JP2014056143A - Toner, manufacturing method of the toner, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that achieves excellent low-temperature fixability and heat-resistance storage stability, suppresses the occurrence of member contamination, and has high manufacturing safety.SOLUTION: A toner contains a first amorphous resin, a second amorphous resin having an SP value lower than that of the first amorphous resin, a crystalline resin, and a mold release agent. The mold release agent is dispersed in the first amorphous resin, and at least a part of the surface of the mold release agent is coated with core-shell particles including the crystalline resin as a core and the second amorphous resin as a shell.

Description

  The present invention relates to a toner adapted to an image forming technique using an electrophotographic process such as a copying machine, a laser printer, and a facsimile, a manufacturing method thereof, and a process cartridge using the toner.

In recent years, in the electrophotographic process, it is required to reduce the energy consumed by the apparatus. However, in the electrophotographic process, a large amount of energy is consumed by heating in the fixing process, so that the temperature required for fixing can be lowered. It is desired.
As one of means for lowering the fixing temperature, the molecular weight or glass transition temperature of the binder resin constituting the toner is lowered, or a crystalline substance is added to the toner, and the toner is dissolved in the binder resin at the time of fixing. A method of fixing at a lower temperature by lowering the melt viscosity is proposed.
However, if the above measures are taken while maintaining the temperature load and heat resistant storage stability in the actual process, if the toner lowers the fixing temperature too much, the Tg of the resin and the compatibility between the crystalline substance and the binder resin will be lost. Depending on the state, the toner may be blocked during storage, cracks and deformations in development and transfer processes, contamination of various members, and the like, and the print image quality may be significantly impaired.

For example, Patent Document 1 (Japanese Patent No. 4075949) discloses a structure in which a crystalline polyester resin is in contact with the surface of dispersed WAX on a cross section of ruthenium-dyed toner for the purpose of achieving both toner fixing performance and heat-resistant storage. A toner is disclosed in which a cross-sectional area ratio of the structure, the release agent alone, and the crystalline polyester resin alone is defined.
However, in the toner described in Patent Document 1, since the binder resin and the crystalline resin partially dissolve in the binder resin during the production process, the storage stability is lowered, and the development and transfer are performed. There is a problem that it is deformed in a process such as, or it becomes easy to adhere to various members.

Patent Document 2 (Japanese Patent Laid-Open No. 2012-53196) grafts a crystalline material (WAX or crystalline resin) for the purpose of providing a toner having no filming and excellent heat-resistant storage stability and fixing characteristics. The dispersibility of the crystalline material is improved by defining the relationship between these SP values in the toner containing the modified graft modified polymer, the amorphous polyester resin, the crystalline polyester resin, and the release agent. A stabilized toner is disclosed.
However, although the dispersibility of the crystalline material is improved, the compatibility is also increased, and a part of the crystalline material is compatible with the binder resin, so that the storage stability is lowered, and in processes such as development and transfer, etc. There exists a problem that it deform | transforms or it becomes easy to adhere to various members.

Further, Patent Document 3 (Japanese Patent Application Laid-Open No. 2011-232738) discloses a crystalline material that is compatible with a main binder for the purpose of providing a toner having a crystalline material that achieves both low-temperature fixability and stress resistance. Shows toner present in the main binder in a state of being encapsulated by a resin different from the main binder.
Although it is similar to the present invention in terms of encapsulating crystalline polyester that is compatible with the binder resin, the SP values of the main binder, the crystalline substance, and the release agent are not described, and the release agent and the binder are bound. There is no description about the relationship of the resin.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, it is an object of the present invention to provide a toner that has both excellent low-temperature fixability and heat-resistant storage stability, little member contamination, and high production stability.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by bringing the release agent into a specific dispersion state, and have reached the present invention.
That is, the toner of the present invention is
A toner containing a first amorphous resin, a second amorphous resin having an SP value lower than that of the first amorphous resin, a crystalline resin, and a release agent, The release agent is dispersed in the first amorphous resin, and at least a part of the surface of the release agent has the crystalline resin as a core and the second amorphous resin as a shell. The toner is characterized by being coated with core-shell particles.

  According to the present invention, it is possible to provide a toner having both excellent low-temperature fixability and heat-resistant storage stability, less member contamination, and high production stability.

FIG. 3 is a schematic diagram illustrating a structure of a toner of the present invention. It is the schematic which shows an example of the process cartridge of this invention.

The toner of the present invention contains a first amorphous resin, a second amorphous resin having an SP value lower than that of the first amorphous resin, a crystalline resin, and a release agent. The release agent is dispersed in the first amorphous resin, and at least a part of the surface of the release agent has the crystalline resin as a core, and the second amorphous resin It is a state covered with core-shell particles as a shell.
That is, as shown in FIG. 1, in the toner according to the present invention, the release agent A is dispersed in the first amorphous resin R, and at least a part of the surface of the release agent is the crystal. In this state, the core resin is coated with core-shell particles having the functional resin B as the core and the second amorphous resin T as the shell.
The fact that the toner of the present invention has such a structure can be determined by contrast of a toner cross-sectional image on TEM by ruthenium staining or the like. Moreover, it can determine, for example using nano-TMA (thermomechanical analysis) of nano-TA2 local thermal analysis system by Anasys Instruments. This is because the probe is stopped on the target sample surface and the temperature is raised to detect the change in the probe tilt due to the softening of the sample and use a device that performs local thermal analysis from the graph of the temperature-displacement curve. It is determined by temperature.
In addition to the method for staining and discriminating the toner cross-sectional image by the TEM, or the method for dyeing and discriminating the toner cross-sectional image by the TEM, it is preferable to perform observation by Nano-TA2.
In the present invention, the determination is made by a method of determining by staining a toner cross-sectional image by TEM.

  The release agent is dispersed in the first amorphous resin, and at least a part of the surface of the release agent is coated with core-shell particles having the crystalline resin as a core and the second amorphous resin as a shell. By ensuring the compatibility of the release agent with the first amorphous resin, the first amorphous resin and the crystalline resin are hardly compatible with each other in the toner. The Tg drop of the first amorphous resin can be suppressed (heat-resistant storage, etc.), and the boundary from the second amorphous resin to the release agent and the crystalline resin is above the melting point of the crystalline resin. It is possible to effectively promote melting point lowering and lowering of viscosity in the region.

Further, when at least a part of the surface of the release agent is covered with core-shell particles having a crystalline resin as a core and a second amorphous resin as a shell, physical stress on the toner and storage The state of the vicinity of the interface between the first amorphous resin or the release agent and the crystalline resin is less likely to change due to heat load due to transportation, change with time, etc., so that long-term characteristics of the toner can be stabilized. .
Further, since the SP values of the release agent and the first amorphous resin are relatively separated from each other, it is easy to create a state in which the release agent is taken into the toner by interposing the core-shell particles. Is difficult to leave. When the coating of the release agent and the core-shell particles is regarded as one particle, the core-shell particles are easily present in the first amorphous resin due to the presence of the core-shell particles on the surface.

To obtain the toner of the present invention, the first amorphous resin is R, the second amorphous resin is T, the crystalline resin is B, the release agent is A, and R, T, B , And A are expressed as Rsp, Tsp, Bsp, and Asp, the SP value is Rsp>Tsp> Asp.
It is preferable to satisfy the relationship.
The SP value preferably further satisfies the following relationship.
1.0 ≦ Rsp−Tsp ≦ 4.0, preferably 1.0 ≦ Rsp−Tsp ≦ 3.0,
| Rsp−Bsp | ≦ 3 Preferably, | Rsp−Bsp | ≦ 2
| Bsp−Tsp | ≦ 3 Preferably, | Bsp−Tsp | ≦ 2
0.1 ≦ Tsp−Asp ≦ 3.0, preferably 0.1 ≦ Tsp−Asp ≦ 2.0
Further, regarding Rsp and Bsp, it is more preferable that there is not much difference between SP values.
Since the first amorphous resin and the crystalline resin have a barrier at the shell, the first amorphous resin at a temperature at which the SP begins to come into contact with each other due to no difference in SP value. The effect of lowering the viscosity is increased.

The higher the SP value, the easier it is to orient and adapt to the water layer side, so the first resin Rsp as the composition that is the most water-side composition among the above, SP for being dispersed and present inside it In order of value.
In the above, if the SP value is too far, there is a difficulty in adhesion at each interface, and if it is too close, it may be too compatible even if the material composition is different.
When the SP value of water is 23,
As a preferred range, Rsp and Bsp have SP values of 8-15.
As a preferable range, Bsp is 8-14.
As a preferable range, Tsp is 7 to 13.
As a preferable range, Asp is 7 to 13
It is.
If the SP values of the second amorphous resin (T) and the crystalline resin (B) are too close, the number of parts that are easily compatible with each other during the preparation of the encapsulated particles increases. It is difficult to separate the layers of the amorphous resin 1 and the encapsulated crystalline resin.
If the difference between the SP values of the second amorphous resin (T) and the crystalline resin (B) is too large, it is difficult not only to form a uniform shell when preparing the core-shell particles, but also a release agent or core-shell particles. Becomes easy to aggregate and release and to cause poor dispersion inside the toner, thereby facilitating member contamination and the like.
Although the SP value adjustment method is not particularly limited, it can be adjusted by the material type, acid value, molecular weight, etc. For example, in the same composition system, increasing the molecular weight decreases the acid value and lowers the SP value, so the molecular weight is controlled. Thus, the SP value can be adjusted.

From the viewpoint of realizing low-temperature fixability of the toner, the first amorphous resin is preferably an amorphous polyester resin and the crystalline resin is preferably a crystalline polyester resin.
When an amorphous polyester resin is used as the first amorphous resin, the structure of the crystalline polyester resin is close to that of the amorphous resin. Therefore, the amorphous polyester resin is easily compatible when the amorphous resin is melted. Before it is applied, it is a polymer and has high mechanical strength, so it has excellent storage stability.
In the present invention, the crystalline resin refers to a resin having a maximum endothermic value (showing a clear peak) at the melting point in DSC measurement, for example. On the other hand, a non-crystalline resin has a gentle curve based on the glass transition.
The melting point of the crystalline resin and the release agent can be calculated from the melting point peak by DSC measurement.
<Measuring method of melting point>
For example, using a differential scanning calorimeter (for example, DSC-6220R: Seiko Instruments Inc.), first, the sample was heated from room temperature to 150 ° C. at a heating rate of 10 ° C./min, then left at 150 ° C. for 10 minutes, The temperature at the peak apex when cooled and allowed to stand for 10 min and heated again to 150 ° C. at a heating rate of 10 ° C./min is defined as the melting point.

