JP6060617B2 - Toner, toner manufacturing method, and process cartridge - Google Patents

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, and a manufacturing method thereof.

In the electrophotographic process, it is required to reduce the energy consumed by the apparatus, and in the electrophotographic process, a large amount of energy is consumed especially by heating in the fixing process, so the temperature required for fixing is lowered. It is hoped that.

One means of lowering the fixing temperature is to lower the glass transition temperature of the binder resin depending on the molecular weight and molecular structure of the binder resin constituting the toner. The nature will decline.

As a means to achieve both heat-resistant storage stability and low-temperature fixability, a crystalline resin that melts sharply with a slight amount of heat is added to the toner particles, and the binder resin is dissolved in the crystalline resin that has melted at the time of fixing. There has been proposed a method of fixing at a lower temperature by lowering.

  In Japanese Patent No. 32333753 of Patent Document 1, in order to improve offset resistance at the time of fixing and to improve fluidity, chargeability, and storage stability before fixing, crystallinity (meta) in the binder resin is disclosed. A toner having a sea-island-sea structure in which a binder resin is further dispersed in a domain of an acrylate polymer is disclosed, but a part of the binder resin and the crystalline resin are compatible. Due to plasticization, the storage stability is not sufficient.

Japanese Patent No. 4075949 discloses a toner in which a structure in which a crystalline polyester resin is in contact with the surface of WAX particles is dispersed in a binder resin for the purpose of achieving both toner fixing performance and heat-resistant storage. It is disclosed.
However, in the toner described in Patent Document 2, a part of the crystalline polyester resin is compatible with the binder resin and plasticized in the production process of the binder resin and the crystalline resin, and the storage stability is not sufficient. However, there is a problem that the crystalline polyester resin is easily softened due to stress in processes such as development and transfer, and is deformed or easily fixed to various members.

Japanese Patent Application Laid-Open No. 2011-232738 of Patent Document 3 encapsulates a crystalline substance compatible with the main binder in order to achieve both low temperature fixability, heat resistant storage stability and stress resistance. It is disclosed that the dispersion prevents the main binder and the crystalline material from being compatible before the fixing step.
However, it does not prevent the release agent in the toner particles from oozing out on the surface due to stress in the development process, resulting in member contamination such as filming due to the release agent, which reduces the cleaning performance of the photoreceptor. Print quality may be significantly impaired.

An object of the present invention is to provide a toner that can achieve both low-temperature fixability and heat-resistant storage stability, further improve stress resistance, and can form a high-quality image without contamination of a member, and a method for producing the toner. To do.

  In the second amorphous resin that is incompatible with the first amorphous resin and dispersed in the first amorphous resin, the present inventors have introduced a release agent and / or crystallinity into the second amorphous resin. By including the resin, compatibility with the first amorphous resin before the fixing process is prevented to improve heat-resistant storage stability, and even if the toner is subjected to physical stress in the development / transfer process, it is released. It is difficult for stress to be applied to the mold agent and the crystalline resin, and it can prevent the release agent from seeping out to the toner particle surface and plasticizing due to the compatibility of the crystalline resin, etc. The present inventors have found that it can be formed and have completed the present invention.

That is, the said subject is solved by following (1)-(9) of this invention.
(1) A toner containing at least a first amorphous resin, a second amorphous resin, a crystalline resin, and a release agent, wherein the second amorphous resin is the first amorphous resin. The amorphous resin is incompatible with the first amorphous resin and is dispersed in the first amorphous resin, and the crystalline resin and the release agent are encapsulated in the second amorphous resin. Toner.
(2) The toner according to item (1), wherein the first amorphous resin is a polyester resin, and the second amorphous resin is a vinyl resin.
(3) The toner according to (1) or (2), wherein the crystalline resin and the release agent have a melting point of 95 ° C. or less, and the crystalline resin is a crystalline polyester resin. .
(4) The glass transition temperature (Tg1) of the first amorphous resin is 50 ° C. or higher and 60 ° C. or lower, and the glass transition temperature (Tg2) of the second amorphous resin is Tg1 + 5 ° C. ≦ Tg2 The toner according to any one of (1) to (3), wherein ≦ Tg1 + 15 ° C. is satisfied.
(5) When the SP values of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent are Rsp, Tsp, Bsp, and Asp, respectively, the following relationship should be satisfied: The toner according to any one of (1) to (4), wherein:
(Rsp)>(Tsp)> (Bsp)
(Rsp)>(Tsp)> (Asp)
(6) Contains at least a first amorphous resin, a second amorphous resin, a crystalline resin, and a release agent, and the second amorphous resin includes the first amorphous resin. A method for producing a toner that is incompatible with a resin and dispersed in the first amorphous resin, and the crystalline resin and the release agent are encapsulated in the second amorphous resin. There,
A step of producing a release agent-containing core-shell particle having the release agent as a core and a second amorphous resin as a shell;
Producing crystalline resin-containing core-shell particles having the crystalline resin as a core and the second amorphous resin as a shell; and
A method for producing a toner, comprising: a dispersion step of dispersing the release agent-containing core-shell particles and the crystalline resin-containing core-shell particles in the first amorphous resin.
(7) When the SP values of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent are Rsp, Tsp, Bsp, Asp, respectively, the following relationship is satisfied:
(Rsp)>(Tsp)> (Bsp)
(Rsp)>(Tsp)> (Asp)
The method for producing a toner according to item (6), wherein the step of producing the release agent-containing core-shell particles and the step of producing the crystalline resin-containing core-shell particles are performed in an aqueous medium.
(8) In the dispersion step, an oil phase obtained by dissolving or dispersing at least the first amorphous resin, the release agent-containing core-shell particles, the crystalline resin-containing core-shell particles, and the colorant in an organic solvent The method for producing a toner according to (6) or (7) above, further comprising a step of preparing an oil droplet dispersion to be dispersed in a medium.
(9) A process cartridge that is integrated with a photosensitive member and a device that develops at least a latent image on the photosensitive member with a developer and is detachable from the image forming apparatus. A process cartridge comprising the toner according to any one of Items (5) to (5).

  As will be understood from the following detailed and specific description, according to the present invention, low-temperature fixability and heat-resistant storage stability are compatible, and further, excellent in stress resistance and stable and high-quality images over a long period of time. A toner that can be formed and a method for producing the toner are provided.

FIG. 3 is a diagram illustrating an example of a toner cross section 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 will be described in detail.
FIG. 1 shows an example of a cross section of the toner of the present invention. In the toner of the present invention, as shown in FIG. 1, the second amorphous resin that is incompatible with the first amorphous resin contains the crystalline resin and the release agent, and the first amorphous resin It is dispersed in an amorphous resin.

