JP2017044933A - Manufacturing method of toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a toner that has a small particle diameter and a sharp particle size distribution, and excellent manufacturing stability.SOLUTION: There is provided a manufacturing method of a toner including the steps of: (a) stirring a mixture of a binder resin, colorant, composite fine particles, organic solvent, and dispersion medium to form droplets containing the binder resin, the colorant, and the organic solvent; and (b) removing the organic solvent included in the droplets to obtain toner particles, wherein the binder resin contains crystalline polyester; the composite fine particles are fine particles obtained by chemically coupling, to the surface of core particles, a vinyl resin obtained by polymerizing a compound 1 having a specific structure and a compound 2 having a specific structure; when the number average diameter (D1) of primary particles of the composite fine particles is d1 (nm) and the number average diameter (D1) of primary particles of the core particles is d2 (nm), d1 is 25 nm or more and 200 nm or less, and d1 and d2 satisfy a specific relationship.SELECTED DRAWING: None

Description

  The present invention relates to a toner manufacturing method used in a recording method using an electrophotographic method, an electrostatic recording method, and a toner jet recording method.

  In recent years, energy saving has been considered as a technical problem in electrophotographic apparatuses, and a drastic reduction in the amount of heat applied to a fixing apparatus has been studied. Accordingly, there is a growing need for so-called “low-temperature fixability” that can fix toner with lower energy. As a method for enabling fixing at a low temperature, there is a method of reducing the glass transition point (Tg) of the binder resin in the toner. However, lowering Tg leads to loss of heat-resistant storage stability of the toner, and it is difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner with this method.

  In recent years, a crystalline resin has attracted particular attention as a binder resin material for achieving both low-temperature fixability and heat-resistant storage stability. It is known that a crystalline resin can form a structure in which polymer chains constituting the resin are regularly arranged, and has a melting point (Tm). Therefore, it is difficult to soften in a temperature region below the melting point of the crystal, and has a property (sharp melt property) in which the crystal melts and sharply decreases at the melting point.

  In addition, regarding the improvement in image quality by toner, it is necessary to suppress variation in performance of each toner. For this purpose, it is effective to make the toner particles equal in particle size, that is, to sharpen the particle size distribution. As a method for producing a toner with relatively easy particle size distribution, a resin solution in which a resin is dissolved in an organic solvent is dispersed in a dispersion medium in the presence of a dispersant to form droplets of the resin solution. Then, a dissolution suspension method is known in which the organic solvent is removed to obtain resin particles. In particular, in a method using a low-polarity medium as a dispersion medium, a dispersant having a low polarity can be used as compared with a method using water as a dispersion medium, and toner particles having excellent electrical stability can be obtained. This is advantageous. Another feature is that inorganic fine particles can be used as a dispersant.

  Patent Documents 1 and 2 propose a production method in which resin particles are produced using liquid or supercritical carbon dioxide as a dispersion medium and silica particles that are inorganic fine particles as a dispersant.

  On the other hand, as one of the techniques for developing high durability, there is a method of fixing inorganic fine particles of about 100 nm on the surface of toner particles. In this case, the inorganic fine particles form irregularities on the surface of the toner, and it is possible to suppress the deterioration of the toner by reducing damage caused by rubbing between the toners caused by stirring in the developing container. This is called the “spacer effect”.

  Patent Document 3 proposes a toner in which silica particles whose primary particles have a volume average diameter of 80 nm to 200 nm are externally added. As a result, the spacer effect is exhibited, and a stable image can be formed even for long-term use.

JP 2007-277511 A JP 2010-168522 A JP 2009-75262 A

  When the present inventors examined the methods described in Patent Documents 1 and 2, it was found that resin particles having a good particle size distribution were not necessarily obtained. The reason is that the number average diameter of the primary particles of the silica particles used is as small as about 15 nm, so that the formed droplets are easily united. Therefore, there has been a problem in further sharpening the particle size distribution.

  When inorganic fine particles are used as a dispersant, the dispersant itself often agglomerates in the dispersion medium, and the function as the dispersant cannot be sufficiently exhibited. In addition, there is a problem that manufacturing is likely to be unstable, such as clogging of piping and the like, and an increase in cleaning frequency.

  On the other hand, in the toner described in Patent Document 3, since the silica particles are fixed to the toner surface by external addition, it is found that the silica particles are not sufficiently fixed and the silica particles are easily released from the toner. .

  Therefore, in order to obtain a toner having a sharp particle size distribution and excellent production stability, there are still problems.

  The present invention provides a toner manufacturing method that solves the above-described conventional problems. That is, the present invention provides a method for producing a toner having a small particle size, a sharp particle size distribution, and excellent production stability.

The present invention is a method for producing a toner having toner particles containing a binder resin, a colorant, and composite fine particles,
The manufacturing method is
a) stirring the mixture of the binder resin, the colorant, the composite fine particles, the organic solvent, and the dispersion medium to form droplets containing the binder resin, the colorant, and the organic solvent;
b) removing the organic solvent contained in the droplets to obtain toner particles;
Have
The binder resin contains crystalline polyester;
The composite fine particles are fine particles obtained by chemically bonding a vinyl resin obtained by polymerizing the compound 1 represented by the following formula (1) and the compound 2 represented by the following formula (2) to the surface of the core particles. And
When the number average diameter (D1) of primary particles of the composite fine particles is d1 (nm) and the number average diameter (D1) of primary particles of the core particles is d2 (nm), d1 is 25 nm or more and 200 nm or less. D1 and d2 satisfy the following formula (3),
5 ≦ d1-d2 ≦ 50 (3)
The ratio L2 / L1 between the average value L1 of the side chain length of the structural unit derived from the compound 1 and the average value L2 of the side chain length of the structural unit derived from the compound 2 is 1.0 or more and 4.0 or less. The present invention relates to a toner manufacturing method.

（式（１）中、Ｒ¹は水素原子またはメチル基を表す。Ｒ²からＲ⁶はそれぞれ独立して炭素数１以上３以下のアルキル基を表す。Ａは１以上３以下の整数であり、Ｂは括弧内の構造の繰り返し数を示し、化合物１における重合度は、１以上である。）

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² to R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms. A is an integer of 1 to 3) , B represents the number of repetitions of the structure in parentheses, and the degree of polymerization in compound 1 is 1 or more.)

（式（２）中、Ｒ⁷は水素原子またはメチル基を表す。ｎは１以上３以下の整数であり、Ｘは０または１である。Ｒ⁸は水素または炭素数１以上３以下のアルキル基を表す。Ｄは１以上の整数である。）

(In formula (2), R ⁷ represents a hydrogen atom or a methyl group. N is an integer of 1 to 3, and X is 0 or 1. R ⁸ is hydrogen or an alkyl having 1 to 3 carbon atoms. Represents a group, D is an integer of 1 or more.)

  According to the present invention, it is possible to provide a method for producing toner particles having a small particle size, a sharp particle size distribution, and excellent production stability.

It is a figure which shows an example of the manufacturing apparatus of the manufacturing method of the toner of this invention.

  Hereinafter, the present invention will be described in more detail with reference to preferred embodiments, but the present invention is not limited thereto.

  In the method for producing a toner of the present invention, after forming droplets of a resin solution in which a resin is dissolved in an organic solvent in a dispersion medium, toner particles are obtained by removing the organic solvent. It is a manufacturing method.

  In the dissolution suspension method, a dispersing agent is often used because the droplets exist stably in the dispersion medium with a good particle size distribution. When the dispersant is not used, if the interface free energy of the droplet and the dispersion medium is high, the dispersion becomes unstable, and the droplets coalesce to reduce the interface as much as possible.

  Dispersants prevent coalescence, and surfactants and solid fine particle dispersants are generally known as dispersants, each having different characteristics. The surfactant is mainly focused on reducing the energy difference at the interface, and is basically an amphipathic molecule composed of a portion that is easily adapted to the droplet and a portion that is easily adapted to the dispersion medium. When a surfactant is present at the time of droplet formation, it is unevenly distributed at the interface between the droplet and the dispersion medium, and the interface free energy is reduced and stabilized, thereby preventing droplet coalescence.