[First Amorphous Resin (R)]
The first amorphous resin (R) is not particularly limited as the type of resin, but when used as an electrostatic latent image developing toner in electrophotography, it is better to use a resin having a polyester skeleton. It is preferable because excellent fixability can be obtained. Examples of the resin having a polyester skeleton include a polyester resin and a block polymer of a polyester and a resin having another skeleton, and the use of the polyester resin is preferable because the uniformity of the colored resin particles obtained is high.

  Examples of polyester resins include ring-opening polymers of lactones, polycondensation products of hydroxycarboxylic acids, polycondensates of polyols (1) and polycarboxylic acids (2), and polyols from the viewpoint of design freedom. A polycondensation product of polycarboxylic acid is preferred.

The peak molecular weight of the polyester resin is usually 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, the heat-resistant storage stability is deteriorated, and if it exceeds 30000, the low-temperature fixability as an electrostatic latent image developing toner is deteriorated.
The glass transition temperature of the polyester resin is 40 ° C. or higher, preferably 50 ° C. or higher, more preferably 60 ° C. or higher. If the temperature is lower than 40 ° C., the obtained colored resin particles may be deformed when placed in a high-temperature environment such as midsummer, or the colored resin particles may stick to each other and behave as original particles. The glass transition temperature is 80 ° C or lower, preferably 70 ° C or lower. When the temperature exceeds 80 ° C., when the colored resin particles are used as a toner for developing an electrostatic latent image, the fixability is deteriorated.

<Polyol>
Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2), (1-1) alone or (1-1) and a small amount of (1-2). Mixtures are preferred.
Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above alicyclic diols; 3, 3 ′ 4,4'-dihydroxybiphenyls such as difluoro-4,4'-dihydroxybiphenyl; bis (3-fluoro-4-hydroxyphenyl) methane, 1-phenyl-1,1-bis (3-fluoro-4- Hydroxyphenyl) ethane, 2,2-bis (3-fluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane (also known as: tetrafluorobisphenol A), 2 , 2-bis (3-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane and other bis (hydroxyphenyl) alkanes; bis (3-fluoro-4-hydroxyphenyl) ether and the like Bis (4-hydroxyphenyl) ethers; alkylene oxides of the above bisphenols (ethylene oxy Id, propylene oxide, and the like butylene oxide, etc.) adducts.

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

  The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

<Polycarboxylic acid>
Examples of polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone or (2-1) and a small amount of ( The mixture of 2-2) is preferred.
Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) , Naphthalenedicarboxylic acid, etc.), 3-fluoroisophthalic acid, 2-fluoroisophthalic acid, 2-fluoroterephthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, 2,3,5,6-tetrafluoroterephthalic acid , 5-trifluoromethylisophthalic acid, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2-bis (3-carboxyphenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) -4,4'-biphenyldicarboxylic acid, 3,3'-bis (trifluoro Chill) -4,4'-biphenyl dicarboxylic acid, 2,2'-bis (trifluoromethyl) -3,3'-biphenyl dicarboxylic acid, and the like hexafluoroisopropylidene diphthalic anhydride. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.

  Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

The ratio of polyol to polycarboxylic acid is usually 2/1 to 1/2, preferably 1.5 / 1 to 1 as the equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH].
1 / 1.5, more preferably 1.3 / 1 to 1 / 1.3. __

  A polyester resin that is at least partially dissolved in an organic solvent is used, but the acid value is preferably 2 to 24 mgKOH / g. When the acid value exceeds 24 mgKOH / g, the transition to the aqueous phase is likely to occur, and as a result, loss in the material balance occurs during the production process, or the dispersion stability of the oil droplets deteriorates. Problems are likely to occur. On the other hand, when the acid value is less than 2 mgKOH / g, the polarity of the resin becomes low, and it becomes difficult to uniformly disperse the colorant having a certain degree of polarity in the oil droplets.

The content of the first amorphous resin in the toner of the present invention is preferably 25 to 90% by mass, more preferably 30 to 80% by mass.
The content of the first amorphous resin is preferably greater than at least the content of the core-shell particles.

[Crystalline resin (B)]
The toner of the present invention contains a crystalline resin (B) in order to improve low-temperature fixability. The crystalline resin is not particularly limited as long as it is crystalline, and examples thereof include polyester resins, urethane-modified polyester resins, urea-modified polyester resins, polyurethane resins, and polyurea resins. As the crystalline resin (B), when the first amorphous resin is a polyester resin, a crystalline polyester resin is preferable.

The crystalline polyester is obtained as a polycondensate of a polyol and a polycarboxylic acid, and the polyol is preferably an aliphatic diol, specifically, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4. -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, neopentyl glycol, 1,4-butenediol, 1,10-decanediol, 1,9-nonanediol and the like, among which 1,4-butanediol, 1,6-hexanediol and 1,8-octanediol are preferable, and 1,6-hexanediol, ethylene glycol, 1 , 10-decanediol, 1,9-nonanediol. The polycarboxylic acid is preferably an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid, or an aliphatic carboxylic acid having 2 to 12 carbon atoms such as adipic acid or 1,10-dodecanedioic acid. An aliphatic carboxylic acid is more preferable in order to increase the ratio.

Examples of the polyurea resin include a polyurea resin synthesized from a diamine component and a diisocyanate component, and a trivalent or higher valent amine component or isocyanate component may be used as necessary.
Examples of the amine component include aliphatic amines and aromatic amines. Among them, aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms are exemplified. If necessary, trivalent or higher amines may be used.
Examples of the aliphatic diamines having 2 to 18 carbon atoms include alkylene diamines having 2 to 6 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.); polyalkylenes having 4 to 18 carbon atoms Diamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; these alkyl groups having 1 to 4 carbon atoms or hydroxyalkyl substituents having 2 to 4 carbon atoms Body (dialkylaminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.); Heterocycle-containing aliphatic diamine {alicyclic diamine having 4 to 15 carbon atoms [1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.] C4-C15 heterocyclic diamine [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4 bis (2-amino-2-methylpropyl) piperazine, 3,9-bis ( 3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.]}; C8-C15 aromatic ring-containing aliphatic amines (xylylenediamine, tetrachloro-p-xylyl) Range amine, etc.).

  Examples of the aromatic diamine having 6 to 20 carbon atoms include unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine. , Crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4, 4 ′, 4 ″ -triamine, naphthylenediamine, etc.]; aromatic diamines having a C1-C4 nucleus-substituted alkyl group [2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltriamine; Range amine, 4,4'-diamino-3,3'-dimethyldiphenyl meta 4,4′-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4- Diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6- Dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,5-diethyl- 3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyl Diphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5 '-Tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.), and mixtures of various proportions of these isomers; nuclear substituted electron withdrawing groups (halogens such as Cl, Br, I, F; methoxy, ethoxy, etc. An aromatic diamine having an alkoxy group (such as a nitro group) [methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4 -Bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-pheny Range amine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane, 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine Bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, Bis (4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodo) Aniline), 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis (2- Luoaniline), 4-aminophenyl-2-chloroaniline and the like]; aromatic diamine having a secondary amino group [the unsubstituted aromatic diamine, the aromatic diamine having a C1-C4 nucleus-substituted alkyl group, and Mixtures of various ratios of these isomers, part or all of the primary amino groups of aromatic diamines having the above-mentioned nucleus-substituted electron withdrawing groups were replaced with secondary amino groups by lower alkyl groups such as methyl and ethyl Those] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene and the like].

  Trivalent or higher amines can be obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mol of acid) polyamines (alkylenediamine, polyalkylenepolyamine etc.). Low molecular weight polyamide polyamine, etc.], polyether polyamine [hydride of cyanoethylated polyether polyol (polyalkylene glycol, etc.), etc.].

The crystalline resin preferably contains a crystalline resin having a melting point of 50 to 105 ° C, more preferably 55 to 80 ° C. When the toner has a melting point of 50 ° C. or higher and the toner is placed in a high temperature environment such as midsummer or when a load is further applied, the toner is easily deformed, and the toner particles stick to each other as original particles. There will be no loss of behavior. Further, the fixing property is improved when the temperature is 105 ° C. or lower. Further, when the temperature is 80 ° C. or lower, the fixing lower limit temperature is lowered, so that the fixing property is further improved.
Further, the crystalline resin preferably contains a crystalline resin having a weight average molecular weight of 10,000 to 40,000. When the crystalline resin having a weight average molecular weight of 10,000 or more is contained, the heat resistant storage stability is improved, and when the weight average molecular weight is 40000 or less, the low temperature fixability is improved.

The content of the crystalline resin (B) is preferably from 0.5% by weight to 20% by weight in the toner, more preferably from 1% by weight to 10% by weight, and even more preferably from 2% by weight to 10% by weight. It is.
When there is little content of crystalline resin (B), the coverage to a mold release agent will worsen and it will become difficult to acquire the effect which accelerates | stimulates melting | fusing point fall when it fuse | melts.

[Second Amorphous Resin (T)]
The second amorphous resin (T) is not particularly limited as long as the SP value is different from the first amorphous resin (R), and can be appropriately selected according to the purpose. A resin obtained by modifying the first amorphous resin (R) may be used, but a resin having a skeleton that is hardly compatible with the crystalline resin (B) is preferable. When a crystalline polyester resin is used, a resin having a skeleton that is hardly compatible with the crystalline polyester resin is preferable, and a vinyl resin is preferable because it is easily available and synthesized.
The method for synthesizing the vinyl resin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a method obtained by polymerizing a monomer having a polymerizable double bond. At this time, a known polymerization initiator may be used.

  The monomer having a polymerizable double bond is not particularly limited and may be appropriately selected depending on the intended purpose. For example, styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert- Butyl styrene, 4-methoxy styrene, 4-ethoxy styrene, 4-carboxy styrene or metal salt thereof, 4-styrene sulfonic acid or metal salt thereof, 1-vinyl naphthalene, 2-vinyl naphthalene, allylbenzene, phenoxyalkylene glycol acrylate, Phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, phenoxy polyalkylene glycol methacrylate, etc. (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate, fumaric acid, monofumaric acid Alkyl, crotonic acid, itaconic acid, itaconic acid monoalkyl, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl, cinnamic acid, etc.), sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters and salts thereof, Examples thereof include phosphate group-containing vinyl monomers and salts thereof.

