core particles in the developing device. If the average circularity is 0.995 or less, the toner is prevented from being overfilled, and even if the low-temperature fixability is improved, a decrease in development stability can be suppressed. Further, since the shape is not too spherical, it is difficult for the cleaning blade to slip through the electrophotographic photosensitive member.

  The measurement method used in the present invention will be described below.

<Surface free energy>
A contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.) is used for measuring the surface free energy. In this contact angle meter, a droplet of a solution is deposited on the surface of the sample, and the contact angle of the measurement sample can be measured from the image of the deposited droplet. As the solution to be used, three kinds of n-hexadecane, diiodomethane, and water are used, and the contact angle of the sample with respect to each solution is measured. The surface free energy is calculated from the obtained contact angle value using the Kitasaki / Hata field equation.

  The contact angle is measured in an environment of 25 ° C. The droplet to be deposited is formed on the needle tip of the syringe and adjusted so that the amount of the droplet dropped is 1.0 μL. Gently raise the sample stage on which the measurement sample is placed, deposit on the surface of the measurement sample, capture an image at 75 msec after the droplet formed on the sample surface, and use the analysis software “FAMAS” attached to the device. Measure the contact angle. In addition, the measurement is performed 3 times or more, and the average value is defined as the contact angle of the sample. Furthermore, using the software, the surface free energy is calculated from the obtained contact angle.

As the measurement sample, a spin coat sample or a pellet sample is used. The spin coat sample is prepared using a spin coater (SPINCATOR 1H-D7, manufactured by Mikasa Co., Ltd.). First, a 10 mass% THF solution in which an arbitrary sample resin is dissolved in THF is prepared. Using this sample solution, several drops are dropped on a slide glass placed on a spin coater, and then rotated under the following conditions to produce a slide glass coated with a resin. The spin coater rotation conditions are as follows.
Rotation speed: 500rpm
Time: 30 seconds For the measurement, a sample dried overnight in a vacuum dryer (25 ° C.) is used to remove the solvent.

  In addition, the pellet sample has a long side of 30.0 mm, a short side of 12.5 mm, a thickness of 2.0 to 3.0 mm, and a temperature of 25 ° C. using a tablet shaper so that the thickness uniformity is ± 0.05 mm. And molding at a pressure of 50 MPa and a pressing time of 30 minutes.

<Average surface roughness Ra (nm)>
The average surface roughness Ra (nm) of the toner particles was evaluated using a scanning probe microscope (SPM). E-sweep (probe station is NanoaviReal) manufactured by SII Nanotechnology Co., Ltd. was used for SPM. The observation area was 1 μm × 1 μm, and the number of x data was 256 and the number of y data was 256. For the observation, a cantilever DF20 (manufactured by SII Nano Technology Co., Ltd.) was used. The obtained SPM image was subjected to a flattening process in software (SPIWin) attached to the apparatus to obtain a surface roughness Ra value. The flattening process is basically a cubic inclination correction, and the flat process is performed as necessary. SPM observation was carried out using three or more toner particles prepared under the same conditions, and the Ra value was an average value.

<Glass-transition temperature>
The glass transition temperature (Tg) of the toner and resin fine particles can be determined as follows using, for example, a differential scanning calorimeter (Q1000) manufactured by TA Instruments.

  First, 6 mg of a sample is precisely weighed in an aluminum pan, and an empty aluminum pan is prepared as a reference pan. Under a nitrogen atmosphere, the measurement temperature range is 20 to 150 ° C., the temperature rising rate is 2 ° C./min, and the modulation amplitude is ± 0.6 The measurement is performed under the conditions of ° C and a frequency of once / minute.

  From the reversing heat flow curve at the time of temperature rise obtained by measurement, draw a tangent line between the endothermic curve and the front and back baselines, find the midpoint of the straight line connecting the intersections of each tangent line, and this is the glass transition Let it be temperature.

<Toner particle size>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As the measuring device, a precision particle size distribution measuring device (trade name: Coulter Counter Multisizer 3, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion exchange water so that the concentration becomes 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  In the “Change Standard Measurement Method (SOMME)” screen of the above-mentioned dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) Put 200 mL of the above electrolytic solution in a glass 250 mL round bottom beaker exclusively for Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) Put 30 mL of the above electrolytic solution into a glass 100 mL flat bottom beaker. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. 0.3) of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispense System Tetra 150” (manufactured by Nikki Bios Co., Ltd.) with an electrical output of 120 W is installed. prepare. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of the above (1) installed in the sample stand, the electrolyte aqueous solution of the above (5) in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to 5%. Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4). The “average diameter” on the “analysis / number statistics (arithmetic average)” screen when the graph / number% is set in the dedicated software is the number average particle diameter (D1).