  On the other hand, when the solid fine particle dispersant has an appropriate wettability on the surface of the solid, it has the same familiarity with both the droplets and the dispersion medium, and is unevenly distributed at the interface to stabilize the interface. In addition, since the solid fine particle dispersant is relatively hard and larger in size than the molecule, it can prevent the droplets from being coalesced by acting as a spacer that prevents the droplets from contacting each other. However, it is not easy to design a solid fine particle dispersant with appropriate wettability, and the effect of lowering the interfacial energy is lower than that of the surfactant.

  The present inventors have used a composite fine particle in which a vinyl resin synthesized from two or more types of monomers is chemically bonded to the surface of a solid core particle as a dispersant, whereby a surfactant and a solid fine particle dispersant are used. It was found that both effects were manifested. As a result, it has been clarified that droplets with a good particle size distribution can be formed, and finally it is possible to obtain toner particles with a good particle size distribution, leading to the present invention.

Specifically, a method for producing a toner of the present invention (hereinafter, also simply referred to as a production method of the present invention) is a method of producing a toner having toner particles containing a binder resin, a colorant, and composite fine particles,
a) stirring the mixture of the binder resin, the colorant, the composite fine particles, the organic solvent, and the dispersion medium to form droplets containing the binder resin, the colorant, and the organic solvent;
b) removing the organic solvent contained in the droplets to obtain toner particles;
Have
The binder resin contains crystalline polyester;
The composite fine particles are fine particles obtained by chemically bonding a vinyl resin obtained by polymerizing the compound 1 represented by the following formula (1) and the compound 2 represented by the following formula (2) to the surface of the core particles. And
When the number average diameter (D1) of primary particles of the composite fine particles is d1 (nm) and the number average diameter (D1) of primary particles of the core particles is d2 (nm), d1 is 25 nm or more and 200 nm or less. And d1 and d2 satisfy the relationship of the following formula (3),
5 ≦ d1-d2 ≦ 50 (3)
The ratio L2 / L1 between the average value L1 of the side chain length of the structural unit derived from the compound 1 in the vinyl resin and the average value L2 of the side chain length of the structural unit derived from the compound 2 is 1.0 or more. It is 4.0 or less.

（式（１）中、Ｒ¹は水素原子またはメチル基を表す。Ｒ²からＲ⁶はそれぞれ独立して炭素数１以上３以下のアルキル基を表す。Ａは１以上３以下の整数であり、Ｂは括弧内の構造の繰り返し数を示し、化合物１における重合度は、１以上である。）

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² to R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms. A is an integer of 1 to 3) , B represents the number of repetitions of the structure in parentheses, and the degree of polymerization in compound 1 is 1 or more.)

（式（２）中、Ｒ⁷は水素原子またはメチル基を表す。ｎは１以上３以下の整数であり、Ｘは０または１である。Ｒ⁸は水素または炭素数１以上３以下のアルキル基を表す。Ｄは１以上の整数である。）

(In formula (2), R ⁷ represents a hydrogen atom or a methyl group. N is an integer of 1 to 3, and X is 0 or 1. R ⁸ is hydrogen or an alkyl having 1 to 3 carbon atoms. Represents a group, D is an integer of 1 or more.)

  The organic solvent in this invention can use a general organic solvent, and the following are mentioned. Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone; ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate; tetrahydrofuran, diethyl ether, dioxane, ethyl cellosolve, butyl cellosolve, etc. Ether solvents; amide solvents such as dimethylformamide and dimethylacetamide; aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene.

  In the production method of the present invention, the dispersion medium is preferably a low-polarity dispersion medium. The low-polarity dispersion medium means a dispersion medium whose polarity is lower than that of the organic solvent capable of dissolving the binder resin. Examples of the low polarity dispersion medium include the following. Hydrocarbon solvents such as pentane, hexane, heptane, octane, decane, hexadecane and cyclohexane; silicone solvents such as polydimethylsiloxane.

  In another preferred embodiment, the dispersion medium is carbon dioxide. Carbon dioxide may be used alone as a dispersion medium, and an organic solvent may be contained as another component. When carbon dioxide contains another organic solvent, the organic solvent preferably uses the low-polarity dispersion medium, preferably carbon dioxide and the organic solvent form a homogeneous phase, and carbon dioxide is the total amount of the dispersion medium. It is preferable that it is 50 mass% or more.

  In the production method of the present invention, the composite fine particles are obtained by polymerizing the compound 1 represented by the formula (1) and the compound 2 represented by the formula (2) on the surface of the core particle. Fine particles chemically bonded.

The compound 1 is a low-polar substance, and the affinity of the particles to the dispersion medium can be increased by chemically bonding the vinyl resin obtained by polymerizing the compound 1 to the core particle surface. In the compound 1, R ¹ represents a hydrogen atom or a methyl group. R ^{2 to} R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms. A is an integer of 1 or more and 3 or less, B represents the number of repetitions of the structure in parentheses, and the degree of polymerization in Compound 1 is 1 or more. Furthermore, the degree of polymerization in Compound 1 is preferably 1 or more and 500 or less, and more preferably 3 or more and 200 or less.

The compound 2 is a substance having an affinity for crystalline polyester, which will be described later, and the affinity of the particles for droplets is increased by chemically bonding a vinyl resin obtained by polymerizing the compound 2 to the core particle surface. It becomes possible. In the compound 2, R ⁷ represents a hydrogen atom or a methyl group. n is an integer of 1 to 3, and X is 0 or 1. R ⁸ represents an alkyl group having 1 to 3 carbon atoms. D is an integer of 1 or more. Furthermore, D is preferably 1 or more and 500 or less, and more preferably 3 or more and 200 or less.

  Moreover, as a preferable structure of the said compound 2, following formula (4) thru | or (8) is mentioned.

  Regarding the identification of the structure, the compound 1 is determined from the structure identification by NMR, and the compound 2 is determined from the manufacturer's catalog.

  The compound 1 may be a mixture of a plurality of compounds as long as the compound satisfies the formula (1) and the compound 2 satisfies the formula (2). In the production method of the present invention, when the number average diameter (D1) of the primary particles of the composite fine particles is d1 (nm) in the production method of the present invention, d1 needs to be 25 nm or more and 200 nm or less. is there. By setting the d1 within this range, it is possible to express a spacer function as a solid dispersant, and to coat droplets of an appropriate size, and finally toner particles having a particle size of several μm. Can be obtained.

  When the d1 is less than 25 nm, the particle size as the solid dispersant is too small, the effect as a spacer cannot be expected, and the dispersion stabilizing action becomes weak. As a result, the coalescence of the droplets proceeds, and the final toner particle size is deteriorated.

  When d1 is larger than 200 nm, it is difficult to uniformly coat small droplets, and the droplets are stabilized in a large state, so that the final toner particle size becomes large, and the characteristics as electrophotography are obtained. Will not be demonstrated.

  The d1 is more preferably 40 nm or more and 150 nm or less.

In the production method of the present invention, when the number average diameter (D1) of the primary particles of the core particles is d2 (nm), it is necessary that the d1 and the d2 satisfy the following formula (3).
5 ≦ d1-d2 ≦ 50 (3)

  The difference between d1 and d2 (d1−d2), that is, the thickness of the vinyl resin is within the range of the above formula (3), so that it is possible to ensure affinity for the droplets and the dispersion medium. It becomes. When (d1-d2) is less than 5 nm, the amount of vinyl resin is small, and the affinity for both the droplet and the dispersion medium is impaired, so that the adsorptivity of the composite fine particles to the droplet surface becomes insufficient. As the droplets coalesce, the particle size distribution of the toner particles deteriorates. Further, the composite fine particles themselves are likely to be aggregated in the dispersion medium, and the function as a dispersant cannot be sufficiently exhibited.

  Further, there is a risk that it may become an obstacle to stable toner production. Specifically, in a toner manufacturing apparatus, a process of transferring a dispersion liquid in which composite fine particles in an organic solvent or a dispersion medium are dispersed often occurs. At this time, when there is a narrowed portion in the middle of the piping or at the entrance / exit, or when a filter for removing foreign matter is provided, clogging may occur due to aggregates of composite fine particles. Further, in a manufacturing apparatus that uses oxygen dioxide as a dispersion medium, a filter for collecting toner may be installed in the apparatus. A few hundred nanometer-sized fine particle aggregates have poor fluidity and can get caught in the filter and also lead to clogging. When such clogging occurs, the production becomes unstable, such as transfer delay and complicated cleaning.

  When (d1-d2) is larger than 50 nm, there is no problem from the viewpoint of technical idea, but the range that can be easily manufactured from the viewpoint of difficulty of polymerization is set to a range of 50 nm or less.

