JP6260124B2 - Toner for electrophotography - Google Patents

Description

  The present invention relates to an electrophotographic toner.

  In an image forming apparatus such as an electrophotographic apparatus or an electrostatic recording apparatus, a toner image is formed by attaching toner to an electrostatic latent image formed on a photoreceptor, and then the toner image is transferred to a recording medium and heated. To fix. When forming a full-color image, generally, toners of four colors of black, yellow, magenta, and cyan are used to superimpose toner images of respective colors on a recording medium and then fixed by heating. Such toners are required to have low-temperature fixability and heat-resistant storage with the development of electrophotographic technology.

In response to these requirements, the binder resin has been reduced in viscosity, but there are problems such as a decrease in heat-resistant storage stability of the toner and carrier spent in the developing device during long-term running, resulting in a decrease in charge. It was. In recent years, with respect to such a problem, an invention has been disclosed regarding a technique using a crystalline resin and an amorphous resin as a binder resin (Japanese Patent Laid-Open No. 2005-234046 and Patent Document 2). JP, 2013-050578, A).
However, these toners mainly use crystalline polyester as a crystalline resin and are compatible with the heat history at the time of fixing and exhibit low-temperature fixability. However, high-temperature offset is not considered. For high temperature offset, for example, a large amount of a release agent is added or a prepolymer is used. When the amount of the shaping agent is increased, the release agent exposed on the surface causes the toners to aggregate together under high temperature and high humidity, or to be fused to a carrier, a regulation blade, or the like during long-term running, resulting in a decrease in charge. Further, when a prepolymer is used, the gloss is lowered, the color developability and saturation of the secondary color due to color toner superposition and the like are lowered, and the color reproducibility of the toner is deteriorated.
In addition, the molecular weight of the crystalline polyester resin is increased by bonding the crystalline polyester resin with urethane and urea, the low molecular weight component of the crystalline polyester resin is reduced, and the high temperature resistance of the toner due to the compatibility with the amorphous resin. It is possible to prevent deterioration of high humidity storage stability.

  Further, a technique of a toner containing a crystalline resin as a main component is disclosed (Japanese Patent Application Laid-Open No. 2005-227672, for example). Although it is said that low temperature fixability can be achieved by using a crystalline resin as a main component, it takes time to recrystallize after heating, so it takes time to cool and solidify after fixing. As a result, there are problems such as soiling the lining of the paper that is overlaid after the paper is discharged, and soiling the conveying member that comes into contact with the paper after fixing.

  The present invention has been made in view of the above, and an object of the present invention is to provide a toner that is excellent in low-temperature fixability and heat-resistant storage stability, has a wide fixable area, and has no image smear after fixing.

As means for solving the above-mentioned problems, the present invention includes the electrophotographic toner described in the following (1) to (12). That is,
(1) In an electrophotographic toner containing at least a binder resin and a release agent, the binder resin contains a crystalline polyester resin having a urethane group and / or urea group bond, and is obtained by an X-ray diffractometer for the toner. In the diffraction spectrum, the ratio (C) / (A) is 0.05 or more when the integrated intensity of the spectrum derived from the crystal structure is (C) and the integrated intensity of the spectrum derived from the amorphous structure is (A). An electrophotographic toner, wherein the toner is 0.15 or less and (C) / (A) after heating and cooling the toner to 120 ° C. is 0.02 or less.
(2) The toner for electrophotography as described in (1) above, wherein the crystalline polyester resin having a urethane group and / or urea group bond has an acid value of 5 to 60 mgKOH / g.
(3) The electrophotographic image described in (1) or (2), wherein the crystalline polyester resin having a urethane group and / or urea group bond is contained in 5 to 30 parts by weight in 100 parts by weight of the toner. Toner.
(4) The electron according to any one of (1) to (3), wherein the polyester resin having crystallinity having a urethane group and / or urea group bond has a weight average molecular weight of 3000 to 30000. Toner for photography.
(5) The electron according to any one of (1) to (4), wherein the crystalline polyester resin having a urethane group and / or urea group bond has a melting point of 50 ° C to 70 ° C. Toner for photography.
(6) The toner for electrophotography according to any one of (1) to (5), wherein the release agent is a monoester wax.
(7) The toner for electrophotography according to any one of (1) to (6), wherein the amount of the release agent added is 3 to 10 parts by weight per 100 parts by weight of the toner.
(8) The electrophotographic toner according to (6) or (7), wherein the monoester wax has a melting point of 55 to 85 ° C.
(9) The electrophotographic toner as described in any one of (6) to (8) above, wherein 45% to 55% of C44 component in the monoester wax is contained.
(10) The electrophotographic toner as described in any one of (6) to (9) above, wherein the monoester wax has a carbon number of C38 or less and a component of 4.0% or less.
Furthermore, the present invention includes the “electrophotographic toner” described in the following (11) and (12).
(11) The electrophotographic toner according to any one of (6) to (10), wherein the monoester wax has a penetration of 7 or less.
(12) An oil phase of an organic solvent liquid in which a binder resin precursor composed of at least a modified polyester resin is dissolved or dispersed is dispersed in an aqueous medium to which a fine particle dispersant is added to form an emulsified dispersion, The electrophotographic toner according to any one of (1) to (11) above, which is obtained by removing a solvent.

  As will be understood from the following detailed and specific description, according to the present invention, a toner having excellent low-temperature fixability and heat-resistant storage stability, a wide fixable area, and no image smear after fixing is provided. An extremely excellent effect is achieved.

It is a figure which shows the example of the diffraction spectrum obtained by the X-ray-diffraction measurement in this invention.