<Volume D50 of resin fine particles>
The volume-based median diameter (D50) of the resin fine particles was measured using a laser diffraction / scattering particle size distribution measuring apparatus. Specifically, it is measured according to JISZ8825-1 (2001). As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used. The measurement procedure is as follows.

  (1) A batch type cell holder is attached to LA-920.

  (2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.

  (3) The inside of the batch cell is stirred using a dedicated stirrer chip.

(4) Press the “Refractive index” button on the “Display condition setting” screen, and set the relative refractive index to a value corresponding to the resin fine particles.

  (5) In the “display condition setting” screen, the particle size standard is set as the volume standard.

  (6) After performing warm-up operation for 1 hour or more, optical axis adjustment, optical axis fine adjustment, and blank measurement are performed.

  (7) 3 mL of the resin fine particle dispersion is placed in a glass 100 mL flat bottom beaker. Further, 57 mL of ion exchange water is added to dilute the resin fine particle dispersion. As a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH7 precision measuring instrument made of an organic builder, Wako Pure Chemical Industries ( 0.3 ml of a diluted solution obtained by diluting 3) by mass with ion-exchanged water is added.

  (8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Disposition System Tetora 150” (manufactured by Nikka Ki Bios Co., Ltd.) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank.

  (9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.

  (10) Continue ultrasonic dispersion for 60 seconds. Moreover, in ultrasonic dispersion | distribution, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.

  (11) The resin fine particle dispersion prepared in the above (10) is immediately added little by little to the batch type cell, taking care not to introduce bubbles, so that the transmittance of the tungsten lamp becomes 90% to 95%. Adjust to. Then, the particle size distribution is measured. Based on the obtained volume-based particle size distribution data, D50 is calculated.

<Content of particles of 2.0 μm or less>
The measurement was performed under the calibration and measurement conditions using a flow-type particle image analyzer (trade name: FPIA-3000, manufactured by Sysmex Corporation).

  The specific measurement method is as follows.

  First, 150 mL of ion-exchanged water from which impure solids are removed in advance in a glass container is prepared. To 150 mL of this ion-exchanged water, 0.5 g of a nonionic surfactant, preferably sodium dodecylbenzenesulfonate, is added as a dispersant, and then 0.15 g of toner is added to prepare a dispersion. Next, a desktop ultrasonic disperser (for example, “VSX-750” (manufactured by SONICS & MATERIALS) and a tap type probe ½ inch (manufactured by SONICS & MATERIALS) is used as a probe) is set so that the oscillation frequency is 20 kHz and the amplitude is 24 μm. After adjusting, the dispersion is subjected to a dispersion treatment for 5 minutes to obtain a first measurement solution. On the other hand, the tabletop ultrasonic disperser is adjusted so that the oscillation frequency is 20 kHz and the amplitude is 120 μm, and the dispersion is subjected to a dispersion treatment for 30 minutes to obtain a second measurement solution. In addition, when ultrasonically treating the dispersion, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or higher and 30 ° C. or lower.

  For the measurement of fine particles released by ultrasonic treatment, the above-described flow-type particle image analyzer equipped with “UPlanApro” (magnification 10 ×, numerical aperture 0.40) as an objective lens is used. As the sheath liquid, a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used. The first measurement solution or the second measurement solution prepared according to the above procedure is introduced into the flow type particle image analyzer and measured in the quantitative count mode in the HPF measurement mode. The particle size distribution of particles having an equivalent circle diameter of less than 690 μm is measured. After the measurement, the abundance ratio [number%] of particles of 0.500 μm or more and less than 1.985 μm is obtained, E1 [number%] is obtained from the result of the first measurement solution, and E2 [ The value of [number%] is obtained. Upon measurement, automatic focus adjustment is performed using standard latex particles (for example, “5100A” manufactured by Duke Scientific is diluted with ion-exchanged water) before the measurement is started. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  When the dispersion is irradiated with ultrasonic waves having a frequency of 20 kHz and an amplitude of 24 μm for 5 minutes, E1 increases mainly due to the release of resin fine particles with low adhesion strength adhering to the surface of the toner particles. On the other hand, when the dispersion is irradiated with ultrasonic waves of 20 kHz and amplitude of 120 μm for 30 minutes, E2 is caused by peeling of the outer shell or cracking of the toner having the core-shell structure in addition to the adhered resin fine particles. To increase.

<Acid value>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. Although the acid value in this invention is measured according to JISK0070-1992, specifically, it measures according to the following procedures.

  Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potentiometric titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / L hydrochloric acid, one prepared according to JISK8001-1998 is used.