  The (d1-d2) is more preferably 10 nm or more and 40 nm or less.

  In the production method of the present invention, the d2 is preferably 20 nm or more and 150 nm or less. When the d2 is 20 nm or more, the surface area is large, and it is difficult to form bonding spots when the vinyl resin is chemically bonded, making it easy to obtain uniform composite fine particles. Further, when the d2 is 150 nm or less, the force for adsorbing and fixing to the droplet surface is sufficient without increasing the thickness of the vinyl resin, and the particle size distribution of the toner particles becomes better. A more preferable range of d2 is 30 nm or more and 100 nm or less.

  In the production method of the present invention, the ratio L2 between the average value L1 of the side chain length of the structural unit derived from the compound 1 and the average value L2 of the side chain length of the structural unit derived from the compound 2 in the vinyl resin. / L1 must be 1.0 or more and 4.0 or less. The side chain length indicates the extended chain length from the carbonyl carbon of the side chain to the end of the side chain in the formulas (1) and (2), and the bond angle is calculated as 180 °. Moreover, when it has a branch in a side chain, let the longest bond length among the branched length be a side chain length. The method for calculating the side chain length is the sum of the covalent bond radii of each element.

  When the compound 1 and the compound 2 are composed of two or more types of monomers, the average value of the average side chain length is obtained from the number of moles charged for each monomer. When L2 / L1 takes a value within the range, it becomes possible to make both the affinity to the dispersion medium and the affinity to the droplet compatible, and it can be unevenly distributed at the interface between the droplet and the dispersion medium. Become. As a result, the droplets can stably exist at a desired particle size, and the final toner particle size distribution is good. When L2 / L1 is less than 1.0, the adsorption ability of the compound 2 to the droplets is insufficient, the coalescence of the droplets proceeds, and the final particle size distribution of the toner particles is deteriorated. When L2 / L1 exceeds 4.0, the affinity of the compound 1 for the dispersion medium is impaired, and the composite fine particles are easily taken into the inside of the droplet. The particle size distribution of typical toner particles is deteriorated. Further, the composite fine particles themselves are likely to be aggregated in the dispersion medium, so that the function as a dispersant cannot be sufficiently exhibited, and the production stability is deteriorated. The L2 / L1 is more preferably 1.2 or more and 3.0 or less.

  The addition amount of the composite fine particles is preferably 3.0% by mass or more and 25.0% by mass or less with respect to the binder resin. By being in this range, the ratio of the solid fine particles to the toner particle surface becomes appropriate, and the granulation property is further improved.

  In the production method of the present invention, it is preferable that the molar fraction of the compound 1 with respect to the total amount of charged monomers when polymerizing the vinyl resin is 0.20 or more and 0.95 or less. When the molar fraction of the compound 1 is within the above-described range, the composite fine particles as a whole can maintain affinity for the dispersion medium and maintain affinity for droplets. It can be unevenly distributed at the interface of the dispersion medium. That is, when the molar fraction of Compound 1 is 0.20 or more, the affinity of the entire composite fine particle to the dispersion medium is maintained, and deterioration of the toner particle size distribution due to coalescence of droplets can be further suppressed. . Further, the composite fine particles themselves are less likely to aggregate in the dispersion medium, and more stable toner production is possible. When the molar fraction of Compound 1 is 0.95 or less, the affinity for the dispersion medium is not too high, the droplets are stably present, and deterioration of the toner particle size distribution is further suppressed. A more preferable range is 0.4 or more and 0.90 or less.

  The core particles used in the production method of the present invention must be solid fine particles insoluble in the organic solvent and the dispersion medium, and are preferably inorganic fine particles. Examples of the inorganic fine particles include fine particles such as silica, alumina, titania, and composite oxide fine particles thereof, and silica fine particles are more preferable.

  As a method for producing silica fine particles, a combustion method obtained by burning a silane compound (that is, a method for producing fumed silica), a deflagration method obtained by explosively burning metal silicon powder, and sodium silicate and mineral acid Examples thereof include a wet method obtained by a neutralization reaction and a sol-gel method (so-called Stöber method) obtained by hydrolysis of an alkoxysilane such as hydrocarbyloxysilane. Among these, as a method for obtaining the silica fine particles having the number average diameter of the primary particles described above, a sol-gel method capable of sharpening the particle size distribution as compared with other methods is preferable.

  The inorganic fine particles may be subjected to a hydrophobic treatment, and the method for the hydrophobic treatment is not particularly limited, and a known method can be used.

  Examples of the hydrophobic treatment agent for the inorganic fine particles include the following. Chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane, vinyltrichlorosilane; tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane , Diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, Dodecyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltrieth Sisilane, diphenyldiethoxysilane, i-butyltriethoxysilane, decyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyl Dimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ -Alkoxysilanes such as (2-aminoethyl) aminopropylmethyldimethoxysilane; hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyl Silazanes such as silazane, hexahexyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyldisilazane; dimethyl silicone oil, methyl hydrogen silicone oil, methylphenyl silicone oil, alkyl modified Silicone oil, chloroalkyl-modified silicone oil, chlorophenyl-modified silicone oil, fatty acid-modified silicone oil, polyether-modified silicone oil, alkoxy-modified silicone oil, carbinol-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, and terminal reaction Silicone oils such as water-soluble silicone oil; hexamethylcyclotrisiloxane, octamethylcyclote Siloxanes such as trasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane; fatty acids and their metal salts such as undecyl acid, lauric acid, tridecylic acid, dodecylic acid, myristic acid, palmitic acid, pentadecylic acid , Stearic acid, heptadecyl acid, arachidic acid, montanic acid, oleic acid, linoleic acid, long chain fatty acids such as arachidonic acid, salts of the fatty acids with metals such as zinc, iron, magnesium, aluminum, calcium, sodium and lithium. Among these, alkoxysilanes, silazanes, and straight silicone oils are preferably used because they can be easily subjected to a hydrophobic treatment. Such hydrophobizing agents can be used alone or in admixture of two or more.

  In the production method of the present invention, the production method of the composite fine particles is not particularly limited, and a general chemical bonding method can be used. When the core particles are silica, it is preferable that the surface is treated with a silane coupling agent, and then the silica particles are combined with each other by polymerizing the monomer containing the compound 1 and the compound 2 to form a composite by radical polymerization. Is preferable. In radical polymerization, the compound 1, the compound 2, other monomers described later, and silica that has been surface-treated with a silane coupling agent are dissolved in an organic solvent, and the mixture can be polymerized by heating after degassing.

  As the silane coupling agent, those having a reactive functional group are preferable, and examples thereof include silane coupling agents having an amino group, an epoxy group, a methacryloyl group, an acryloyl group, a vinyl group, a mercapto group, and a halogen. Among these, a silane coupling agent having a halogen that can be a polymerization initiation point is more preferable.

  In the production method of the present invention, it is also possible to use three or more kinds from among the compound 1 and the compound 2. Moreover, the monomer to superpose | polymerize may contain compounds other than the said compound 1 and the said compound 2, and it is possible to use the monomer which has a general unsaturated bond, and the following monomers are mentioned.

  Aliphatic vinyl hydrocarbons: alkenes (ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, other α-olefins); alkadienes (butadiene, isoprene, 1,4-pentadiene) 1,6-hexadiene and 1,7-octadiene).

  Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes (cyclohexene, cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene); terpenes (pinene, limonene, indene).

  Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted products (α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene , Phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene); and vinylnaphthalene.

  Carboxyl group-containing vinyl monomer and metal salt thereof: unsaturated monocarboxylic acid having 3 to 30 carbon atoms, unsaturated dicarboxylic acid and anhydride and monoalkyl [1 to 11 carbon atoms] ester (acrylic acid, methacrylic acid) , Maleic acid, maleic anhydride, maleic acid monoalkyl ester, fumaric acid, fumaric acid monoalkyl ester, crotonic acid, itaconic acid, itaconic acid monoalkyl ester, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl ester, Cinnamic acid carboxyl group-containing vinyl monomer).

  Vinyl esters (vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, vinyl methoxy Acetate, vinyl benzoate, ethyl α-ethoxy acrylate), alkyl acrylate and alkyl methacrylate having 1 to 11 carbon atoms (linear or branched) (methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethyl Hexyl acrylate, 2-ethylhexyl methacrylate, dialkyl fumarate (dialkyl fumarate) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl Maleate (maleic acid dialkyl ester) (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), polyallyloxyalkanes (diallyloxyethane) Triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane).