The present invention is described in detail below.
As described above, in the toner of the present invention, at least the binder resin includes a crystalline polyester resin having a urethane group / and / or a urea group bond, and the diffraction structure obtained by the X-ray diffractometer of the toner has a crystal structure. The ratio (C) / (A) when the integrated intensity of the spectrum derived from (C) and the integrated intensity of the spectrum derived from the amorphous structure as (A) is 0.06 or more and 0.15 or less, (C) / (A) after heating and cooling the toner to 120 ° C. is 0.02 or less.
The crystalline polyester resin having a urethane group and / or urea group bond is used as the binder resin. The crystalline polyester is excellent in low-temperature fixability, but the storage elastic modulus at the high temperature portion is lowered and high temperature offset is likely to occur. Because it becomes. By introducing a urethane group and / or a urea group bond into the binder resin, it is possible to prevent a decrease in storage elastic modulus and achieve both low temperature fixing and high temperature offset prevention. Further, by introducing a urethane group and / or urea group bond, the reaction of unreacted oligomer components proceeds, the remaining oligomers are reduced, and the storage stability is improved.

  In the diffraction spectrum obtained by the X-ray diffractometer for the toner, the ratio (C) is the integral intensity of the spectrum derived from the crystal structure, and (A) is the integral intensity of the spectrum derived from the amorphous structure ( C) / (A) is 0.05 or more and 0.15 or less. The ratio (C) / (A) is an index indicating the amount of crystallization sites in the binder resin, and the area of the main diffraction peak and halo derived from the crystal structure in the diffraction spectrum obtained by X-ray diffraction measurement. Is the ratio. If the intensity ratio of the X-ray diffraction spectrum is less than 0.05, the ratio of the crystalline component in the toner is small, and therefore the ratio of the crystalline resin compatible with the amorphous resin is small. Insufficient low-temperature fixability cannot be obtained. On the other hand, when the intensity ratio of the X-ray diffraction spectrum is larger than 0.15, the ratio of the crystal component is large, and thus the crystalline resin is the main component. As described above, since crystalline resin requires time to recrystallize after heating, it takes time to cool and solidify after fixing, and after the paper is discharged, the lining of the overlying paper is soiled or the paper is transported after fixing Inconveniences such as fouling a conveying member that sometimes comes into contact.

  Further, when the integrated intensity of the spectrum derived from the crystal structure after heating and cooling the toner to 120 ° C. is (C) and the integrated intensity of the spectrum derived from the amorphous structure is (A), the ratio (C) / ( A) is 0.02 or less. Since the amorphous resin and the crystalline resin exist in an incompatible state when not heated, the amorphous resin is not reduced in viscosity and maintains the storage elastic modulus, so that storability is ensured.

On the other hand, when heated at the time of fixing, the amorphous resin and the crystalline resin are compatible with each other, the storage elastic modulus of the amorphous resin is lowered, and low temperature fixing becomes possible. Here, when the intensity ratio of the X-ray diffraction spectrum is larger than 0.02, it indicates that a large amount of the crystalline resin that cannot be compatible with the amorphous resin is contained.
Since the crystalline resin is soft, if there is a crystalline resin that is incompatible with the toner particle surface, it will aggregate between the toner particles or will be non-uniformly present in the toner particles and will adhere to the belt at the time of fixing, and a small amount of low-temperature offset May occur. Here, the temperature of 120 ° C. is assumed to be a temperature at which the toner is heated such as during fixing, and may be any temperature as long as the temperature is sufficiently compatible.

The X-ray diffraction measurement in the present invention was performed using a two-dimensional detector-mounted X-ray diffraction apparatus (D8 DISCOVER with GADDS / Bruker).
The capillary used for the measurement was a mark tube (Lindenman glass) having a diameter of 0.70 mm. The sample was packed up to the top of the capillary tube and measured. Further, tapping was performed when filling the sample, and the number of tapping was 100 times. Detailed measurement conditions are shown below.
Tube current: 40 mA
Tube voltage: 40 kV
Goniometer 2θ axis: 20.0000 °
Goniometer Ω axis: 0.0000 °
Goniometer φ axis: 0.0000 °
Detector distance: 15cm (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2
Measurement time: 600 sec

For the incident optical system, a collimator having a pinhole of φ1 mm was used. The obtained two-dimensional data was integrated with the attached software (chi axis is 3.2 ° to 37.2 °) and converted into one-dimensional data of diffraction intensity and 2θ. A method for calculating the ratio (C) / (A) based on the obtained X-ray diffraction measurement result will be described below. Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. 1 (A) and 1 (B). The horizontal axis is 2θ, the vertical axis is the X-ray diffraction intensity, and both are linear axes. In the X-ray diffraction spectrum in FIG. 1A, there are main peaks (P1, P2) at 2θ = 21.3 ° and 24.2 °, and a halo (h) is observed in a wide range including these two peaks. . Here, the main peak is derived from the crystal structure, and the halo is derived from the amorphous structure. These two main peaks and halos are Gaussian functions,
f _p1 (2θ) = a _p1 exp {− (2θ−b _p1 ) ² / (2c _p1 ² )} (Formula A (1))
f _p2 (2θ) = a _p2 exp {− (2θ−b _p2 ) ² / (2c _p2 ² )} (Formula A (2))
f _h (2θ) = a _h exp {− (2θ−b _h ) ² / (2c _h ² )} (Equation A (3))
(F _p1 (2θ), f _p2 (2θ), and f _h (2θ) are functions corresponding to the main peaks P1, P2, and halo, respectively),
And the sum of these three functions f (2θ) = f _p1 (2θ) + f _p2 (2θ) + f _h (2θ) (Equation A (4))
Was the fitting function of the entire X-ray diffraction spectrum (shown in FIG. 1B), and fitting by the least square method was performed. Fitting variables _are nine of _{a p1, b p1, c p1} , a p2, b p2, c p2, a h, b h, c h. As initial values of fitting of each variable, b _p1 , b _p2 , and b _h are X-ray diffraction peak positions (in the example of FIG. 1A, b _p1 = 21.3, b _p2 = 24.2, b _h = 22.5) were appropriately input for other variables, and values obtained by matching the two main peaks and the halo with the X-ray diffraction spectrum as much as possible were set. Fitting can be performed using, for example, Microsoft 2003 Excel 2003 solver.