The mass ratio (B) / (T) between the crystalline resin (B) and the second amorphous resin (T) encapsulated in the core-shell particles is not particularly limited and is appropriately selected depending on the purpose. However, 0.1 to 2.5 is preferable, and 0.5 to 2.5 is more preferable. When the mass ratio is less than 0.1, the low-temperature fixability may be deteriorated, and when it exceeds 2.5, contamination properties such as heat-resistant storage property and filming may be deteriorated.
On the other hand, it is preferable that the mass ratio is in a more preferable range from the viewpoint of excellent heat-resistant storage stability, low-temperature fixability, and hot offset resistance.

  The method for analyzing the second amorphous resin (T) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a gas chromatograph mass spectrometer (GC-MS) or nuclear magnetic A method of analyzing the second amorphous resin (T) in the toner using a resonance apparatus (NMR), and dissolving and removing other materials in the toner using an organic solvent, and the amorphous resin ( Examples include a method of analyzing the resin (T) after separating T).

Specifically, the resin composition and the composition ratio can be calculated from the ¹³ C-NMR spectrum and GC-MS measurement analyzed by the method described below.
Measurement of the ¹³ C-NMR, the sample were placed 50mg in capped glass tube and heated for 1 minute in a high-frequency heating apparatus (QUICKER1010, manufactured by DIC Corporation), the decomposition product deuterochloroform (CDCl ₃₎ 30.5 mL and The relaxation reagent Tris (2,4-pentanedionato) chromium (III) (Cr (acac) ₃ ) is added, and the measurement can be performed using a nuclear magnetic resonance apparatus JNM-LA300 (manufactured by JEOL Ltd.).
For the GC-MS measurement, a mass spectrometer (JMS-K9, manufactured by Honden Electronics Co., Ltd.) was used, and the column was INERT CAP 5MS / Sil (30 m × 0.25 mm, ID 0.25 μm) (GL Science) A pyrolysis GC-MS measurement can be performed under the conditions of a temperature rising rate of 40 ° C. (3 minutes), then 10 ° C./minute, and then 300 ° C. (5 minutes).

<Release agent>
As the release agent, a material such as wax or silicone oil, which has a sufficiently low viscosity when heated in the fixing process and does not easily dissolve or swell on the surface of the fixing member with other materials of the toner, is used. Considering the storage stability of the toner itself, it is preferable to use a wax that exists as a solid in the toner during normal storage.

  Examples of the wax include hydrocarbons and carbonyl group-containing waxes. As the hydrocarbon wax, a long-chain hydrocarbon wax is preferable. As the long-chain hydrocarbon wax, a polyolefin wax (polyethylene wax, polypropylene wax, etc.); In addition to wax (paraffin wax, sazol wax, microcrystalline wax, etc.); Fischer-Tropsch wax is also included.

  Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1, 18-octadecanediol distearate etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide etc.); polyalkylamides (trimellitic acid tristearyl amide etc.) ); And dialkyl ketones (such as distearyl ketone).

Of these, hydrocarbon waxes having particularly good releasability are preferred. Furthermore, when a long-chain hydrocarbon wax is used as a release agent, a carbonyl group-containing wax may be used in combination.
The release agent may be contained in the toner in an amount of 2 to 25% by mass, preferably 3 to 20% by mass, more preferably 4 to 15% by mass. If it is less than 2% by mass, the effect of improving the fixing releasability cannot be exhibited, and if it exceeds 25% by mass, the mechanical strength of the toner is lowered.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent (A), Although it can select suitably according to the objective, Less than 80 degreeC is preferable and 50 to 77 degreeC is more preferable. When the melting point of the release agent (A) is 80 ° C. or higher, the hot offset resistance may be deteriorated, and when it is less than 50 ° C., the heat resistant storage stability may be deteriorated.
The melting point of the release agent (A) can be measured by, for example, a differential scanning calorimetry (DSC) apparatus (for example, DSC-6220R: Seiko Instruments Inc.).

The coverage of the core-shell particles on the release agent is preferably 50% or more, more preferably 70% or more. More preferably, it is 80% or more.
The dispersed particle diameter of the release agent is preferably ¼ or less of the average toner particle diameter.
Release agent dispersed particle size> core shell particle size, and the core shell particle size is preferably 1/5 or less, more preferably 1/7 or less, relative to the release agent dispersed particle size.
If the core-shell particles are too small in size, or if the amount of the core-shell particles added to the toner is too large, the oil phase viscosity at the time of toner preparation becomes too high, which may cause poor emulsification.
When the particle diameter of the core-shell particles is large, there may be particles that cannot be dispersed or taken into the toner, and may obstruct free fine powder of toner or uniform emulsification of toner.
If the addition amount of the core-shell particles to the toner is small, the effect of reducing the viscosity at the time of melting is almost lost.

  The release agent is preferably not present in the vicinity of the toner surface (200 or 300 nm or less). However, if the coating rate of the core-shell particles to the release agent is high, member contamination due to crystalline substances such as the release agent In particular, there is no problem unless the release agent is selectively oriented on the toner surface.

The glass transition temperature (Tg) of the second amorphous resin is preferably equal to or higher than the glass transition temperature (Tg) of the first amorphous resin (R).
Particularly when the Tg of the second amorphous resin is lower by 5 ° C. or more than the Tg of the first amorphous resin, the heat resistance characteristics of the toner originally derived from the first amorphous resin may be deteriorated. is there. The ratio of the second amorphous resin as a whole of the toner is considerably small, but it exists near the interface of the material that causes plasticization or a melting point drop due to compatibility or the like, which may affect the heat resistance characteristics of the toner.

  Although there is no particular limitation, the binder resin may be a linear or non-linear resin, one of which may be graft-modified, or may be combined with an ester elongation method.

<Calculation method and analysis method of various characteristics of toner and toner component>
<< SP value >>
The SP value (solubility parameter / Solubility Parameter) will be described. The SP value is called a solubility parameter, and is a numerical value of how easily each other is soluble.
The SP value is expressed as a square root of an attractive force between molecules, that is, a cohesive energy density (CED).
The CED is the amount of energy required to evaporate 1 mL.
The calculation of the SP value in the present invention can be performed using the following formula (I) by the Fedors method.
SP value (dissolution parameter) = (CED value) ^1/2 = (E / V) ^1/2 ··· Formula (I)
In the above formula (I), E is the molecular cohesive energy (cal / mol), V is the molecular volume (cm ³ / mol), the evaporation energy of the atomic group is Δei, and the molar volume is Δvi, (II), represented by formula (III).
E = ΣΔei Formula (II)
V = ΣΔvi Formula (III)
Although there are various theories on the calculation method of the SP value, the Fedors method generally used in the present invention is used.
The data described in “Basic Theory of Adhesion” (Akira Imoto, published by Kobunshi Shuppankai, Chapter 5) are used for this calculation method and various data of evaporation energy Δei and molar volume Δvi of each atomic group.
For those not shown, such as —CF ₃ group, R.I. F. Fedors, Polym. Eng. Sci. 14, 147 (1974).
For reference, when the SP value represented by the formula (I) is converted to (J / cm ³ ) ^1/2 , 2.046 is converted to SI unit (J / m ³ ) ^1/2 . In that case, it may be multiplied by 2,046.

For example, when the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent are synthesized and mixed, these SP values are as described above. Easy to calculate.
Usually, it is difficult to calculate the SP value from the charged composition ratio in a resin in which a monomer is added during the polymerization to change the resin skeleton.
In addition, the composition of the components contained in the toner is generally unknown, and it is difficult to calculate the SP value.
However, the calculation of the SP value by the Fedors method can be performed by specifying the type and ratio of the monomer constituting the resin or the like.
For example, a mixture of the first amorphous resin, the second amorphous resin and the crystalline resin or the release agent is separated by GPC, and each separated component is analyzed later. The SP value can be calculated by adopting a method.
That is, in GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire integral of the elution curve are collected.
After concentrating and drying this collected eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and 1H-NMR measurement is performed. From the integration ratio of each element, The constituent monomer ratio can be calculated.
Another method is to calculate the constituent monomer ratio by concentrating the eluate, hydrolyzing with sodium hydroxide, etc., and performing qualitative quantitative analysis of the decomposition products using high performance liquid chromatography (HPLC). Can do.

  The SP value calculated by the Fedors method can be calculated by specifying the type and ratio of the monomer constituting the resin, but the SP value in the present invention is the ratio when the monomer type is specified by the above analysis. The respective composition ratios were added in order from the highest, and the composition was calculated from the monomer composition when the total reached 90 mol% of the total (that is, the SP value was calculated for the remaining monomers). We decided not to add).

First, 1 g is put into 100 mL of THF, and a solution in which the soluble component is dissolved is obtained while stirring for 30 minutes under the condition of 25 ° C.
This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner.
Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.
On the other hand, a fraction collector is placed at the eluate discharge port of GPC, and the eluate is collected at every predetermined count. Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). .

The first and second amorphous resins contained in the toner, the crystalline resin, the monomer composition of the release agent, and the composition ratio can be obtained from the peak integration ratio of the obtained spectrum.
For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
Peak assignment is, for example, around 8.25 ppm: derived from the benzene ring of trimellitic acid (for one hydrogen), from 8.07 ppm to 8.10 ppm: derived from the benzene ring of terephthalic acid (for four hydrogens), from 7.1 ppm to Around 7.25 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens), around 6.8 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens) and derived from double bond of fumaric acid (for 2 hydrogens) 2 ppm to 5.4 ppm vicinity: bisphenol A propylene oxide adduct derived from methine (1 hydrogen) 3.7 ppm to 4.7 ppm vicinity: bisphenol A propylene oxide adduct derived from methylene (2 hydrogens) and bisphenol A ethylene Oxide adduct derived from methylene (4 hydrogens) around 1.6 ppm: methyl bisphenol A It can be derived from (6 pieces of hydrogen).
From these results, the SP values of the amorphous resin, the crystalline resin, and the release agent can be calculated from the formula (I).

  As described above, the SP values of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent can be calculated from the toner. Similarly, the SP value can also be calculated from the single material of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent. The SP value calculated from the toner and the SP value of the material alone are almost the same value. In the present invention, the SP value measured by the material alone is used.