Since the crystalline resin and the release agent are included in the second amorphous resin that is incompatible with the first amorphous resin, the crystalline resin and the release agent are not compatible with the first amorphous resin. Even if the toner is subjected to physical stress, it is difficult for stress to be applied to the release agent and the crystalline resin in the toner particles, and the release agent can be prevented from seeping out to the toner particle surface and the plasticization of the crystalline resin and the like. .

The domain of the second amorphous resin encapsulating the crystalline resin and the release agent is contained in the first amorphous resin in a state of encapsulating one domain of the crystalline resin or one release agent domain. The domains of the second amorphous resin may be aggregated and coalesced, and may be dispersed in a state where a plurality of domains of the crystalline resin and / or the release agent are included.

Since the crystalline resin and / or the release agent is included in the second amorphous resin, the crystalline resin and / or the release agent is not exposed on the surface of the toner particles. The domains of the functional resin may exist in the vicinity of the toner particle surface, but are preferably present in the toner particles.

  Further, the second amorphous resin domain is preferably spherical or substantially spherical. The second amorphous resin domain is spherical or substantially spherical. Even if the particles are subjected to local physical stress (stress), the domain of the second amorphous resin is not easily broken, plasticization by the compatibility of the first amorphous resin and the crystalline resin, and Prevents the release agent from seeping out.

  The dispersion state of the second amorphous resin, the crystalline resin, and the release agent in such toner particles can be determined by comparing a cross-sectional cut image with TEM by contrast by ruthenium staining or the like, or Nano-TA2 (TMA The probe is changed to a dedicated probe so that the temperature at the tip of the probe can be adjusted.) Using a device that can detect displacement even in a very small region of about 100 nm, the material can be specified with the specific melting point. Can be confirmed.

<First amorphous resin>
The first amorphous resin is not particularly limited, but it is preferable to use a resin having a polyester skeleton because good fixability can be obtained. Examples of the resin having a polyester skeleton include a polyester resin and a block polymer of a polyester and a resin having another skeleton, and it is preferable to use a polyester resin because the uniformity of the obtained colored resin particles is high.

Examples of the polyester resin include a polycondensate of polyol (1) and polycarboxylic acid (2), a ring-opening polymer of lactones, a polycondensation product of hydroxycarboxylic acid, and the like, from the viewpoint of design freedom. A polycondensation product of polycarboxylic acid is preferred.

<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.) adduct of the above alicyclic diol; 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;
Examples thereof include alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols.

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.

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

<Polycarboxylic acid>
Examples of the 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 The mixture of (2-2) is preferable.

Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid) 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 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) Romechiru) -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 (such as trimellitic acid and pyromellitic acid).
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 the polyol and the polycarboxylic acid is usually 2/1 to 1/2, preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1.5, more preferably 1.3 / 1 to 1 / 1.3.

The first amorphous resin preferably has a glass transition temperature (Tg1) in DSC (1st) of 50 ° C. or higher and 60 ° C. or lower, and more preferably 52 ° C. or higher and 57 ° C. or lower.
When the glass transition temperature (Tg1) is less than 50 ° C, the heat-resistant storage stability may be lowered, and when it exceeds 60 ° C, the low-temperature fixability may be lowered.

Further, the first amorphous resin has a solubility parameter (SP value) in order to prevent the second amorphous resin from being included and exposed to the surface when toner particles are granulated in an aqueous medium. However, it is preferable that it is larger than SP value of the 2nd amorphous resin mentioned later, and it is preferable that the upper limit is 14 or less.
Specifically, it is preferably 9 or more and 14 or less, more preferably 10 or more and 13 or less.
If the SP value exceeds 14, the transition to the water phase is likely to occur, resulting in problems such as loss in the material balance during the production process or deterioration in the dispersion stability of the oil droplets. It becomes easy to do. On the other hand, if the SP value is too low, the polarity of the resin becomes low, and the dispersibility of the colorant having polarity may be lowered.

The weight average molecular weight of the first amorphous resin polyester resin is 1000 to 30000, preferably 1500 to 10000, and more preferably 2000 to 8000. If it is less than 1000, the heat-resistant storage stability deteriorates, and if it exceeds 30000, the low-temperature fixability as an electrostatic latent image developing toner may deteriorate.

<Second amorphous resin>
The second amorphous resin is a resin that is incompatible with the first amorphous resin, and is present between the first amorphous resin and the crystalline material. Suppresses the plasticization phenomenon due to the compatibility between the first amorphous resin and the crystalline resin due to stress before fixing, etc., and eliminates the need for an annealing step for recrystallization during toner production, It stabilizes productivity and quality.
In the present invention, “incompatible” means that the first amorphous resin does not form a continuous layer but has an interface. The presence or absence of an interface can be confirmed by X-ray analysis.

  As the second amorphous resin, any resin that is incompatible with the first amorphous resin can be used, but a resin having a skeleton that is not compatible with the encapsulating crystalline polyester resin is used. A vinyl-based resin is preferable because it is easily available and easily designed.

The vinyl resin can be obtained by polymerizing a monomer having a polymerizable double bond.
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 a phosphoric acid group-containing vinyl monomer and a salt thereof, and a known polymerization initiator may be used.

The glass transition temperature (Tg2) of the second amorphous resin is preferably higher by 5 ° C. or more and 15 ° C. or less than the glass transition temperature (Tg1) of the first amorphous resin, and more preferably 5 ° C. or more. It is preferably 10 ° C. or lower.
When the difference between the glass transition temperature (Tg2) of the second amorphous resin and the glass transition temperature (T1) of the first amorphous resin is less than 5 ° C., the crystalline resin and the first amorphous resin The ability to prevent compatibility with the resin is lowered, and the heat-resistant storage stability may be lowered due to plasticization or the like, and the release agent may ooze out on the surface of the toner particles to contaminate members such as a photoreceptor.
If the difference in glass transition temperature exceeds 15 ° C., the viscosity of the toner due to the crystalline resin at the time of fixing may not be reduced, and the low-temperature fixability may be deteriorated. An offset may occur without bleeding out.

Examples of the method of encapsulating the crystalline resin and the release agent described later in the second amorphous resin include the following methods.
(1) A method in which fine particles of a crystalline resin and / or a release agent are prepared in advance, and the periphery of the fine particles is coated with a second amorphous resin.
(2) After preparing a droplet in which the crystalline resin and / or the release agent and the second amorphous resin are dissolved in the solvent, the solvent is removed and the crystalline resin and / or the release agent and the second liquid are dissolved. A method of encapsulating an amorphous resin while performing phase separation.
(3) After preparing fine particles of a dispersion liquid in which the crystalline resin and / or the release agent are dispersed as fine particles in a solution in which the second amorphous resin is dissolved, the solvent is removed to remove the crystalline resin and / or Alternatively, a method for producing fine particles encapsulating a release agent (4) Second non-crystalline solution in which a crystalline resin and / or a release agent are dissolved and / or dispersed as fine particles in a monomer constituting the second amorphous resin A method of obtaining a crystalline resin and / or a release agent encapsulated by a second amorphous resin by obtaining a monomer solution of the crystalline resin and then polymerizing the monomer to obtain a second amorphous resin However, the method (4) mentioned at the end is preferable because the crystalline resin and / or the release agent are uniformly encapsulated and spherical capsule particles are easily obtained.