The measurement conditions for the acid value measurement are shown below.
Titration apparatus: potentiometric titration apparatus AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview
The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration mode: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter End point judgment potential: 30 dE
End point determination potential value: 50 dE / dmL
End point detection judgment: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL
main exam;
0.100 g of a measurement sample is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved for 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.
Blank test;
Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
(In the above formula, A: acid value (mgKOH / g), B: amount of potassium hydroxide ethyl alcohol solution in blank test (mL), C: amount of potassium hydroxide ethyl alcohol solution in this test (mL), f : Factor of potassium hydroxide solution, S: Sample (g))

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to these Examples.

<Synthesis Example 1: Resin Fine Particle B-1>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 100.0 parts by mass of methyl ethyl ketone, and the temperature was raised to 80 ° C. in a nitrogen atmosphere. Next, 3.0 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was added to a mixture comprising the following monomers, and the mixture was added dropwise over 2 hours while stirring.
Styrene: 72.2 parts by mass n-butyl acrylate (n-butyl acrylate): 14.0 parts by mass Acrylic acid: 7.8 parts by mass Next, a polymerization reaction is performed for 10 hours while maintaining the above temperature, and after cooling, The reaction solution was dropped into hexane for reprecipitation purification, filtered and dried to obtain Resin B-1.

  In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 150.0 parts by mass of methyl ethyl ketone was charged, and 100.0 parts by mass of the resin B-1 was added and dissolved.

  Next, 9.0 parts by mass of dimethylaminoethanol was added and stirred for 10 minutes, and then 500.0 parts by mass of ion-exchanged water was added and dispersed in water.

  The obtained aqueous dispersion was distilled under reduced pressure to remove the solvent, and ion exchange water was added to prepare a resin concentration in the dispersion of 20%. This was designated as an aqueous dispersion of resin fine particles B-1.

<Synthesis Example 2: Resin Fine Particle B-2>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 200 parts by mass of xylene and refluxed under a nitrogen stream. As a monomer
2-acrylamido-2-methylpropanesulfonic acid: 6.0 parts by mass Styrene: 72.0 parts by mass 2-Ethylhexyl acrylate: 18.0 parts by mass were mixed and added dropwise to the reaction vessel with stirring for 10 hours. . Thereafter, distillation was performed to distill off the solvent, followed by drying at 40 ° C. under reduced pressure to obtain Resin B-2.

  Into a 1 L tall beaker, 100 parts by mass of tetrahydrofuran (THF) was added, and while stirring, resin B-260 parts by mass was added little by little and dissolved. Thereto was added 1.50 parts by mass of dimethylaminoethanol and mixed well. While stirring, 180 parts by mass of distilled water was added dropwise over 30 minutes, and then THF was removed by an evaporator to obtain an aqueous dispersion of resin fine particles B-2.

<Synthesis Example 3: Resin Fine Particle B-3>
The following monomers were charged into a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction tube, 0.03 parts by mass of tetrabutoxy titanate was added as an esterification catalyst, and the temperature was raised to 220 ° C. in a nitrogen atmosphere. Then, the reaction was carried out for 5 hours with stirring.
Bisphenol A-propylene oxide 2-mol adduct: 46.5 parts by mass Ethylene glycol: 8.4 parts by mass Terephthalic acid: 23.5 parts by mass Isophthalic acid: 15.6 parts by mass Trimellitic anhydride: 2.0 parts by mass The reaction was further carried out for 5 hours while reducing the pressure inside the reaction vessel to 5 to 20 mmHg to obtain Resin B-3.

  In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, the obtained resin B-3100.0 parts by mass, 45.0 parts by mass of methyl ethyl ketone, and 45.0 parts by mass of tetrahydrofuran were charged and dissolved. Thereafter, 8.4 parts by mass of triethylamine was added for neutralization.

  Next, 300.0 parts by mass of ion-exchanged water was added and dispersed in water with stirring, and the resulting aqueous dispersion was transferred to a distillation apparatus and distilled until the fraction temperature reached 100 ° C.

  After cooling, ion-exchanged water was added to the obtained aqueous dispersion to adjust the resin concentration in the dispersion to 20%. From this, an aqueous dispersion of resin fine particles B-3 was obtained.

<Synthesis Example 4: Resin Fine Particle C-1>
The following monomers were charged into a reaction vessel equipped with a stirrer, condenser, thermometer and nitrogen introduction tube, 0.03 parts by mass of tetrabutoxy titanate was added as an esterification catalyst, and the temperature was raised to 220 ° C. in a nitrogen atmosphere. Then, the reaction was carried out for 5 hours with stirring.
Bisphenol A-propylene oxide 2 mol adduct: 50.0 parts by mass Ethylene glycol: 10.0 parts by mass Terephthalic acid: 25.0 parts by mass Isophthalic acid: 25.0 parts by mass Trimellitic anhydride: 5.0 parts by mass The reaction was further carried out for 5 hours while reducing the pressure in the reaction vessel to 5 to 20 mmHg to obtain Resin C-1.

