JP2019040205A - Method for manufacturing toner, method for manufacturing developer, and image forming method - Google Patents

Abstract

Kind Code: A1 A method for producing a toner having excellent low-temperature fixability and excellent anti-blocking property is provided. Kind Code: A1 A toner manufacturing method includes a droplet ejection step of ejecting a toner composition liquid in the form of droplets from at least one ejection hole, wherein the toner formed from the toner composition liquid contains a binder resin. and the binder resin contains a crystalline polyester and an amorphous polyester, and the tetrahydrofuran is removed by heating from an extracted solution obtained by extracting the binder resin from the toner using tetrahydrofuran. The molded product obtained by the above method has spherical domains of the crystalline polyester, and the average particle size of the spherical domains is 7.0 μm or less. [Selection drawing] Fig. 1

Description

  The present invention relates to a toner manufacturing method, a developer manufacturing method, and an image forming method.

  Conventionally, in an electrophotographic image forming apparatus or the like, a latent image formed electrically or magnetically has been visualized with an electrophotographic toner (hereinafter also simply referred to as “toner”). . For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper, and then fixed onto the transfer material. In the fixing step for fixing the toner image on the transfer material, a heat fixing method such as a heating roller fixing method and a heating belt fixing method is widely used because of its energy efficiency.

  In recent years, demands from the market for increasing the speed and energy saving of image forming apparatuses are increasing, and there is a demand for toners that are excellent in low-temperature fixability and can provide high-quality images. In order to achieve low-temperature fixability of the toner, it is necessary to lower the softening temperature of the binder resin of the toner. If the softening temperature of the binder resin is low, a part of the toner image is fixed at the time of fixing. A so-called offset is likely to occur, which adheres to the surface of the member and transfers it onto the copy sheet. Further, the heat-resistant storage stability of the toner is lowered, and so-called blocking occurs in which toner particles are fused with each other particularly in a high temperature environment. In addition, there are problems that the toner is fused and contaminated inside the developing device and the carrier in the developing device, and that the toner is likely to be filmed on the surface of the photoreceptor.

  As a technique capable of solving these problems, a technique using a crystalline resin as a toner binder resin has been proposed (see, for example, Patent Documents 1 and 2). Since the crystalline resin has a characteristic that it softens rapidly from the crystallized state at the melting point, the fixing temperature of the toner can be greatly lowered.

  However, it is easy to phase separate by simply blending a crystalline resin and an amorphous resin. Therefore, when a crystalline resin is used as the binder resin of the toner, it is excellent in toughness while being soft and easily plastically deformed. Therefore, simply using a crystalline resin as a binder resin reduces the heat storage stability (blocking resistance) of the toner, and the toner aggregates in the toner storage container and the image forming apparatus. There is a problem that the toner density is lowered and an abnormal image is formed.

  On the other hand, the crystalline resin can be finely dispersed in the toner by applying an external force in the step of emulsifying or melt-kneading a component containing a binder resin composed of a crystalline resin and an amorphous resin. However, this method has a problem that when the heat and external force are applied again, the dispersibility of the crystalline resin is deteriorated, and the low-temperature fixability and the blocking resistance are lowered.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a toner that not only has excellent low-temperature fixability but also has excellent blocking resistance.

Means for solving the problems are as follows. That is,
The toner of the present invention is a toner containing a binder resin,
The binder resin contains a crystalline polyester and an amorphous polyester;
A molded product obtained by removing tetrahydrofuran by heating from an extraction solution obtained by extracting the binder resin from the toner using tetrahydrofuran has a spherical domain of the crystalline polyester, and further has a spherical domain. The average particle size is 7.0 μm or less.

  According to the present invention, the above-described problems can be solved, and a toner not only having excellent low-temperature fixability but also excellent blocking resistance can be provided.

FIG. 1 is a schematic diagram showing an example of a crystalline polyester domain. FIG. 2 is a cross-sectional view showing an example of the liquid column resonance droplet discharge means. FIG. 3 is a schematic diagram illustrating an example of a toner manufacturing apparatus. FIG. 4 is a schematic configuration diagram showing an example of the image forming apparatus of the present invention. FIG. 5 is a partially enlarged view of FIG.

(toner)
The toner of the present invention contains at least a binder resin, and further contains other components as necessary.
The binder resin contains a crystalline polyester and an amorphous polyester.
A molded product obtained by removing tetrahydrofuran by heating from an extraction solution obtained by extracting the binder resin from the toner using tetrahydrofuran has spherical domains of the crystalline polyester. Furthermore, the average particle diameter of the spherical domain is 7.0 μm or less.

The present inventors have found that a domain of tens to hundreds of micrometers composed of the crystalline resin is formed by simply blending the crystalline resin and the amorphous resin. In addition, simply using a crystalline resin as a binder resin may result in insufficient dispersion of the crystalline resin, that is, the heat resistant storage stability (blocking resistance) of the toner may be reduced by increasing the domain size. I found out.
On the other hand, the crystalline resin can be finely dispersed in the toner by applying an external force in the step of emulsifying or melt-kneading a component containing a binder resin composed of a crystalline resin and an amorphous resin. However, this method has been found to be low in compatibility between the crystalline resin and the amorphous resin because it is forcibly finely dispersed by an external force. Therefore, when heat and external force are applied again, the dispersibility of the crystalline resin is deteriorated, and the low-temperature fixability and blocking resistance are reduced.

  Based on the above findings, as a result of intensive studies, the present inventors have found that the toner containing a binder resin containing a crystalline polyester and an amorphous polyester has a low-temperature fixability and anti-blocking property that dissolves the binder resin. It has been found that this greatly depends on the domain size of the crystalline polyester in the molded product obtained from the solution. That is, a combination of a crystalline polyester and an amorphous polyester in which the crystalline polyester spontaneously finely disperses is advantageous in terms of low-temperature fixability and blocking resistance.

Further, this spontaneous fine dispersion is caused by the respective viscosities of the crystalline polyester and the amorphous polyester, the content ratio of the crystalline polyester and the amorphous polyester, the surface freeness of the crystalline polyester and the amorphous polyester. The present inventors have clarified that this can be achieved by appropriately selecting a combination of the crystalline polyester and the amorphous polyester in consideration of an energy difference or the like.
The viscosity ratio and quantity ratio of crystalline polyester and amorphous polyester are determined by the molecular weight of crystalline polyester and amorphous polyester and the content of crystalline polyester in the same composition at the same temperature. Affects the domain size of polyester.
The combination of the crystalline polyester and the amorphous polyester having a smaller difference in surface free energy can reduce the domain size. This is because when the difference in surface free energy between the crystalline polyester and the amorphous polyester is reduced, the interfacial tension is reduced and the compatibility between the crystalline polyester and the amorphous polyester is improved. Therefore, in order to reduce the domain size of the crystalline polyester, the combination of the raw material monomers of the crystalline polyester and the amorphous polyester can be appropriately selected using the surface free energy as an index.

  As described above, in order to improve the low-temperature fixability and anti-blocking property of the toner, in addition to the thermal characteristics of the amorphous polyester and the crystalline polyester, for the purpose of reducing the domain size of the crystalline polyester, Paying attention to the molecular weight of the amorphous polyester and the crystalline polyester, their content ratio, and their surface free energy difference, the present inventors have completed the present invention.

<Domain of crystalline polyester>
A molded product obtained by removing tetrahydrofuran by heating from an extraction solution obtained by extracting the binder resin from the toner using tetrahydrofuran has spherical domains of the crystalline polyester. Furthermore, the average particle diameter of the spherical domain is 7.0 μm or less. When the average particle diameter exceeds 7.0 μm, the compatibility between the crystalline polyester and the amorphous polyester is poor, and the low-temperature fixability or blocking resistance is poor.
The spherical shape in the spherical domain is not limited to a true sphere and includes an ellipsoid.
The shape of the crystalline polyester domain in the molded body is preferably only spherical.
The spherical domain is observed, for example, as a circle or an ellipse when the molded body is observed in cross section.
Here, the “average particle diameter” is an arithmetic average value obtained by arbitrarily measuring 20 diameters in the case where the spherical domain is a true sphere and in the case of a non-spherical shape.

  There is no restriction | limiting in particular as an aspect-ratio of the said spherical domain, Although it can select suitably according to the objective, 3 or less is preferable and 2 or less is more preferable. When the aspect ratio is greater than 3, the compatibility between the crystalline polyester and the amorphous polyester is too high, the crystallinity of the crystalline polyester may be lowered, and the blocking resistance may be inferior. is there.

The average size of the crystalline polyester domains in the toner is preferably 150 nm or less. When the average size exceeds 150 nm, the compatibility between the crystalline polyester and the amorphous polyester is poor, and the low-temperature fixability or blocking resistance may be inferior.
Here, the “average size” is an arithmetic average value obtained by arbitrarily measuring 20 domain sizes.

It is preferable that the crystalline polyester domains in the toner have only a spherical shape.
When the crystalline polyester domains in the toner and the molded body are needle-shaped, rod-shaped, plate-shaped, or amorphous, the phase separation structure is not fixed, that is, amorphous portions and crystals There is a tendency that it is difficult to maintain sufficient anti-blocking property because the compatibility with the mass part is good, and many crystalline polymer chains that cannot grow into crystals remain in the amorphous part. This tendency becomes remarkable when the shape of the domain is indefinite.

  When producing the molded body, the binder resin may be extracted from the toner, or the amorphous polyester and the crystalline polyester may be weighed at an arbitrary ratio (a ratio in the toner). The obtained mixture may be dissolved in THF (tetrahydrofuran) to replace the extract.

  The binder resin can be extracted from the toner by mixing 100 parts by mass or more of THF with 100 parts by mass of toner after weighing the toner and stirring at room temperature or with heating. Components other than the binder resin contained in the obtained binder resin extract, such as a mold release agent, a charge control agent, a colorant (for example, a pigment), and the like can be removed by centrifugation, filtration, washing, and the like. Is possible. Further, the binder resin extract is cast on a support (for example, a Teflon (registered trademark) sheet), and then the solvent (THF) is removed to obtain a film-like molded product. The solvent removal method is preferably performed by evaporation of the solvent, and examples of the method for evaporating the solvent include methods such as heating, decompression, and ventilation. Furthermore, when the solvent is removed, it is preferably performed under standing, and external force (for example, compression, shearing, etc.) is not applied. The domain size of the crystalline polyester can be measured from the molded body with a transmission electron microscope (TEM).