The integrated area (S) for each of the Gaussian functions f _p1 (2θ), f _p2 (2θ) corresponding to the two main peaks (P1, P2) after fitting, and the Gaussian function f _h (2θ) corresponding to the halo. _{From (P1} , S _p2 , S _h ), when (S _p1 + S _p2 ) is (C) and (S _p1 + S _p2 + S _h ) is (A), the ratio (C) ) / (A) can be calculated. The crystallinity of the crystalline resin can be freely controlled by the constituting monomer, molecular weight, and urethane group concentration.

  The toner of the present invention preferably contains 5 to 30 parts by weight of a crystalline polyester resin having a urethane group and / or a urea group bond in 100 parts by weight of the toner. When the amount is less than 5 parts by weight, the low-temperature fixability cannot be obtained because the ratio of the crystalline resin in the toner is small as described above. On the other hand, if the ratio is larger than 30 parts by weight, the ratio of the crystalline resin is large, so that problems such as contamination of the fixing member that occurs during conveyance of the paper after fixing occur. By setting the mixing ratio of the crystalline resin to 5 to 30 parts by weight, the toner can be free from problems such as storage stability and fixability and fixing member contamination.

  In the toner of the present invention, the acid value of the crystalline polyester resin having a urethane group / and / or urea group bond is preferably 5 to 60 mgKOH / g. If the acid value of the crystalline polyester resin is less than 5 mgKOH / g, the crystalline polyester resin cannot be uniformly dispersed in the amorphous polyester. On the other hand, if it is more than 60 mgKOH / g, the amorphous polyester resin is compatible with the crystalline polyester before heating, and the toner becomes low-viscosity at room temperature, so that the storage stability is deteriorated. By setting the acid value of the crystalline polyester resin to 5 to 60 mgKOH / g, it is possible to achieve both storability and fixability.

  In the toner of the present invention, the polyester resin having crystallinity having a urethane group / and / or urea group bond preferably has a weight average molecular weight of 3,000 to 30,000. When the weight average molecular weight is from 3000 to 30000, if it is 3000 or less, the endothermic start temperature in the DSC 1st run resulting from the crystalline resin is lowered, and the storage stability is deteriorated. On the other hand, if it is 30000 or more, the storage elastic modulus of the toner does not decrease even if it is compatible, and sufficient low-temperature fixability cannot be obtained.

In the toner of the present invention, the melting point of the polyester resin having crystallinity having a urethane group / or urea group bond is preferably 50 ° C. to 70 ° C. The reason why the melting point of the crystalline polyester resin is set to 50 ° C. to 70 ° C. is that when the temperature is 50 ° C. or less, the endothermic start temperature in the DSC 1st run caused by the crystalline resin is lowered as described above, and the storage stability is deteriorated. .
On the other hand, when the temperature is 70 ° C. or higher, the storage elastic modulus of the toner does not decrease even when the components are compatible, so that sufficient low-temperature fixability cannot be obtained.

The release agent used in the toner of the present invention is preferably a monoester wax.
Since the monoester wax has a sharp distribution, the melt viscosity is low and the releasability is excellent, and since there are few low molecular components, a toner free from volatile substances can be obtained at the time of fixing.
The monoester wax used in the present invention is not particularly limited, but a synthetic ester wax is preferable. Compared to natural sources, it is easier to control the molecular weight distribution, and it can produce a sharp molecular weight distribution. If the molecular weight is sharp, a wax having low viscosity and no impurities or low molecular components can be obtained.
The monoester wax refers to a product produced by condensation polymerization of a monovalent acid and an alcohol.
Diester waxes and triester waxes made from polyhydric acids and alcohols have many branches, so they have a high viscosity at the time of melting, and also hinder movement inside the resin, so low temperature fixability and high temperature release properties Adversely affected.
The monoester wax used in the present invention is composed of a higher alcohol or a higher carboxylic acid component and is usually obtained from a natural product, and is generally composed of a mixture having an even number of carbon atoms. When these mixtures are esterified as they are, by-products having various similar structures in addition to the target ester compound are produced as a by-product, which tends to adversely affect the properties of the toner.
Therefore, the ester wax used by this invention can be obtained by refine | purifying a raw material and a product using solvent extraction or vacuum distillation operation.
The addition amount of the monoester wax used in the present invention per 100 parts by weight of toner is preferably 3 to 10 parts by weight. If the amount is less than 3 parts by weight, sufficient releasability cannot be obtained, and high temperature offset tends to occur. If the amount is more than 10 parts by weight, the toner is solidified at high temperature storage, or charging is reduced by running at high temperature. Occur.

In the toner of the present invention, the melting point of the monoester wax is preferably 55 ° C. to 85 ° C. The melting point of the monoester wax can be determined by DSC similarly to the binder resin.
The melting point is set to 55 ° C. to 85 ° C. When the melting point is lower than 55 ° C., the toner is solidified at high temperature storage, or charging is reduced by running at high temperature. On the other hand, when the temperature is higher than 85 ° C., the releasability from the fixing member is deteriorated because the high-temperature release property is poor.