  In a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, 100.0 parts by mass of the obtained resin a, 45.0 parts by mass of methyl ethyl ketone, and 45.0 parts by mass of tetrahydrofuran were charged and dissolved.

  Next, after adding 9.1 parts by mass of dimethylaminoethanol and 300.0 parts by mass of ion-exchanged water and dispersing in water, the resulting aqueous dispersion was transferred to a distillation apparatus until the fraction temperature reached 100 ° C. Distillation was performed.

  After cooling, ion-exchanged water was added to the obtained aqueous dispersion to adjust the resin concentration in the dispersion to 20%. Thus, an aqueous dispersion of resin fine particles C-1 was obtained.

<Synthesis Example 5: Resin fine particles C-2>
An aqueous dispersion of resin fine particles C-2 was obtained in the same manner as in Synthesis Example 1 except that the amount of monomer charged was changed as follows.
Styrene: 75.0 parts by mass n-butyl acrylate: 20.0 parts by mass Acrylic acid: 5.0 parts by mass <Synthesis Example 6: resin fine particles C-3>
An aqueous dispersion of resin fine particles C-3 was obtained in the same manner as in Synthesis Example 1 except that the amount of monomer charged was changed as follows.
Styrene: 70.0 parts by mass Acrylic acid: 20.0 parts by mass 2-Hydroxyethyl methacrylate: 10.0 parts by mass Table 2 shows the particle diameters and physical properties of the obtained resin fine particles.

<Synthesis Example 7: Polar resin F-1>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 500.0 parts by mass of xylene, and heated to reflux in a nitrogen atmosphere. Next, 0.1 part by mass of t-butylperoxy-2-ethylhexanoate was added as a polymerization initiator to a mixture comprising the following monomers, and the mixture was added dropwise over 2 hours with stirring.
Styrene: 83.8 parts by weight Methyl methacrylate: 2.5 parts by weight Methacrylic acid: 1.7 parts by weight n-Butyl acrylate: 12.0 parts by weight Next, a polymerization reaction is carried out for 10 hours while maintaining the above temperature, followed by cooling. Thereafter, the reaction solution was dropped into hexane for reprecipitation purification, filtered and dried to obtain polar resin F-1.

<Synthesis Example 8: Polar resin F-2>
A reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube was charged with 500.0 parts by mass of xylene, and heated to reflux in a nitrogen atmosphere. Next, 0.5 parts by mass of t-butylperoxy-2-ethylhexanoate was added as a polymerization initiator to a mixture comprising the following monomers, and the mixture was added dropwise over 2 hours with stirring.
Methacrylic acid 2,2,3,3-tetrafluoropropyl: 23.0 parts by mass Light ester FM-108 (manufactured by Kyoeisha Chemical Co., Ltd.): 22.0 parts by mass Methacrylic acid: 53.0 parts by mass Acrylic acid: 2 Next, the polymerization reaction is carried out for 10 hours while maintaining the above temperature, and after cooling, the reaction solution is dropped into hexane for reprecipitation purification, filtered and dried to obtain the polar resin F-1. Obtained.

  Table 3 shows the physical property values of the obtained polar resin.

  Mw in the table means the weight average molecular weight.

[Example 1]
<Preparation of Toner 1>
(Preparation of dispersion A having polymer particles A)
In a four-necked vessel equipped with a reflux tube, a stirrer, a thermometer, and a nitrogen introduction tube, 1000 parts by mass of a 0.125 mol / L Na ₃ PO ₄ aqueous solution and 24.0 parts by mass of a 1.0 mol / L aqueous HCl solution were added. The mixture was added and kept at 60 ° C. while stirring at 12,000 rpm using a high-speed stirring device TK-homomixer. To this, 85 parts by mass of a 1.25 mol / L-CaCl ₂ aqueous solution was gradually added to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .
Styrene: 70.0 parts by mass n-butyl acrylate: 30.0 parts by mass Polar resin F-1: 5.0 parts by mass Pigment Blue 15: 3: 6.0 parts by mass Aluminum salicylate compound (trade name: Bontron E-88 Manufactured by Orient Chemical Co., Ltd.): 1.2 parts by mass Divinylbenzene: 0.04 parts by mass Release agent (Fischer-Tropsch wax, endothermic main peak temperature: 77.1 ° C.): 9.0 parts by mass Was dispersed with an attritor for 3 hours, and the polymerizable monomer composition 1 obtained was held at 60 ° C. for 20 minutes. Thereafter, 10.0 parts by mass (50% toluene solution) of t-butyl peroxypivalate as a polymerization initiator was added to the polymerizable monomer composition 1. The polymerizable monomer composition 1 after addition of the polymerization initiator was put into an aqueous medium, and granulated for 10 minutes while maintaining the rotation speed of the high-speed stirrer at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 70 ° C., and the reaction was allowed to proceed for 6 hours with slow stirring. A small amount of the dispersion B containing the polymer particles B after the reaction was extracted, cooled to room temperature, adjusted to pH = 1.5 by adding dilute hydrochloric acid, stirred for 1 hour or longer, filtered, washed with water, and dried. The physical properties of the polymer particles A were measured. The glass transition temperature (Tg) was 47.2 ° C. The weight average particle diameter (D4) was 6.40 μm, the number average particle diameter (D1) was 5.66 μm, and D4 / D1 = 1.13, confirming that the particle size distribution was good. Furthermore, the surface free energy was 70.0 mJ / m ² .