<< Method for observing domain size of crystalline polyester >>
The toner or the molded body is subjected to vapor dyeing using a commercially available 5% by mass aqueous solution of ruthenium tetroxide. After dyeing, it is embedded in an epoxy resin and sectioned with a diamond knife using a microtome (Ultracut-E). The thickness of the section is adjusted to around 100 nm using the interference color of the epoxy resin. Further, the slice is placed on a copper grid mesh and vapor-stained using a commercially available 5% by weight aqueous solution of ruthenium tetroxide. Observation is performed using a transmission electron microscope (for example, JEM-2100F, manufactured by JEOL Ltd.), and an image of a cross section of the molded body in the section is recorded. By observing the cross section of the molded body, the domain formed by the crystalline polyester is observed, and the presence state of the amorphous polyester and the crystalline polyester is evaluated.
The crystalline polyester is obtained as a clear contrast by dyeing after sectioning. The crystalline polyester is dyed weaker than the amorphous polyester. This is presumably because the soaking of the dyed material into the crystalline polyester is weaker than the amorphous polyester because of the difference in density.
In this way, the amount of ruthenium atoms varies depending on the intensity of the staining, so the portion that is strongly stained has many of these atoms, the electron beam does not pass through, and it becomes black on the observed image and is weakly stained. This part is easily transmitted through the electronic gland and becomes white on the observed image.

  An example of the cross section of the molded body is shown in FIG. The schematic diagram of FIG. 1 is a schematic diagram of a preferred embodiment having only spherical domains having a diameter of 0.3 μm to 3.0 μm. In addition, FIG. 1 is a schematic diagram of a cross section of a molded body of Example 4 to be described later.

<Thermal characteristics>
TMA (Thermo Mechanical) at 200 mN under conditions of 40 ° C. and 80% relative humidity of a molded article obtained by removing tetrahydrofuran by heating from the extraction solution obtained by extracting the binder resin from the toner using tetrahydrofuran. The analysis) compression deformation rate (TMA%) is preferably 3.0% or less. If the TMA% exceeds 3.0%, it means that it can be easily deformed when it is assumed that it is transported in the summer or by sea, and static storage obtained by a penetration test or the like. This means that even if the stability and storage stability under dry conditions are excellent, the storage stability is poor under dynamic conditions including error factors. In other words, it means that blocking resistance can be deteriorated. That is, if the TMA% exceeds 3.0%, the toner is easily agglomerated, transportability, and transfer when considering the toner summer transportation, the toner summer storage in the warehouse, the temperature inside the copying machine, and the like. This is not preferable because the image quality deteriorates and directly leads to poor image quality.

<Binder resin>
The binder resin contains at least the crystalline polyester and the amorphous polyester, and further contains other components as necessary.

<< Crystalline Polyester >>
There is no restriction | limiting in particular as said crystalline polyester, Although it can select suitably according to the objective, From the point which has the outstanding sharp melt property and high crystallinity, it is preferable that it is an aliphatic polyester.

  The aliphatic polyester is obtained by polycondensation of a polyhydric alcohol and a polyhydric carboxylic acid such as polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, polycarboxylic acid ester, and / or a derivative thereof, and has a branched structure. It is preferable not to have.

-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.

  Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, a linear saturated aliphatic diol is preferable, and a linear saturated aliphatic diol having 2 to 12 carbon atoms is more preferable. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester may be lowered, and the melting point may be lowered. If the saturated aliphatic diol has more than 12 carbon atoms, it may be difficult to obtain the material. Therefore, the carbon number is more preferably 12 or less.

Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10- in that the crystalline polyester has high crystallinity and excellent sharp melt properties. Decanediol and 1,12-dodecanediol are particularly preferred.

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

-Multivalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.

  Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Examples thereof include aromatic dicarboxylic acids such as mesaconic acid, anhydrides thereof, and lower (carbon number 1 to 3) alkyl esters thereof. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, or anhydrides thereof, or these Lower (carbon number 1 to 3) alkyl ester and the like. These may be used individually by 1 type and may use 2 or more types together.

  In addition to the saturated aliphatic dicarboxylic acid and the aromatic dicarboxylic acid, the polyvalent carboxylic acid may contain a dicarboxylic acid having a sulfonic acid group, a dicarboxylic acid having a double bond, and the like.

  The crystalline polyester is preferably obtained by condensation polymerization of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. As a result, the resulting crystalline polyester has high crystallinity and excellent sharp melt properties, and therefore can exhibit excellent low-temperature fixability of toner.

  The crystalline polyester may be a block copolymer of crystalline polyester and amorphous polyester. There is no restriction | limiting in particular as a preparation method of the said block copolymer, According to the objective, it can select suitably, For example, the method in any one of the following (1) to (3) etc. are mentioned, Can also be suitably used.

(1) Amorphous polyester previously prepared by a polymerization reaction and crystalline polyester previously prepared by a polymerization reaction are dissolved or dispersed in a suitable solvent, and a hydroxyl group at the end of a polymer chain such as an isocyanate group, an epoxy group, or a carbodiimide group. Or a method of copolymerization by reacting with an extender having two or more functional groups that react with carboxylic acid.
(2) A method in which an amorphous polyester prepared in advance by a polymerization reaction and a crystalline polyester prepared in advance by a polymerization reaction are melt-kneaded and prepared by transesterification under reduced pressure.
(3) A method in which a hydroxyl group of a crystalline polyester prepared in advance by a polymerization reaction is used as a polymerization initiation component, and the amorphous polyester is subjected to ring-opening polymerization and copolymerization from the polymer chain end of the crystalline polyester.

  In the preparation of the block copolymer, the ratio of the amorphous polyester to the crystalline polyester is not particularly limited as a mass ratio and can be appropriately selected according to the purpose. The range of the property polyester = 20 / 80-90 / 10 is preferable.

  By using the block copolymer as a crystalline resin, since the degree of phase mixing between the amorphous part and the crystalline part is improved, the domain size is reduced, and as a result, the linkage of both components is increased. This improves the handling of crystalline polyester and improves the plasticizing effect at high temperatures.

  There is no restriction | limiting in particular as molecular weight of the said crystalline polyester, Although it can select suitably according to the objective, In GPC measurement, weight average molecular weight (Mw) 3,000-35,000 are preferable, 10,000- 35,000 is more preferable, and 10,000 to 30,000 is particularly preferable. When the weight average molecular weight is less than 3,000, the toner tends to be inferior in blocking resistance and durability against stress such as stirring in the developing device. Viscoelasticity tends to be high and low temperature fixability tends to be poor.

There is no restriction | limiting in particular as melting | fusing point (Tm) of the said crystalline polyester, Although it can select suitably according to the objective, 40 to 140 degreeC is preferable and 60 to 120 degreeC is more preferable. When the Tm is less than 40 ° C., the crystalline polyester tends to melt at a low temperature and the blocking resistance of the toner tends to be reduced. When the Tm exceeds 140 ° C., the crystalline polyester is heated by fixing. Insufficient melting tends to reduce low temperature fixability.
The melting point can be measured by an endothermic peak value of a DSC chart in a differential scanning calorimeter (DSC) measurement.

  There is no restriction | limiting in particular as content of the said crystalline polyester in the said binder resin, Although it can select suitably according to the objective, 1 mass%-30 mass% are preferable with respect to the said binder resin, More preferred is 20% by mass to 20% by mass, and particularly preferred is 5% by mass to 20% by mass. When the content is less than 1% by mass, the low-temperature fixability may be lowered. When the content exceeds 30% by mass, the domain size of the crystalline polyester is increased, and as a result, the blocking resistance is lowered. Sometimes.

  About crystallinity, molecular structure, etc. of the crystalline polyester, NMR measurement, differential scanning calorimeter (DSC) measurement, X-ray diffraction measurement, GC / MS measurement, LC / MS measurement, infrared absorption (IR) spectrum measurement, etc. Can be confirmed.

<< Amorphous polyester >>
The amorphous polyester is obtained by using a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester, and preferably has a branched structure. No.

-Polyhydric alcohol component-
Examples of the polyhydric alcohol component include divalent alcohols (diols), specifically, alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4 -Butylene glycol, 1,6-hexanediol, etc.); C4-C36 alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.); C6-C36 An alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); an alkylene oxide having 2 to 4 carbon atoms of the alicyclic diol [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as EO); O), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition moles 1-30); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) alkylene oxides having 2 to 4 carbon atoms (EO, PO, BO, etc.) Additives (addition mole number 2-30) etc. are mentioned.

  Further, in addition to the divalent diol, an alcohol component having 3 or more valences (3 to 8 or more) may be contained. The above aliphatic polyhydric alcohols (alkane polyols and intramolecular or intermolecular dehydrates such as glycerin, triethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, dipentaerythritol; saccharides and derivatives thereof For example, sucrose and methyl glucoside; etc.]; adducts having 2 to 4 carbon atoms of the aliphatic polyhydric alcohols (EO, PO, BO, etc.) (addition moles 1 to 30); trisphenols (trisphenol) Adducts of C2-C4 alkylene oxide (EO, PO, BO, etc.) Addition number of moles 2 to 30); Novolak resin (phenol novolak, cresol novolak, etc .: average degree of polymerization 3 to 60) alkylene oxide (EO, PO, BO, etc.) adduct (addition number of moles 2 to 2) 30). These may be used individually by 1 type and may use 2 or more types together.

-Polycarboxylic acid component-
Examples of the polyvalent carboxylic acid component include divalent carboxylic acids (dicarboxylic acids), specifically, alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, apidic acid, sebacic acid, etc.), alkenyl succinic acids (dodecenyl succinic acid). C4-C36 alicyclic dicarboxylic acid (dimer acid (dimerized linoleic acid), etc.); C4-C36 alkene dicarboxylic acid (maleic acid, fumaric acid, citraconic acid, mesaconic acid, etc.) An aromatic dicarboxylic acid having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, naphthalenedicarboxylic acid, etc.). Among these, alkane dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable. Examples of the polyvalent carboxylic acid component include acid anhydrides and lower alkyl (C1-4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above. These may be used individually by 1 type and may use 2 or more types together.