  The monoester wax used in the toner of the present invention has 45% to 55% of the C44 component in the carbon number distribution. The number of carbon atoms was measured by a gas chromatograph apparatus (a high-sensitivity TGA TGA instrument model Q5000IR type manufactured by TA Instruments) equipped with a capillary column. The carbon number distribution was obtained by calculating the percentage of the peak area of the linear monoester of 44 components with respect to the total peak area on the gas chromatogram chart. The ratio of the carbon number distribution C44 of the wax of the present invention is 45% or more because when the ratio of the C44 component is less than 45%, the distribution becomes broad, which adversely affects heat storage stability and spent, This is because the separability deteriorates. On the other hand, if it is less than 55%, the distribution becomes sharp if it is 55% or more, and the strength of the wax solid becomes weak and soft, so that the spent on the charging member is generated due to the influence of the wax existing on the surface.

  Furthermore, the carbon number C38 or less component of the monoester wax used in the present invention is 4.0% or less. The percentage of the carbon number component of C38 or less is obtained in the same manner as described above. C38 or less is set to 4.0% or less. If it is larger than 4.0%, volatile components volatilize when the toner is heated, causing contamination in the copying machine, and contamination of the exposed and charged parts. This is because an abnormal image occurs.

  The wax of the present invention has a penetration of 7 or less. If it is larger than 7, it is soft, and due to the influence of the wax exposed on the surface, adhesion to the charging member, so-called spent, is likely to occur during long-term running, and abnormal images such as background contamination due to poor charging and toner scattering occur.

The binder resin used in the present invention includes a crystalline polyester resin having a urethane group and / or a urea group bond. The crystalline resin having at least one of a urethane bond and a urea bond is not particularly limited and may be appropriately selected depending on the purpose. For example, at least one of a urethane bond and a urea bond, a crystalline polyester unit, And a crystalline resin, a crystalline polyurethane resin, and a crystalline polyurea resin. Among these, a crystalline resin having at least one of a urethane bond and a urea bond and a crystalline polyester unit is preferable.
Examples of the crystalline resin having a urethane skeleton and / or urea skeleton used in the present invention include a polyester resin, a polyurethane resin, a polyurea resin, a polyamide resin and a composite resin having a urethane skeleton and / or a urea skeleton.
In particular, a polyurethane resin or a polyurea resin obtained by extending and / or crosslinking reaction of a polyester resin obtained by polycondensation of an alcohol component and an acid component with a divalent or higher isocyanate compound has a high hardness. This is preferable from the viewpoint of easy exudation of the release agent in the invention. Moreover, it is preferable that the said polyester resin is a linear polyester resin and composite resin containing it from the point of the crystallinity height.
As the polyester resin, a polycondensation polyester resin synthesized from a diol component and a dicarboxylic acid component is preferable from the viewpoint of crystallinity, but a tri- or higher functional alcohol component or carboxylic acid component may be used as necessary. . In addition to the polycondensation polyester resin, a polyester resin using a lactone ring-opening polymer and polyhydroxycarboxylic acid is also preferable. The polyester resin having a urethane skeleton and / or a urea skeleton may be a resin synthesized from a diol component or a dicarboxylic acid component having a urethane group or a urea group.

  Examples of the polyurethane resin include a polyurethane resin synthesized from a diol component and a diisocyanate component. A trifunctional or higher functional alcohol component or isocyanate component may be used as necessary.

  Examples of the polyurea resin include a polyurea resin synthesized from a diamine component and a diisocyanate component. A trifunctional or higher functional amine component or isocyanate component may be used as necessary.

Examples of the polyamide resin include a polyamide resin synthesized from a diamine component and a dicarboxylic acid component. A trifunctional or higher functional amine component or carboxylic acid component may be used as necessary.
Hereinafter, the alcohol component, carboxylic acid component, isocyanate component, and amine component used in the crystalline polycondensed polyester resin, the crystalline polyurethane resin, the crystalline polyamide resin, and the crystalline polyurea resin will be described.

As said alcohol component, aliphatic diol is preferable and it is preferable that chain carbon number is the range of 2-36. As the aliphatic diol, there are a linear type and a branched type, and a linear type aliphatic diol is more preferable. A plurality of diol components may be used, but the ratio of the linear aliphatic diol to the total amount of the diol component is preferably 80 mol% or more, more preferably 90 mol% or more. If it is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between low-temperature fixability and heat-resistant storage stability is good, and the resin hardness tends to improve, which is preferable.
Examples of the linear 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, Examples include, but are not limited to, 1,18-octadecanediol, 1,20-eicosanediol, and the like.
Among these, considering availability, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable. .

Other diols used as necessary include aliphatic diols other than those having 2 to 36 carbon atoms (1,2-propylene glycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, Neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.).
Also, alkylene ether glycols having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols having 4 to 36 carbon atoms (1,4 -Cyclohexanedimethanol, hydrogenated bisphenol A, etc.).
Further, alkylene oxide (hereinafter abbreviated as AO) of the above alicyclic diol [ethylene oxide (hereinafter abbreviated as EO)], propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO). Etc.] Additives (number of added moles 1-30). Furthermore, AO (EO, PO, BO, etc.) adducts of bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (addition mole number 2-30); polylactone diol (poly-ε-caprolactone diol, etc.); And polybutadiene diol.

Moreover, you may use the diol which has another functional group, for example, the diol which has a carboxyl group, the diol which has a sulfonic acid group, or a sulfamic acid group, these salts, etc. are mentioned.
Examples of the diol having a carboxyl group include dialkyrol alkanoic acids [C6-24, such as 2,2-dimethylolpropionic acid (DMPA), 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptane. Acid, 2,2-dimethylol octanoic acid, etc.].