<Step of obtaining dispersion B containing polymer particles B (surface treatment step)>
The reflux tube was removed from the reaction apparatus for dispersion A containing polymer particles A after the reaction, and a distillation apparatus was attached. Distillation at a temperature of 100 ° C. in the vessel was performed for 5 hours. The distillation fraction was 500 parts by mass. Thereafter, 6.1 parts by mass of methyltrimethoxysilane was added as an alkoxysilane at the distillation temperature and stirred for 2 hours. 100 parts by mass of a fraction containing alcohol was recovered. Thus, a dispersion B containing the polymer particles B was obtained. A small amount of dispersion B was extracted, cooled to room temperature, adjusted to pH = 1.5 by adding dilute hydrochloric acid, stirred for 1 hour or longer, filtered, washed with water and dried, and the surface free energy of polymer particles B was measured. did. Table 4 shows.

<Process for obtaining toner particles by applying resin fine particles C (adhesion smoothing process)>
Dispersion B containing the obtained polymer particles B was prepared to have a solid content of 20%, and 500.0 parts by mass (solid content: 100.0 parts by mass) was set to 80 ° C. An aqueous sodium carbonate solution was added so that the temperature was maintained at 80 ° C. and the pH was 8.5. Next, resin fine particles C-115.0 parts by mass (solid content: 3.0 parts by mass) were slowly added, and stirring was performed at 200 rpm for 60 minutes. Then, after cooling to 20 ° C. at a rate of 1.0 ° C./min, 10% hydrochloric acid was added and stirred until the pH reached 1.5. Then, it was filtered, washed with water, and dried to obtain toner particles 1. A part of the sample immediately after the addition of the resin fine particles C-1 and after the fixing and smoothing step was collected, and the surface state was observed by SEM. Immediately after the addition, it was observed that the resin fine particles C-1 were uniformly attached on the polymer particles B. In addition, it was confirmed that the smoothing proceeded sufficiently after the fixing and smoothing step, and the resin fine particles B were covered with the resin fine particles C-1.

(External)
Hydrophobic silica fine particles having a primary particle size of 12 nm and a BET specific surface area of 120 m ² / g are obtained by treating 100 parts by mass of silica fine particles with 10 parts by mass of hexamethyldisilazane and further with 10 parts by mass of silicone oil. Was prepared. Next, 1100.0 parts by mass of the classified toner particles are weighed out, 1.0 part by mass of the hydrophobic silica fine particles are added, and mixed using a Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner 1. It was.

[Examples 2 to 10]
The same procedure as in Example 1 was performed until a dispersion A having polymer particles A was prepared. Thereafter, toners 2 to 10 were obtained in the same manner as in the production method of Example 1 except that the raw materials and production conditions were changed as shown in Table 4.

Example 11
The same procedure as in Example 1 was performed until a dispersion A having polymer particles A was prepared. The obtained dispersion A having polymer particles A was prepared so that the solid content was 20%, and set to 500.0 parts by mass (solid content: 100.0 parts by mass) at 80 ° C. An aqueous sodium carbonate solution was added so that the pH was kept at 80 ° C. and 8.5. Next, resin fine particle B-15.0 mass part (solid content: 1.0 mass part) was added, and it stirred for 30 minutes (surface treatment process). Thus, a dispersion B containing the polymer particles B was obtained. Thereafter, resin fine particles C-115.0 parts by mass (solid content: 3.0 parts by mass) were slowly added and stirred at 200 rpm for 60 minutes (adhesion smoothing step). Then, after cooling to 20 ° C. at a rate of 1.0 ° C./min, 10% hydrochloric acid was added and stirred until the pH reached 1.5. Thereafter, the resultant was filtered, washed with water, dried, and classified to obtain toner particles 11.

  A small amount of the dispersion B was extracted, cooled to room temperature, adjusted to pH = 1.5 by adding dilute hydrochloric acid, stirred for 1 hour or longer, filtered, washed with water, dried, and the surface free energy of the polymer particles B Was measured. It is described in Table 4. Moreover, a part of the sample immediately after the addition of the resin fine particles C-1 and after the fixing and smoothing step was collected, and the surface state was observed by SEM. Immediately after the addition, it was observed that the resin fine particles C-1 were uniformly attached on the polymer particles B. In addition, it was confirmed that the smoothing proceeded sufficiently after the fixing and smoothing step, and the resin fine particles B were covered with the resin fine particles C-1.