  In addition, ring-opening polymerization systems such as polylactic acid and polycarbonate diol can also be suitably used.

  The molecular weight of the amorphous polyester is not particularly limited and may be appropriately selected depending on the intended purpose. However, in GPC measurement, a weight average molecular weight (Mw) of 10,000 to 35,000 is preferable, and 15,000. ~ 30,000 is more preferred.

  There is no restriction | limiting in particular as glass transition temperature (Tg) of the said amorphous polyester, Although it can select suitably according to the objective, 50 to 80 degreeC is preferable. When the Tg is less than 50 ° C., the heat resistant storage stability of the toner and durability against stress such as agitation in the developing device may be inferior. And low temperature fixability may be inferior.

  There is no restriction | limiting in particular as softening temperature of the said amorphous polyester, Although it can select suitably according to the objective, 130 to 180 degreeC is preferable.

  The molecular structure of the amorphous polyester can be confirmed by GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid.

The amorphous polyester may have a carboxyl group at the terminal as long as it does not impair the present invention for the purpose of improving the dispersibility of various pigments containing carbon black and charge control agents and raising the charge level. .
The acid value in the amorphous polyester is preferably 20 mgKOH / g or less, and more preferably 18 mgKOH / g or less. When the acid value exceeds 20 mgKOH / g, it leads to poor formation of domains due to an increase in polar groups, environmental stability, particularly a decrease in toner storage stability and charge amount against humidity fluctuations, and embrittlement of the resin. It is not preferable.
The acid value can be imparted to the amorphous polyester by, for example, utilizing a trivalent or higher carboxylic acid component during the synthesis of the amorphous polyester. Examples of the trivalent or higher carboxylic acid component include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanenetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2, Examples include 4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, anhydrides of these acids, and lower alkyl esters. .
As the method for imparting an acid value to the amorphous polyester, any of the conventionally known methods can be adopted. From the viewpoint of controllability of the acid value, after synthesizing the hydroxyl-terminated polyester, for example, trimellitic anhydride is used as an acid. A method of adding the acid value to the end of the polyester resin by adding them so as to match the value is preferable.
In addition, for the resin to which acid is added to the terminal, alkanolamines are added as counter ions at the time of resin synthesis completion or solution preparation for the purpose of further improving the pigment dispersibility within the scope of the present invention. It is also possible to carry out salt formation and / or partial amide modification by adding polyethylenimine, polyallylamine or the like. The polyethyleneimine and allylamine are preferably branched rather than linear.

<< Combination of crystalline polyester and amorphous polyester >>
The surface free energy difference between the crystalline polyester and the amorphous polyester is not particularly limited and can be selected according to the purpose, but is preferably 6.0 mJm ^{−2 to} 15.0 mJm ⁻² , 0.0mJm- ^{2 to} 12.5mJm- ² is more preferable. If the surface free energy difference is less than 6.0 mJm ^-2 , a spherical domain is not obtained, and if it exceeds 15.0 mJm ^-2 , the crystalline polyester has a large domain size, resulting in blocking resistance. May decrease.

The method for analyzing the surface free energy is not particularly limited and can be selected according to the purpose. For example, the surface free energy can be analyzed using the following method.
The surface free energy γs of the crystalline polyester and the amorphous polyester is calculated from the following extended Fowkes theory.
Here, in the above formula, “θ” represents the contact angle between the resin thin film and the solvent used for analysis. “Γ _L ” and “γ _s ” respectively represent the solvent used for the analysis and the surface free energy of the resin. “D”, “p”, and “h” respectively represent a surface free energy dispersion component, a polar component, and a hydrogen bond component, and the surface free energies are “γ = γ ^d + γ ^p + γ ^h ”. The relationship is established. Solvents used for the analysis are “γ ^d _L ”, “γ ^p _L ” and “γ ^h _{L L} ” as described in non-patent literature [Japan Adhesion Association Journal 8 (3), 131-141 (1972)]. "Is a known solvent, but there is no problem. For example, pure water, ethylene glycol, and formamide can be used.

  In the measurement of the contact angle, the amount of the solvent to be dripped and how many seconds after the solvent reaches the thin film surface, the contact angle is measured (measurement time) affects the result. Therefore, it is necessary to unify the liquid volume with a liquid volume that has little influence on the contact angle, and to determine the measurement time to a time with little change with time for each solvent. There are no restrictions on the amount of the solvent to be dropped and the measurement time. For example, when the amount of the solvent to be dropped is unified to 4 μL, the measurement time for pure water, ethylene glycol, and formamide is 5, respectively. It can be measured by setting to 000 msec, 25,000 msec, and 5,000 msec.

  The thin film used for the measurement of the contact angle preferably has a smooth surface. The method for obtaining a smooth film is not particularly limited. For example, the resin can be obtained by dissolving the resin in a solvent such as tetrahydrofuran (THF) or chloroform and depositing the solvent on an aluminum plate by a casting method. .

<Other ingredients>
The other component of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a colorant, a release agent, a charge control agent, and a fluidizing agent.

<< Colorant >>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, solvent yellow (21, 77, 114 etc.) ), Pigment Yellow (12, 14, 17, 83, etc.), Indian First Orange, Irgasin Red, Paranitaniline Red, Toluidine Red, Solvent Red (17, 49, 128, 5, 13, 22, 48, 2 etc.) ), Disper Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Solvent Blue (25, 94, 60, 15.3, etc.), Pigment Blue, Brilliant Guri Down, phthalocyanine green, oil yellow GG, Kayaset YG, Orazole Brown B, such as oil pink OP, and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 0.1 mass part-40 mass parts are preferable with respect to 100 mass parts of said binder resins, 0 More preferably, 5 parts by mass to 10 parts by mass.

<< Releasing agent >>
The release agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, polyolefin wax, natural wax (for example, carnauba wax, montan wax, paraffin wax, rice wax, etc.), carbon number Examples thereof include 30 to 50 aliphatic alcohols (for example, triacontanol), fatty acids having 30 to 50 carbon atoms (for example, triacontane carboxylic acid), and mixtures thereof.

  Examples of the polyolefin wax include (co) polymer [(co) polymerization of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modified products of olefin (co) polymers [eg maleic acid and derivatives thereof] Modified products (such as maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate)], olefins and unsaturated carboxylic acids [(meth) acrylic acid, itaconic acid, maleic anhydride, etc.] and / or unsaturated carboxylic acids Alkyl ester [alkyl (meth) acrylate (alkyl having 1 to 18 carbon atoms)] Copolymers with stealth, alkyl maleates (alkyls having 1 to 18 carbon atoms), etc., polymethylene (eg, Fischer-Tropsch wax such as sazol wax), fatty acid metal salts (eg calcium stearate), fatty acid esters (Behenyl behenate, etc.).

  There is no restriction | limiting in particular as softening temperature of the said mold release agent, Although it can select suitably according to the objective, 50 to 170 degreeC is preferable.

  There is no restriction | limiting in particular as content of the said mold release agent, According to the objective, it can select suitably.

<< Charge Control Agent >>
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a triphenylmethane dye, a quaternary ammonium salt, a polyamine resin containing a nigrosine dye, a tertiary amine as a side chain. , Imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, benzylic acid boron complexes, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatic ring-containing polymers, salicylic acid Examples thereof include metal complexes of alkyl derivatives and cetyltrimethylammonium bromide.

  There is no restriction | limiting in particular as content of the said charge control agent, According to the objective, it can select suitably.

<< Fluidizer >>
The fluidizing agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder, barium titanate, magnesium titanate, and calcium titanate. Strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate and the like.

  There is no restriction | limiting in particular as content of the said fluidizing agent, According to the objective, it can select suitably.

  The composition ratio in the toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, the binder resin is preferably 30% by mass to 97% by mass, and more preferably 40% by mass to 95% by mass. 45 mass% to 92 mass% is particularly preferable. The colorant is preferably 0.05% by mass to 60% by mass, more preferably 0.1% by mass to 55% by mass, and particularly preferably 0.5% by mass to 50% by mass. The release agent is preferably 0% by mass to 30% by mass, more preferably 0.5% by mass to 20% by mass, and particularly preferably 1% by mass to 10% by mass. The charge control agent is preferably 0% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 7.5% by mass. The fluidizing agent is preferably 0% by mass to 10% by mass, more preferably 0% by mass to 5% by mass, and particularly preferably 0.1% by mass to 4% by mass.

<Toner production method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a kneading and pulverizing method, a suspension polymerization method, an emulsion polymerization aggregation method, and a jet / spray granulation method. .

  Examples of the kneading and pulverizing method include a method in which the binder resin is melt-kneaded with the colorant and the like, and then finely pulverized and further classified.

  As the suspension polymerization method, for example, a monomer, a polymerization initiator, the colorant, the mold release agent, and the like are added to an aqueous phase containing a dispersion stabilizer while stirring to form oil droplets, and then the temperature is increased. Examples thereof include a method of obtaining toner particles by heating to cause a polymerization reaction.

  As the emulsion polymerization aggregation method, for example, the binder resin is emulsified and dispersed in an aqueous phase, and then the fine particles obtained by removing the solvent, the colorant, the release agent and the like are dispersed in the aqueous phase. For example, a method of producing toner particles by agglomerating the dispersion formed by heating and fusing it with heat can be used.

As the jetting / spray granulation method, for example, a toner composition liquid in which a toner composition is dissolved or dispersed in an organic solvent is sprayed into a gas phase to form droplets, and then the organic solvent is removed to form toner particles. And the like.
Among these, the spray / spray granulation method is preferable because the crystalline polyester can easily obtain a desired domain size. Details of the spray / spray granulation method will be described below.

<< Injection / spray granulation method >>
The method for producing the toner by the spray / spray granulation method includes at least a droplet discharge step and a droplet solidification step, and further includes other steps as necessary.