  The second amorphous resin is easy to completely coat the crystalline resin and / or the release agent when encapsulating the crystalline resin and / or the release agent in the aqueous medium, and has dispersibility. It is preferable that the solubility parameter (SP value will be described later) is larger than the SP values of the crystalline resin and the release agent described later.

When the SP values of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent are Rsp, Tsp, Bsp, Asp, respectively, (Rsp)>(Tsp)> ( When Bsp) and (Rsp)>(Tsp)> (Asp), encapsulation and domaining can be easily formed even if the amount of the second amorphous resin is relatively small.
As described above, Rsp is preferably 9 ≦ (Rsp) ≦ 14, more preferably 10 ≦ (Rsp) ≦ 13, and Tsp is preferably 8.5 ≦ (Tsp) ≦ 12.5. 8.5 ≦ (Tsp) ≦ 12 is more preferable. Further, Asp and Bsp are preferably 7.5 ≦ (Asp) ≦ 11.5 and 7.5 ≦ (Bsp) ≦ 11.5, respectively.

The mass ratio [second amorphous resin / (crystalline resin or mold release agent)] between the second amorphous resin and the crystalline resin or the release agent is determined as long as the second non-resin can be encapsulated and domain-encapsulated. Although the amount of the crystalline resin may be small, for example, 0.4 to 2.0 is preferable, and 0.6 to 1.6 is more preferable.
If it is 0.4 or less, the encapsulation / domain encapsulation is likely to be uneven and insufficient, and if it is twice or more, the second amorphous resin is relatively increased and the dispersibility in the toner particles is increased. In some cases, the low temperature fixability and release effect may be difficult to be exhibited.

The content of the second amorphous resin particles (domains) encapsulating the crystalline resin and / or release agent in the toner is preferably 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 40% by mass. More preferably, it is 10 mass% or less and 35 mass% or less.
When the content of the second amorphous resin domain in the toner is less than 5% by mass, the effect of contributing to the fixing characteristics is reduced. When the content exceeds 50% by mass, aggregation occurs, and the domain becomes too large. It is difficult to be incorporated into the particles and is likely to be unevenly distributed, and when the toner particles are granulated, the oil phase viscosity (shear torque) increases, which may inhibit toner particle formation.
The domain dispersed particle size in the toner particles of the second amorphous resin particles is preferably 1/4 or less of the average particle size of the toner.

The content of the crystalline resin included in the second amorphous resin in the toner is preferably 1% by mass or more and 15% by mass or less, and more preferably 2% by mass or more and 12% by mass or less. . The content of the release agent resin encapsulated in the second amorphous resin in the toner is preferably 1% by mass or more and 15% by mass or less, and preferably 2% by mass or more and 12% by mass or less. Is more preferable.
However, the total amount of the crystalline resin and the release agent included in the second amorphous resin in the toner is preferably 2% by mass or more and 20% by mass or less, and more preferably 4% by mass or more and 15% by mass. % Or less is preferable.

  The method for confirming the second amorphous resin in the toner particles is not particularly limited and can be appropriately selected depending on the purpose. For example, a gas chromatograph mass spectrometer (GC-MS) or nuclear magnetic There are a method of analyzing using a resonance apparatus (NMR), a method of analyzing and removing the amorphous resin after dissolving and removing other materials in the toner using an organic solvent, and the like. Can be mentioned.

Specifically, the resin composition and the composition ratio can be calculated from the 13C-NMR spectrum and GC-MS measurement analyzed by the method described below.
In the 13C-NMR measurement, 50 mg of a sample was placed in a cap-type glass test tube and heated with a high-frequency heating apparatus (QUICKER1010, manufactured by DIC) for 1 minute, and this decomposition product was 30.5 mL of deuterated chloroform (CDCl3) and a relaxation reagent. Tris (2,4-pentanedionato) chromium (III) (Cr (acac) 3) is added, and 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).

<Crystalline resin>
The crystalline resin is not particularly limited as long as it can be included in the second amorphous resin, but is preferably a crystalline polyester resin from the viewpoint of fixability.
The crystalline polyester resin contains a polyhydric alcohol unit and a carboxylic acid unit, -O COC-R-COO- (CH ₂ ) n- (wherein R is a linear non-linear group having 2 to 20 carbon atoms. A saturated aliphatic group, and n represents an integer of 2 to 20) at least 60 mol% of all ester bonds in the entire resin. In the above formula, R preferably represents a linear unsaturated aliphatic divalent carboxylic acid residue, has 2 to 20 carbon atoms, and more preferably 2 to 4 linear unsaturated aliphatic. It is a group. n is an integer of 2-6.

Specific examples of the linear unsaturated aliphatic group include linear unsaturated divalent carboxylic acids such as maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid, and 1,4-n-butene dicarboxylic acid. Mention may be made of linear unsaturated aliphatic groups derived from acids.

The (CH ₂ ) n represents a linear aliphatic dihydric alcohol residue. Specific examples of the linear aliphatic dihydric alcohol residue in this case include linear aliphatic dihydric alcohols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Those derived from dihydric alcohols can be indicated. Since the crystalline polyester resin uses a linear unsaturated aliphatic dicarboxylic acid unit as a carboxylic acid unit, the crystalline polyester resin has an effect of easily forming a crystal structure as compared with the case of using an aromatic dicarboxylic acid unit. Show.

The crystalline polyester resin is a polyvalent carboxylic acid comprising (1) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (an acid anhydride, a lower alkyl ester acid halide having 1 to 4 carbon atoms, etc.). It can be produced by subjecting a unit and (2) a polyhydric alcohol unit comprising a linear aliphatic diol to a polycondensation reaction by a conventional method. In this case, the polyvalent carboxylic acid unit may contain a small amount of other polyvalent carboxylic acid units as necessary. In this case, the polyvalent carboxylic acid unit includes (1) an unsaturated aliphatic divalent carboxylic acid unit having a branched chain, (2) a saturated aliphatic divalent carboxylic acid, a saturated aliphatic trivalent carboxylic acid, etc. In addition to aliphatic polyvalent carboxylic acid units, (3) aromatic polyvalent carboxylic acid units such as aromatic divalent carboxylic acids and aromatic trivalent carboxylic acids are included. The content of these polyvalent carboxylic acid units is usually preferably 30 mol% or less, more preferably 10 mol% or less, based on the total carboxylic acid, and is suitably added within the range where the resulting polyester has crystallinity. The

Specific examples of polyvalent carboxylic acid units that can be added as needed include malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid Divalent carboxylic acid units such as: trimetic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid Trivalent or higher polyvalent carboxylic acid units such as acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid, etc. Can be mentioned.