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

-Master batch-
The colorant can also be used as a master batch combined with a resin (binder resin).
The masterbatch resin kneaded with the colorant in the masterbatch is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polystyrene, poly p-chlorostyrene, and polyvinyltoluene. Styrene and its substituted polymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic acid Butyl copolymer, styrene-α-chloromethacryl Methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer Styrene copolymers such as styrene-maleic acid ester copolymer, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide , Polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. Moreover, the same thing as the said amorphous resin (R), the modified resin mentioned later, etc. can be used. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as a manufacturing method of the said masterbatch, According to the objective, it can select suitably, For example, the resin for said masterbatch and a coloring agent are mixed and / or kneaded applying a high shear force. The method etc. are mentioned. At this time, an organic solvent may be used in order to enhance the interaction between the colorant and the resin for the masterbatch.
Also, a so-called flushing method called an aqueous paste containing water of a colorant is mixed and / or kneaded together with the resin and organic solvent for the masterbatch, and the colorant is transferred to the resin side for the masterbatch, Also, the method of removing the organic solvent component is preferably used because the wet cake of the colorant can be used as it is, and does not need to be dried.
The mixing and / or kneading method is not particularly limited and may be appropriately selected depending on the intended purpose. However, a method using a high shearing dispersion apparatus such as a three-roll mill is preferable.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass%-30 mass% are preferable in the said toner, and 3 mass%-20 mass% are more. preferable. When the content of the colorant is less than 1% by mass, the density of printed characters and images may be reduced, and the image quality may be reduced. When the content exceeds 30% by mass, the resin component is relatively As a result, the toner may be difficult to fix on the paper.

<Other ingredients>
The other components in the toner are not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose. Examples thereof include a charge control agent, a dispersion stabilizer, a magnetic material, and fluidity. Examples thereof include an improver and a cleaning property improver. Moreover, the modified resin and amine compound which are mentioned later may be included.
Further, the content of the other components is not particularly limited as long as the effects of the present invention are not impaired, and can be appropriately selected according to the purpose.

-Charge control agent-
The charge control agent is not particularly limited and all known ones can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines Quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. .

  Specific examples of the charge control agent include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, and salicylic acid. -Based metal complex E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Co., Ltd.) Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, Hoechst), LRA-901 LR-147 which is a boron complex (manufactured by Nippon Carlit Co., Ltd.) , Copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt. These may be used alone or in combination of two or more.

  The content of the charge control agent is not particularly limited as long as the effect of the present invention is not hindered and the fixing property is not hindered, and can be appropriately selected according to the purpose. 0.5 mass%-5 mass% are preferable, and 0.8 mass%-3 mass% are more preferable.

-Dispersion stabilizer-
There is no restriction | limiting in particular as said dispersion stabilizer, According to the objective, it can select suitably, For example, an inorganic dispersant, a protective colloid, etc. are mentioned.
The inorganic dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

  The protective colloid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid Acids such as maleic acid and maleic anhydride; β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-methacrylate Hydroxypropyl, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate (Meth) acrylic monomers containing hydroxyl groups such as oxalate, N-methylolacrylamide, N-methylolmethacrylamide; vinyl alcohols such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, or ethers with vinyl alcohol Vinyl acetates such as vinyl acetate, vinyl propionate and vinyl butyrate; vinyl alcohols such as acrylamide, methacrylamide and diacetone acrylamide; esters of the vinyl alcohol and a compound containing a carboxyl group, or methylol compounds thereof; Acid chlorides such as acrylic acid chloride and methacrylic acid chloride; homopolymers such as those having a nitrogen atom such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine or its heterocyclic ring Limer or copolymer; polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl Examples include polyoxyethylenes such as phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonylphenyl ester; and celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. These may be used alone or in combination of two or more.

-Magnetic material-
There is no restriction | limiting in particular as said magnetic body, According to the objective, it can select suitably, For example, iron oxide containing magnetic iron oxides, such as a magnetite, a maghemite, a ferrite, or another metal oxide; Iron, cobalt Metal such as nickel, or these metals and metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium Alloys; or mixtures thereof are used.

Examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , and PbFe. Examples thereof include ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, and nickel powder. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of iron trioxide and γ-iron trioxide are particularly preferable.

-Fluidity improver-
As the fluidity improver, there is no particular limitation as long as it has a function of performing surface treatment to increase hydrophobicity and preventing deterioration of flow characteristics and charging characteristics even under high humidity, and it is appropriately selected according to the purpose. Examples thereof include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. These may be used alone or in combination of two or more.
Silica and titanium oxide in the inorganic fine particles are preferably subjected to surface treatment with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.

-Cleaning improver-
The cleaning property improver is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid; polymethyl methacrylate fine particles, polystyrene fine particles and the like. Examples thereof include fine polymer particles produced by soap-free emulsion polymerization. These may be used alone or in combination of two or more.
The polymer fine particles preferably have a relatively narrow particle size distribution, and the volume average particle size of the polymer fine particles is preferably 0.01 μm to 1 μm.

The volume average particle size (Dv) of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 2 μm to 8 μm, and more preferably 4 μm to 6.5 μm.
The number average particle diameter (Dn) of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.6 μm to 8 μm, more preferably 3.2 μm to 5.2 μm. . The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is not particularly limited and may be appropriately selected depending on the intended purpose. Preferably, 1.00 to 1.15 is more preferable. When the Dv / Dn is within the above preferable range, all the performances of low-temperature fixability, hot offset resistance, and heat-resistant storage stability are excellent, and particularly when used in a full-color copying machine, the glossiness of the image is excellent. This is advantageous. Furthermore, in a two-component developer, even if a long-term toner balance is made, fluctuations in the toner particle size in the developer are reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. This is advantageous.

  In the toner of the present invention, the average circularity value measured by the flow type particle image analyzer is preferably 0.97 or more. When the average circularity measured by the flow type particle image analyzer is 0.97 or more, a good image with few transfer omissions in the line image can be obtained. More preferably, the average circularity is 0.98 or more. This is presumably because the surface of the toner is sufficiently smooth, so that the contact point with the image support is reduced and the toner bite transfer failure from the electrostatic charge holding member to the transfer material is reduced.

In the present invention, the average circularity can be measured using a flow particle image analyzer (FPIA-2100, manufactured by Sysmex Corporation). An outline of the apparatus and measurement is described in JP-A-8-136439. In the measurement, after preparing a 1% by mass sodium chloride aqueous solution using primary sodium chloride, 50 mL to 100 mL of a solution passed through a 0.45 μm filter was added with a surfactant, preferably an alkylbenzene sulfonate, as a dispersant. Add 1 mL to 5 mL and add 1 mg to 10 mg of sample. This is subjected to a dispersion treatment for 1 minute with an ultrasonic disperser, and measurement is performed using a dispersion liquid in which the particle concentration is adjusted to 5,000 / μL to 15,000 / μL.
The particle concentration is calculated by taking the diameter of a circle having the same area as the two-dimensional image area captured by the CCD camera as the equivalent circle diameter. From the accuracy of CCD pixels, the effective circle diameter is 0.6 μm or more, and the number of particles is obtained. The average circularity X is obtained by the following formula.
Average circularity X = Σ (L0 / L) / n
However, “L0” represents the perimeter of a circle having the same projected area as the particle image, “L” represents the perimeter of the projected image of the particle, and “n” represents the total number of particles.
The average circularity in the toner of the present invention is an index of the degree of unevenness of the toner shape, and is 1.0 when the toner is perfectly spherical, and the average circularity becomes smaller as the surface shape becomes more complicated.

The volume average particle diameter (Dv) and number average particle diameter (Dn) of the toner are measured by a particle size distribution measuring device (for example, Coulter Counter TA-II, Coulter Multisizer II, Coulter Multisizer III (all Etc.) and the like.
Specifically, 0.1 mL to 5 mL of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% by mass sodium chloride aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic solution in which the measurement sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the particle size distribution measuring apparatus is used to measure the volume and number of toner particles or toner using a 100 μm aperture. And volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter and number average particle diameter of the toner can be obtained.
As a channel, it is 2.00 micrometers or more and less than 2.52 micrometers; 2.52 micrometers or more and less than 3.17 micrometers; 3.17 micrometers or more and less than 4.00 micrometers; 4.00 micrometers or more and less than 5.04 micrometers; 5.04 micrometers or more and less than 6.35 micrometers; .35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; Less than 40 μm; 25.40 μm or more and less than 32.00 μm; 3 channels of 32.00 μm or more and less than 40.30 μm are used, and particles having a particle size of 2.00 μm or more and less than 40.30 μm are targeted.

The method for producing a toner of the present invention includes a first amorphous resin, a second amorphous resin having an SP value lower than that of the first amorphous resin, a crystalline resin, a release agent, The mold release agent is dispersed in the first amorphous resin, and at least a part of the surface of the mold release agent has the crystalline resin as a core and the second amorphous resin. A method for producing toner in a state of being coated with core-shell particles having a resin shell, wherein the second amorphous resin has at least a vinyl polymer, and the crystalline resin and the second amorphous resin A core-shell particle forming step formed by:
A dispersion step of dispersing the core-shell particles in the first amorphous resin.

When the first amorphous resin is dissolved in the oil phase, if the crystalline resin is added here, the degree of crystallization in the final toner (recrystallization or compatibility state) due to a compatibility phenomenon or the like ) Must be controlled during the manufacturing process. For example, crystallization of a crystalline resin and recrystallization of a compatible interface can be promoted by annealing after preparing toner base particles, but it is necessary to apply heat uniformly for a long time at a low temperature (for example, 50 ° C., 10h). The low temperature is set in a region below the melting point peak of the crystalline resin and in a region that is not too high together with less than Tg of the toner. It is preferable to spend time slowly for less uniform influence on the toner and more uniform crystallization. However, this is in conflict with productivity.
In the present invention, the crystalline resin can be shelled and introduced into the oil phase in the form of particles whose crystal state has been adjusted in advance. The state can be prevented from changing.

The toner production process is a process using a solvent, and it is more preferable to carry out the oil phase preparation, oil droplet dispersion preparation, and desolvation at 50 ° C. or lower, more preferably 40 ° C. or lower.
In the step of preparing the oil droplet dispersion, both the release agent and the core-shell particles are preferably present as a dispersion, and the viscosity is preferably adjusted when the oil phase is dispersed. If the viscosity is too high, oil droplets for forming toner particles will not be formed well or it will be difficult to adjust the desired particle size.
The resin of the core-shell particles is dissolved in the oil droplet dispersion preparation step, and may be appropriately swollen unless the shell is broken.
Whether or not the toner itself is shelled is not particularly limited.