Examples of the diol having a sulfonic acid group or a sulfamic acid group include a sulfamic acid diol [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) or an AO adduct thereof (EO as EO or Examples thereof include 1 to 6 moles of added AO such as PO. For example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N-bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, etc.]; bis (2-hydroxyethyl) phosphate and the like can be mentioned.
Examples of salts of these diols include tertiary amine salts having 3 to 30 carbon atoms (such as triethylamine salts) and alkali metal salts (such as sodium salts).
Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof.

In addition, as the alcohol component having 3 to 8 or more valences, which is used as necessary, a polyhydric aliphatic alcohol having 3 to 8 or more carbon atoms having 3 to 36 carbon atoms (an alkane polyol and an intramolecular or intermolecular dehydrated product thereof). Glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; sugars and derivatives thereof such as sucrose and methylglucoside); AO adducts of trisphenols (such as trisphenol PA) (Addition mole number 2-30); AO addition product (addition mole number 2-30) of novolak resin (phenol novolak, cresol novolak, etc.); acrylic polyol [copolymerization of hydroxyethyl (meth) acrylate and other vinyl monomers Etc.]; etc.
Among these, preferred are trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts, and more preferred are novolak resin AO adducts.

The carboxylic acid component is preferably an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid. The aliphatic dicarboxylic acid includes a straight-chain type and a branched type, and a straight-chain dicarboxylic acid is more preferable.
Examples of the dicarboxylic acid include alkane dicarboxylic acids having 4 to 36 carbon atoms (succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc.); alicyclic having 6 to 40 carbon atoms Dicarboxylic acid [dimer acid (dimerized linoleic acid), etc.], C4-C36 alkene dicarboxylic acid (alkenyl succinic acid such as dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, maleic acid, fumar Acid, citraconic acid, etc.]; aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, etc. ) And the like.

Examples of the tri- to hexa-valent or higher polycarboxylic acid used as necessary include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
In addition, as the dicarboxylic acid or the polycarboxylic acid having 3 to 6 or more valences, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) may be used. Good.
Among these dicarboxylic acids, the aliphatic dicarboxylic acids (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) are particularly preferably used alone. Those obtained by copolymerizing dicarboxylic acids (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, and lower alkyl esters thereof) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

  Examples of the isocyanate component include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and araliphatic isocyanates. Among them, the number of carbon atoms excluding carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate and these. Examples thereof include modified diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products) and mixtures of two or more thereof. If necessary, trivalent or higher isocyanates may be used in combination.

  Specific examples of the aromatic isocyanate include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, and 2,4 ′. -And / or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [condensation product of formaldehyde with an aromatic amine (aniline) or a mixture thereof; diaminodiphenylmethane and a small amount (e.g. 5-20] Phosgenation product: polyallyl polyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m -And p-isocyanatophenylsulfonyl isocyanate, etc. It is.

  Specific examples of the aliphatic isocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, Lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate Etc.

  Specific examples of the alicyclic isocyanates include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2 -Isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane diisocyanate.

  Specific examples of the araliphatic isocyanates include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified product of diisocyanate include urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, and oxazolidone group-containing modified product. Specifically, modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified products of diisocyanates such as urethane-modified TDI, and mixtures of two or more of these (for example, modified MDI and urethane-modified TDI) (Combined use with (isocyanate-containing prepolymer)).
Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms excluding carbon in the NCO group, 4 to 12 aliphatic diisocyanates, and 4 to 15 alicyclic diisocyanates, and particularly preferred are TDI. , MDI, HDI, hydrogenated MDI, and IPDI.

Examples of the amine component include aliphatic amines and aromatic amines, among which aliphatic diamines having 2 to 18 carbon atoms and aromatic diamines having 6 to 20 carbon atoms are preferable. If necessary, trivalent or higher amines may be used.
Examples of the aliphatic diamines having 2 to 18 carbon atoms include alkylene diamines having 2 to 6 carbon atoms (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.); polyalkylenes having 4 to 18 carbon atoms Diamines [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.]; these C1-C4 alkyls or C2-C4 hydroxyalkyl substitutions (Dialkylaminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, etc.); alicyclic or complex Ring-containing aliphatic diamine {alicyclic diamine having 4 to 15 carbon atoms [1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc.], C4-C15 heterocyclic diamine [piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3,9-bis ( 3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane etc.]}; C8-C15 aromatic ring-containing aliphatic amines (xylylenediamine, tetrachloro-p-xylyl) Range amine, etc.).

Examples of the aromatic diamine having 6 to 20 carbon atoms include unsubstituted aromatic diamine [1,2-, 1,3- and 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine. , Crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4, 4 ′, 4 ″ -triamine, naphthylenediamine, etc.).
In addition, aromatic diamines having a nucleus-substituted alkyl group having 1 to 4 carbon atoms [2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyltolylenediamine, 4,4′-diamino-3, 3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene 1,4-diisopropyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene 2,6-dimethyl-1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4, 4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3 '-Dimethyldiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl ether, 3,3', 5,5′-tetraisopropyl-4,4′-diaminodiphenylsulfone, etc.].
Furthermore, a mixture of these isomers in various proportions; an aromatic diamine [methylene bis-- having a nucleus-substituted electron withdrawing group (halogen such as Cl, Br, I, F; alkoxy group such as methoxy, ethoxy; nitro group, etc.) o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro -1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromo-diphenylmethane 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4 Amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) tellide Bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline), 4,4′-methylenebis (2-bromoaniline), 4 , 4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.].
Furthermore, an aromatic diamine having a secondary amino group [the unsubstituted aromatic diamine, the aromatic diamine having a C1-C4 nucleus-substituted alkyl group, and a mixture of these isomers in various proportions, A part or all of the primary amino group of an aromatic diamine having a nucleus-substituted electron withdrawing group is replaced with a secondary amino group by a lower alkyl group such as methyl or ethyl] [4,4′-di (methylamino) ) Diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene, etc.].
In addition to these, the diamine component may be obtained by condensation of polyamide polyamine [dicarboxylic acid (dimer acid etc.) and excess (more than 2 mol per mol of acid) polyamines (the above alkylenediamine, polyalkylene polyamine etc.). And low molecular weight polyamide polyamines, etc.], polyether polyamines [hydride of cyanoethylated polyether polyols (polyalkylene glycol, etc.), etc.].