If necessary, the polyhydric alcohol unit may contain a trivalent or higher polyhydric alcohol unit in addition to a small amount of an aliphatic branched dihydric alcohol unit or cyclic dihydric alcohol unit. The content thereof is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total alcohol units, and is suitably added within the range in which the resulting polyester has crystallinity.
Examples of polyhydric alcohol units added as necessary include 1,4-bis (hydroxymethyl) cyclohexane units, polyethylene glycol units, bisphenol A ethylene oxide adduct units, bisphenol A propylene oxide adduct units, glycerin units, and the like. Is mentioned.

The melting point of the crystalline resin is preferably less than 110 ° C, more preferably 60 ° C to 95 ° C, and further preferably 65 ° C to 90 ° C.
If it is 95 ° C. or higher, the effect on the lower limit of fixing becomes poor, and if it is lower than 60 ° C., the solidification temperature during cooling decreases due to the hysteresis inherent in the crystalline material. Contamination due to reflection or adhesion may occur.
The melting point of the crystalline resin is preferably equal to or higher than the Tg of the first amorphous resin,
More preferably, it is higher by 5 ° C. than the Tg of the first amorphous resin. Furthermore, from the viewpoint of plasticization, the melting point of the crystalline resin is more preferably equal to or higher than the Tg of the second amorphous resin.

<Release agent>
The release agent can be used as long as it is conventionally used as a release agent for toner, but it has a sufficiently low viscosity when heated in the fixing process, and other materials and In particular, it is difficult to be compatible or swell on the surface of the fixing member, and in order to sufficiently exhibit releasability, it is particularly preferable that it is incompatible with the first amorphous resin.

Examples of the release agent include long chain hydrocarbons and carbonyl group-containing waxes.
Examples of the long chain hydrocarbon include polyolefin wax (polyethylene wax, polypropylene wax, etc.); petroleum wax (paraffin wax, sazol wax, microcrystalline wax, etc.); and Fischer-Tropsch wax,
Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1 , 18-octadecanediol distearate); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide) And dialkyl ketone (such as distearyl ketone).

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, It is preferable that it is 60 to 100 degreeC, and it is more preferable that it is 65 to 95 degreeC. .
When the melting point of the release agent is 100 ° C. or higher, the hot offset resistance may be deteriorated, and when it is less than 60 ° C., the heat resistant storage stability may be deteriorated.
Further, the melting point of the release agent is preferably higher by 5 ° C. than the Tg of the first amorphous resin, and preferably higher by 10 ° C. than the Tg of the first amorphous resin. Further, from the viewpoint of plasticization, the melting point of the release agent is more preferably equal to or higher than the Tg of the second amorphous resin.

  The melting points of the release agent and the crystalline resin can be measured by, for example, a differential scanning calorimetry (DSC) apparatus (for example, TG-DSC system TAS-100, manufactured by Rigaku Corporation).

<Colorant>
As the colorant of the present invention, known dyes and pigments can be used, such as carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow (5G) , R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa red, parachlortoni Roaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, 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, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake, Fu Talocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used.

<Colorant masterbatch>
The colorant used in the present invention can also be used as a master batch combined with a resin.
As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the polyester resin, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substituted polymer; styrene-p-chlorostyrene Polymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer Polymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer , Styrene-acrylo Tolyl copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used, and these can be used alone or in combination.

<Master batch production method>
The master batch can be obtained by mixing and kneading the resin for the master batch and the colorant under high shearing force and kneading. At this time, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<Toner production method>
Next, a toner manufacturing method will be described.
The toner of the present invention includes a release agent-containing core-shell particle having a release agent as a core and a second amorphous resin as a shell, and a crystal having a crystalline resin as a core and a second amorphous resin as a shell. An oil phase prepared by dissolving or dispersing the first amorphous resin, the release agent-containing core-shell particles, the crystalline resin-containing core-shell particles, and the colorant in an organic solvent. It is preferable to prepare by dispersing in a medium, removing the solvent, washing and drying.

Each step will be specifically described below.
<Production of oil phase>
The oil phase contains a first amorphous resin, a release agent-containing core-shell particle, a crystalline resin-containing core-shell particle, and a colorant, and if necessary, a modified resin, an amine compound, the charge control agent, and the like. You may contain.
There is no restriction | limiting in particular as said oil phase preparation method, According to the objective, it can select suitably. For example, there may be mentioned a method in which the toner material is gradually added to an organic solvent while stirring and dissolved or dispersed.

At this time, when a pigment is used as a colorant or when a material 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 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)
In addition, in order to increase the mechanical strength of the obtained toner particles, a modified resin having an isocyanate group at the terminal is dissolved in the oil phase for the purpose of preventing high temperature offset during fixing in addition to the previous mechanical strength. Thus, colored resin particles may be obtained.

As a method for obtaining a modified resin, a method for obtaining a resin having an isocyanate group by polymerizing with an isocyanate-containing monomer, a method for obtaining a resin having an active hydrogen at the terminal, and then reacting with a polyisocyanate. Although the method of introduce | transducing an isocyanate group into a polymer terminal etc. is mentioned, The latter method can be preferably employ | adopted from the controllability of introducing an isocyanate group into a terminal.

Examples of the active hydrogen include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferable. As the skeleton of the modified resin, in consideration of the uniformity of the particles, it is preferable to use the same resin as that dissolved in the organic solvent, and it is preferable to have a polyester skeleton. As a method for obtaining a resin having an alcoholic hydroxyl group at the end of the polyester, in the polycondensation of the polyol and the polycarboxylic acid, the polycondensation reaction may be performed by making the number of functional groups of the polyol larger than the number of functional groups of the polycarboxylic acid .

(Amine compound)
The isocyanate group of the modified resin is hydrolyzed in the process of dispersing the oil phase in the aqueous phase to obtain particles, and part of it becomes an amino group. The generated amino group reacts with the unreacted isocyanate group, and is elongated. The reaction proceeds. In addition to the above reaction, an amine compound can be used in combination for the purpose of reliably reacting the extension reaction or introducing a crosslinking point. As the amine compound (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and B1-B5 amino group blocked (B6) etc. are mentioned.

Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, tetrafluoro-p-xylylenediamine, tetrafluoro-p-phenylenediamine, etc.); alicyclic diamines ( 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, etc .; and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecafluorohexylenediamine, tetracosafluorododecylene) Amine).

Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.

Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

The ratio of amines (B) is such that the number of amino groups [NHx] in amines (B) is 4 times or less the number of isocyanate groups [NCO] in prepolymer (A) having an isocyanate group, preferably 2 It is not more than twice, more preferably not more than 1.5 times, and still more preferably not more than 1.2 times. If it exceeds 4 times, the excess amino group blocks the isocyanate and the extension reaction of the modified resin does not occur, so the molecular weight of the polyester is lowered and the hot offset resistance is deteriorated.

(Charge control agent)
Known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified quaternary salts). Secondary ammonium salts or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt. The charge control agent only needs to be used in an amount that exhibits performance and does not impair fixing properties, and is contained in the toner in an amount of 0.5 to 5% by weight, preferably 0.8 to 3% by weight. .

<Aqueous medium>
As an aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination.
Examples of the solvent miscible with water include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

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

(Surfactant)
A surfactant is used to produce droplets by dispersing the oil phase in an aqueous medium.
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. Further, as the cationic surfactant, 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.

(Inorganic dispersant)
The dissolved or dispersed toner composition may be dispersed in the aqueous medium in the presence of an inorganic dispersant or resin fine particles. As the inorganic dispersant, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like are used. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

(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, maleic anhydride, and other (meth) acrylic single monomers containing hydroxyl groups 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 -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Vinyl acetate, vinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having a nitrogen atom or a heterocyclic ring thereof, 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 may remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

<Oil droplet dispersion preparation process>
The oil droplet dispersion preparation process is a process in which the oil phase is dispersed in the aqueous phase to prepare an oil droplet dispersion in which 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 preparation process, 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.
Also, if the melting point of the crystalline resin is -20 ° C. or lower, the change in the crystal structure and the change in the state of the boundary with the amorphous resin are suppressed at the time of production. It is preferable because it can be dispersed and introduced.

<Desolvation>
The solvent removal treatment is a treatment for 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 treatment 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 solvent removal treatment is preferably the method described in (1).

  In the solvent removal treatment, (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 solvent removal treatment can be performed using an apparatus, and examples of the apparatus include a spray dryer, a belt dryer, and a rotary kiln. 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 the toner particles from the dispersion slurry, the dispersion slurry obtained by the solvent removal treatment 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 include an aging step, a crushing step, and an external addition step such as inorganic fine particles. Can be mentioned.
(Aging process)
The aging step is a step performed after the oil droplet dispersion preparation treatment in the dispersion step and before the solvent removal treatment. 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 it is −20 ° C. or lower than the melting point of the crystalline resin, it is possible to suppress the change of the crystal structure and the state of the boundary portion with the amorphous resin even if it is kept for a long time during the production.

(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.

(External addition process of inorganic fine particles)
The external addition step of inorganic fine particles or the like is a step of attaching inorganic fine particles such as silica and titanium oxide to the surface of the toner base particles after the toner base particles are prepared, and can improve the fluidity and storage stability of the toner particles. In order to adhere to the surface of the toner base particles, the toner base particles can be mixed together with inorganic fine particles and applied by applying a mechanical impact force.
As a method of applying a mechanical impact force, for example, a method of applying an impact force to particles using a blade rotating at high speed, a particle in which particles are injected into a high-speed air stream and accelerated to form particles or a composite particle And a method in which an impact force is applied by colliding with a suitable collision plate. As a device for applying a mechanical impact force, for example, an ong mill (manufactured by Hosokawa Micron Co., Ltd.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, and a hybridization system (Manufactured by Nara Machinery Co., Ltd.), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

The toner of the present invention can be used as a one-component developer or a two-component developer mixed with a carrier.

In addition, the toner of the present invention may be incorporated in the apparatus in the form of a process cartridge which is integrated with an apparatus for developing a latent image on a photoreceptor with a developer and is detachable from the image forming apparatus. Good.
The process cartridge is an apparatus (part) that contains an image carrier (photoconductor) and further includes a means selected from a charging unit, an exposure unit, a developing unit, a transfer unit, and a cleaning unit. If necessary, other means such as a static elimination means may be included. There are many shapes and the like of the process cartridge, but a general example is the one shown in FIG. Here, the process cartridge includes a photosensitive member (101), and includes a charging unit (102), an exposure unit (103), a developing unit (104), and a cleaning unit (107). It has the means of. In the figure, (105) is a recording medium (transfer body), and (108) is a transfer means.

<Method for analyzing characteristics of toner and toner constituents>
(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 dissolves.

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 aggregation 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, respectively. It is represented by Formula (II) and Formula (III).

E = ΣΔei Formula (II)
V = ΣΔvi Formula (III)

Although there are various theories about the calculation method of SP value, the method of Fedors generally used in the present invention was 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 -CF3 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 an amorphous polyester resin, a crystalline polyester resin, a release agent, and a graft-modified polymer are synthesized and mixed, these SP values can be easily calculated as described above.
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, and the first amorphous resin, the second amorphous resin, The SP value can be calculated in the same manner from the single material of the 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.

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.
Further, 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 amorphous resin and the crystalline resin or the release agent is separated by GPC, and an analysis method described later is applied to the separated components to obtain the SP value. Calculation is possible.

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 the 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 analyzing the decomposition products qualitatively and quantitatively with high performance liquid chromatography (HPLC). Can do.

  The SP value by the Fedors method can be calculated by specifying the type and ratio of the monomer constituting the resin. However, 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 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). Not to be added).

First, 1 g is put into 100 mL of THF, and a solution having a soluble component dissolved therein is obtained while stirring for 30 minutes at 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 arranged at the eluate discharge port of GPC, and the eluate is collected at every predetermined count, and the eluate is eluted every 5% by area ratio from the elution curve elution start (curve rise). Get.
Next, for each eluate, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05 volume% tetramethylsilane (TMS) is added as a reference substance.
The solution is filled into a glass tube for NMR measurement with a diameter of 5 mm, 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 amorphous resin, the crystalline resin, the monomer composition of the release agent, and the composition ratio contained in the toner 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) 8.07 ppm to 8.10 ppm: derived from the benzene ring of terephthalic acid (for four hydrogens) 7.1 ppm ˜7.25 ppm: derived from the benzene ring of bisphenol A (for 4 hydrogens) 6.8 ppm: derived from the benzene ring of bisphenol A (for 4 hydrogens) and derived from the double bond of fumaric acid (for 2 hydrogens) 5 .About.2 ppm to about 5.4 ppm: bisphenol A propylene oxide adduct derived from methine (for one hydrogen) 3.7 ppm to about 4.7 ppm: bisphenol A propylene oxide adduct derived from methylene (for two hydrogens) and Bisphenol A ethylene oxide adduct derived from methylene (for 4 hydrogens) Around 1.6 ppm: Bisphenol A It can be derived from a methyl group (6 pieces of hydrogen).
From these results, the SP values of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent can be calculated from the formula (I).