<Core shell particle formation process>
As a method of obtaining the toner of the present invention, a crystalline resin such as a crystalline polyester resin is encapsulated with a second amorphous resin, the encapsulated crystalline resin is a core, and the second amorphous resin is a shell. It is preferable to have a core-shell particle forming step for producing core-shell particles.
As a method for encapsulating the crystalline resin, (1) a method in which fine particles of a crystalline resin are prepared in advance and the periphery of the fine particles is coated with a second amorphous resin, and (2) the crystalline resin is encapsulated in a solvent. (3) a method of forming a capsule structure while producing fine particles in which the second amorphous resin is dissolved, and then removing the solvent and phase-separating the crystalline resin and the second amorphous resin; (4) a method of producing fine particles of a dispersion liquid in which a crystalline resin is dispersed as fine particles in a solution in which the amorphous resin is dissolved, and then removing the solvent to produce fine particles containing the crystalline resin; After obtaining fine particles of the monomer solution in which the crystalline resin is dissolved or dispersed as fine particles in the monomer of the second amorphous resin, the monomer is polymerized to form a resin, which is used by the second amorphous resin. Method for obtaining an encapsulated crystalline resin And the like, but preferable because the easily obtained a uniform capsule particle method mentioned last (4).

  In the method described in (4), there is no particular limitation as to a method for obtaining fine particles in which the release agent (A) is dispersed as fine particles in the monomer solution of the second amorphous resin. The monomer solution is prepared in an aqueous medium and the release agent (A) is dispersed in the aqueous medium. The second amorphous resin (T) can be selected later. It is preferable in that the monomer used as a raw material is easily polymerized. There is no restriction | limiting in particular as a polymerization method of the monomer used as the raw material of said 2nd amorphous resin (T), According to the objective, it can select suitably, For example, a suspension polymerization method, a miniemulsion polymerization method, etc. Is mentioned.

<Dispersing process>
The dispersion step is a step of dispersing the core-shell particles in the first amorphous resin (R).
Through this dispersion step, the core-shell particles (BT) can be introduced into the toner.
Examples of the method for performing the dispersing step include the methods described in the following (1) to (3).
(1) A method of preparing an oil droplet dispersion containing oil droplets containing the core-shell particles by preparing an oil phase in which the core-shell particles (BT) are dissolved or dispersed, and dispersing the oil phase in an aqueous phase.
(2) When preparing an aqueous phase in which the core-shell particles (BT) are dispersed and preparing oil droplets by dispersing the oil phase in the aqueous phase, the core-shell particles (BT) are placed inside the oil droplets. How to incorporate.
(3) An oil phase dispersion containing oil droplets is prepared by dispersing an oil phase in an aqueous phase, the core shell particles (BT) are added to the oil droplet dispersion, and the core shell particles are contained inside the oil droplets. A method of incorporating (BT).
Among these, the method described in (1) is preferable in that the core-shell particles (BT) can be reliably taken into the oil droplets. Therefore, the dispersion step includes an oil phase preparation step for preparing an oil phase in which at least the first amorphous resin, the core-shell particles, and the release agent are dissolved or dispersed in an organic solvent, and at least in an aqueous medium. An aqueous phase preparation step for producing an aqueous phase having a surfactant, and an oil droplet dispersion preparation step for producing a dispersion in which the oil phase is dispersed in the aqueous phase and particles comprising the oil phase are dispersed. It is preferable. More preferably, after the oil droplet dispersion preparation step, a solvent removal step for removing the solvent in the oil phase, a washing step for washing the toner particles, and a drying step for removing moisture by drying are included. .

-Oil phase preparation process-
The oil phase preparation step is a step of preparing an oil phase in which at least the first amorphous resin, core-shell particles (BT), and a release agent are dissolved or dispersed in an organic solvent. The oil phase may contain a colorant, a modified resin, an amine compound, the charge control agent, and the like as necessary.
There is no restriction | limiting in particular as said oil phase preparation process, According to the objective, it can select suitably, For example, said core shell particle | grains (BT), a coloring agent, etc. are gradually added in an organic solvent, stirring. And a method of dissolving or dispersing.

  At this time, when a pigment is used as the colorant, or when a substance that is difficult to dissolve in an organic solvent such as a charge control agent is added, it is preferable to make the particles small prior to the addition to the organic solvent. The method for reducing the particles of the colorant (pigment) is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include a method using the masterbatch as the colorant. The same method as the master batch can be applied to the control agent.

  Further, as another method for reducing the particles of the colorant, etc., a method of adding a dispersion aid as necessary in an organic solvent and dispersing the colorant in a wet manner to obtain a wet master; When dispersing those that melt below the boiling point of the solvent, add a dispersion aid as necessary in the organic solvent, heat with stirring with the dispersoid, dissolve once, and then stir or shear. And a method of crystallizing by cooling while producing dispersoid microcrystals.

  The colorant dispersed using these methods may be further dispersed after being dissolved or dispersed together with the capsule containing the release agent (A) in an organic solvent. For dispersion, a known disperser such as a bead mill or a disk mill can be used.

There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The volatile organic solvent whose boiling point is less than 100 degreeC is preferable at the point from which the solvent removal process mentioned later becomes easy.
Examples of such organic solvents include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples include ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These may be used alone or in combination of two or more.
When the resin dissolved or dispersed in the organic solvent is a resin having a polyester skeleton, the organic solvent may be an ester solvent such as methyl acetate, ethyl acetate, or butyl acetate, or methyl ethyl ketone, methyl isobutyl ketone, or the like. Ketone solvents are preferred because of their high solubility.
Among these, as the organic solvent, methyl acetate, ethyl acetate, and methyl ethyl ketone are particularly preferable from the viewpoint of easy solvent removal treatment.

--Modified resin--
The oil phase has an isocyanate terminal at the end for the purpose of increasing the mechanical strength of the resulting toner or preventing hot offset resistance during fixing in addition to the mechanical strength when used as a toner for developing an electrostatic latent image. A modified resin having a group (also referred to as “prepolymer”) may be contained.
The isocyanate group of the modified resin is partly converted to an amino group by hydrolysis in the process of obtaining particles (oil droplets) in which the oil phase is dispersed in the aqueous phase in the oil droplet dispersion preparation step described later. . The produced amino group reacts with an unreacted isocyanate group, and an elongation reaction proceeds.
The content of the modified resin is preferably 30% by mass or less, more preferably 20% by mass or less with respect to the first amorphous resin.

  There is no restriction | limiting in particular as a manufacturing method of the said modified resin, According to the objective, it can select suitably, For example, (1) The method of obtaining the resin which has an isocyanate group by carrying out a polymerization reaction with the monomer containing isocyanate, (2) A method in which an isocyanate group is introduced into a polymer terminal by reacting with a polyisocyanate after polymerization is obtained by polymerizing a resin having active hydrogen at the terminal. Among these, the method described in the latter (2) can be preferably employed because of the controllability of introducing an isocyanate group at the terminal.

  The active hydrogen in the resin having an active hydrogen at the terminal is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, A mercapto group etc. are mentioned. Among these, an alcoholic hydroxyl group is preferable.

  The skeleton of the modified resin is not particularly limited and may be appropriately selected depending on the purpose. However, in consideration of the uniformity of the particles, the same as the first amorphous resin (R) that dissolves in the organic solvent. Those having a polyester skeleton are particularly preferable.

  When the active hydrogen in the resin having active hydrogen at the terminal is an alcoholic hydroxyl group and the skeleton of the modified resin is a polyester skeleton, a method for producing a modified resin having the alcoholic hydroxyl group at the terminal of the polyester skeleton is as follows. For example, in the polycondensation of a polyol and a polycarboxylic acid, there may be mentioned a method in which the polycondensation reaction is performed with the number of functional groups of the polyol being larger than the number of functional groups of the polycarboxylic acid.

--Amine compound--
The oil phase is preferably used in combination with an amine compound for the purpose of reliably reacting the extension reaction of the modified resin or introducing a crosslinking point.
Examples of the amine compound (B) include a diamine (B1), a trivalent or higher polyamine (B2), an amino alcohol (B3), an amino mercaptan (B4), an amino acid (B5), and any one of the amino acids B1 to B5. What blocked the group (B6) etc. are mentioned. These may be used alone or in combination of two or more.

  The diamine (B1) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, Aromatic diamines such as tetrafluoro-p-phenylenediamine; alicyclic diamines such as 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine; ethylenediamine, tetramethylenediamine, hexamethylenediamine And aliphatic diamines such as dodecafluorohexylenediamine and tetracosafluorododecylenediamine.

The trivalent or higher polyamine (B2) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The amino alcohol (B3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.

The amino mercaptan (B4) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.
The amino acid (B5) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.

  The block (B6) in which the amino group of B1 to B5 is blocked is not particularly limited and may be appropriately selected depending on the purpose. For example, the amines and ketones of B1 to B5 (acetone, acetone, And ketimine compounds and oxazoline compounds obtained from methyl ethyl ketone, methyl isobutyl ketone and the like.

  Among these amine compounds (B), the diamine (B1) and a mixture of the diamine (B1) and a small amount of trivalent or higher polyamine (B2) are preferable.

  There is no restriction | limiting in particular as a ratio of the said amine compound (B), Although it can select suitably according to the objective, The number of the amino groups [NHx] in the said amine compound (B) is an isocyanate group at the said terminal. It is preferably 4 times or less, more preferably 2 times or less, still more preferably 1.5 times or less, and particularly preferably 1.2 times or less, of the number of isocyanate groups [NCO] in the modified resin. When the ratio of the amine compound (B) ([NHx] / [NCO]) exceeds four times, excess amino groups block the isocyanate, and the extension reaction of the modified resin does not occur. The hot offset resistance may be deteriorated.

-Aqueous phase preparation process-
The aqueous phase preparation step is a step of preparing an aqueous phase having at least a surfactant in an aqueous medium.

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

(Inorganic dispersant and organic resin fine particles)
In the aqueous medium, when dispersing the dispersion or dispersion such as the binder resin, the colorant and the release agent, by dispersing the inorganic dispersant or the organic resin fine particles in the aqueous medium in advance, This is preferable in that the particle size distribution becomes sharp and the dispersion is stable. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. As the resin forming the organic resin fine particles, any resin can be used as long as it can form an aqueous dispersion, and it may be a thermoplastic resin or a thermosetting resin. Includes vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. These resins may be used in combination of two or more. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable from the viewpoint that an aqueous dispersion of fine spherical resin particles is easily obtained.

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

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

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

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

-Dispersion stabilizer-
The aqueous phase may contain the dispersion stabilizer such as an inorganic dispersant and a protective colloid for the purpose of improving the dispersibility of the oil droplets in the oil droplet dispersion preparing step described later. It is preferable that the aqueous phase contains a dispersion stabilizer because the particle size distribution of the obtained toner becomes sharp and the dispersion is stable.