  Examples of the lactone ring-opening polymer as the polyester resin include monolactones having 3 to 12 carbon atoms such as β-propiolactone, γ-butyrolactone, δ-valerolactone, and ε-caprolactone (one ester group in the ring). ) And the like can be obtained by ring-opening polymerization using a catalyst such as a metal oxide or an organometallic compound. Of these, preferred lactone is ε-caprolactone from the viewpoint of crystallinity.

  Further, it may be a lactone ring-opening polymer having a hydroxyl group at the terminal obtained by ring-opening polymerization of the above lactone using glycol (for example, ethylene glycol, diethylene glycol or the like) as an initiator. Moreover, the terminal may be modified so as to be, for example, a carboxyl group. Moreover, you may use a commercial item, for example, highly crystalline polycaprolactone, such as H1P, H4, H5, H7 of the PLACEL series by Daicel Corporation.

The polyhydroxycarboxylic acid as the polyester resin can be obtained by directly dehydrating and condensing hydroxycarboxylic acids such as glycolic acid and lactic acid (L-form, D-form, racemic form).
Cyclic ester having 4 to 12 carbon atoms corresponding to a dehydration condensate between two or three molecules of a hydroxycarboxylic acid such as glycolide or lactide (L-form, D-form, racemate) (2 to 3 ester groups in the ring) ) Is preferably ring-opening polymerized using a catalyst such as a metal oxide or an organometallic compound from the viewpoint of adjusting the molecular weight. Among these, preferable cyclic esters are L-lactide and D-lactide from the viewpoint of crystallinity. These polyhydroxycarboxylic acids may be modified so that the terminal is a hydroxyl group or a carboxyl group.

  The crystalline resin used in the present invention may be a block resin having a crystalline part and an amorphous part, and the above crystalline resin can be used for the crystalline part. Examples of the resin used for the non-crystalline part include a polyester resin, a polyurethane resin, a polyurea resin, and a polyamide resin, but are not particularly limited. The monomer for forming these amorphous parts is not particularly limited as long as it becomes an amorphous resin, and the same diol component, dicarboxylic acid component, diisocyanate component, and diamine component as those for the crystalline part are used. be able to.

  The crystalline resin used in the present invention is obtained by using a modified crystalline resin having a functional group capable of reacting with an active hydrogen group as a binder resin precursor, and extending or cross-linking when granulating in an aqueous medium. A crystalline resin may be contained. As the modified crystalline resin, the above crystalline resin can be used. The modified crystalline resin can be made to have a high molecular weight by reacting with a compound such as a resin having an active hydrogen group or a crosslinking agent or an extender having an active hydrogen group in the production process of the toner. it can.

  There is no restriction | limiting in particular as a functional group which can react with the said active hydrogen group, For example, functional groups, such as an isocyanate group, an epoxy group, carboxylic acid, and an acid chloride group, are mentioned. From the viewpoints of reactivity and stability, an isocyanate group is preferred.

  Examples of the modified crystalline resin include a crystalline polyester resin having a functional group capable of reacting with the active hydrogen group, a crystalline polyurethane resin, a crystalline polyurea resin, and a crystalline polyamide resin.

  The resin having an active hydrogen group and a compound such as a crosslinking agent and an extending agent having an active hydrogen group are not particularly limited as long as they have an active hydrogen group, and can be appropriately selected according to the purpose. For example, when the functional group capable of reacting with the active hydrogen group is an isocyanate group, examples of the active hydrogen group include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. From the viewpoint of reaction rate, amines are particularly preferable.

A resin obtained by reacting a modified crystalline resin having an isocyanate group at the terminal with an amine is a crystalline resin having a urethane skeleton and / or a urea skeleton.
There is no restriction | limiting in particular as said amines, According to the objective, it can select suitably. For example, phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine , Triethylenetetramine, ethanolamine, hydroxyethylaniline, aminoethyl mercaptan, aminopropyl mercaptan, aminopropionic acid, aminocaproic acid and the like. In addition, ketimine compounds, oxazolidone compounds, and the like in which these amino groups are blocked with ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) may be mentioned.

The binder resin in the present invention uses an amorphous resin together with the crystalline resin.
The non-crystalline resin is not particularly limited as long as it is non-crystalline, and can be appropriately selected from known ones according to the purpose. Examples thereof include polystyrene, poly-p-styrene, polyvinyltoluene and other styrene or substituted homopolymers, styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyltoluene copolymers. Copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-methacrylic acid copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic acid Butyl copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene -Isopropylene copolymer, styrene-male Styrenic copolymers such as acid ester copolymers, polythyme methacrylate resin, polybutyl methacrylate resin, polyvinyl chloride resin, polyvinyl acetate resin, polyethylene resin, polyester resin, polyurethane resin, epoxy resin, polyvinyl butyral resin, Modified to have a functional group capable of reacting with an active hydrogen group, such as polyacrylic acid resin, rosin resin, modified rosin resin, terpene resin, phenol resin, aliphatic or aromatic hydrocarbon resin, aromatic petroleum resin, etc. These resins are also included. These may be used individually by 1 type and may use 2 or more types together.