(Measurement of number average molecular weight and weight average molecular weight)
The number average molecular weight and the weight average molecular weight were measured by gel permeation chromatography (GPC) under the following conditions.
Apparatus: GPC-150C (manufactured by Waters)
Column: Shodex (registered trademark) KF801-807 (manufactured by Showa Denko KK)
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Detector: RI (refractive index) detector Sample: 0.1 mL of a sample having a concentration of 0.05% to 0.6% by mass is injected from the molecular weight distribution of the resin measured under the above conditions. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were calculated using a molecular weight calibration curve prepared with a polystyrene standard sample. As a standard polystyrene sample for preparing a calibration curve, the Std. Of Shodex (registered trademark) STANDARD (manufactured by Showa Denko KK) was used. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 were used.

(Measurement of glass transition temperature)
The glass transition temperature (Tg) was measured by the following method using a differential scanning calorimetry (DSC) apparatus (TG-DSC system TAS-100, manufactured by Rigaku Corporation).
About 10 mg of a measurement sample was placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, and the sample was cooled to room temperature and then left for another 10 minutes. DSC measurement was performed by heating at a temperature of ° C / min. The glass transition temperature (Tg) was calculated from the contact point between the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

(Measurement of acid value)
The acid value was measured under the following conditions based on the measurement method described in JIS K0070-1992.
A measurement sample (polyester resin) 0.5 g (0.3 g in the case of ethyl acetate soluble component) was added to 120 mL of toluene and dissolved by stirring at room temperature (about 23 ° C.) for about 10 hours. Further, 30 mL of ethanol was added to prepare a measurement sample solution. Using this measurement sample solution, the acid value was calculated using an apparatus described in JIS K0070-1992. Specifically, titration was performed using N / 10 caustic potash to alcohol solution that had been previously standardized, and the acid value was calculated from the following formula (3) from the consumption of the alcohol potash solution.
Acid value = KOH (number of mL) × N × 56.1 / mass of sample: Formula (3)
In the formula (3), “N” represents a factor of N / 10 KOH.

(Average toner particle size)
The volume average particle diameter (Dv) and the 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 of which are Coulter Counter). Etc.)).

  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.

(Confirm capsule structure)
Whether the crystalline resin and the release agent in the toner are encapsulated is determined by cutting the microcapsule with the toner embedded in the embedding resin to produce a flake, and then scanning the flake with a scanning transmission electron microscope. Observed at.

(Measurement of particle size of fine particles in crystalline resin particle dispersion and release agent dispersion)
The volume average particle diameter of the fine particles in the dispersion was measured using a dynamic light scattering nanotrack particle size analyzer (UPA-150EX, manufactured by Nikkiso Co., Ltd.) with the following measurement parameters.
In addition, it measured by adjusting the density | concentration of a measurement sample so that a loading index might be in the range of 1-1.5 on the following conditions.
Particle permeability: transmission Particle refractive index: 1.59
Particle shape: Spherical type Solvent type: WATER
Monodisperse: Disabled

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. However, Examples 2, 4, and 8 are read as reference examples.

[Synthesis of Amorphous Polyester 1]
In a reaction vessel equipped with a cooling pipe stirrer and a nitrogen introduction tube, 421 parts of bisphenol A ethylene oxide 2-mole adduct, 353 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 for 5 hours under a reduced pressure of 10 to 15 mmHg, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. ] Was synthesized.

The obtained [Amorphous Polyester 1] had an SP value of 12.1, a weight average molecular weight of 5800, and a glass transition temperature of 56 ° C.

[Synthesis of Amorphous Polyester 2]
778 parts of bisphenol A propylene oxide 2-mole adduct, 208 parts of terephthalic acid, 23 parts of isophthalic acid, 24 parts of adipic acid, and 2 parts of dibutyltin oxide are charged in a reaction vessel equipped with a condenser and a nitrogen introducing tube. The mixture was reacted at 230 ° C. for 8 hours under normal pressure.

Next, after reacting under reduced pressure of 10 to 15 mmHg for 4 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure. ] Was synthesized.

The obtained [Amorphous Polyester 2] had an sp value of 11.3, a weight average molecular weight of 6400, and a glass transition temperature of 64 ° C.

[Synthesis of Crystalline Polyester Resin 1]
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple, 2,120 g of 1,10-decanedicarboxylic acid, 1,080 g of 1,8-octanediol, 1,4-butane Diol 1,410 g and hydroquinone 3.9 g were added, reacted at 180 ° C. for 6 hours, then heated to 200 ° C. for 2 hours, and further reacted at a pressure of 8.3 kPa for 1 hour to obtain crystallinity. A polyester resin 1 was obtained. The crystalline polyester resin 1 had an SP value of 9.5 and a melting point of 65 ° C.

[Synthesis of Crystalline Polyester Resin 2]
Into a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1260 g of 1,4-butanediol, 120 g of ethylene glycol, 1400 g of fumaric acid, 350 g of trimellitic anhydride, tin octylate 3. 5 g and 1.5 g of hydroquinone were added, reacted at 180 ° C. for 6 hours, heated to 200 ° C. and reacted for 2 hours, and further reacted at a pressure of 8.3 kPa for 1 hour to obtain crystalline polyester resin 2. Obtained. Crystalline polyester 2 had a melting point of 87 ° C. and an SP value of 9.4.

[Synthesis of Crystalline Polyester Resin 3]
To a 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple, 2,120 g of 1,10-decanedicarboxylic acid, 1,080 g of 1,8-octanediol, 1,4-butane Diol 1,410 g and hydroquinone 3.9 g were added and reacted at 180 ° C. for 8 hours, then heated to 200 ° C. and reacted for 3 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain crystallinity. A polyester resin 3 was obtained. The crystalline polyester resin 3 had an SP value of 9.3 and a melting point of 73 ° C.

[Synthesis of Crystalline Polyester Resin 4]
Into a 5 L four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, 1284 g of fumaric acid, 167 g of trimellitic anhydride, 215 g of 1,6-hexanediol, 1344 g of 1,4-butanediol and hydroquinone After adding 2.2 g and reacting at 180 ° C. for 8 hours, the temperature was raised to 200 ° C. and reacted for 2 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain a crystalline polyester resin 4. The crystalline polyester resin 4 had an SP value of 9.6 and a melting point of 104 ° C.

[Synthesis of Crystalline Polyester Resin 5]
A 5 L four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple was charged with 1160 g of fumaric acid, 1520 g of 1,10-decanedicarboxylic acid, 1020 g of 1,6-octanediol, 1,4-butane. 1300 g of diol and 4.6 g of hydroquinone were added, reacted at 180 ° C. for 7 hours, heated to 200 ° C. for 2 hours, and further reacted at a pressure of 8.3 kPa for 2 hours to obtain a crystalline polyester resin 5 was obtained. The crystalline polyester resin 5 had an SP value of 11.3 and a melting point of 76 ° C.