-Oil droplet dispersion preparation process-
The oil droplet dispersion preparing step is a step of preparing an oil droplet dispersion in which the oil phase is dispersed in the aqueous phase and oil droplets composed of the oil phase are dispersed.
The method for preparing the oil droplet dispersion is not particularly limited and may be appropriately selected depending on the purpose. For example, a low-speed shearing method, a high-speed shearing method, a friction method, a high-pressure jet method, an ultrasonic wave, or the like is used. The method of preparing using a well-known apparatus is mentioned. Among these, a high-speed shearing type is preferable in that oil droplets having a desired particle diameter can be prepared.

  There is no restriction | limiting in particular as a volume average particle diameter of the oil droplet in the said oil droplet dispersion liquid, Although it can select suitably according to the objective, 2 micrometers-20 micrometers are preferable and 2 micrometers-10 micrometers are more preferable.

There is no restriction | limiting in particular as temperature which performs the said oil-drop dispersion liquid, Although it can select suitably according to the objective, 0 to 40 degreeC is preferable and 10 to 30 degreeC is more preferable. When the temperature exceeds 40 ° C., molecular motion becomes active, so that dispersion stability may be reduced and aggregates and coarse particles may be easily generated. When the temperature is less than 0 ° C., the viscosity of the dispersion liquid may be reduced. The production efficiency may decrease because the shear energy required for dispersion increases and the shear energy increases.
If the melting point of the crystalline resin is −20 ° C. or lower, the change in crystal structure and the change in the state of the boundary with the amorphous resin (here, resin (T)) are suppressed during production. A particulate material is preferable because it can be dispersed and introduced into the toner.

-Solvent removal process-
The solvent removal step is a step of preparing a dispersion slurry containing the aqueous medium and toner particles by removing the organic solvent from the oil droplet dispersion. In the present invention, the dispersed slurry refers to a fluid state in which toner particles are dispersed in an aqueous medium.

Examples of the method for removing the solvent in the solvent removal step include the methods described in the following (1) to (3). These methods may be carried out singly or in combination of two or more.
(1) A method in which the entire oil droplet dispersion is gradually heated while stirring to completely evaporate and remove the organic solvent in the oil droplet dispersion (in the oil droplets).
(2) A method of completely removing the organic solvent in the oil droplet dispersion (in the oil droplets) by spraying the oil droplet dispersion in a dry atmosphere while stirring the entire oil droplet dispersion.
(3) A method of depressurizing the whole oil droplet dispersion while stirring to evaporate and remove the organic solvent in the oil droplet dispersion (in the oil droplet).
Among these, the method described in (1) is preferable for the solvent removal step.

  In the solvent removal step, (2) the oil droplet dispersion is sprayed into a dry atmosphere while stirring the entire oil droplet dispersion, and the organic solvent in the oil droplet dispersion (in the oil droplets) is sprayed. The dry atmosphere is not particularly limited and can be appropriately selected depending on the purpose, for example, a gas, oil heated with air, nitrogen, carbon dioxide gas, combustion gas, etc. Examples include various air currents heated to a temperature equal to or higher than the maximum boiling point of the organic solvent in the droplet dispersion. These may be used alone or in combination of two or more.

  The said solvent removal process can be performed using an apparatus, As this apparatus, a spray dryer, a belt dryer, a rotary kiln etc. are mentioned, for example. By using these apparatuses, it is possible to obtain a toner having a sufficiently desired quality with a short processing time.

<Washing process>
The cleaning step is a step of cleaning the toner particles. In order to take out only toner particles from the dispersion slurry, the dispersion slurry obtained by the solvent removal process may contain secondary materials such as a surfactant and a dispersion stabilizer in addition to the toner particles. It is preferable to perform washing.
There is no restriction | limiting in particular as the method of wash | cleaning in the said washing | cleaning process, According to the objective, it can select suitably, For example, the centrifugation method, the reduced pressure filtration method, the filter press method etc. are mentioned.
Either method can produce a cake body composed of toner particles. However, if the cake cannot be sufficiently washed by a single operation, the obtained cake is dispersed again in an aqueous solvent to form a dispersed slurry, and the washing step is repeated. May be.

In the case where the washing step is performed by a reduced pressure filtration method or a filter press method, a method may be employed in which an aqueous solvent is passed through the cake body made of the toner particles to wash away the auxiliary material that the toner particles have embraced.
As the aqueous solvent used in the washing step, usually water or a mixed solvent obtained by mixing water and alcohol such as methanol or ethanol is used. Among these, water is preferable in terms of environmental load due to cost and wastewater treatment.

When a dispersion stabilizer is added to the aqueous phase and an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is added with an acid such as hydrochloric acid. A method of washing with water after dissolution is preferred. Moreover, you may use the method decomposed | disassembled with an enzyme.
When the dispersion stabilizer is used, the dispersion stabilizer can remain on the surface of the toner particles, but it is preferable to remove it by washing from the charged surface of the toner.

<Drying process>
The drying step is a step of removing the aqueous medium from the toner particles after the washing step and drying. As a result, only toner particles can be obtained from the toner particles after the washing step in which a large amount of the aqueous medium is embraced.
The drying step is preferably performed until the water content of the toner particles finally becomes less than 1% by mass with respect to the toner particles.
The method for drying the toner in the drying step is not particularly limited as long as the aqueous medium can be removed from the toner particles after the washing step, and can be appropriately selected depending on the purpose. Examples include a method using a dryer such as a dryer, a vacuum freeze dryer, a vacuum dryer, a stationary shelf dryer, a mobile shelf dryer, a fluidized tank dryer, a rotary dryer, and a stirring dryer.

<Other processes>
The other steps are not particularly limited as long as the effects of the present invention are not hindered, and can be appropriately selected according to the purpose. Examples thereof include an aging step and a crushing step.

-Aging process-
The aging step is a step performed after the oil droplet dispersion preparation step of the dispersion step and before the solvent removal step, and when the oil phase contains a modified resin having an isocyanate group at the terminal, the isocyanate This is a step of allowing group extension reaction and / or crosslinking reaction to proceed.
There is no restriction | limiting in particular as temperature which performs the said aging process, Although it can select suitably according to the objective, 0 to 40 degreeC is preferable and 15 to 30 degreeC is more preferable.
There is no restriction | limiting in particular as time to perform the said aging process, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
Similarly to the above, if the melting point of the crystalline resin is -20 ° C. or less, the change in the crystal structure and the state of the amorphous resin (in this case, the boundary portion with the resin T are suppressed even when the manufacturing time is long. Therefore, it is preferable because the original particulate matter can be dispersed and introduced into the toner.

-Crushing process-
The crushing step is a step performed after the drying step, and is a step of loosening the soft-aggregated toner particles when the toner particles are soft-aggregated.
Examples of the method for pulverizing the toner particles softly aggregated in the pulverization step include a method using a device such as a jet mill, a Henschel mixer, a super mixer, a coffee mill, an auster blender, and a food processor.

A process cartridge according to the present invention is a process cartridge configured so that a photosensitive member and at least a latent image on the photosensitive member are developed with a developer so as to be detachable from the image forming apparatus. The toner of the present invention is contained therein.
For example, as shown in FIG. 2, the process cartridge includes a latent image carrier (101), and includes a charging device (102), a developing device (104), and a cleaning unit (107). It has other means. In FIG. 2, (103) shows exposure from the exposure apparatus, and (105) shows recording paper. Any latent image carrier can be used as the latent image carrier (101). An arbitrary charging member is used for the charging device (102).
Referring to the image forming process by the process cartridge shown in FIG. 2, the latent image carrier (101) is charged by the charging device (102) while being rotated in the direction of the arrow, and exposure by the exposure means (not shown) (103). As a result, an electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed with toner by a developing device (104), and the toner development is transferred onto a recording sheet (105) by a transfer roller (108) and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit (107), further neutralized by a neutralizing means (not shown), and the above operation is repeated again.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a present Example.
In addition, the number of parts in an Example represents a mass part.

[Synthesis of Polyester 1]
In a reaction vessel equipped with a cooling tube stirrer and a nitrogen introduction tube, 128 parts of bisphenol A ethylene oxide 2-mole adduct, 650 parts of bisphenol A propylene oxide 2-mole adduct, 208 parts of terephthalic acid, 23 parts of isophthalic acid, adipic acid 24 parts and 2 parts of dibutyltin oxide were charged and reacted at 230 ° C. for 7 hours under normal pressure.
Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize [Polyester 1]. did.
The obtained [Polyester 1] had an SP value of 12.8, a weight average molecular weight of 6400, a glass transition temperature of 62 ° C., and an acid value of 21 mgKOH / g.

[Synthesis of Polyester 2]
In a reaction vessel equipped with a cooling pipe stirrer and a nitrogen introduction tube, 128 parts of bisphenol A ethylene oxide 2-mole adduct, 650 parts of bisphenol A propylene oxide 2-mole adduct, 208 parts of terephthalic acid, 23 parts of isophthalic acid, adipic acid 24 parts and 2 parts of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure.
Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 3 hours under normal pressure to synthesize [Polyester 2]. did.
The obtained [Polyester 2] had an SP value of 11.6, a weight average molecular weight of 6800, a glass transition temperature of 65 ° C., and an acid value of 16 mgKOH / g.

[Synthesis of Crystalline Polyester Resin 1]
146 parts of adipic acid, 175 parts of 1,10-decanediol, and 0.14 part of dibutyltin oxide were stirred at 180 ° C. for 5 hours in a nitrogen atmosphere. Thereafter, the mixture was stirred while reducing the pressure, and the reaction was stopped by selecting the time when the number average molecular weight Mn was 6500 while checking the molecular weight by GPC. As a result, [Crystalline Polyester Resin 1] having a weight average molecular weight Mw = 16200 and a number average molecular weight Mn = 6400 was obtained. Further, when the melting point of [Crystalline Polyester Resin 1] was measured using a differential scanning calorimeter (DSC), it had a clear peak, the peak top temperature was 67 ° C., and the SP value was 11.5. .

[Synthesis of Crystalline Polyester Resin 2]
In the same manner as the synthesis of the crystalline polyester resin 1, the stirring time was selected so that the number average molecular weight Mn was 5800, and the reaction was stopped. As a result, [Crystalline Polyester Resin 2] having a weight average molecular weight Mw = 14700 and a number average molecular weight Mn = 5900 was obtained. Further, when the melting point of [Crystalline Polyester Resin 2] was measured using a differential scanning calorimeter (DSC), it had a clear peak, the peak top temperature was 61 ° C., and the SP value was 12.3. .