  Moreover, the monomer which can take a crystal structure after superposition | polymerization can also be used, The following are mentioned.

  Alkyl acrylate or alkyl methacrylate having 12 or more carbon atoms in the alkyl group is preferable, and examples thereof include the following. Lauryl acrylate, lauryl methacrylate, myristyl acrylate, myristyl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacrylate, eicosyl acrylate, eicosyl methacrylate, behenyl acrylate, behenyl methacrylate.

  In the production method of the present invention, it is important that the binder resin contains the crystalline polyester. That polyester is crystalline means a resin having a structure in which molecular chains of polyester are regularly arranged. Therefore, in the temperature range lower than the melting point, it is hardly softened, and when it exceeds the melting point, melting occurs and it softens rapidly. Such a resin exhibits a clear melting point peak in differential scanning calorimetry using a differential scanning calorimeter (DSC). By incorporating a crystalline polyester having such characteristics, both low-temperature fixability and heat-resistant storage stability can be achieved.

  The crystalline polyester is preferably obtained by reacting an aliphatic diol and an aliphatic dicarboxylic acid, and reacts an aliphatic diol having 2 to 20 carbon atoms with an aliphatic dicarboxylic acid having 2 to 18 carbon atoms. It is more preferable to be obtained.

  The aliphatic diol is preferably linear. A polyester with higher crystallinity is obtained by being a linear type.

  Examples of the linear aliphatic diol having 2 to 20 carbon atoms include the following compounds.

  1,2-ethanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1 , 10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol and 1,20-eicosanediol.

  Among these, from the viewpoint of melting point, 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol 1,10-decanediol is more preferred. These may be used alone or in combination of two or more.

  An aliphatic diol having a double bond can also be used. Examples of the aliphatic diol having a double bond include the following compounds. 2-butene-1,4-diol, 3-hexene-1,6-diol and 4-octene-1,8-diol.

  The aliphatic dicarboxylic acid is particularly preferably a linear aliphatic dicarboxylic acid from the viewpoint of crystallinity.

  Examples of the linear aliphatic dicarboxylic acid having 2 to 18 carbon atoms include the following compounds.

  Succinic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-tridecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,16-hexadecanedicarboxylic acid and 1,18-octadecanedicarboxylic acid, or their lower alkyl esters and acid anhydrides object.

  Of these, sebacic acid, adipic acid and 1,10-decanedicarboxylic acid, and their lower alkyl esters and acid anhydrides are preferred. These may be used alone or in combination of two or more.

  Aromatic carboxylic acids can also be used. Examples of the aromatic dicarboxylic acid include the following compounds. Terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and 4,4'-biphenyldicarboxylic acid.

  Among these, terephthalic acid is preferable in terms of availability and easy formation of a low melting point polymer.

  A dicarboxylic acid having a double bond can also be used. A dicarboxylic acid having a double bond can be suitably used in order to prevent hot offset at the time of fixing, because the entire resin can be crosslinked using the double bond.

  Examples of such dicarboxylic acids include fumaric acid, maleic acid, 3-hexenedioic acid and 3-octenedioic acid. These lower alkyl esters and acid anhydrides are also included. Among these, fumaric acid and maleic acid are more preferable in terms of cost.

  There is no restriction | limiting in particular as a manufacturing method of crystalline polyester, It can manufacture by the polymerization method of the general polyester resin which makes an acid component and an alcohol component react. For example, a direct polycondensation method or a transesterification method can be used, and production can be carried out depending on the type of monomer.

  The production of the crystalline polyester is preferably carried out at a polymerization temperature of 180 ° C. or higher and 230 ° C. or lower, and the reaction system is preferably decompressed as necessary, and reacted while removing water and alcohol generated during condensation. . When the monomer is not dissolved or compatible at the reaction temperature, an organic solvent having a high boiling point is preferably added as a solubilizer and dissolved. In the polycondensation reaction, the dissolution auxiliary organic solvent is distilled off. In the case where a monomer having poor compatibility exists in the polymerization reaction, it is preferable to condense the monomer having poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance, and then polycondense together with the main component.

  Examples of the catalyst that can be used during the production of the crystalline polyester include the following compounds. Titanium catalysts such as titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide and titanium tetrabutoxide, or tin catalysts such as dibutyltin dichloride, dibutyltin oxide and diphenyltin oxide.

  The melting point of the crystalline polyester in the production method of the present invention is preferably 50 ° C. or higher and 90 ° C. or lower. Within this range, it becomes easy to soften at the time of fixing, and good low-temperature fixability is easily obtained. That is, when the temperature is 50 ° C. or higher, storage stability is not deteriorated, and when the temperature is 90 ° C. or lower, softening is easily performed during fixing, and good low-temperature fixability is obtained.

  The binder resin in the present invention can contain a vinyl resin as a resin capable of taking a crystal structure. Examples of the vinyl resin capable of having a crystal structure that can be contained include a resin obtained by polymerizing a vinyl monomer containing a linear alkyl group in the molecular structure.

  The vinyl monomer containing a linear alkyl group in the molecular structure is preferably an alkyl acrylate or alkyl methacrylate having 12 or more carbon atoms in the alkyl group, and examples thereof include the following. Lauryl acrylate, lauryl methacrylate, myristyl acrylate, myristyl methacrylate, cetyl acrylate, cetyl methacrylate, stearyl acrylate, stearyl methacrylate, eicosyl acrylate, eicosyl methacrylate, behenyl acrylate, behenyl methacrylate.

  The method for producing a vinyl resin capable of taking the crystal structure is preferably polymerized at a temperature of 40 ° C. or higher, and generally 50 ° C. or higher and 90 ° C. or lower.

  The binder resin in the present invention can contain an amorphous resin. By containing an amorphous resin, the elasticity of the toner in the fixing region after sharp melting is easily maintained.

  The amorphous resin is not particularly limited as long as it does not show a clear maximum endothermic peak in differential scanning calorimetry, and is the same as an amorphous resin generally used as a resin for toner. Can be used. However, the glass transition point (Tg) of the amorphous resin is preferably 50 ° C. or higher and 130 ° C. or lower, and more preferably 70 ° C. or higher and 130 ° C. or lower.

  Specific examples of the amorphous resin include amorphous polyester resin, polyurethane resin, and vinyl resin. Further, these resins may be modified with urethane, urea, or epoxy. Among these, amorphous polyester resins and polyurethane resins can be preferably exemplified from the viewpoint of maintaining elasticity.

  Hereinafter, the amorphous polyester resin will be described. Examples of the monomer that can be used for the production of the amorphous polyester resin include conventionally known divalent or trivalent or higher carboxylic acids and divalent or trivalent or higher alcohols. Specific examples of these monomers include the following.

  Examples of the divalent carboxylic acid include the following compounds. Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenyl succinic acid, their anhydrides or their lower alkyl esters, and maleic acid, fumaric acid, itacone Aliphatic unsaturated dicarboxylic acids such as acids and citraconic acid.

  Examples of the trivalent or higher carboxylic acid include the following compounds. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and anhydrides or lower alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the divalent alcohol include the following compounds. Alkylene glycol (ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol and polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol) A); an alkylene oxide (ethylene oxide and propylene oxide) adduct of an alicyclic diol.

  The alkyl part of alkylene glycol and alkylene ether glycol may be linear or branched. In the present invention, an alkylene glycol having a branched structure can also be preferably used.

  Examples of the trivalent or higher alcohol include the following compounds. Glycerin, trimethylolethane, trimethylolpropane and pentaerythritol. These may be used individually by 1 type and may use 2 or more types together.

  For the purpose of adjusting the acid value and the hydroxyl value, a monovalent acid such as acetic acid and benzoic acid, and a monovalent alcohol such as cyclohexanol and benzyl alcohol can be used as necessary.

  The method for synthesizing the amorphous polyester resin is not particularly limited, and for example, a transesterification method or a direct polycondensation method can be used alone or in combination.

  Next, an amorphous polyurethane resin will be described. The polyurethane resin is a reaction product of a diol and a substance containing a diisocyanate group, and a resin having various functions can be obtained by adjusting the diol and the diisocyanate.