<<< Droplet Ejecting Step and Droplet Ejecting Means >>>
The droplet discharge step is a step of discharging the toner composition liquid in droplets from at least one discharge hole, and can be suitably performed by a droplet discharge unit. In the present invention, in the droplet discharge step, a vibration is imparted to the toner composition liquid in the liquid column resonance liquid chamber in which the discharge hole is formed to form a pressure standing wave by liquid column resonance, and the pressure control is performed. The toner composition liquid is ejected in the form of droplets from the ejection holes arranged in the region where the wave is present, and the droplet ejection step can be suitably performed by the droplet ejection means.

  The droplet discharge means includes a liquid column resonance liquid chamber in which the discharge hole is formed, and a vibration generation unit that applies vibration to the toner composition liquid in the liquid column resonance liquid chamber. A vibration is applied to the toner composition liquid in the liquid column resonance liquid chamber to form a pressure standing wave by liquid column resonance, and the toner composition is formed from the discharge hole disposed in a region that is antinode of the pressure standing wave. The liquid is discharged in the form of droplets.

  The discharge hole is not particularly limited as long as it is disposed in a region that becomes the antinode of the pressure standing wave, and can be appropriately selected according to the purpose. It is preferable that a plurality of regions are arranged in at least one of the regions, and a plurality of regions are preferably arranged in one liquid column resonance liquid chamber.

  The region that becomes the antinode of the pressure standing wave is a region where the amplitude of the pressure wave of the liquid column resonance standing wave is large and the pressure fluctuation is large, and the pressure fluctuation is large enough to discharge a droplet. It is an area | region which has. There is no particular limitation on the region that becomes the antinode of such a pressure standing wave, and it can be appropriately selected according to the purpose. However, the position where the amplitude of the pressure standing wave becomes a maximum (as a velocity standing wave) ± 1/3 wavelength is preferable from the section of (1) to the position where it becomes the minimum, and ± 1/4 wavelength is more preferable. When the discharge hole is formed in a region that becomes the antinode of the pressure standing wave, even if a plurality of discharge holes are opened, a substantially uniform droplet can be formed from each discharge hole. Furthermore, it is preferable in that the droplets can be efficiently discharged and the discharge holes are not easily clogged.

The liquid column resonance liquid chamber is a liquid chamber capable of forming a pressure standing wave by vibration applied by the vibration generating unit in accordance with the principle of the liquid column resonance phenomenon described later. A discharge hole is formed in the region, and a communication port for supplying the toner composition liquid is provided at the end of the liquid column resonance liquid chamber in the longitudinal direction. A reflection wall surface perpendicular to the longitudinal axis is provided at least at one end or both ends. The liquid column resonance liquid chamber preferably has a vibration generating portion disposed on one of the walls parallel to the longitudinal direction of the liquid column resonance liquid chamber, and faces the wall on which the vibration generating portion is disposed. It is preferable that a discharge hole is formed in the wall.
The shape of the liquid column resonance liquid chamber is not particularly limited as long as a pressure standing wave can be formed by the vibration, and can be selected as appropriate. For example, a quadrangular column (a rectangular parallelepiped), a cylinder, a truncated cone, etc. Can be mentioned.
It is preferable that a reflection wall surface is provided on at least a part of both ends in the longitudinal direction of the liquid column resonance liquid chamber. Here, the “reflective wall surface” refers to a wall surface formed by a member that is hard enough to reflect the sound wave of the liquid, for example, a metal member such as aluminum or stainless steel, a member such as silicone, or the like.

<<< Droplet solidification step and droplet solidification means >>>
The droplet solidifying step is a step of solidifying the droplet, and can be performed by a droplet solidifying means. Specifically, it is a step and means for solidifying (drying) the droplets of the toner composition liquid discharged into the gas from the droplet discharge means described above, and may further include a step and means for collecting. Good. Hereinafter, a droplet solidification step and a solidification unit (also referred to as “dry collection step” and “dry collection unit”) that perform solidification (drying) and collection will be described.

Hereinafter, an embodiment of a toner manufacturing apparatus for carrying out the toner manufacturing method of the present invention will be described with reference to FIGS.
FIG. 2 is a cross-sectional view showing the configuration of the liquid column resonance droplet discharge means.
The liquid column resonance droplet discharge means 511 shown in FIG. 2 includes a liquid common supply path 517 and a liquid column resonance liquid chamber 518. The liquid column resonance liquid chamber 518 communicates with a liquid common supply path 517 provided on one of the wall surfaces at both ends in the longitudinal direction. In addition, the liquid column resonance liquid chamber 518 is provided on the wall surface facing the discharge hole 519 and the discharge hole 519 for discharging the droplet 521 to one wall surface of the wall surfaces connected to both ends. Vibration generating means 520 for generating high-frequency vibration to form a standing wave. The vibration generating means 520 is connected to a high-frequency power source (not shown).

  A toner composition liquid (hereinafter simply referred to as “toner composition liquid”) 514 in which the toner composition is dissolved or dispersed is passed through a liquid supply pipe by a liquid circulation pump (not shown), and the liquid column resonance droplet discharge shown in FIG. The liquid column resonance liquid chamber 518 of the means 511 is supplied. In the liquid column resonance liquid chamber 518 filled with the toner composition liquid 514, a pressure distribution is formed by the liquid column resonance standing wave generated by the vibration generating means 520. Then, the droplet 521 is ejected from the ejection hole 519 disposed in a region where the amplitude of the liquid column resonance standing wave is large and the pressure fluctuation is large and which is an antinode of the standing wave. The region that becomes the antinode of the standing wave due to the liquid column resonance means a region other than the node of the standing wave. Preferably, it is a region where the pressure fluctuation of the standing wave has an amplitude large enough to discharge the liquid, and more preferably a position where the amplitude of the pressure standing wave becomes a maximum (a section as a velocity standing wave). ) To a minimum position in a range of ± 1/4 wavelength. If the region is an antinode of a standing wave, even if there are a plurality of discharge holes, substantially uniform droplets can be formed from each, and moreover, the droplets can be discharged efficiently. And clogging of the discharge holes is less likely to occur. The toner composition liquid 514 that has passed through the liquid common supply path 517 flows through a liquid return pipe (not shown) and is returned to the raw material container. When the amount of the toner composition liquid 514 in the liquid column resonance liquid chamber 518 decreases due to the ejection of the liquid droplets 521, the suction force due to the action of the liquid column resonance standing wave in the liquid column resonance liquid chamber 518 acts, and the liquid common supply The flow rate of the toner composition liquid 514 supplied from the path 517 increases, and the toner composition liquid 514 is replenished in the liquid column resonance liquid chamber 518. When the toner composition liquid 514 is replenished into the liquid column resonance liquid chamber 518, the flow rate of the toner composition liquid 514 passing through the liquid common supply path 517 is restored.

  The liquid column resonance liquid chamber 518 in the liquid column resonance droplet discharge means 511 has a frame formed of a material having such a high rigidity that does not affect the resonance frequency of the liquid at a driving frequency such as metal, ceramics, or silicon. It is formed by bonding. Further, as shown in FIG. 2, the length L between the wall surfaces at both ends in the longitudinal direction of the liquid column resonance liquid chamber 518 is determined based on the liquid column resonance principle as described later.

Further, the vibration generating unit 520 in the liquid column resonant droplet discharging unit 511 is not particularly limited as long as it can be driven at a predetermined frequency, and can be appropriately selected according to the purpose. The form bonded to is preferable. The elastic plate constitutes a part of the wall of the liquid column resonance liquid chamber so that the piezoelectric body does not come into contact with the liquid. Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). In general, the displacement is small, and the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO _{3, and the} like can be given. Furthermore, it is preferable that the vibration generating means 520 is arranged so that it can be individually controlled for each liquid column resonance liquid chamber. In addition, the block-shaped vibrating member made of one material is partially cut in accordance with the arrangement of the liquid column resonance liquid chambers, and each liquid column resonance liquid chamber can be individually controlled via an elastic plate. preferable.

  There is no restriction | limiting in particular as a diameter of the opening part of the discharge hole 519, Although it can select suitably according to the objective, 1 micrometer-40 micrometers are preferable. When the diameter is smaller than 1 μm, the formed droplets may be very small, so that the toner may not be obtained. In the case where the toner contains a solid fine particle such as a pigment as a component of the toner, There is a risk that the discharge holes 519 are frequently clogged to reduce productivity. When the diameter exceeds 40 μm, the diameter of the droplet is large, and when this is dried and solidified to obtain a desired toner particle diameter of 3 μm to 6 μm, the toner composition is diluted with an organic solvent into a very dilute liquid. In some cases, a large amount of drying energy may be required to obtain a certain amount of toner.

Next, the mechanism of droplet formation by the droplet formation unit in liquid column resonance will be described.
First, the principle of the liquid column resonance phenomenon occurring in the liquid column resonance liquid chamber 518 in the liquid column resonance liquid droplet ejection means 511 in FIG. 2 will be described. The sound velocity of the toner composition liquid in the liquid column resonance liquid chamber is c, and vibration is generated. When the driving frequency given to the toner composition liquid as a medium from the means 520 is f, the wavelength λ at which the liquid resonance occurs is
λ = c / f (Formula 1)
Are in a relationship.

Further, in the liquid column resonance liquid chamber 518 in FIG. 2, the length from the end of the frame on the fixed end side to the end on the liquid common supply path 517 side is L, and further, the end of the frame on the liquid common supply path 517 side The height h1 (about 80 μm) is about twice as high as the communication port height h2 (about 40 μm). Resonance is most efficiently formed when L matches an even multiple of a quarter of the wavelength λ. That is, it is expressed by the following formula 2.
L = (N / 4) λ (Expression 2)
(L: length in the longitudinal direction of the liquid column resonance liquid chamber, N: even number)

Furthermore, the above formula 2 is also established in the case of a double-sided open end where both ends are completely open.
Similarly, when one side is equivalent to an open end having a pressure relief portion and the other side is closed (fixed end), that is, one side fixed end or one side open end, the length L is the wavelength λ. Resonance is most efficiently formed when it matches an odd multiple of a quarter. That is, N in Expression 2 is expressed as an odd number.