  External addition was performed in the same manner as in Example 1 to obtain toner 11.

[Examples 12 to 16]
As shown in Table 5, toners 12 to 16 were obtained in the same manner as in the production method of Example 11, except that the raw materials and production conditions were changed.

Example 17
The same procedure as in Example 1 was performed until a dispersion A having polymer particles A was prepared. The obtained dispersion A having polymer particles A was prepared so that the solid content was 20%, and set to 500.0 parts by mass (solid content: 100.0 parts by mass) at 80 ° C. An aqueous sodium carbonate solution was added so that the pH was kept at 80 ° C. and 8.5. Next, 1.6 parts by mass (solid content: 0.5 parts by mass) of a water-soluble resin (trade name: Joncryl 61, manufactured by BASF) was added and stirred for 5 minutes, so that the pH became 6.8. % Hydrochloric acid was added dropwise to precipitate a water-soluble resin and stirred for 30 minutes (surface treatment step). In this way, the water-soluble resin deposited on the surface of the polymer particles A was adhered to obtain a dispersion B containing the polymer particles B. Thereafter, resin fine particles C-115.0 parts by mass (solid content: 3.0 parts by mass) were slowly added and stirred at 200 rpm for 60 minutes (adhesion smoothing step). Then, after cooling to 20 ° C. at a rate of 1.0 ° C./min, 10% hydrochloric acid was added and stirred until the pH reached 1.5. Thereafter, it was filtered, washed with water, dried and classified to obtain toner particles 17.

  A small amount of the dispersion B was extracted, cooled to room temperature, adjusted to pH = 1.5 by adding dilute hydrochloric acid, stirred for 1 hour or longer, filtered, washed with water, dried, and the surface free energy of the polymer particles B Was measured. Table 6 shows. Moreover, a part of the sample immediately after the addition of the resin fine particles C-1 and after the fixing and smoothing step was collected, and the surface state was observed by SEM. Immediately after the addition, it was observed that the resin fine particles C-1 were uniformly attached on the polymer particles B. In addition, it was confirmed that the smoothing proceeded sufficiently after the fixing and smoothing step, and the resin fine particles B were covered with the resin fine particles C-1.

  External addition was performed in the same manner as in Example 1 to obtain toner 17.

[Examples 18 to 20]
As shown in Table 6, toners 18 to 20 were obtained in the same manner as in the production method of Example 17 except that the raw materials and production conditions were changed.

[Comparative Example 1]
The process was carried out in the same manner as in Example 1 until a dispersion liquid A having polymer particles A was produced, and a dispersion liquid A having polymer particles A was obtained. The obtained dispersion A having polymer particles A was prepared so that the solid content was 20%, and set to 500.0 parts by mass (solid content: 100.0 parts by mass) at 80 ° C. An aqueous sodium carbonate solution was added so that the pH was kept at 80 ° C. and 8.5. Next, resin fine particles C-115.0 parts by mass (solid content: 3.0 parts by mass) were slowly added and stirred at 200 rpm for 60 minutes (adhesion smoothing step). Then, after cooling to 20 ° C. at a rate of 1.0 ° C./min, 10% hydrochloric acid was added and stirred until the pH reached 1.5. Thereafter, the resultant was filtered, washed with water, and dried to obtain toner particles 21. When the surface state of the toner particles 21 was observed by SEM, it was confirmed that the polymer particles A were covered with the resin fine particles C-1, but the unevenness derived from the resin fine particles C-1 remained.

  External addition was performed in the same manner as in Example 1 to obtain toner 21.

[Comparative Example 2]
A toner 22 was obtained in the same manner as in Comparative Example 1 except that the fixing smoothing in Comparative Example 1 was changed from 60 minutes to 180 minutes. The surface state of the toner particles 22 was observed by SEM. It was confirmed that smoothing was in progress.

[Comparative Example 3]
Toner 23 was obtained in the same manner as in Example 17 except that resin fine particle C-1 was changed to resin fine particle B-2. When the surface state was observed by SEM, it was confirmed that the unevenness derived from the resin fine particles B-2 remained.

[Comparative Example 4]
Preparation of toner composition mixture:
Copolymerized polyester resin of bisphenol A propylene oxide adduct / bisphenol A ethylene oxide adduct / terephthalic acid derivative (glass transition temperature (Tg): 62 ° C., softening point: 102 ° C., weight average molecular weight (Mw): 21000): 100 parts by mass I. Pigment Blue 15: 3: 5.00 parts by mass Paraffin wax (melting point: 72.3 ° C.): 8.00 parts by mass Aluminum salicylate compound (Bontron E-88: manufactured by Orient Chemical Co., Ltd.): 1.2 parts by mass Part: Ethyl acetate: 100 parts by mass After the above material was well premixed in a container, it was dispersed in a bead mill for 6 hours while keeping it at 20 ° C. or lower to prepare a toner composition mixture.