  Examples of the diisocyanate component include the following. Aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same shall apply hereinafter), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and these diisocyanates Modified products (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group, hereinafter also referred to as “modified diisocyanate”), and these A mixture of two or more of the following.

  Aromatic diisocyanates include the following. m- and / or p-xylylene diisocyanate (XDI) and α, α, α ', α'-tetramethylxylylene diisocyanate.

  Moreover, the following are mentioned as aliphatic diisocyanate. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and dodecamethylene diisocyanate.

  Moreover, the following are mentioned as alicyclic diisocyanate. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate and methylcyclohexylene diisocyanate.

  Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are XDI. , IPDI and HDI.

  Further, in addition to the diisocyanate component, a trifunctional or higher functional isocyanate compound may be used.

  As the diol component that can be used for the polyurethane resin, the same divalent alcohol that can be used for the amorphous polyester described above can be used.

  The amorphous vinyl resin is described below. As a monomer that can be used for the production of an amorphous vinyl resin, the monomers having general unsaturated bonds listed in the above-mentioned method for producing composite fine particles can be used, and the following monomers are also used. It can be used.

  Vinyl monomers having a polyalkylene glycol chain (polyethylene glycol (molecular weight 300) monoacrylate, polyethylene glycol (molecular weight 300) monomethacrylate, polypropylene glycol (molecular weight 500) monoacrylate, polypropylene glycol (molecular weight 500) monomethacrylate, methyl alcohol ethylene oxide (Ethylene oxide is abbreviated as EO hereinafter) 10 mol adduct acrylate, methyl alcohol ethylene oxide (ethylene oxide is abbreviated as EO hereinafter) 10 mol adduct methacrylate, lauryl alcohol EO 30 mol adduct acrylate lauryl alcohol EO 30 mol adduct methacrylate ), Polyacrylates and polymethacrylates (polyamides of polyhydric alcohols) Relates and polymethacrylates: ethylene glycol diacrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyethylene Glycol diacrylate, polyethylene glycol dimethacrylate.

  Furthermore, in the production method of the present invention, it is also one of preferable modes to use a block polymer in which a crystalline polyester and an amorphous resin are chemically bonded.

  The block polymer includes an XY type diblock polymer, an XYX type triblock polymer, a YXY type triblock polymer, an XYXY... Type multiblock polymer of a crystalline resin component (X) and an amorphous resin component (Y). Any form can be used.

  In the production method of the present invention, the block polymer is prepared by separately preparing a crystalline polyester and an amorphous resin and bonding them together (two-stage method), a crystalline polyester, and an amorphous resin. The method of preparing these materials simultaneously and preparing them at one time (one-step method) can be used.

  The block polymer in the present invention can be selected from various methods in consideration of the reactivity of each terminal functional group to be a block polymer.

  When the binder is used, the following binders are exemplified. Polyvalent carboxylic acid, polyhydric alcohol, polyvalent isocyanate, polyfunctional epoxy, polyhydric acid anhydride. These binders can be used for synthesis by dehydration reaction or addition reaction.

  On the other hand, in the case where the amorphous resin is a polyurethane resin, each component can be prepared separately and then urethanized with the alcohol terminal of the polyester resin and the isocyanate terminal of the polyurethane resin. The synthesis can also be performed by mixing a polyester resin having an alcohol terminal with a diol and a diisocyanate constituting a polyurethane resin and heating. At the initial stage of the reaction when the diol and diisocyanate concentrations are high, the diol and diisocyanate react selectively to form a polyurethane resin. After the molecular weight has increased to some extent, a urethanization reaction between the isocyanate terminal of the polyurethane resin and the alcohol terminal of the polyester resin occurs, whereby a block polymer can be obtained.

  The content of the crystalline polyester in the binder resin is preferably 30.0% by mass or more, and more preferably 50.0% by mass or more.

  In the production method of the present invention, the mixture may contain a wax if necessary. As the wax, it is preferable that the peak temperature of the maximum endothermic peak of the wax is higher than the peak temperature of the maximum endothermic peak of the crystalline polyester in the DSC measurement of the toner particles. Examples of the wax include, but are not limited to, the following.

  Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat A wax mainly composed of a fatty acid ester such as an aromatic hydrocarbon ester wax; and a partially or completely deoxidized fatty acid ester such as a deoxidized carnauba wax; a partial ester of a fatty acid and a polyhydric alcohol such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  The wax particularly preferably used in the present invention is, in the dissolution suspension method, easy preparation of the wax dispersion, easy incorporation into the prepared toner, seepage from the toner during fixing, release From the viewpoint of properties, aliphatic hydrocarbon waxes and ester waxes are preferred. In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

Examples of the synthetic ester wax include monoester waxes synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated aliphatic alcohol. The long-chain linear saturated fatty acid is represented by the general formula C _n H _{2n + 1} COOH, and those having n = 5 to 28 are preferably used. The long-chain straight-chain saturated aliphatic alcohol is represented by C _n H _{2n + 1} OH, and n = 5 to 28 is preferably used. Examples of natural ester waxes include candelilla wax, carnauba wax, rice wax, and derivatives thereof.

  Of these, synthetic ester waxes composed of long-chain straight chain saturated fatty acids and long-chain straight chain saturated aliphatic alcohols or natural waxes based on the above esters are preferred. Further, in the present invention, it is more preferable that the ester is a monoester in addition to the linear structure described above. In the present invention, it is also a preferred form to use a hydrocarbon wax.

  The content of the wax is 1.0 part by mass or more and 20.0 parts by mass or less, more preferably 2.0 parts by mass or more and 15.0 parts by mass with respect to 100 parts by mass of the toner particles. By adjusting the wax content within the above range, the toner releasability can be further improved, and even when the fixing body is at a low temperature, the transfer paper is less likely to be wound. Furthermore, since the exposure of the wax on the toner surface can be brought into an appropriate state, the heat resistant storage stability can be further improved.

  In the present invention, the wax preferably has a maximum endothermic peak at 60 ° C. or more and 120 ° C. or less in DSC measurement. More preferably, it is 60 degreeC or more and 90 degrees C or less. By adjusting the maximum endothermic peak within the above range, the exposure of the wax on the toner surface can be brought into an appropriate state, so that the heat resistant storage stability can be further improved. On the other hand, since the wax is easily melted appropriately at the time of fixing, the low-temperature fixing property and the offset resistance can be further improved.

  In the toner production method of the present invention, the toner particles contain a colorant in order to impart coloring power. Preferred examples of the colorant include organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic powder. Colorants that are conventionally used in toners can be used.

  Examples of the colorant for yellow include the following. Condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds and allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168 and 180 are preferably used.

  Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, and 254 are preferably used.

  Examples of the colorant for cyan include the following. Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 are preferably used.

  These colorants can be used alone or in combination, and further in a solid solution state. The colorant to be used is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner composition.

  The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the toner particles. Similarly, when carbon black is used as the black colorant, the amount is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

  In the toner production method of the present invention, a charge control agent may be contained in the toner particles as necessary. Further, the toner particles may be externally added. By blending the charge control agent, the charge characteristics can be stabilized and the optimum triboelectric charge amount can be controlled according to the development system.

  As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable.

  As the charge control agent, organic metal compounds and chelate compounds are effective for controlling the toner to be negatively charged. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids Examples thereof include acid and dicarboxylic acid metal compounds. Examples of toners that are positively charged include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganotin borates, guanidine compounds, and imidazole compounds.

  A preferable blending amount of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, more preferably 0.5 parts by mass or more and 10.0 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows.

  In the toner production method of the present invention, inorganic fine powder can be externally added to the toner particles. The inorganic fine powder has a function of improving the fluidity of the toner and a function of making the toner charge uniform.

  Examples of the inorganic fine powder include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, and composite oxide fine powder thereof. Among these inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.

Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less Na ₂ O and SO ₃ ²⁻ is preferable. The dry silica may be a composite fine powder of silica and another metal oxide produced by using a metal halide compound such as aluminum chloride or titanium chloride together with a silicon halide in the production process.

  In addition, as the inorganic fine powder, the inorganic fine powder itself is hydrophobized, so that adjustment of the charge amount of the toner, improvement of environmental stability, and improvement of characteristics under a high humidity environment can be achieved. More preferably, an inorganic fine powder subjected to a hydrophobic treatment is used. When the inorganic fine powder externally added to the toner absorbs moisture, the charge amount as the toner is reduced, and the developability and transferability are likely to be reduced.