The most efficient drive frequency f is obtained from the above formula 1 and the above formula 2.
f = N × c / (4L) (Formula 3)
(L: length of liquid column resonance liquid chamber in longitudinal direction, c: velocity of sound wave of toner composition liquid, N: natural number)
It is guided. However, in reality, since the liquid has a viscosity that attenuates the resonance, the vibration is not amplified infinitely, and has a Q value. As shown in equations 4 and 5, which will be described later, Resonance also occurs at frequencies near the highly efficient drive frequency f.

FIG. 3 is a cross-sectional view of an example of an apparatus for carrying out the toner manufacturing method of the present invention. The toner manufacturing apparatus 501 mainly includes a droplet discharge unit 502 and a dry collection unit 560.
As the droplet discharge means 502, the above-described liquid column resonance droplet discharge means 512 can be suitably used. The droplet discharge means 502 supplies the raw material container 513 for storing the toner composition liquid 514 and the toner composition liquid 514 stored in the raw material container 513 to the droplet discharge means 502 through the liquid supply pipe 516. A liquid circulation pump 515 that pumps the toner composition liquid 514 in the liquid supply pipe 516 to return to the raw material container 513 through the liquid return pipe 522 is connected to the liquid droplet discharge means 502 as needed. Can supply. The liquid supply pipe 516 is provided with a pressure measuring device P1 and the dry collecting unit is provided with a pressure measuring device P2. The pressure of the liquid feeding to the droplet discharge means 502 and the pressure in the dry collecting unit are respectively pressure gauges. Managed by P1 and P2. At this time, if the pressure measurement value of P1 is larger than the pressure measurement value of P2, the toner composition liquid 514 may ooze out from the ejection hole, and the pressure measurement value of P1 is smaller than the pressure measurement value of P2. In this case, it is preferable that the pressure measurement value of P1 and the pressure measurement value of P2 are substantially the same because there is a possibility that gas enters the droplet discharge means 502 and the discharge stops.

The dry collection unit 560 shown in FIG. 3 includes a chamber 561, a toner collection unit 562, and a toner storage unit 563.
The droplets 521 formed by discharging the toner composition liquid 514 are in a liquid state immediately after being discharged from the droplet discharge means 502, but are volatilized in the toner composition liquid while being transported in the chamber. As the solvent volatilizes, drying proceeds and changes from liquid to solid. In such a state, no coalescence occurs even when the particles come into contact with each other, so that the toner can be collected by the toner collecting means 562 and stored in the toner storage portion 563. The toner stored in the toner storage unit 563 is further dried in another process as necessary.

  In the chamber 561, a carrier airflow 601 formed from the carrier airflow inlet 564 is formed. Since the droplets 521 ejected from the droplet ejection means 502 are transported downward not only by gravity but also by the transporting air flow 601, it is possible to prevent the ejected droplets 521 from being decelerated due to air resistance. it can. Thus, when the droplets 521 are continuously ejected, the droplets 521 ejected before are decelerated by air resistance before drying, and the droplets 521 ejected later are droplets 521 ejected before. By catching up with the droplets 521, it is possible to prevent the droplets 521 from being joined and integrated to increase the particle size of the droplets 521. In FIG. 3, the droplet discharge means 502 discharges the droplet 521 toward the direction of gravity, but this is not always necessary, and the discharge angle can be selected as appropriate. As the air flow generation means, either a method of providing a blower at the transport air flow inlet 564 at the upper part of the chamber 561 and pressurizing it, or a method of suctioning from the transport air flow outlet 565 can be employed.

The carrier air flow 601 is not particularly limited as a state of the air flow as long as the coalescence of the droplets 521 can be suppressed, and may be, for example, a laminar flow, a swirl flow, a turbulent flow, or the like. Further, a means for changing the airflow state of the carrier airflow 601 may be provided in the chamber 561.
There are no particular restrictions on the type of gas constituting the carrier airflow 601, and it may be air or a non-combustible gas such as nitrogen. However, as described above, the droplets 521 are bonded together by drying. Therefore, it is preferable to have conditions that can promote drying of the droplets 521. Accordingly, it is preferable that the solvent vapor contained in the toner composition liquid 514 is not included. Further, the temperature of the carrier airflow 601 can be adjusted as appropriate, and it is preferable that there is no fluctuation during production.
Note that the carrier air flow 601 may be used not only to prevent the adhesion of the droplets 521 but also to prevent the droplets 521 from adhering to the chamber 561.

  There is no restriction | limiting in particular as the toner collection means 562, A well-known collection apparatus can be used, For example, a cyclone collection machine, a back filter, etc. are mentioned.

When the amount of residual organic solvent contained in the toner particles obtained by the dry collection means shown in FIG. 3 is large, secondary drying is preferably performed as necessary to reduce this. If the organic solvent remains in the toner, not only the toner characteristics such as heat-resistant storage property, fixing property and charging property change with time, but also the organic solvent volatilizes at the time of fixing with heating. The potential for adverse effects is increased.
There is no restriction | limiting in particular as said secondary drying, A general well-known drying means like fluid bed drying or vacuum drying can be used.

<< Kneading and grinding method >>
The kneading and pulverizing method includes, for example, a step of mixing toner materials, a step of melt-kneading, a step of pulverizing, a step of classifying, and a step of adding an external additive in this order, and further if necessary. , Including other steps.
In the step of mixing the toner material and the step of melt-kneading, the powder other than the particles that are products obtained in the step of pulverizing or the step of classifying may be returned and reused.

-Step of mixing toner materials-
In the step of mixing the toner material, a binder resin, a release agent, a charge control agent, a colorant, and the like are appropriately selected as necessary and mixed with a known mixer such as a Henschel mixer.

-Melting and kneading process-
When the step of mixing the toner materials is completed, the mixture is then charged into a melt kneader and melt kneaded.
As the melt kneader, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used.
Commercially available products of the melt kneader include, for example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by K.C.K. A PCM type twin screw extruder manufactured by Tosho Co., Ltd., a Kneader manufactured by Busus, etc. are preferably used.
It is important that this melt-kneading is performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken.
Specifically, the melt kneading temperature should be performed with reference to the softening point of the binder resin. If the temperature is too low, the molecular chain is severely cut, and if the temperature is too high, the dispersion of the crystalline polyester does not proceed.
Moreover, you may adjust temperature arbitrarily with respect to melting | fusing point of crystalline polyester or a mold release agent.

-Crushing process-
When the above melt-kneading step is completed, the kneaded product is then pulverized.
In this pulverizing step, it is preferable to first coarsely pulverize and then finely pulverize. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

-Classifying process-
After the pulverization step is completed, the pulverized product is classified in an air stream by centrifugal force or the like, thereby producing toner base particles having a predetermined particle size, for example, an average particle size of 6 μm to 10 μm.

-External mixing process-
By mixing the obtained toner base particles and an external additive such as inorganic fine particles, the external additive is fixed and fused on the surface of the toner base particles, and different kinds of particles from the surface of the resulting composite particles are obtained. Particle detachment can be prevented.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there.
Examples of the apparatus include a Henschel mixer (manufactured by Mitsui Mining) and a super mixer (manufactured by Kawata).
Thereafter, sieving is performed with a predetermined spread mesh to remove foreign matters and the like.

(Developer)
The developer of the present invention contains at least the toner and, if necessary, other components such as a carrier as appropriate.
For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.

  When the developer is used as a one-component developer, even if the balance of the toner is performed, there is little fluctuation in the particle size of the toner, and members such as a filming of the toner on the developing roller and a blade for thinning the toner The toner is less fused to the toner, and good and stable developability and images can be obtained even with long-term stirring in the developing device.

  When the developer is used as a two-component developer, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter is small, and good and stable developability and images can be obtained even with long-term stirring in the developing device. can get.

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.

<< Core material >>
The material for the core material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 50 emu / g to 90 emu / g manganese-strontium-based material, 50 emu / g to 90 emu / g manganese- Examples include magnesium-based materials. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.

  These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. When the volume average particle diameter is more than 150 μm, the specific surface area is decreased, and the toner In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

  When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. It is 90 to 98 parts by mass with respect to 100 parts by mass of the two-component developer. Part is preferable, and 93 parts by mass to 97 parts by mass is more preferable.

  The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, thermal CVD (chemical vapor deposition, Chemical Vapor Deposition) is formed on the support. ), A photo-CVD method, a plasma CVD method, or the like, a photoconductor having a photoconductive layer made of a-Si can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

  There is no restriction | limiting in particular as a shape of the said electrostatic latent image carrier, Although it can select suitably according to the objective, A cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and more preferably 10 mm to 30 mm. Particularly preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

<< Exposure member and exposure >>
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
There is no restriction | limiting in particular as a light source used for the said exposure member, According to the objective, it can select suitably, For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser General light emitting materials such as (LD) and electroluminescence (EL).
In addition, various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Developing means and development process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. Can be selected as appropriate.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with toner to form a visible image. For example, it can be carried out by the developing means.

The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . The magnet roller is disposed in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, an intermediate transfer member is used, and the transfer step can be performed on the intermediate transfer member. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed by, for example, charging the visible image using a transfer charger and the transfer unit.
Here, when the image to be secondarily transferred onto the recording medium is a color image composed of a plurality of colors of toner, the toner of each color is sequentially superimposed on the intermediate transfer member by the transfer means. An image can be formed on the body, and the image on the intermediate transfer body can be collectively transferred onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed every time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state where the toners of the respective colors are stacked.
The fixing step can be performed by the fixing unit.
The heating in the heating and pressing member is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing unit depending on the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, is preferably ^{10N / cm 2 ~80N / cm 2} .

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

<< Static elimination means and static elimination process >>
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

<< Recycling means and recycling process >>
The recycling unit is not particularly limited as long as it is a unit that causes the developing device to recycle the toner removed in the cleaning step, and can be appropriately selected depending on the purpose. Can be mentioned.
The recycling process is not particularly limited as long as it is a process for recycling the toner removed in the cleaning process to the developing device, and can be appropriately selected according to the purpose. For example, the recycling unit performs the recycling process. Can do.