Preparation of toner particles:
After adding 78.0 parts by mass of 0.100 mol / L-Na ₃ PO ₄ aqueous solution to 240 parts by mass of ion-exchanged water and heating to 60 ° C., it was adjusted to 14,000 rpm using Kleamix (M Technique Co., Ltd.). And stirred. To this, 12 parts of a 1.00 mol / L-CaCl ₂ aqueous solution was added to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ . Furthermore, 1.00 part by mass of carboxymethylcellulose (trade name: Serogen BS-H, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added and stirred for 10 minutes.

While the dispersion medium prepared in the container of the homomixer is adjusted to 30 ° C. and stirred, 180 parts by mass of the toner composition mixed solution adjusted to 30 ° C. is added, stirred for 1 minute, and then stopped. Thus, a toner composition dispersion suspension was obtained. The obtained toner composition dispersion suspension was stirred at a constant temperature of 40 ° C., and the gas phase on the surface of the suspension was forcibly renewed by an evacuation device and kept for 17 hours to remove the solvent. In this way, a dispersion before surface treatment was obtained. In addition, after cooling a part of the obtained dispersion liquid to room temperature, hydrochloric acid is added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water, and dried to remove toner particles before surface treatment. Obtained. The surface free energy of the obtained toner particles before the surface treatment was 65.3 mJ / m ² .

  The obtained dispersion before surface treatment was prepared so that the solid content was 20%, and was set to 500.0 parts by mass (solid content: 100.0 parts by mass) at 80 ° C. An aqueous sodium carbonate solution was added so that the pH was kept at 80 ° C. and 8.5. Next, resin fine particle B-15.0 mass part (solid content: 1.0 mass part) was added, and it stirred for 30 minutes (surface treatment process). In this way, a dispersion after the surface treatment was obtained. Thereafter, resin fine particles C-115.0 parts by mass (solid content: 3.0 parts by mass) were slowly added and stirred at 200 rpm for 60 minutes (adhesion smoothing step). Then, after cooling to 20 ° C. at a rate of 1.0 ° C./min, 10% hydrochloric acid was added and stirred until the pH reached 1.5. Thereafter, it was filtered, washed with water, and dried to obtain toner particles 20. When the surface state of the toner particles 20 was observed with an SEM, it was confirmed that the adhesion of the resin fine particles C-1 was uneven.

A small amount of the dispersion after the surface treatment is extracted, cooled to room temperature, adjusted to pH = 1.5 by adding dilute hydrochloric acid, stirred for 1 hour or longer, filtered, washed with water, dried, and toner after the surface treatment. The surface free energy of the particles was measured. It was 63.5 mJ / m ² .

  External addition was performed in the same manner as in Example 1 to obtain toner 24.

[Comparative Example 5]
A dispersion A having polymer particles A was obtained in the same manner as in Example 1 except that the polar resin F-1 was changed to the polar resin F-2. A portion of the resulting dispersion was cooled to room temperature, and then hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) ₂ , filtered, washed with water, and dried to obtain toner particles 25. The glass transition temperature (Tg) was 49.3 ° C. The surface free energy was 23.2 mJ / m ² . Further, the weight average particle diameter (D4) was 5.55 μm, the number average particle diameter (D1) was 3.95 μm, and D4 / D1 = 1.41. Therefore, it did not carry out after the surface treatment process.

  Table 7 shows the relationship between the surface free energy in Examples 1 to 20 and Comparative Examples 1 to 4 and the physical properties of the obtained toner.

  The obtained toner particles 1 to 24 and toners 1 to 24 were evaluated as follows.

<Smoothness>
After the toner particles were placed on a conductive tape and platinum was deposited, the above average surface roughness Ra was measured. Table 8 shows the obtained surface roughness Ra value.

<Heat-resistant>
Toner particles (5.0 g) were weighed into a 100 mL polycup and placed in a thermostatic chamber with an internal temperature of 55 ° C. and left for 5 days. Thereafter, the polycup was taken out and the degree of aggregation was measured.

  As the measuring device, a powder display tester (trade name) (manufactured by Hosokawa Micron Co., Ltd.) with a digital display vibrometer (trade name: Digivibro Model 1332A, Showa Sokki Co., Ltd.) connected to the side of the vibration table is used. It was. Then, a sieve having a mesh size of 250 μm (60 mesh), a sieve having a mesh size of 500 μm (30 mesh), and a sieve having a mesh size of 710 μm (22 mesh) were set on the vibrating table of the powder tester. The measurement was performed as follows in an environment of 23 ° C. and 60% RH.