  As treatment agents for the hydrophobic treatment of inorganic fine powder, unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds and organotitanium Compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, when the inorganic fine powder is hydrophobized with a coupling agent, or simultaneously with the treatment, the hydrophobized inorganic fine powder treated with silicone oil treated with silicone oil increases the charge amount of the toner even in a high humidity environment. It is good for maintaining and reducing selective developability.

  The amount of the inorganic fine powder added is preferably 0.1 parts by mass or more and 4.0 parts by mass or less, more preferably 0.2 parts by mass or more and 3.5 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows.

  In the production method of the present invention, a) a mixture of a binder resin, a colorant, composite fine particles, an organic solvent, and a dispersion medium is stirred, and droplets containing the binder resin, the colorant, and the organic solvent are added. Forming in the dispersion medium.

  The mixing of the binder resin, the colorant, the composite fine particles, the organic solvent, and the dispersion medium is not particularly limited as long as they are uniformly mixed using a general mixing device.

  Examples of a general mixing apparatus include a disperser such as a homogenizer, a ball mill, a colloid mill, and an ultrasonic disperser. Further, the order of mixing is not particularly limited.

  As the dispersion medium, a method using carbon dioxide as a dispersion medium is particularly suitable in that the crystallinity of the crystalline polyester can be maintained at a higher level. In this case, it is preferable that a resin composition in which the binder resin, the colorant, and the organic solvent are mixed is prepared and then mixed with the dispersion medium to obtain a mixture, and the composite microparticles are the resin composition and the dispersion medium. Either of them may be contained.

  In the production method of the present invention, any method may be used as a method of dispersing the resin composition in the dispersion medium. As a specific example, there is a method of introducing a resin composition into a container containing a dispersion medium containing high-pressure carbon dioxide in a state where a dispersant is dispersed, using a high-pressure pump. Moreover, you may introduce | transduce into the dispersion medium containing the carbon dioxide of the high voltage | pressure state of the state which disperse | distributed the dispersing agent to the container prepared with the resin composition.

  In the production method of the present invention, when granulation is performed by dispersing the resin composition in carbon dioxide, a part of the organic solvent in the droplets is transferred into the dispersion. At this time, when the carbon dioxide phase and the organic solvent phase exist in a separated state, the stability of the droplets tends to decrease. Therefore, it is preferable to adjust the temperature and pressure of the dispersion medium and the amount of the resin composition with respect to carbon dioxide within a range in which carbon dioxide and the organic solvent can form a homogeneous phase.

  In addition, regarding the temperature and pressure of the dispersion medium, attention should be paid to granulation properties (easy to form oil droplets) and solubility of constituent components in the resin composition in the dispersion medium. For example, the binder resin or wax in the resin composition may be dissolved in the dispersion medium depending on the temperature condition or pressure condition. Usually, the lower the temperature and the lower the pressure, the more the solubility of the above components in the dispersion medium is suppressed, but the formed oil droplets are likely to agglomerate and coalesce, and the granulation property is lowered. On the other hand, although the granulation property is improved as the temperature and pressure are increased, the components tend to be easily dissolved in the dispersion medium. Therefore, in the production of toner particles, the temperature of the dispersion medium is preferably in the temperature range of 10 ° C. or higher and 40 ° C. or lower.

  Moreover, the pressure in the container forming the dispersion medium is preferably 1.0 MPa or more and 20.0 MPa or less, and more preferably 2.0 MPa or more and 15.0 MPa or less. In addition, the pressure in the manufacturing method of this invention shows the total pressure, when components other than a carbon dioxide are contained in a dispersion medium.

  In the production method of the present invention, b) a step of removing the organic solvent contained in the droplets to obtain toner particles is necessary. In the step b), after forming the droplet, it is preferable to remove the organic solvent remaining in the droplet through a dispersion medium containing carbon dioxide. Specifically, carbon dioxide is further mixed into the dispersion medium in which the droplets are dispersed, the remaining organic solvent is extracted into the phase of the dispersion medium, and the dispersion medium containing the organic solvent is further substituted with carbon dioxide. By doing.

  And as a method of substituting carbon dioxide containing an organic solvent with carbon dioxide, there is a method of circulating carbon dioxide while keeping the pressure in the container constant. At this time, the toner particles formed are captured while being captured by a filter.

  If the carbon dioxide is not sufficiently substituted and the organic solvent remains in the dispersion medium, the organic solvent dissolved in the dispersion medium is condensed when the container is decompressed in order to recover the obtained toner particles. In some cases, the toner particles may be redissolved or the toner particles may be united. Therefore, the replacement with carbon dioxide is preferably performed until the organic solvent is completely removed. The amount of carbon dioxide to be circulated is preferably 1 to 100 times, more preferably 1 to 50 times, and still more preferably 1 to 30 times the volume of the dispersion medium.

  The finally obtained toner particle surface does not need to be coated with composite fine particles, and may be extracted and removed together with the organic solvent in the step b).

  Below, the measuring method of each physical property value prescribed | regulated by this invention is described.

<Measurement Method of Toner Weight Average Particle Size (D4) and Number Average Particle Size (D1)>
In the present invention, the weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are calculated as follows.

  As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method 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-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

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

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “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) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred 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) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml 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 Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 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 the ultrasonic dispersion, the temperature of 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 (1) installed in the sample stand, the electrolytic solution of (5) still dispersed using a pipette is dropped and adjusted so that the measured concentration is about 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 statistic (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Measurement Method of Degree of Polymerization B in Compound 1>
The degree of polymerization B in compound 1 is measured by ¹ H-NMR under the following conditions.
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 64 times Measurement temperature: 30 ° C
Sample: 50 mg of compound 1 to be measured is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare.

From the obtained ¹ H-NMR chart, an integrated value S ₁ of a peak (about 0.0 ppm) attributed to hydrogen bonded to carbon bonded to silicon is calculated. Similarly, an integral value S ₂ of a peak (about 6.0 ppm) attributed to one of the terminal hydrogens of the vinyl group is calculated. The degree of polymerization B is determined as follows using the integral value S ₁ and the integral value S ₂ . Here, n ₁ is the sum of the number of hydrogen atoms linked to carbon atoms of R ² and R ^3, if R ² and R ³ in Formula (1) is each a methyl group, n ₁ becomes 6 In the case of each ethyl group or more, n ₁ is 4. N ₂ is the total number of hydrogen atoms bonded to the carbons of R ⁴ , R ⁵ and R ⁶ .
Degree of polymerization B = {(S ₁ −n ₂ ) / n ₁ } / S ₂

<Measuring method of melting point of crystalline polyester and wax>
The melting points of the crystalline polyester and the wax are measured under the following conditions using DSC Q2000 (manufactured by TA Instruments).

Temperature increase rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 5 mg of a sample is precisely weighed, placed in a silver pan, and measured once. A silver empty pan is used as a reference. The peak temperature of the maximum endothermic peak at that time is defined as the melting point.

<Measurement of glass transition point (Tg)>
The glass transition point of the amorphous resin is drawn from the reversing heat flow curve at the time of temperature rise obtained by the DSC measurement, and a tangent line between the curve showing the maximum endotherm and the baseline before and after is drawn. The midpoint of the connecting line is obtained, and the temperature at that point is taken as the glass transition point.

<Method of measuring number average molecular weight (Mn) and weight average molecular weight (Mw)>
In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin in tetrahydrofuran (THF) are measured by gel permeation chromatography (GPC) as follows.

(1) Preparation of measurement sample Resin (sample) and THF are mixed at a concentration of about 0.5 to 5.0 mg / ml (for example, about 5 mg / ml), and several hours (for example, 5 to 6 hours) at room temperature. After leaving it to stand, it was sufficiently shaken, and the THF and the sample were mixed well until the sample was not united. Furthermore, it left still at room temperature for 12 hours or more (for example, 24 hours). At this time, the time from the start of mixing the sample and THF to the end of standing was set to 24 hours or longer.

  Thereafter, a sample processing filter (pore size 0.45 to 0.50 μm, Mysori Disc H-25-2 [manufactured by Tosoh Corp.], Excro Disc 25CR [manufactured by Gelman Science Japan Ltd.] can be preferably used) is passed. This was used as a GPC sample.