<< Control means and control process >>
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
The control process is not particularly limited as long as it can control the movement of each process, and can be appropriately selected according to the purpose. For example, the control process can be performed by the control means.

FIG. 4 shows another example of the image forming apparatus of the present invention. The image forming apparatus shown in FIG. 4 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 4. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer member 50 stretched between the support roller 14 and the support roller 15 is a tandem type in which four image forming units 18 of yellow, cyan, magenta, and black are arranged to face each other along the conveyance direction. A developing device 120 is disposed. In the vicinity of the tandem developing device 120, an exposure device 21 as the exposure member is disposed. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. In the vicinity of the secondary transfer device 22, a fixing device 25 as the fixing means is arranged. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven. Then, the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Forming means). In each image forming unit, black, yellow, magenta, and cyan toner images are formed. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image carrier 10 is exposed to the image corresponding to each color image based on the color image information and the charging device 160 as the charging means for uniformly charging the electrostatic latent image carrier 10 (FIG. 5). L), and an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And cyan tona ), A developing device 61 as the developing means for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, The static eliminator 64 is provided. Each image forming unit 18 can form each monochrome image (black image, yellow image, magenta image, and cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one by the separation roller 145, sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copier body 150, and abutted against the registration roller 49 to stop. It is done. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. Then, the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. By doing so, a color image is transferred and formed on the sheet (recording paper). The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by a switching claw 55 and discharged by a discharge roller 56 and is stacked on a discharge tray 57. Alternatively, the sheet is switched by the switching claw 55 and reversed by the sheet reversing device 28 and guided to the transfer position again. After the image is recorded on the back surface, the sheet is discharged by the discharge roller 56 and stacked on the discharge tray 57. Is done.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. “Part” represents “part by mass” unless otherwise specified. “%” Represents “% by mass” unless otherwise specified.

The measuring methods of various physical properties in the following synthesis examples, examples and comparative examples are shown below.
<Molecular weight>
Apparatus: GPC (manufactured by Tosoh Corporation), detector: RI, measurement temperature: 40 ° C.
Mobile phase: tetrahydrofuran, flow rate: 0.45 mL / min.
The number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) are measured by GPC (gel permeation chromatography) using a calibration curve created from a polystyrene sample with a known molecular weight as a standard. Number average molecular weight, weight average molecular weight, and molecular weight distribution. In addition, the column used the thing which connected the exclusion limit 60,000, 20,000, and 10,000 things in series.

<Softening temperature>
Using a Koka-type flow tester (CFT-500D, manufactured by Shimadzu Corporation), 1 g of measurement sample was preheated at 50 ° C, and then heated at a rate of temperature increase of 5 ° C / min. , Push out from a nozzle with a diameter of 0.5 mm and a length of 1 mm, and draw a graph of “plunger drop amount (flow value)” and “temperature” to ½ of the maximum plunger drop amount The corresponding temperature was read from the graph, and this value (temperature at which half of the measurement sample flowed out) was taken as the softening temperature.

<Glass transition temperature (Tg), melting point (Tm)>
5 mg of resin was sealed in a T-Zero simple sealed pan manufactured by TA Instruments, and measurement was performed using a differential scanning calorimeter (DSC) (Q2000 manufactured by TA Instruments). Measurement was performed at 10 ° C./min. From 40 ° C. to 150 ° C. under a nitrogen stream. The temperature was raised and the thermal change was measured, and a graph of “amount of heat generation / absorption” and “temperature” was drawn. The characteristic inflection observed at this time was defined as Tg. In addition, the value obtained by the midpoint method from DSC curve was used for Tg. The maximum endothermic peak was defined as the melting point (Tm).

<Measurement of domain size>
Amorphous polyester and crystalline polyester were weighed at an arbitrary ratio, and then 100 parts by mass of tetrahydrofuran (THF) was added to 100 parts by mass of the total resin, and heated and dissolved at 50 ° C. The obtained solution was cast on a Teflon sheet, and then dried at 60 ° C. under normal pressure for 5 hours and then at 120 ° C. until the THF was removed under reduced pressure. After the obtained film-like molded body was stored at 40 ° C. for 24 hours, a cross section of the molded body was observed with a TEM. The domain size of the crystalline polyester was arbitrarily selected at 20 locations, and the average particle size was selected.
The domain size of the crystalline polyester in the toner was measured from the cross section of the toner.

<TMA%>
Amorphous polyester and crystalline polyester were weighed at an arbitrary ratio, and then 100 parts by mass of tetrahydrofuran (THF) was added to 100 parts by mass of the total resin, and heated and dissolved at 50 ° C. The obtained solution was cast on a Teflon sheet, and then dried at 60 ° C. under normal pressure for 5 hours and then at 120 ° C. until the THF was removed under reduced pressure. The obtained resin body was pulverized and tableted with a tableting machine having a diameter of 10 mm (manufactured by Shimadzu Corporation), and subjected to a thermomechanical measuring device (manufactured by SII Nano Technologies, Inc .: EXSTAR7000). The measurement was performed by compressing at 40 ° C. under a relative humidity of 80% and a compressive force of 20 mN / min. From the graph of time and compression displacement (deformation rate) obtained, the compression displacement (deformation rate) corresponding to 200 mN was read from the graph, and this value was defined as TMA%.

(Synthesis Example 1)
<Synthesis of Amorphous Polyester A1>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, propylene glycol as a diol, terephthalic acid and adipic acid as dicarboxylic acids, molar ratio (terephthalic acid / adipic acid) = 85/15 and OH / COOH (molar ratio) were set to 2.0. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over 2 hours, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and amorphous polyester A1 was obtained.
The obtained resin has an acid value (AV) of 0.9 mgKOH / g, a hydroxyl value (OHV) of 12.8 mgKOH / g, a glass transition temperature (Tg) of 62.5 ° C., a softening temperature of 148.3 ° C., and a weight average molecular weight ( Mw) 22,000.

(Synthesis Example 2)
<Synthesis of Amorphous Polyester A2>
Amorphous polyester A2 was obtained by the same procedure as in Synthesis Example 1 except that the reaction time at 230 ° C. was reduced to 1 hour under reduced pressure.
The obtained resin has an acid value (AV) of 0.4 mg KOH / g, a hydroxyl value (OHV) of 21.0 mg KOH / g, a glass transition temperature (Tg) of 60.2 ° C., a softening temperature of 134.5 ° C., and a weight average molecular weight ( Mw) 18,000.

(Synthesis Example 3)
<Synthesis of Amorphous Polyester A3>
Amorphous polyester A3 was obtained by the same procedure as in Synthesis Example 1, except that terephthalic acid and succinic acid were used as the dicarboxylic acid in a molar ratio (terephthalic acid / succinic acid) = 80/20.
The obtained resin has an acid value (AV) of 0.9 mgKOH / g, a hydroxyl value (OHV) of 15.2 mgKOH / g, a glass transition temperature (Tg) of 58.6 ° C., a softening temperature of 139.3 ° C., and a weight average molecular weight ( Mw) 17,900.

(Synthesis Example 4)
<Synthesis of Amorphous Polyester A4>
Amorphous polyester A4 was obtained by the same procedure as in Synthesis Example 1 except that terephthalic acid was used as the dicarboxylic acid.
The resulting resin has an acid value (AV) of 0.8 mg KOH / g, a hydroxyl value (OHV) of 12.5 mg KOH / g, a glass transition temperature (Tg) of 90.0 ° C., a softening temperature of 190.0 ° C., and a weight average molecular weight ( Mw) 20,000.

(Synthesis Example 5)
<Synthesis of Amorphous Polyester A5>
Propylene glycol and bisphenol A ethylene oxide 2-mole adduct as a diol are molar ratio (propylene glycol / bisphenol A ethylene oxide 2-mole adduct) = 75/25, and terephthalic acid and adipic acid are used as dicarboxylic acids in a molar ratio (terephthalic acid / Amorphous polyester A5 was obtained by the same procedure as in Synthesis Example 1 except that (adipic acid) = 80/20.
The obtained resin has an acid value (AV) of 0.6 mg KOH / g, a hydroxyl value (OHV) of 10.9 mg KOH / g, a glass transition temperature (Tg) of 58.2 ° C., a softening temperature of 143.4 ° C., and a weight average molecular weight ( Mw) 23,700.

(Synthesis Example 6)
<Synthesis of Amorphous Polyester A6>
Amorphous polyester A6 was obtained by the same procedure as in Synthesis Example 1 except that terephthalic acid and adipic acid were used as the dicarboxylic acid in a molar ratio (terephthalic acid / adipic acid) = 80/20.
The obtained resin has an acid value (AV) of 0.9 mgKOH / g, a hydroxyl value (OHV) of 17.2 mgKOH / g, a glass transition temperature (Tg) of 48.4 ° C., a softening temperature of 123.2 ° C., and a weight average molecular weight ( Mw) 16,700.

(Synthesis Example 7)
<Synthesis of Amorphous Polyester A7>
Amorphous polyester A7 was obtained by the same procedure as in Synthesis Example 1 except that the reaction time at 230 ° C. was reduced to 5 minutes under reduced pressure.
The obtained resin has an acid value (AV) of 0.19 mg KOH / g, a hydroxyl value (OHV) of 77.5 mg KOH / g, a glass transition temperature (Tg) of 31.5 ° C., a softening temperature of 85.6 ° C., and a weight average molecular weight ( Mw) 4,000.