  (1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display vibrometer was 0.60 mm (peak-to-peak).

  (2) 5 g of toner was gently placed on a sieve having a mesh opening of 710 μm.

(3) After vibrating the screen for 15 seconds, the mass of the toner remaining on each screen was measured, and the degree of aggregation was calculated based on the following equation. The degree of aggregation obtained is shown in Table 8.
Aggregation degree (%) = {(Sample mass (g) / 5 (g)} on a sieve having an opening of 710 μm} × 100
+ {(Sample mass (g) / 5 (g)} × 100 × 0.6 on a sieve having an opening of 500 μm)
+ {(Sample mass (g) / 5 (g)} on a sieve having an opening of 250 μm} × 100 × 0.2
<Content of particles of 2.0 μm or less>
Regarding toner particles 1 to 24, the content of particles of 2.0 μm or less was determined according to the method for measuring the content of particles of 2.0 μm or less described above. E1 and E2 are shown in Table 8.

<durability>
Using a color laser printer (trade name: LBP-7700C, manufactured by Canon Inc.), the toner from the cyan cartridge was taken out and charged with 90 g of the toner. The cyan cartridge was allowed to stand for 10 days in an environment of a temperature of 30 ° C. and a humidity of 80% RH. The cartridge is mounted on the cyan station of the printer, and a 2% printing rate chart is obtained using normal temperature and humidity (23 ° C., 60% RH) and image receiving paper (an office planner 64 g / m ² manufactured by Canon Inc.). 8000 images were output continuously and a halftone image was output. The number of streaks on the developing roller after outputting 8,000 images and in the halftone part of the halftone image was confirmed. The results are shown in Table 8.

Claims (10)

(I) adding a polymerizable monomer composition containing a polymerizable monomer and a colorant to an aqueous medium to form particles of the polymerizable monomer composition in the aqueous medium;
(Ii) polymerizing the polymerizable monomer contained in the particles to obtain a dispersion A of polymer particles A containing polymer particles A;
(Iii) treating the surface of the polymer particles A contained in the dispersion A to obtain a dispersion B containing polymer particles B whose surface free energy is smaller than the surface free energy of the polymer particles A Obtaining a step;
(Iv) adding resin fine particles C to the dispersion B, and applying the resin fine particles C to the surface of the polymer particles B to obtain the dispersion C;
(V) heating the dispersion C to a glass transition temperature (Tg) or higher of the resin fine particles C to obtain toner particles in this order,
The surface free energy value of the polymer particles A is EA, the surface free energy value of the polymer particles B is EB, the surface free energy value of the resin fine particles C is EC, and the surface free energy of water is When the value is EW, the following formulas (1) to (3):
EW>EA> EC (1)
EA> EB (2)
EW>EC> EB (3)
A toner particle manufacturing method characterized by satisfying the relationship:   The method for producing toner particles according to claim 1, wherein the polymerizable monomer includes a styrene monomer and at least one of acrylic acid esters and methacrylic acid esters.   The method for producing toner particles according to claim 1, wherein the resin fine particles C contain a polyester resin.   The step (iii) is a step of obtaining the dispersion B containing the polymer particles B by applying a material having a surface free energy smaller than EC to the surface of the polymer particles A. 4. The method for producing toner particles according to any one of 3 above.   In the step (iii), an alkoxysilane is added to the dispersion A, and then the dispersion A is heated to give the organosilicon polymer derived from the alkoxysilane to the surface of the polymer particles A. The method for producing toner particles according to claim 4, which is a step of obtaining the dispersion liquid B containing the polymer particles B. The method for producing toner particles according to claim 5, wherein the alkoxysilane is a compound represented by the following formula (Z).

(In Formula (Z), R ¹ represents a methyl group, a vinyl group, an amino group, an epoxy group, a methacryloyl group, or a mercapto group. R ² , R ^3, and R ⁴ are each independently a halogen atom. Represents a hydroxy group or an alkoxy group, provided that one or more of R ² , R ³ and R ⁴ are alkoxy groups.)   In the step (iii), resin fine particles B having a surface free energy smaller than EC are added to the dispersion A, and the resin fine particles B are applied to the surface of the polymer particles A, whereby the polymer particles B The method for producing toner particles according to claim 4, which is a step of obtaining the dispersion B contained.   The method for producing toner particles according to claim 7, wherein the resin fine particles B are a polyester resin.   The step (iii) is a step of obtaining the dispersion B containing the polymer particles B by applying a water-soluble resin having a surface free energy smaller than EC to the surface of the polymer particles A. 5. A method for producing toner particles according to 4. A toner production method for producing a toner having toner particles and inorganic fine particles externally added to the toner particles,
A step of producing the toner particles by the production method according to claim 1;
And a step of externally adding the inorganic fine particles to the toner particles in this order.