[Synthesis of Crystalline Polyester Resin 3]
In the same manner as the synthesis of the crystalline polyester resin 1, the stirring time was selected so that the number average molecular weight Mn was 7100, and the reaction was stopped. As a result, [Crystalline Polyester Resin 3] having a weight average molecular weight Mw = 17900 and a number average molecular weight Mn = 7100 was obtained. Further, when the melting point of [Crystalline Polyester Resin 2] was measured using a differential scanning calorimeter (DSC), it had a clear peak, the peak top temperature was 75 ° C. and the SP value was 10.9 .

[Synthesis of Crystalline Polyester Resin 4]
232 parts of fumaric acid, 238 parts of 1,6-hexanediol, and 0.12 part of dibutyltin oxide were stirred at 180 ° C. for 5 hours in a nitrogen atmosphere. Thereafter, the mixture was stirred while reducing the pressure, and the reaction was stopped by selecting the time when the number average molecular weight Mn was 6800 while confirming the molecular weight by GPC. As a result, [crystalline polyester resin 4] having a weight average molecular weight Mw = 18900 and a number average molecular weight Mn = 6800 was obtained. Further, when the melting point of [Crystalline Polyester Resin 4] was measured using a differential scanning calorimeter (DSC), it had a clear peak, the peak top temperature was 102 ° C., and the SP value was 11.8. .

[Synthesis of Crystalline Polyester Resin 5]
In the same manner as the synthesis of the crystalline polyester resin 4, the stirring time was selected so that the number average molecular weight Mn was 5500, and the reaction was stopped. As a result, [Crystalline Polyester Resin 5] having a weight average molecular weight Mw = 14600 and a number average molecular weight Mn = 5400 was obtained. Further, when the melting point of [Crystalline Polyester Resin 5] was measured using a differential scanning calorimeter (DSC), it had a clear peak, the peak top temperature was 76 ° C., and the SP value was 14.1. .

[Production of core-shell particle dispersion 1]
In 281 parts of ion exchange water, 0.4 part of sodium dodecyl sulfate was added and dissolved by heating to 70 ° C. to obtain an aqueous medium.
Separately, 30 parts of styrene monomer, 30 parts of methyl methacrylate, 5 parts of butyl acrylate, 2 parts of methacrylic acid, and 33 parts of [Crystalline Polyester Resin 1] were stirred while heating to 80 ° C. in a nitrogen atmosphere to obtain a uniform monomer solution. Obtained.
The obtained monomer solution was put into an aqueous medium, and while maintaining at 80 ° C., ultrasonic irradiation was performed at 90 to 110 W for 10 minutes using an ultrasonic homogenizer VCX750 in a nitrogen atmosphere to disperse the monomer solution in the aqueous medium. It was.
In the middle, the liquid temperature increased by ultrasonic irradiation, but was adjusted to 75 to 85 ° C. with a water bath or the like.
The obtained dispersion was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, maintained at 80 ° C. with stirring, and 0.5 part of potassium persulfate was dissolved in 19 parts of ion-exchanged water. The polymerization reaction was carried out for 180 minutes.
Then, it cooled and the white [core shell particle dispersion liquid 1] with a volume average particle diameter of 106 nm was obtained.
Fine particles in the obtained core-shell particle dispersion liquid embedded with an embedding resin were cut with a microtome to produce thin pieces and observed with a scanning transmission electron microscope. The fine particles had a capsule structure. Was confirmed.
Further, from the SP value measurement method, the (second) amorphous resin content in the shell portion was 9.8, and the crystalline polyester resin content in the core portion was 11.5. Even when compared with the SP value of the crystalline resin alone, an equivalent numerical value is obtained.

In order to measure the SP value of the second amorphous resin content of the core-shell particles alone, a second amorphous resin was synthesized by the following method, and the SP value was measured.
(Synthesis 1 of second amorphous resin)
In 281 parts of ion exchange water, 0.4 part of sodium dodecyl sulfate was added and dissolved by heating to 70 ° C. to obtain an aqueous medium.
Separately, 30 parts of styrene monomer, 30 parts of methyl methacrylate, 5 parts of butyl acrylate, and 2 parts of methacrylic acid as the second amorphous resin 1 were stirred while heating to 80 ° C. in a nitrogen atmosphere, and uniform. A monomer solution was obtained.
The obtained monomer solution was put into the aqueous medium and subjected to ultrasonic irradiation at 90 W to 110 W for 10 minutes using an ultrasonic homogenizer (VCX750, Tokyo Rika Machinery Co., Ltd.) under a nitrogen atmosphere while maintaining at 80 ° C. The monomer solution was dispersed in an aqueous medium. During the ultrasonic irradiation, the liquid temperature was increased by the ultrasonic irradiation, but was adjusted to 75 ° C. to 85 ° C. with a water bath.
The obtained dispersion was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and maintained at 80 ° C. with stirring, and 0.5 part of potassium persulfate was dissolved in 19 parts of ion-exchanged water. Then, the polymerization reaction of each component in the monomer solution was performed for 180 minutes. Then, it cooled and white [2nd resin dispersion liquid-1] was obtained.
The SP value of the fine particles in the obtained [second resin dispersion-1] was 9.8.

[Production of core-shell particle dispersions 2 to 5]
Core-shell particle dispersions 2 to 5 were produced in the same manner as the core-shell particle dispersion 1, except that the crystalline resin was changed.
Core shell particle dispersion 2:
A white [core-shell particle dispersion 2] of 98 nm was obtained in the same manner except that the crystalline polyester resin 2 was used.
Core shell particle dispersion 3:
A white [core-shell particle dispersion 3] of 105 nm was obtained in the same manner except that the crystalline polyester resin 3 was used.
Core shell particle dispersion 4:
A white [core-shell particle dispersion 4] of 118 nm was obtained in the same manner except that the crystalline polyester resin 4 was used.
Core shell particle dispersion 5:
A 109 nm white [core shell particle dispersion 5] was obtained in the same manner except that the crystalline polyester resin 5 was used.
When the fine particles in the obtained core-shell particle dispersion are embedded with an embedding resin, they are cut with a microtome to produce flakes and observed with a scanning transmission electron microscope. The core-shell particle dispersions 2 to 4 have a capsule structure. It was confirmed that the core-shell particle dispersion 5 did not have a uniform core-shell structure.

[Production of core-shell particle dispersion 6]
In 281 parts of ion exchange water, 0.4 part of sodium dodecyl sulfate was added and dissolved by heating to 70 ° C. to obtain an aqueous medium.
Separately, 60 parts of styrene monomer, 5 parts of butyl acrylate, 35 parts of methacrylic acid, and 33 parts of [Crystalline Polyester Resin 1] were stirred while heating to 80 ° C. in a nitrogen atmosphere to obtain a uniform monomer solution.
The obtained monomer solution was put into the aqueous medium and subjected to ultrasonic irradiation at 90 to 110 W for 10 minutes using an ultrasonic homogenizer (VCX750, Tokyo Rika Machinery Co., Ltd.) under a nitrogen atmosphere while maintaining at 80 ° C. The monomer solution was dispersed in an aqueous medium.
In the middle, the liquid temperature increased by ultrasonic irradiation, but was adjusted to 75 to 85 ° C. with a water bath or the like.
The obtained dispersion was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, maintained at 80 ° C. with stirring, and 0.5 part of potassium persulfate was dissolved in 19 parts of ion-exchanged water. The polymerization reaction was carried out for 150 minutes.
Then, it cooled and the white [core shell particle dispersion liquid 6] with a volume average particle diameter of 115 nm was obtained.
Fine particles in the obtained core-shell particle dispersion liquid embedded with an embedding resin were cut with a microtome to produce thin pieces and observed with a scanning transmission electron microscope. The fine particles had a capsule structure. Was confirmed.
From the SP value measurement method, the (second) amorphous resin content in the shell portion was 12.1, and the crystalline polyester resin content in the core portion was 11.5. Even when compared with the SP value of the crystalline resin alone, an equivalent numerical value is obtained.

In order to measure the SP value of the second amorphous resin content of the core-shell particles alone, a second amorphous resin was synthesized by the following method, and the SP value was measured.
(Synthesis 2 of second amorphous resin)
In 281 parts of ion exchange water, 0.4 part of sodium dodecyl sulfate was added and dissolved by heating to 70 ° C. to obtain an aqueous medium.
Separately, 60 parts of styrene monomer, 5 parts of butyl acrylate, and 35 parts of methacrylic acid as the second amorphous resin 2 were stirred while heating to 80 ° C. in a nitrogen atmosphere to obtain a uniform monomer solution.
The obtained monomer solution was put into the aqueous medium and subjected to ultrasonic irradiation at 90 W to 110 W for 10 minutes using an ultrasonic homogenizer (VCX750, Tokyo Rika Machinery Co., Ltd.) under a nitrogen atmosphere while maintaining at 80 ° C. The monomer solution was dispersed in an aqueous medium. During the ultrasonic irradiation, the liquid temperature was increased by the ultrasonic irradiation, but was adjusted to 75 ° C. to 85 ° C. with a water bath.
The obtained dispersion was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and maintained at 80 ° C. with stirring, and 0.5 part of potassium persulfate was dissolved in 19 parts of ion-exchanged water. Then, the polymerization reaction of each component in the monomer solution was performed for 150 minutes. Then, it cooled and white [2nd resin dispersion liquid-1] was obtained. The SP value of the fine particles in the obtained [second resin dispersion-2] was 12.1.

<Example 1>
[Production of master batch (MB)]
1,200 parts of water, carbon black (manufactured by Printex 35 Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], 540 parts, and 1,200 parts of “amorphous polyester resin 1” were added. (Mitsui Mining Co., Ltd.), and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

[Prepolymer synthesis]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 And 2 parts of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1].
[Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a Tg of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained.
[Prepolymer 1] had a free isocyanate weight% of 1.53%.

[Oil phase preparation process]
In a container equipped with a stir bar and a thermometer, 545 parts of [Polyester 1], [manufactured by Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8] 181 parts, ethyl acetate 1450 Then, the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour.
Next, 500 parts of [Masterbatch 1] and 100 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution 1].
[Raw material solution 1] 1500 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 70% by volume. The pigment and WAX were dispersed under the conditions of filling and 3 passes.
Next, 655 parts of a 66% ethyl acetate solution of [Polyester 1] was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / WAX Dispersion 1].
[Pigment / WAX Dispersion 1] 976 parts and Isophoronediamine 2.6 parts were mixed for 1 minute at 5,000 rpm with a TK homomixer (made by Tokushu Kika), and then 596 parts of [Core Shell Particle Dispersion 1] were added. The mixture was mixed at 8,000 rpm for 1 minute, and then 88 parts of [Prepolymer 1] were added and mixed at 5,000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika) to obtain [Oil Phase 1].