(Synthesis Example 8)
<Synthesis of Amorphous Polyester A8>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, a molar ratio of neopentyl glycol and ethylene glycol (neopentyl glycol / ethylene glycol) = 50/50 as a diol and many As the carboxylic acid, terephthalic acid, isophthalic acid, and adipic acid were charged in a molar ratio (terephthalic acid / isophthalic acid / adipic acid) = 40/55/5 and OH / COOH (molar ratio) = 1.2. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. After raising the temperature to 230 ° C. over 2 hours and reacting until the effluent water disappeared, the reaction was carried out under reduced pressure of 10 mmHg to 30 mmHg for 4 hours. Thereafter, 2.5 mol% of trimellitic anhydride was added to the charged amount of polycarboxylic acid, reacted at 180 ° C. under normal pressure for 2 hours, and further reacted at 8 kPa to produce amorphous polyester. A8 was obtained.
The obtained resin has an acid value (AV) of 10 mg KOH / g, a hydroxyl value (OHV) of 18.5 mg KOH / g, a glass transition temperature (Tg) of 58.7 ° C., a softening temperature of 145.3 ° C., and a weight average molecular weight (Mw). It was 31,300.

(Synthesis Example 9)
<Synthesis of Amorphous Polyester A9>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol as a diol, terephthalic acid and succinic acid as dicarboxylic acids, molar ratio (terephthalic acid / succinic acid) = 90/10 and OH / COOH (molar ratio) = 2.0. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over 2 hours, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 1 hour, and amorphous polyester A9 was obtained.
The obtained resin has an acid value (AV) of 0.2 mg KOH / g, a hydroxyl value (OHV) of 22.2 mg KOH / g, a glass transition temperature (Tg) of 71.0 ° C., a softening temperature of 135.8 ° C., and a weight average molecular weight ( Mw) 12,800.

(Synthesis Example 10)
<Synthesis of Amorphous Polyester A10>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol as a diol, terephthalic acid and succinic acid as dicarboxylic acids, molar ratio (terephthalic acid / succinic acid) = 85/15 and OH / COOH (molar ratio) were set to 2.0. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over 2 hours, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and amorphous polyester A10 was obtained.
The resulting resin has an acid value (AV) of 1.48 mg KOH / g, a hydroxyl value (OHV) of 10.5 mg KOH / g, a glass transition temperature (Tg) of 69.2 ° C., a softening temperature of 152.1 ° C., and a weight average molecular weight ( Mw) 19,700.

(Synthesis Example 11)
<Synthesis of Amorphous Polyester A11>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol as a diol, terephthalic acid as a dicarboxylic acid, and OH / COOH (molar ratio) = 2.0. It was prepared as follows. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over 2 hours, and the reaction was continued until there was no effluent water. Then, it was made to react for 1 hour under pressure reduction of 10 mmHg-30 mmHg, and amorphous polyester A11 was obtained.
The obtained resin has an acid value (AV) of 0.38 mg KOH / g, a hydroxyl value (OHV) of 35.6 mg KOH / g, a glass transition temperature (Tg) of 77.9 ° C., a softening temperature of 140.4 ° C., and a weight average molecular weight ( Mw) 9,000.

(Synthesis Example 12)
<Synthesis of Amorphous Polyester A12>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol as a diol, terephthalic acid and succinic acid as dicarboxylic acids, molar ratio (terephthalic acid / succinic acid) = 90/10 and OH / COOH (molar ratio) = 2.0. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over 2 hours, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and amorphous polyester A12 was obtained.
The obtained resin had an acid value (AV) of 1.02 mgKOH / g, a hydroxyl value (OHV) of 14.8 mgKOH / g, a glass transition temperature (Tg) of 77.3 ° C., a softening temperature of 166.9 ° C., and a weight average molecular weight ( Mw) 22,700.

(Synthesis Example 13)
<Synthesis of Amorphous Polyester A13>
After completion of the reduced pressure reaction in Synthesis Example 10, the system was cooled to 175 ° C. under a nitrogen stream. Thereafter, trimellitic anhydride was added at a target acid value (AV) of 6.0 (mgKOH / g) and reacted for 1 hour to obtain amorphous polyester A13.
The input amount of trimellitic anhydride relative to the target acid value was derived from the following equation.
Trimellitic anhydride input = A / B
A: Resin weight before acid correction × (target acid value−acid value before acid correction)
B: Acid value of trimellitic anhydride-target acid value The obtained resin had an acid value (AV) of 6.28 mgKOH / g, a glass transition temperature (Tg) of 69.6 ° C., a softening temperature of 151.2 ° C., and a weight average. The molecular weight (Mw) was 19,200.

(Synthesis Example 14)
<Synthesis of Amorphous Polyester A14>
Amorphous polyester A14 was obtained in the same manner as in Synthesis Example 13 except that the target acid value (AV) was 17 (mgKOH / g).
The obtained resin had an acid value (AV) of 17.2 mgKOH / g, a glass transition temperature (Tg) of 72.1 ° C., a softening temperature of 153.6 ° C., and a weight average molecular weight (Mw) of 18,700.

(Synthesis Example 15)
<Synthesis of crystalline polyester B1>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 1,6-hexanediol as a diol and sebacic acid as a dicarboxylic acid were COOH / OH (molar ratio) = 1.10. It was prepared to become. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over 2 hours, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and crystalline polyester B1 was obtained.
The obtained resin had an acid value (AV) of 27.5 mgKOH / g, a melting point (Tm) of 64.0 ° C., and a weight average molecular weight (Mw) of 15,000.

(Synthesis Example 16)
<Synthesis of crystalline polyester B2>
Crystalline polyester B2 was obtained by the same procedure as in Synthesis Example 15 except that COOH / OH (molar ratio) was set to 1.03.
The obtained resin had an acid value (AV) of 17.4 mgKOH / g, a melting point (Tm) of 66.2 ° C., and a weight average molecular weight (Mw) of 25,000.

(Synthesis Example 17)
<Synthesis of crystalline polyester B3>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, ethylene glycol as diol and dodecanedioic acid as dicarboxylic acid become OH / COOH (molar ratio) = 1.03. It was prepared as follows. After sufficiently replacing the inside of the reaction vessel with nitrogen gas, 300 ppm (based on the monomer) of titanium tetraisopropoxide was added, and the temperature was raised to 200 ° C. in about 4 hours under a nitrogen gas stream. The temperature was raised to 230 ° C. over 2 hours, and the reaction was continued until there was no effluent water. Then, it was made to react under reduced pressure of 10 mmHg-30mmHg for 4 hours, and crystalline polyester B3 was obtained.
The obtained resin had a melting point (Tm) of 84.5 ° C. and a weight average molecular weight (Mw) of 18,000.

(Synthesis Example 18)
<Synthesis of crystalline polyester B4>
300 g of amorphous polyester A9 obtained in Synthesis Example 9 and 1,000 g of ethyl acetate were charged into a 2 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, Stir until visually uniform at 50 ° C. until uniform. Next, a molar ratio of NCO / (OH of amorphous resin + OH of crystalline resin) = 0.6 amount of 4,4′-diphenylmethane diisocyanate was added, and after homogenization, 2-ethylhexanoic acid with a solid content of 200 ppm Tin was added and the temperature was raised to 75 ° C. After reacting for 1 hour, 700 g of the pulverized crystalline polyester B1 obtained in Synthesis Example 15 was added, and the reaction was further continued for 5 hours to obtain crystalline polyester B4.
The obtained resin had a melting point (Tm) of 62.0 ° C. and a weight average molecular weight (Mw) of 28,000.

(Synthesis Example 19)
<Synthesis of crystalline polyester B5>
300 g of amorphous polyester A9 obtained in Synthesis Example 9 and 1,000 g of ethyl acetate were charged into a 2 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, Stir until visually uniform at 50 ° C. until uniform. Next, a molar ratio of NCO / (OH of amorphous resin + OH of crystalline resin) = 0.6 amount of 4,4′-diphenylmethane diisocyanate was added, and after homogenization, 2-ethylhexanoic acid with a solid content of 200 ppm Tin was charged and the temperature was raised to 78 ° C. After reacting for 1 hour, 700 g of the crystalline polyester B3 pulverized product obtained in Synthesis Example 17 was added, and further reacted for 5 hours to obtain crystalline polyester B5.
The obtained resin had a melting point (Tm) of 84.5 ° C. and a weight average molecular weight (Mw) of 30,000.

(Preparation of black colorant dispersion)
17 parts of carbon black (Rega L400; manufactured by Cabot) and 3 parts of a pigment dispersant were primarily dispersed in 80 parts of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion is finely dispersed by a strong shearing force using a bead mill (LMZ type manufactured by Ashizawa Finetech Co., Ltd., zirconia bead diameter 0.3 mm), and the secondary dispersion in which aggregates of 5 μm or more are completely removed. A liquid (black colorant dispersion) was prepared.

(Preparation of release agent dispersion)
18 parts of carnauba release agent and 2 parts of release agent dispersant were primarily dispersed in 80 parts of ethyl acetate using a mixer having stirring blades. The obtained primary dispersion was heated to 80 ° C. while stirring to dissolve the carnauba release agent, and then the temperature of the solution was lowered to room temperature to precipitate release agent particles so that the maximum diameter was 3 μm or less. As the release agent dispersant, a polyethylene release agent grafted with a styrene-butyl acrylate copolymer was used. The obtained dispersion is further finely dispersed by a strong shearing force using a bead mill (LMZ type manufactured by Ashizawa Finetech Co., Ltd., zirconia bead diameter 0.3 mm), and the maximum diameter is adjusted to 1 μm or less, and then released. An agent dispersion was obtained.

Example 1
<Preparation of toner composition liquid>
Each dispersion or solution so that the binder resin [amorphous polyester A1 / crystalline polyester B1 (mass ratio) = 90/10], the colorant, and the release agent have the composition shown in Table 1, Using a mixer having stirring blades, the mixture was stirred for 10 minutes in a heating environment at 60 ° C. and uniformly dispersed to obtain a toner composition liquid. The pigment and release agent particles did not aggregate due to the shock caused by solvent dilution. As the solvent, ethyl acetate was used.

<Production of toner>
The toner composition liquid was ejected as droplets under the following conditions using the toner production apparatus of FIG. 3 having the droplet ejection head shown in FIG. 2 as droplet ejection means. Thereafter, the liquid droplets were dried and solidified, collected by a cyclone, and then secondarily dried at 35 ° C. for 48 hours to prepare toner 1.