(2) Sample measurement The column was stabilized in a heat chamber at 40 ° C., and THF as an organic solvent was allowed to flow through the column at this temperature at a flow rate of 1 ml / min. Measurement was made by injecting 50 to 200 μl of a THF sample solution of the resin adjusted to / ml.

  In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared from several monodisperse polystyrene standard samples and the number of counts.

As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Manufactured by Toyo Soda Kogyo Co., Ltd. and having molecular weights of 6.0 × 10 ² , 2.1 × 10 ³ , 4.0 × 10 ³ , 1.75 × 10 ⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2.0 × 10 ⁶ , 4.48 × 10 ⁶ were used. An RI (refractive index) detector was used as the detector.

As the column, in order to accurately measure a molecular weight region of 1 × 10 ^{3 to} 2 × 10 ⁶ , a plurality of commercially available polystyrene gel columns were used in combination as described below. The measurement conditions of GPC in the present invention are as follows.

[GPC measurement conditions]
Apparatus: LC-GPC 150C (manufactured by Waters)
Column: 7 series of Showdex KF801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK) Column temperature: 40 ° C
Mobile phase: THF (tetrahydrofuran)

<Measuring method of particle diameter of core particle, composite particle, wax particle and colorant particle>
In the present invention, the particle size of each fine particle is measured using a Microtrac particle size distribution measuring device HRA (X-100) (manufactured by Nikkiso Co., Ltd.) with a range setting of 0.001 μm to 10 μm, and the number average particle size, volume Measured as average particle size (μm or nm). Acetone is used as the diluted organic solvent.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

<Synthesis of crystalline polyester 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Sebacic acid 123.9 parts by mass-1,6-hexanediol 76.1 parts by mass-Dibutyltin oxide 0.1 parts by mass

  After replacing the interior of the system with nitrogen by depressurization, the mixture was stirred at 180 ° C. for 6 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing stirring, and the temperature was further maintained for 2 hours. Crystalline polyester 1 was synthesize | combined by air-cooling when it became a viscous state and stopping reaction. The number average molecular weight (Mn) of the crystalline polyester 1 was 5500, the weight average molecular weight (Mw) was 12300, and the melting point was 67 ° C.

<Synthesis of block polymer 1>
The following raw materials were charged into a heat-dried two-necked flask while introducing nitrogen.
-Xylylene diisocyanate (XDI) 56.0 parts by mass-Cyclohexanedimethanol (CHDM) 34.0 parts by mass-Tetrahydrofuran (THF) 80.0 parts by mass

  The mixture was heated to 50 ° C. and subjected to urethanization reaction for 10 hours. Thereafter, a solution prepared by dissolving 1,210.0 parts by mass of crystalline polyester in 220.0 parts by mass of THF was gradually added, and further stirred at 50 ° C. for 5 hours. Then, it cooled to room temperature and the block polymer 1 was synthesize | combined by distilling THF which is an organic solvent off. The number average molecular weight (Mn) of the block polymer 1 was 16800, the weight average molecular weight (Mw) was 35500, and melting | fusing point was 56 degreeC.

<Preparation of block polymer solution 1>
In a beaker equipped with a stirrer, 100.0 parts by mass of acetone and 100.0 parts by mass of block polymer 1 were added, and the mixture was heated to 50 ° C. and stirred until completely dissolved to prepare block polymer solution 1. .

<Preparation of core particle 1>
In a 3 L glass reactor equipped with a stirrer, a dropping funnel and a thermometer, 6.00 parts by mass of methanol, 0.42 parts by mass of pure water and 0.47 parts by mass of 28% by mass ammonia water were mixed. The resulting solution was adjusted to 35 ° C., and 11.00 parts by mass of tetramethoxysilane and 3.95 parts by mass of 5.4% by mass aqueous ammonia were begun simultaneously with stirring. Tetramethoxysilane was added dropwise over 7 hours and ammonia water over 6 hours. Even after the completion of the dropping, the mixture was further stirred for 0.2 hours for hydrolysis to obtain a methanol-water dispersion of spherical sol-gel silica fine particles. Thereafter, the dispersion was sufficiently dried at 80 ° C. under reduced pressure to obtain core particles 1. Table 1 shows the physical properties of the core particle 1.

<Preparation of core particles 2 to 10>
Core particles 2 to 10 were obtained in the same manner except that the amount of methanol added in preparation of the core particle 1 was changed to the conditions described in Table 1. The physical properties of the obtained core particles 2 to 10 are shown in Table 1.

<Preparation of composite fine particle precursor dispersion 1>
0.37 parts by mass of the core particle 1 and 45.79 parts by mass of ethanol are placed in a 1 L eggplant flask, and the core particles are irradiated with ultrasonic waves for 5 minutes using an ultrasonic disperser (manufactured by Nikka Ki Bios). 1 ethanol dispersion was prepared.

  Further, 4.17 parts by mass of ammonia water (28% by mass) was added and stirred at 40 ° C. for 1 hour. After 1 hour, 0.038 parts by mass of (2-Bromo-2methyl) propionoxyhexyltrimethylsilane, 0.28 parts by mass of Hextrimethylsilane, and 2.50 parts by mass of ethanol were added, and the mixture was further stirred at 40 ° C. for 18 hours.

  Next, after separating into eight centrifuge tubes, 4.00 parts by mass of 2-propanol was added to each centrifuge tube.

  After rotating at 14500 rpm and 8 ° C. for 30 minutes, 60.00 parts by mass of the supernatant of each centrifuge tube was removed, and 6.00 parts by mass of 2-propanol was added to each centrifuge tube again. This operation was repeated three times, and the respective centrifuge tubes were combined again into one vial to obtain a composite fine particle precursor dispersion 1. It was 3.11 mass% as a result of solid content measurement.

<Preparation of Composite Fine Particle Precursor Dispersions 2 to 10>
The composite fine particle precursor dispersions 2 to 10 were obtained in the same manner except that the type of the core particles in the preparation of the composite fine particle precursor dispersion 1 was changed from the core particles 1 to the core particles 2 to 10.

<Preparation of composite fine particle 1>
The following raw materials were charged into a heat-dried 100 ml flask.
The composite fine particle precursor dispersion 1 24.00 parts by mass Compound 1 (X-22-2475: Shin-Etsu Chemical Co., Ltd.) 11.88 parts by mass Compound 2 (Light acrylate 130A: Kyoeisha Chemical) 17.20 parts by mass 2,2′-bipyridine 0.40 parts by mass / ethyl 2-bromoisobutyrate 0.0096 parts by mass

  The flask was immersed in liquid nitrogen to freeze the contents, and then the system was depressurized by depressurization. After fully depressurizing, nitrogen was introduced to melt the contents. By performing this operation three times, the raw material was dehydrated and degassed.

  Next, 0.042 parts by mass of copper (I) chloride was charged into a heat-dried 300 ml three-necked flask, and then the contents of the 100 ml flask were charged, and the raw material was frozen by immersing the flask in liquid nitrogen, The system was depressurized by depressurization. After fully depressurizing, nitrogen was introduced to melt the contents. By performing this operation three times, the raw material was dehydrated and degassed. Thereafter, polymerization was carried out at 70 ° C. for 5 hours in a sealed state to obtain a 2-propanol dispersion of composite fine particles 1.

  Next, after separating into 8 centrifuge tubes, 40.00 parts by mass of acetone was added to each centrifuge tube.

  After rotating for 30 minutes at 14500 rpm and 8 ° C., 60.00 parts by mass of the supernatant of each centrifuge tube is collected, vinyl resin not complexed is removed, and 60.00 parts by mass of acetone is added to each centrifuge tube again. did. This operation was repeated three times, and acetone was added to adjust the solid content concentration to 5.00% by mass, whereby an acetone dispersion of composite fine particles 1 was obtained.

  Table 2 shows the physical properties of Compound 1 used in Examples and Comparative Examples, and Table 3 shows the physical properties of Compound 2.

<Preparation of composite fine particles 2 to 32>
Composite fine particles 2 to 32 were obtained in the same manner except that the conditions for producing the composite fine particles 1 were changed to the conditions shown in Table 4. Table 4 shows the obtained physical properties of 2 to 32.

<Preparation of non-composite fine particle dispersion 1>
5.00 parts by mass of the core particle 1 and 95.00 parts by mass of acetone were mixed and dispersed for 3 minutes with an ultrasonic disperser (manufactured by Nikka Ki Bios Co., Ltd.) to prepare an uncomposited fine particle dispersion 1. .