  In the toner of the present invention, a colorant can be used depending on the purpose. There is no restriction | limiting in particular as a coloring agent to be used, According to the objective, it can select suitably from well-known dyes and pigments. Examples include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, isoindolinone yellow, bengara, red lead, red lead, cadmium red, cadmium mercurial red, antimony red, permanent red 4R, para red, phis red, parachlor ortho nitroaniline red, risor fast scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, oil red, quinacridone red, pyrazolone red, polyazo red, chrome vermilion, ben Gin orange, Perinone orange, Oil orange, Cobalt blue, Cerulean blue, Alkaline blue rake, Peacock blue rake, Victoria blue rake, Metal-free phthalocyanine blue, phthalocyanine blue, Fast sky blue, Indanthrene blue (RS, BC), Indigo, ultramarine blue, bitumen, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide, pyridian, emerald green, pigment green B, naphthol green B , Green Gold, Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium oxide, zinc white, lithopone, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular in the color of the said coloring agent, According to the objective, it can select suitably, For example, the thing for black, the thing for color, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the black pigment include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black and channel black, metals such as copper and iron (CI pigment black 11), Examples thereof include metal compounds such as titanium oxide and organic pigments such as aniline black (CI Pigment Black 1).

  Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 177, 179, 202, 206, 207, 209, 211; C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of cyan pigments include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45, copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, green 7 and green 36, and the like.

  Examples of yellow pigments include C.I. I. Pigment Yellow 0-16, 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 151, 154, 180; C.I. I. Bat yellow 1, 3, 20, orange 36 and the like.

  There is no restriction | limiting in particular in content in the toner of the said coloring agent, Although it can select suitably according to the objective, 1 to 15 weight% is preferable and 3 to 10 weight% is more preferable. When the content is less than 1% by weight, the coloring power of the toner is decreased. When the content exceeds 15% by weight, poor dispersion of the pigment in the toner occurs, resulting in a decrease in coloring power and a decrease in electrical characteristics of the toner. Sometimes.

  The colorant may be used as a master batch combined with a resin. There is no restriction | limiting in particular as this resin, According to the objective, it can select suitably from well-known things. Examples include polymers of styrene or its substitutes, styrene copolymers, polymethyl methacrylate resins, polybutyl methacrylate resins, polyvinyl chloride resins, polyvinyl acetate resins, polyethylene resins, polypropylene resins, polyester resins, epoxies. Resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorination Examples include paraffin and paraffin. These may be used individually by 1 type and may use 2 or more types together. Further, there is no problem even if these masterbatch resins are crystalline resins in the present invention.

Examples of the styrene or substituted polymer thereof include polyester resin, polystyrene resin, poly p-chlorostyrene resin, and polyvinyl toluene resin.
Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - like maleic acid ester copolymer.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin or an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

  The toner of the present invention contains a charge control agent, an external additive, and other additives as necessary in addition to the binder resin, the colorant, and the release agent within the range not impairing the effects of the present invention. Also good.

  The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. However, since a color tone may be changed when a colored material is used, a colorless or nearly white material is preferable. Examples include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten Or a compound thereof, a fluorine-based activator, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Commercially available charge control agents include, for example, quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89. (All manufactured by Orient Chemical Co., Ltd.), TP-302 and TP-415 of quaternary ammonium salt molybdenum complex (both manufactured by Hodogaya Chemical Co., Ltd.), copy charge PSY VP2038 of quaternary ammonium salt, triphenylmethane Copy blue PR of derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (both manufactured by Hoechst); LRA-901, LR-147 which is a boron complex (manufactured by Nippon Carlit); quinacridone, azo Pigments, other sulfonic acid groups, carboxyl groups, quaternary ammonia And high molecular weight compounds having a functional group such as a salt.

  The charge control agent may be melted and kneaded with the master batch and then dissolved and / or dispersed, or may be added together with the toner components when dissolved and / or dispersed, or the toner particles You may fix to the toner surface after manufacture.

  The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence / absence of the additive, the dispersion method, etc., and cannot be generally specified. For example, for 100 parts by weight of the binder resin, 0.1-10 weight part is preferable and 0.2-5 weight part is more preferable. If the content is less than 0.1 part by weight, the charge controllability may not be obtained. If the content exceeds 10 parts by weight, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced, and development is performed. The electrostatic attraction force with the roller may increase, leading to a decrease in developer fluidity and a decrease in image density.

In the toner of the present invention, an external additive can be added separately from the resin fine particles.
There is no restriction | limiting in particular as an external additive, According to the objective, it can select suitably from well-known things. Examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (eg, zinc stearate, aluminum stearate, etc.); metal oxides (eg, titania, alumina, tin oxide, antimony oxide, etc.), fluoropolymers, and the like. . Among these, hydrophobized silica fine particles, hydrophobized titania fine particles, hydrophobized titanium oxide fine particles, and hydrophobized alumina fine particles are preferable.

Commercially available silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Also manufactured by Nippon Aerosil Co., Ltd.). Moreover, as a commercial item of the said titania microparticles, P-25 (made by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all are made by Titanium Industry Co., Ltd.), TAF-140 (made by Fuji Titanium Industry Co., Ltd.), Examples thereof include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika).
Moreover, as a commercial item of the said hydrophobized titanium oxide microparticles | fine-particles, T-805 (made by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (all are the titanium industrial company make); TAF-500T, TAF- 1500T (all manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (all manufactured by Teika Co., Ltd.), IT-S (manufactured by Ishihara Sangyo Co., Ltd.) and the like.