-Liquid column resonance condition-
Resonance mode: N = 2
Length between both ends in the longitudinal direction of the liquid column resonance liquid chamber: L = 1.8 mm
Height of end of frame on liquid common supply path side of liquid column resonance liquid chamber: h1 = 80 μm
The height of the communication port of the liquid column resonance liquid chamber: h2 = 40 μm

-Preparation conditions of toner base particles-
Dispersion specific gravity: ρ = 1.1 g / cm ³
Discharge port shape: perfect circle Discharge port diameter: 7.5μm
Number of discharge ports: 4 per liquid column resonance liquid chamber Minimum distance between adjacent discharge ports: 130 μm (all at equal intervals)
Dry air temperature: 40 ° C
Applied voltage: 10.0V
Drive frequency: 395 kHz

<Creation of carrier>
The following raw materials were dispersed with a homomixer for 20 minutes to prepare a resin layer coating solution. Thereafter, the resin layer coating solution was applied to the surface of 1,000 parts of spherical ferrite having a volume average particle size of 35 μm using a fluidized bed type coating apparatus to prepare a carrier.
・ Silicone resin (organostraight silicone) 100 parts ・ γ- (2-aminoethyl) aminopropyltrimethoxysilane 5 parts ・ Carbon black 10 parts ・ Toluene 100 parts

<Production of developer>
A developer was prepared by mixing 5 parts of toner 1 and 95 parts of the carrier.

<Evaluation>
The following evaluation was performed. The results are shown in Table 2.
<< Fixing temperature limit >>
Using the tandem-type full-color image forming apparatus shown in FIG. 4, the toner adhesion amount after transfer is 0.85 ± 0.10 mg / cm ² on transfer paper (manufactured by Ricoh Business Expert Co., Ltd., copy printing paper <70>). A solid image (image size: 3 cm × 8 cm) was formed.
Fixing is performed by changing the temperature of the fixing belt, and the surface of the obtained fixed image is drawn with a ruby needle (tip radius 260 to 320 μmR, tip angle 60 degrees) using a drawing tester AD-401 (manufactured by Ueshima Seisakusho). Drawing was carried out with a load of 50 g, and the drawing surface was rubbed strongly 5 times with fibers (Hanicot # 440, manufactured by Hanilon Co., Ltd.), and the fixing belt temperature at which image shaving was almost eliminated was defined as the minimum fixing temperature. The solid image was created on the transfer paper at a position 3.0 cm from the front end in the paper passing direction. The speed of passing through the nip portion of the fixing device is 280 mm / s. The lower the fixing minimum temperature, the better the low-temperature fixing property. Therefore, the following criteria were evaluated based on the fixing minimum temperature.
〔Evaluation criteria〕
○: Minimum fixing temperature is 120 ° C. or lower Δ: Lower fixing temperature exceeds 120 ° C., 130 ° C. or lower ×: Lower fixing temperature exceeds 130 ° C.

<< Blocking property (penetration) >>
Each toner was filled in a 50 mL glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JISK 2235-1991) and evaluated according to the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of less than 5 mm, there is a high possibility of problems in use.
In the present invention, the penetration is expressed by the penetration depth (mm).
〔Evaluation criteria〕
○: Needle penetration is 10 mm or more △: Needle penetration is 5 mm or more and less than 10 mm ×: Needle penetration is less than 5 mm

(Example 2)
Example 1 except that crystalline polyester B2 was used as the crystalline polyester, and the mass ratio of amorphous polyester to crystalline polyester (noncrystalline polyester A1 / crystalline polyester B2) was 85/15. Toner 2 was prepared by the same procedure.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 3)
Toner 3 was prepared in the same procedure as in Example 1 except that amorphous polyester A2 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 4
Toner 4 was prepared in the same procedure as in Example 1 except that amorphous polyester A3 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 5)
Toner 5 was prepared in the same procedure as in Example 1 except that amorphous polyester A4 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 6)
Toner 6 was prepared in the same procedure as in Example 1 except that amorphous polyester A5 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 7)
Toner 7 was prepared in the same procedure as in Example 1 except that amorphous polyester A9 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 8)
Toner 8 was prepared in the same procedure as in Example 1 except that amorphous polyester A10 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

Example 9
Toner 9 was prepared in the same procedure as in Example 1 except that amorphous polyester A11 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 10)
Toner 10 was prepared in the same procedure as in Example 1 except that amorphous polyester A12 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 11)
Example 8 except that crystalline polyester B4 was used as the crystalline polyester and the mass ratio of amorphous polyester to crystalline polyester (noncrystalline polyester A10 / crystalline polyester B4) was 86/14. Toner 11 was prepared by the same procedure.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 12)
Toner 12 was prepared in the same procedure as in Example 11 except that crystalline polyester B5 was used as the crystalline polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 13)
Toner 13 was prepared in the same procedure as in Example 8, except that crystalline polyester B3 was used as the crystalline polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 14)
100 parts of binder resin used in Example 1, 10 parts of release agent used in Example 1, 0.5 part of release agent dispersant used in Example 1, 5 parts of colorant used in Example 1 And 1 part of the charge control agent used in Example 1 were sufficiently mixed with a Henschel mixer, and the resulting mixture was melt-kneaded with a twin-screw extrusion kneader (TEM-50 manufactured by Toshiba Machine Co., Ltd.). The kneaded product was rolled using a cooling press roller so as to have a thickness in the range of 2 mm to 5 mm, gradually cooled with a conveyor belt, and then coarsely pulverized using a feather mill to obtain a coarsely crushed product.
The coarsely pulverized product was pulverized with a jet mill pulverizer (IDS; manufactured by Nippon Pneumatic Kogyo Co., Ltd.) and classified with a rotor type classifier (teaplex type classifier type: 100 ATP) to obtain toner 14.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 15)
Toner 15 was prepared in the same procedure as in Example 1 except that amorphous polyester A13 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 16)
Toner 16 was prepared in the same procedure as in Example 1 except that amorphous polyester A14 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 1)
Toner 17 was prepared in the same procedure as in Example 1 except that amorphous polyester A6 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 2)
Toner 18 was prepared in the same procedure as in Example 2, except that the mass ratio of amorphous polyester to crystalline polyester (amorphous polyester A1 / crystalline polyester B2) was 70/30.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 3)
Toner 19 was prepared in the same procedure as in Example 1 except that amorphous polyester A7 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 4)
Toner 20 was prepared in the same procedure as in Example 1 except that amorphous polyester A8 was used as the amorphous polyester.
Each characteristic value was measured and evaluated in the same manner as in Example 1. The results are shown in Table 2.

*) In the molded body of Comparative Example 1, since the spherical domain and the linear domain were mixed, the domain diameter could not be measured.

Aspects of the present invention are as follows, for example.
<1> A toner containing a binder resin,
The binder resin contains a crystalline polyester and an amorphous polyester;
A molded product obtained by removing tetrahydrofuran by heating from an extraction solution obtained by extracting the binder resin from the toner using tetrahydrofuran has a spherical domain of the crystalline polyester, and further has a spherical domain. A toner having an average particle size of 7.0 μm or less.
<2> The toner according to <1>, wherein the average size of the crystalline polyester domains in the toner is 150 nm or less.
<3> TMA compression deformation of a molded product obtained by removing tetrahydrofuran by heating from an extraction solution obtained by extracting a binder resin from toner with tetrahydrofuran at 200 mN at 40 ° C. and 80% relative humidity. The toner according to any one of <1> to <2>, wherein the ratio (TMA%) is 3.0% or less.
<4> The toner according to any one of <1> to <3>, wherein the content of the crystalline polyester is 1% by mass to 20% by mass with respect to the binder resin.
<5> The amorphous polyester has a weight average molecular weight of 10,000 to 35,000, a glass transition temperature of 50 ° C. to 80 ° C., and a softening temperature of 130 ° C. to 180 ° C. <1 > To <4>.
<6> The toner according to any one of <1> to <5>, wherein the crystalline polyester has a melting point of 60 ° C to 120 ° C and a weight average molecular weight of 10,000 to 35,000.
<7> A developer comprising the toner according to any one of <1> to <6> and a carrier.
<8> an electrostatic latent image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier;
Developing means comprising toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image;
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <6>.

Japanese Patent No. 3949553 Japanese Patent No. 4155108

Claims (10)

A toner manufacturing method including a droplet discharge step of discharging a toner composition liquid into droplets from at least one discharge hole,
The toner formed from the toner composition liquid contains a binder resin,
The binder resin contains a crystalline polyester and an amorphous polyester;
A molded product obtained by removing tetrahydrofuran by heating from an extraction solution obtained by extracting the binder resin from the toner using tetrahydrofuran has a spherical domain of the crystalline polyester, and further has a spherical domain. A method for producing a toner, wherein the average particle diameter is 7.0 μm or less.   The method for producing a toner according to claim 1, wherein the crystalline polyester does not have a branched structure.   The method for producing a toner according to claim 1, wherein the amorphous polyester does not have a branched structure.   The method for producing a toner according to claim 1, wherein an average size of the crystalline polyester domains in the toner is 150 nm or less.   TMA compression deformation rate at 200 mN of the molded product obtained by removing tetrahydrofuran by heating from an extraction solution obtained by extracting a binder resin from the toner with tetrahydrofuran under the conditions of 40 ° C. and 80% relative humidity. The toner production method according to claim 1, wherein (TMA%) is 3.0% or less.   The method for producing a toner according to claim 1, wherein the content of the crystalline polyester is 1% by mass to 20% by mass with respect to the binder resin.   The weight average molecular weight of the amorphous polyester is 10,000 to 35,000, the glass transition temperature is 50 ° C to 80 ° C, and the softening temperature is 130 ° C to 180 ° C. The method for producing a toner according to any one of the above.   The method for producing a toner according to claim 1, wherein the crystalline polyester has a melting point of 60 ° C. to 120 ° C. and a weight average molecular weight of 10,000 to 35,000.   A developer production method comprising producing a developer containing the toner produced by the toner production method according to claim 1 and a carrier. An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier;
And developing a visible image by developing the electrostatic latent image formed on the electrostatic latent image carrier with toner,
An image forming method, wherein the toner is a toner manufactured by the toner manufacturing method according to claim 1.