<Preparation of wax dispersion 1>
Dipentaerythritol palmitate wax 17.0 parts by weight Wax dispersant 8.0 parts by weight (in the presence of 15.0 parts by weight of polyethylene, 50.0 parts by weight of styrene, 25.0 parts by weight of n-butyl acrylate) , A copolymer having a peak molecular weight of 8,500 copolymerized with 10.0 parts by mass of acrylonitrile)
Acetone 75.0 parts by mass The above material was put into a glass beaker (made by IWAKI glass) with a stirring blade, and the system was heated to 50 ° C. to dissolve the wax in acetone.

  Then, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.

  This solution was put into a heat-resistant container together with 20.0 parts by mass of 1 mm glass beads, and dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki) to obtain wax dispersion 1.

  The volume average particle diameter of the wax was 150 nm, and the melting point was 72 ° C.

<Preparation of Colorant Dispersion 1>
・ C. I. Pigment Blue 15: 3 100.0 parts by mass, acetone 150.0 parts by mass, glass beads (1 mm) 200.0 parts by mass The above materials are put into a heat-resistant glass container, and dispersed in a paint shaker for 5 hours. The glass beads were removed with a nylon mesh to obtain a colorant dispersion. The solid content concentration was 40.0% by mass.

[Example 1]
In the apparatus shown in FIG. 1, with the valves V1, V2, and V3 closed, the tank Ta1
-Block polymer solution 1 173.0 parts by mass-Wax dispersion 1 30.0 parts by mass-Colorant dispersion 1 15.0 parts by mass-Acetone 15.0 parts by mass were adjusted to an internal temperature of 50C. Next, while stirring the inside of the tank Ta1 at a rotational speed of 300 rpm, the valve V1 is opened, carbon dioxide (purity 99.99%) is introduced into the tank Ta1 from the cylinder B1, and the internal pressure reaches 3.0 MPa. Valve V1 was closed.

  Next, 45.0 parts by mass of vinyl resin solution P1 is charged into a pressure resistant granulation tank Ta2 equipped with a filter for capturing toner particles and a stirring mechanism, the pressure adjustment valve V4 is closed, and the internal temperature is set to 20 ° C. It was adjusted.

  Next, the valve V3 was opened, carbon dioxide was introduced from the cylinder B1 into the granulation tank Ta2, and the valve V3 was closed when the internal pressure reached 1.0 MPa.

  Next, the valve V2 is opened, and the contents of Ta1 are introduced into the granulation tank Ta2 using the pump P2 while stirring the inside of the granulation tank Ta2 at a rotational speed of 1000 rpm. Closed. Thereafter, the valve V3 was opened, carbon dioxide was further introduced from the cylinder B1 using the pump P1, and the valve V3 was closed. After the introduction, the temperature of the granulation tank Ta2 was 25 ° C., and the internal pressure was 5.0 MPa. The mass of the total carbon dioxide introduced was measured using a mass flow meter and was 280.0 parts by mass.

  Thereafter, the inside of the granulation tank Ta2 was stirred for 10 minutes at a rotational speed of 1000 rpm for dispersion.

  Next, the valve V3 was opened, and carbon dioxide was introduced into the granulation tank Ta2 from the cylinder B1 using the pump P1. At this time, the pressure adjusting valve V4 was set to 10.0 MPa, and carbon dioxide was further circulated for 1 hour at a flow rate of 50 g / min while maintaining the internal pressure of the granulation tank Ta1 at 10.0 MPa. By this operation, carbon dioxide containing the organic solvent (mainly acetone) extracted from the granulated droplets was discharged to the organic solvent recovery tank Ta3, and the organic solvent and carbon dioxide were separated.

  Finally, the pressure regulating valve V4 was opened little by little, and the internal pressure of the granulation tank Ta2 was reduced to atmospheric pressure, whereby the toner particles 1 were recovered.

<Evaluation method>
The toner particles thus obtained were evaluated for particle size and particle size distribution.

For the evaluation of the particle diameter, the number average particle diameter (D1) was determined based on the following criteria. The evaluation results are shown in Table 6.
A: D1 value is less than 5.50 μm B: D1 value is 5.50 μm or more and less than 6.00 μm C: D1 value is 6.00 μm or more and less than 6.50 μm D: D1 value is 6.50 μm or more

For the evaluation of the particle size distribution, D4 / D1 was determined based on the following criteria. The evaluation results are shown in Table 6.
A: D4 / D1 value is less than 1.15 B: D4 / D1 value is 1.15 or more and less than 1.20 C: D4 / D1 value is 1.20 or more and less than 1.25 D: D4 / D1 value is 1. 25 or more and less than 1.30 E: D4 / D1 value is 1.30 or more

  Also, in the stable production of toner particles, clogging of piping and filters in the production apparatus is not preferable from the viewpoint of increasing the frequency of cleaning and deteriorating the efficiency of content transfer. Therefore, it is installed in the granulation tank Ta2 of FIG.

This time, we checked the clogging condition of the composite fine particles in the filter for collecting the toner installed in the toner production equipment, and judged the influence on stable production visually. The evaluation results are shown in Table 6.
A: No clogging can be confirmed B: A part of the aggregate is derived from the composite fine particles C: Aggregation from the composite fine particles is observed D: Many aggregates derived from the composite fine particles are observed E: The entire filter is a composite fine particle Covered with aggregates of origin

[Examples 2 to 28]
Toner particles 2 to 28 were produced in the same manner except that the composite fine particle dispersion was changed as shown in Table 5 in the production of toner particles 1. Table 6 shows the evaluation results.

[Comparative Examples 1 to 9]
Toner particles 29 to 37 were produced in the same manner except that the composite fine particle dispersion was changed as shown in Table 5 in the production of toner particles 1. Table 6 shows the evaluation results.

  Ta1: tank, Ta2: granulation tank, Ta3: solvent recovery tank, B1: container (carbon dioxide cylinder), P1, P2: pump (compression pump), V1, V2, V3: valve, V4: pressure regulating valve

Claims (7)

A method for producing a toner having toner particles containing a binder resin, a colorant, and composite fine particles,
The manufacturing method is
a) stirring the mixture of the binder resin, the colorant, the composite fine particles, the organic solvent, and the dispersion medium to form droplets containing the binder resin, the colorant, and the organic solvent;
b) removing the organic solvent contained in the droplets to obtain toner particles;
Have
The binder resin contains crystalline polyester;
The composite fine particles are fine particles obtained by chemically bonding a vinyl resin obtained by polymerizing the compound 1 represented by the following formula (1) and the compound 2 represented by the following formula (2) to the surface of the core particles. And
When the number average diameter (D1) of primary particles of the composite fine particles is d1 (nm) and the number average diameter (D1) of primary particles of the core particles is d2 (nm), d1 is 25 nm or more and 200 nm or less. D1 and d2 satisfy the following formula (3),
5 ≦ d1-d2 ≦ 50 (3)
The ratio L2 / L1 between the average value L1 of the side chain length of the structural unit derived from the compound 1 and the average value L2 of the side chain length of the structural unit derived from the compound 2 is 1.0 or more and 4.0 or less. A method for producing a toner, comprising:

(In Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² to R ⁶ each independently represents an alkyl group having 1 to 3 carbon atoms. A is an integer of 1 to 3) And B represents the number of repetitions of the structure in parentheses, and the degree of polymerization in Compound 1 is 1 or more.

(In Formula (2), R ⁷ represents a hydrogen atom or a methyl group. N is an integer of 1 to 3, and X is 0 or 1. R ⁸ is an alkyl group having 1 to 3 carbon atoms. D represents an integer of 1 or more.)   The toner production method according to claim 1, wherein the d2 is 20 nm or more and 150 nm or less.   The method for producing a toner according to claim 1, wherein the amount of the composite fine particles added in the step a) is 3.0% by mass or more and 25.0% by mass or less with respect to the binder resin.   4. The method for producing a toner according to claim 1, wherein a molar fraction of the compound 1 with respect to a total amount of charged monomers when polymerizing the vinyl resin is 0.20 or more and 0.95 or less. 5.   The method for producing a toner according to claim 1, wherein the core particle is an inorganic fine particle.   The method for producing a toner according to claim 5, wherein the inorganic fine particles are silica fine particles.   The method for producing a toner according to claim 1, wherein the dispersion medium contains carbon dioxide.

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