[Production of crystalline resin particle dispersion 1]
<Encapsulation process>
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 56 parts of [Crystalline Polyester Resin 1] are 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 ultrasonic irradiation was performed at 90 to 110 W for 10 minutes using an ultrasonic homogenizer VCX750 in a nitrogen atmosphere while maintaining the temperature at 80 ° C. 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 [crystalline resin particle dispersion liquid 1] with a volume average particle diameter of 106 nm was obtained.

Fine particles in the obtained [crystalline resin particle dispersion 1] embedded with an embedding resin were cut with a microtome to produce a thin piece, which was observed with a scanning transmission electron microscope. It was confirmed that the

Further, when measured by the SP value measurement method, the (second) amorphous resin content in the shell portion was 9.9, and the crystalline polyester resin content in the core portion was 9.5.

[Production of crystalline resin particle dispersion 2]
A white [crystalline resin particle dispersion 2] of 98 nm was obtained in the same manner as [crystalline resin particle dispersion 1] except that the crystalline polyester resin 2 was used.

[Production of crystalline resin particle dispersion 3]
A white [crystalline resin particle dispersion 3] of 105 nm was obtained in the same manner as [crystalline resin particle dispersion 1] except that the crystalline polyester resin 3 was used.

[Production of crystalline resin particle dispersion 4]
A white [crystalline resin particle dispersion 4] of 118 nm was obtained in the same manner as [crystalline resin particle dispersion 1] except that the crystalline polyester resin 4 was used.

[Production of crystalline resin particle dispersion 5]
A white [crystalline resin particle dispersion 5] of 109 nm was obtained in the same manner as [crystalline resin particle dispersion 1] except that the crystalline polyester resin 5 was used.

[Preparation of Release Agent Dispersion-1]
<Encapsulation process>
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, and carnauba wax as a release agent (manufactured by Celalica Noda, WA-05: melting point 86 ° C., SP value) 9.3) 56 parts 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 180 minutes. Then, it cooled and white [release agent dispersion liquid-1] was obtained.
The volume average particle diameter of the fine particles in the obtained [Releasing Agent Dispersion-1] was 130 nm, and it was confirmed to have a capsule structure.
Further, when measured by the SP value measurement method, the second amorphous resin content in the shell portion was 9.9, and the release agent content in the core portion was 9.3.

[Preparation of release agent dispersion-2]
98 nm white as in [Releasing Agent Dispersion-1] except that hydrocarbon wax (Nippon Seiki Co., Ltd., HNP-9: melting point 75 ° C., SP value 8.8) was used as the release agent. [Release Agent Dispersion-2] was obtained.

[Preparation of release agent dispersion-3]
115 nm in the same manner as [Releasing agent dispersion-1] except that microcrystalline wax (manufactured by Nippon Seiki Co., Ltd., HI-MIC-1090: melting point 88 ° C., SP value 9.0) was used as the releasing agent. White [release agent dispersion-3] was obtained.

[Preparation of release agent dispersion-4]
Polyethylene wax (manufactured by Sanyo Chemical Co., Ltd., high wax 200P: melting point 122 ° C., SP value 8.3) was used as the release agent in the same manner as in [Release Dispersant-1], a white 148 nm [release] Agent dispersion-4] was obtained.

[Preparation of release agent dispersion-5]
In a container equipped with a stirring bar and a thermometer, 545 parts of [Amorphous Polyester 1], 181 parts of Carnauba wax (manufactured by Celalica Noda, WA-05: melting point 86 ° C., SP value 9.3), acetic acid 1450 parts of ethyl was charged, heated 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 conditions of filling and 3 passes to obtain 110 [white] (release agent dispersion-5).

Further, only the second amorphous resin having the same composition used for the release agent capsule and the crystalline resin capsule was synthesized alone, and the physical properties were confirmed by the following methods.

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 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 180 minutes. Then, it cooled and white [2nd resin dispersion liquid-1] was obtained.
The volume average particle diameter of the fine particles in the obtained [second resin dispersion-1] is 102 nm and the sp value is 9.9, and the second resin contained in the crystalline resin particle dispersion and the release agent dispersion. This was the same value as the SP value of the amorphous resin.

[Example 1]
[Synthesis 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 [amorphous polyester resin 1] 1,200 parts were added, and Henschel After mixing with a mixer (manufactured by Mitsui Mining Co., Ltd.), 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 condenser, a stirrer and a nitrogen introduction tube, 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, 22 parts of trimellitic anhydride Then, 2 parts of dibutyltin oxide was added, reacted at 230 ° C. under normal pressure for 8 hours, and further reacted at reduced pressure of 10-15 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%.

<Pigment dispersion preparation process>
545 parts of [Amorphous polyester 1], 500 parts of [Masterbatch 1] and 1450 parts of ethyl acetate were charged in a container equipped with a stirrer and a thermometer, 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 was dispersed under the conditions of filling and 3 passes.
Next, 655 parts of a 66% ethyl acetate solution of [Polyester 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment dispersion 1].

<Oil phase preparation process>
[Pigment dispersion 1] 426 parts and isophoronediamine 2.6 parts were mixed with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, then [release agent dispersion 1] 556 parts, [crystal Resin particle dispersion 1] 596 parts are added and mixed at 8,000 rpm for 1 minute, then [Prepolymer 1] 88 parts are added and mixed at 5,000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika). [Oil phase 1] was obtained.

<Toner particle preparation process>
The obtained [Oil Phase 1] is added to 1100 parts of [Aqueous Phase 1] and cooled 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 speed of 8,000-15,000 rpm using a TK homomixer and mixed for 2 minutes, then adjusted at a 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 liquid of (2) had a pH of 4, and the mixture was filtered as it was 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].

When the cross section of the toner was dyed with ruthenium and confirmed by TEM, it was confirmed that the crystalline second resin and the release agent were encapsulated in the spherical second amorphous resin particles (domains).

[Example 2]
[Toner 2] was obtained in the same manner as in Example 1 except that [Crystalline resin particle dispersion 1] was changed to [Crystalline resin particle dispersion 2].

[Example 3]
[Toner 3] was obtained in the same manner as in Example 1 except that [Crystalline resin particle dispersion 1] was changed to [Crystalline resin particle dispersion 3].

[Example 4]
[Toner 4] was obtained in the same manner as in Example 1, except that [Crystalline resin particle dispersion 1] was changed to [Crystalline resin particle dispersion 4].

[Example 5]
[Toner 5] was obtained in the same manner as in Example 1 except that [Crystalline resin particle dispersion 1] was changed to [Crystalline resin particle dispersion 5].

[Example 6]
[Toner 5] was obtained in the same manner as in Example 1 except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 2].