[Aqueous phase preparation process]
<Water phase creation process>
970 parts of ion-exchanged water, 40 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl diphenyl ether When 95 parts of a 48.5% aqueous solution of sodium disulfonate and 98 parts of ethyl acetate were mixed and stirred, the pH reached 6.2. A 10% aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH to 9.5 to obtain [Aqueous Phase 1].

[Oil droplet dispersion preparation process]
Add 1100 parts of [Aqueous phase 1] to the obtained [Oil phase 1], and cool in a water bath to suppress the temperature rise due to shear heat of the mixer so that the temperature in the liquid is in the range of 20-23 ° C. , Adjusted at a rotation speed of 8,000-15,000 rpm using a TK homomixer and mixed for 2 minutes, and then adjusted at a rotation speed of 130-350 rpm with a three-one motor with an anchor blade attached for 10 minutes. The mixture was stirred to obtain [Particle Slurry 1] in which droplets of an oil phase serving as particles were dispersed in an aqueous phase.

[Demelting process]
[Particle slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours while stirring to obtain [Dispersion slurry 1].

[Washing and drying process]
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered.
This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].

[Filtration cake 1] was dried at 32 ° C. for 48 hours in a circulating drier, and sieved with a mesh of 75 μm, and [Toner base 1] (volume average particle diameter (Dv) was 6.4 μm).
Next, 100 parts of [Toner Base 1] were mixed with 0.7 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain [Toner 1] of the present invention.

<Example 2>
[Toner 2] was obtained in the same manner as in Example 1 except that [Core-shell particle dispersion 1] was changed to [Core-shell particle dispersion 2].
<Example 3>
[Toner 3] was obtained in the same manner as in Example 1 except that [Core-shell particle dispersion 1] was changed to [Core-shell particle dispersion 3].
<Example 4>
[Toner 4] was obtained in the same manner as in Example 1, except that [WAX] was changed to [WA-05, Carnauba wax, melting point 86 ° C., SP value 9.3, manufactured by Toa Kasei Co., Ltd.].
<Example 5>
[Core-shell particle dispersion 1] [Toner 5] was obtained in the same manner as in Example 1 except that 596 parts were changed to 976 parts.
<Example 6>
[Toner 6] was obtained in the same manner as in Example 1 except that [Core-shell particle dispersion 1] was changed to [Core-shell particle dispersion 4].

<Comparative Example 1>
[Toner 7] was changed in the same manner as in Example 1 except that “Polyester resin 1” was changed to “Polyester resin 2” and the particle content of [Core shell particle dispersion 1] was changed to [Crystalline polyester resin 1]. Obtained.
<Comparative example 2>
[Toner 8] was obtained in the same manner as in Example 1, except that "Polyester resin 1" was changed to "Polyester resin 2" and [Core-shell particle dispersion 1] was changed to [Core-shell particle dispersion 6].
<Comparative Example 3>
[Toner 9] was obtained in the same manner as in Example 1, except that "Polyester resin 1" was changed to "Polyester resin 2" and [Core-shell particle dispersion 1] was changed to [Core-shell particle dispersion 5].

<Preparation of developer>
-Fabrication of carrier-
Add 100 parts of silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black to 100 parts of toluene, disperse for 20 minutes with a homomixer, and apply resin layer A liquid was prepared.
Using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having an average particle size of 50 μm to prepare a carrier.
-Production of developer-
Using a ball mill, 15 parts of the toner and 95 parts of the carrier were mixed to prepare a developer.

The obtained toner and developer were evaluated for the following heat-resistant storage stability and fixability.
1. Heat resistant storage stability (1)
20 g of a toner sample is put in a 20 ml glass bottle and allowed to stand in a thermostatic bath at 50 ° C. for 24 hours, then the toner is cooled to 24 ° C., and the penetration is measured by a penetration test (JIS K2235-1991). Went.
In the present invention, the penetration refers to a value indicating the depth of penetration in mm, and a toner having a larger value has better storage stability against heat.
If this value is less than 10 mm, there is a high possibility of problems in use.
Judgment criteria for thermal storage stability based on the penetration is as follows.
◎: 20 mm or more ○: 15 mm or more and less than 20 mm △: 10 mm or more and less than 15 mm ×: less than 10 mm

2. Heat resistant storage stability (2)
A toner sample (20 g) was placed in a 20 ml glass bottle and allowed to stand in a constant temperature bath at 40 ° C. and 90% RH for 120 hours. -1991). The penetration was measured.
A toner having a larger value has better storage stability against heat.
If this value is less than 10 mm, there is a high possibility of problems in use.
Judgment criteria for thermal storage stability based on the penetration is as follows.
◎: 20 mm or more ○: 15 mm or more and less than 20 mm △: 10 mm or more and less than 15 mm ×: less than 10 mm

3. Fixability (fixing lower limit temperature) (1)
Toner was put in a modified IPSiO SP C220, and 19 sheets of 40 mm square unfixed solid images were printed on a Ricoh type 6200Y eye paper so that the adhesion amount was 8 g / m ² .
Next, using the modified fixing unit, the system speed was set to 500 mm / sec, and the prepared unfixed solid image was passed through to fix the image.
The fixing temperature is tested from 120 ° C. to 200 ° C. in increments of 5 ° C., and the fixed image is drawn using a drawing tester AD-401 manufactured by Ueshima Seisakusho. The colored portion of the fixed image (B) has a sapphire needle of 125 μR and a needle rotation diameter. The sapphire needle tip was run under the condition of 8 mm and a load of 1 g. The running surface of the sapphire needle tip was visually observed, and the temperature at which scratches were clearly recognized as white spots was defined as NG.
The lowest temperature that does not result in NG was defined as the minimum fixing temperature.
○: Fixing lower limit temperature is 130 ° C. or less Δ: Fixing lower limit temperature is 135 to 145 ° C.
×: The minimum fixing temperature is 150 ° C. or higher.

4). Component contamination (filming)
The image forming apparatus MF2800 (manufactured by Ricoh Co., Ltd.) was used to visually inspect the photoconductor after 10,000 images were formed, and the toner component, mainly the release agent, was fixed to the photoconductor. It was evaluated according to the following evaluation criteria.
A: The toner component is not fixed to the photoconductor. A: The toner component is fixed to the photoconductor. However, this is not a practical problem. Δ: The toner component is fixed to the photoconductor. , Is a level that causes a problem in practical use. ×: The toner component can be firmly fixed to the photosensitive member, and is a level having a large problem in practical use.

In the toners of Examples 1 to 6, by TEM observation, the release agent is dispersed in the first amorphous resin, and at least a part of the surface of the release agent has the crystalline resin as a core, It was confirmed that the core was coated with core-shell particles having the second amorphous resin as a shell. Moreover, it was excellent in heat resistant storage stability and fixability, and no member contamination was observed.
In the toner of Comparative Example 1, since the crystalline resin does not have a core-shell structure, there are many portions that are particularly compatible with the amorphous resin. Further, since the SP value is far from that of WAX and the probability that the dispersion in the toner exists near the surface is increased, contamination of the member due to crystalline resin or WAX is caused.
In the toner of Comparative Example 2, the crystalline resin has a core-shell structure, but there are toners that are present alone in the vicinity of the toner surface, and the coverage with the release agent was small. Further, since a large amount of release agent is generally present on the surface side inside the toner, the lower limit of fixing was effective, but the contamination of the member was worsened. This is presumably because the SP value of the second amorphous resin was larger than that of the first amorphous resin, so that the second amorphous resin was pulled to the toner surface layer side (a state in which it was easily oriented).
In Comparative Example 3, since the SP value of the crystalline resin in the core portion was too high at the stage of producing the core-shell particles, it became a mottled shell. As a result, when the core-shell particles are added to the emulsification step of the toner, a portion that is compatible with the first amorphous resin or the like appears, which adversely affects the heat-resistant storage property. Further, since the SP value of the crystalline resin part of the core was high, there was a tendency that the core was easily pulled and oriented by the toner surface side.

Japanese Patent No. 4075949 JP 2012-53196 A JP 2011-232738 A

Claims (8)

  A toner containing a first amorphous resin, a second amorphous resin having an SP value lower than that of the first amorphous resin, a crystalline resin, and a release agent, The release agent is dispersed in the first amorphous resin, and at least a part of the surface of the release agent has the crystalline resin as a core and the second amorphous resin as a shell. A toner that is covered with core-shell particles. When the first amorphous resin is R, the second amorphous resin is T, the release agent is A, and the SP values of R, T, and A are expressed as Rsp, Tsp, and Asp , SP value is Rsp>Tsp> Asp
The toner according to claim 1, wherein:   The toner according to claim 1, wherein the first amorphous resin is an amorphous polyester resin, and the crystalline resin is a crystalline polyester resin.   The toner according to claim 1, wherein the release agent contains at least a hydrocarbon wax.   The toner according to claim 1, wherein the crystalline resin has a melting point of 80 ° C. or less. Containing a first amorphous resin, a second amorphous resin having a SP value lower than that of the first amorphous resin, a crystalline resin, and a release agent, , Dispersed in the first amorphous resin, and at least part of the surface of the release agent is coated with core-shell particles having the crystalline resin as a core and the second amorphous resin as a shell. A method for producing a toner in a finished state, wherein the second amorphous resin has at least a vinyl polymer, the core is the crystalline resin, and the second amorphous resin is the shell. A step of producing
A dispersion step of dispersing the core-shell particles in the first amorphous resin.   The dispersion step includes an oil phase preparation step for preparing an oil phase in which at least the first amorphous resin, the core-shell particles, and the release agent are dissolved or dispersed in an organic solvent, and at least a surface activity in the aqueous medium. An aqueous phase preparation step for producing an aqueous phase having an agent, and an oil droplet dispersion preparation step for producing a dispersion in which the oil phase is dispersed in the aqueous phase and particles comprising the oil phase are dispersed, and The toner manufacturing method according to claim 6, comprising at least a solvent removal step for removing the solvent, a washing step for washing the toner particles, and a drying step for drying to remove moisture.   A process cartridge comprising a photosensitive member and a device for developing at least a latent image on the photosensitive member with a developer, wherein the process cartridge is configured to be detachable from the image forming apparatus. A process cartridge comprising the toner according to any one of the above.