[Example 7]
[Toner 6] was obtained in the same manner as in Example 1 except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 3].

[Example 8]
[Toner 8] was obtained in the same manner as in Example 1 except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 4].

[Example 9]
[Toner 9] was obtained in the same manner as in Example 1 except that [Amorphous polyester 1] was changed to [Amorphous polyester 2].

When the cross sections of the toners of Examples 2 to 9 were dyed with ruthenium in the same manner as in Example 1 and confirmed by TEM, the crystalline resin and the release agent were found in the spherical second amorphous resin particles (domains). Was confirmed to be included.

[Comparative Example 1]
[Toner 10] was obtained in the same manner as in Example 1 except that [Releasing Agent Dispersion 1] was changed to [Releasing Agent Dispersion 5].
In Comparative Example 1, the crystalline resin is encapsulated in the second amorphous resin, but the release agent is not encapsulated.

[Comparative Example 2]
[Toner 11] was obtained in the same manner as in Example 1 except that [crystalline polyester 1] was used instead of [crystalline resin particle dispersion 1] in the oil phase preparation step.
In Comparative Example 2, the crystalline resin is not included.

[Comparative Example 3]
[Toner 12] was obtained in the same manner as in Comparative Example 2, except that the release agent dispersion 1 was changed to [release agent dispersion 5].
In Comparative Example 3, neither the crystalline resin nor the release agent is encapsulated.

<Preparation of developer>
-Production of carrier-
To 100 parts of toluene, 100 parts of a silicone resin organostraight silicone, 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added and dispersed with a homomixer for 20 minutes to form a resin layer. A coating solution was prepared.
Using a fluidized bed type coating apparatus, a 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.

95 parts of the carrier and 15 parts of the [Toners 1 to 12] were mixed using a ball mill to prepare [Developers 1 to 12].
[Developers 1 to 12] were evaluated by the following methods. The evaluation results are shown in Table 1.

<Heat resistant storage stability>
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 to less than 20 mm Δ: 10 mm to less than 15 mm x: less than 10 mm

<Fixability>
A copying test was performed on type 6200 paper (manufactured by Ricoh Co., Ltd.) using an apparatus in which the fixing unit of the copying machine MF2200 (manufactured by Ricoh Co., Ltd.) using a Teflon (registered trademark) roller as a fixing roller was modified .
The evaluation conditions were a paper feed linear velocity of 120 mm to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The fixing temperature was tested from 120 ° C. to 200 ° C. in increments of 5 ° C., and the fixed image was scanned using a drawing tester AD-401 manufactured by Ueshima Seisakusho in a high temperature and high humidity environment of 30 ° C./80% Rh. Run with the sapphire needle 125μR, needle rotation diameter 8mm, load 1g in contact with the colored part, and visually observe the running surface of the sapphire needle tip, the lowest temperature at which scratches are clearly recognized as white spots Was defined as the minimum fixing temperature.

<Parts contamination (filming)>
The image forming apparatus MF2800 (manufactured by Ricoh Co., Ltd.) was used to visually inspect the photoreceptor after forming 10,000 images in a high-temperature and high-humidity environment at 30 ° C./80% Rh. Whether the release agent was fixed to the photoconductor was evaluated according to the following evaluation criteria.
○: The toner component is not fixed to the photosensitive member.
(Triangle | delta): Although adhesion of the toner component to a photoreceptor can be confirmed, it is not a level which becomes a problem practically.
X: Adherence of the toner component to the photosensitive member can be confirmed, which is a level that causes a practical problem.

DESCRIPTION OF SYMBOLS 101 Photoconductor 102 Charging means 103 Exposure means 104 Development means 105 Recording medium 107 Cleaning means 108 Transfer means

Japanese Patent No. 3233754 Japanese Patent No. 4075949 JP 2011-232738 A

Claims (9)

A toner containing at least a first amorphous resin, a second amorphous resin, a crystalline resin, and a release agent,
The crystalline resin has a melting point of 65 ° C to 76 ° C, and the release agent has a melting point of 75 ° C to 88 ° C.
The second amorphous resin is incompatible with the first amorphous resin and is dispersed in the first amorphous resin;
The toner according to claim 1, wherein the crystalline resin and the release agent are substantially independently contained in the second amorphous resin.   The toner according to claim 1, wherein the first amorphous resin is a polyester resin, and the second amorphous resin is a vinyl resin. The toner according to claim 1 or 2 before Symbol crystalline resin characterized in that it is a crystalline polyester resin.   The glass transition temperature (Tg1) of the first amorphous resin is 50 ° C. or more and 60 ° C. or less, and the glass transition temperature (Tg2) of the second amorphous resin is Tg1 + 5 ° C. ≦ Tg2 ≦ Tg1 + 15 ° C. The toner according to claim 1, wherein: When the SP values of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent are Rsp, Tsp, Bsp, and Asp, respectively, the following relationship is satisfied: The toner according to claim 1.
(Rsp)>(Tsp)> (Bsp)
(Rsp)>(Tsp)> (Asp) Containing at least a first amorphous resin, a second amorphous resin, a crystalline resin, and a release agent;
The crystalline resin has a melting point of 65 ° C to 76 ° C, and the release agent has a melting point of 75 ° C to 88 ° C.
The second amorphous resin is incompatible with the first amorphous resin and is dispersed in the first amorphous resin, and the crystalline resin and the release agent are A method for producing a toner substantially independently contained in a second amorphous resin,
A step of producing a release agent-containing core-shell particle having the release agent as a core and a second amorphous resin as a shell;
Producing crystalline resin-containing core-shell particles having the crystalline resin as a core and the second amorphous resin as a shell; and
A method for producing a toner, comprising: a dispersion step of dispersing the release agent-containing core-shell particles and the crystalline resin-containing core-shell particles in the first amorphous resin. When the SP values of the first amorphous resin, the second amorphous resin, the crystalline resin, and the release agent are Rsp, Tsp, Bsp, and Asp, respectively, the following relationship is satisfied:
(Rsp)>(Tsp)> (Bsp)
(Rsp)>(Tsp)> (Asp)
The method for producing a toner according to claim 6, wherein the step of producing the release agent-containing core-shell particles and the step of producing the crystalline resin-containing core-shell particles are performed in an aqueous medium.   In the dispersion step, an oil phase in which at least the first amorphous resin, the release agent-containing core-shell particles, the crystalline resin-containing core-shell particles, and the colorant are dissolved or dispersed in an organic solvent is contained in an aqueous medium. The method for producing a toner according to claim 6, further comprising a step of preparing an oil droplet dispersion to be dispersed.   6. A process cartridge that is integrated with a photosensitive member and a device that develops at least a latent image on the photosensitive member with a developer and is detachable from the image forming apparatus, wherein the developer is in the developer. A process cartridge comprising the toner according to claim 1.

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