  The hydrophobized oxide microparticles, hydrophobized silica microparticles, hydrophobized titania microparticles, and hydrophobized alumina microparticles are hydrophilic microparticles such as methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxy. It can be obtained by treating with a silane coupling agent such as silane. Also suitable are silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating inorganic fine particles with silicone oil by applying heat if necessary.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, α-methylstyrene-modified silicone oil, and the like can be used.

  Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.

  The amount of the external additive added is preferably 0.1 to 5% by weight, more preferably 0.3 to 3% by weight, based on the toner. The average particle size of the primary particles of the inorganic fine particles is preferably 100 nm or less, and more preferably 3 to 70 nm. If it is smaller than 3 nm, the inorganic fine particles are buried in the toner, and its function is hardly exhibited effectively. On the other hand, if it is larger than 100 nm, the surface of the electrostatic latent image carrier is not uniformly damaged.

As the external additive, inorganic fine particles or hydrophobic treated inorganic fine particles can be used in combination. The average particle size of the hydrophobized primary particles is preferably 1 to 100 nm, particularly at least 5 to 70 nm inorganic fine particles. It is more preferable to include two types. Further, it is more preferable that at least two types of inorganic fine particles having an average particle diameter of 20 nm or less of the primary particles subjected to the hydrophobization treatment and at least one type of inorganic fine particles of 30 nm or more are included. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

  Examples of the surface treatment agent for the external additive containing the fine oxide particles include silane coupling agents such as dialkyl dihalogenated silane, trialkyl halogenated silane, alkyl trihalogenated silane, and hexaalkyldisilazane, silylating agents, and fluorine. Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and silicone varnishes.

The method for producing the toner of the present invention is preferably a dissolution suspension method from the viewpoint of granulation properties (easiness of particle size distribution control, particle shape control, etc.) using a crystalline resin.
Hereinafter, as an example of the dissolution suspension method, preparation of an aqueous medium phase, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, removal of a solvent, and the like are performed. The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium. The addition amount of the resin particles in the aqueous medium is preferably 0.5 to 10% by weight.

  The oil phase containing the toner material can be prepared by dissolving or dispersing a toner material such as a compound, a colorant, a release agent, a charge control agent, and the polyester resin in a solvent. In the toner material, components other than the colorant and the polyester resin may be added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium, or the oil phase containing the toner material may be mixed in the aqueous medium. When added to the aqueous medium, it may be added to the aqueous medium.

The emulsification or dispersion of the toner material can be performed by dispersing an oil phase containing the toner material in an aqueous medium.
Dispersion can be performed using a known disperser, and examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Can be mentioned. A high-speed shearing disperser is preferable because the particle diameter of the dispersion can be controlled to 2 to 20 μm. When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch method, the dispersion time is preferably from 0.1 to 5 minutes, and the dispersion temperature is preferably from 0 to 150 ° C, more preferably from 40 to 98 ° C under pressure. In general, the dispersion temperature is easier to disperse at a higher temperature.

  The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 to 2000 parts by weight and more preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the toner material. If the amount used is less than 50 parts by weight, the dispersion state of the toner material may be deteriorated, and toner base particles having a predetermined particle size may not be obtained. If the amount used exceeds 2000 parts by weight, the production cost may increase.

  In the step of emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoints of stabilizing the dispersion such as oil droplets so as to obtain a desired shape and sharpening the particle size distribution. The dispersant can be appropriately selected according to the purpose, and examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids, and surfactants are preferred. These may be used alone or in combination of two or more.

As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.
Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, and the like, and those having a fluoroalkyl group are preferably used. As an anionic surfactant having a fluoroalkyl group, a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6-C11) oxy ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid or Its metal salt, perfluoroalkylcarboxylic acid (C7 to C13) or its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid or its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctance Examples include sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like.

  Commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Fluorard FC-93, FC-95, FC-98, FC-129. (Above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F- 833 (above, manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), Footage 100, 150 (above, manufactured by Neos).

  As cationic surfactants, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts And quaternary ammonium salt type surfactants such as alkylisoquinolinium salts and benzethonium chloride. In addition, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, Examples include pyridinium salts and imidazolinium salts.

  Commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Fluorad FC-135 (Sumitomo 3M Co.); -824 (Dainippon Ink Co., Ltd.); Xtop EF-132 (Toke Products Co., Ltd.);

  Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.

  Specific examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

  Specific examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

  Polymeric protective colloids include monomers having a carboxyl group, alkyl (meth) acrylate monomers having a hydroxyl group, vinyl ether monomers, vinyl carboxylate monomers, amide monomers, acid chloride monomers, nitrogen atoms or heterocyclic rings thereof. Examples thereof include homopolymers or copolymers obtained by polymerizing monomers and the like, polyoxyethylene resins, and celluloses. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

  Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like.

Specific examples of the (meth) acrylic monomer containing a hydroxyl group include acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, acrylic Acid-γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin mono Examples include acrylate and glycerin monomethacrylate.
Specific examples of the vinyl ether monomer include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like.
Specific examples of the vinyl carboxylate monomer include vinyl acetate, vinyl propionate, vinyl butyrate and the like.

  Specific examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. Specific examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride. Specific examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine.

  Specific examples of the polyoxyethylene resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Examples include polyoxyethylene lauryl phenyl ether, polyoxyethylene phenyl stearate, and polyoxyethylene pelargonate phenyl.

  Specific examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

  As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets. When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, or classification may be performed after drying.

The toner obtained as described above is mixed with the external additive to form a final toner.
At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles. As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned. As an apparatus used for this method, an ong mill (manufactured by Hosokawa Micron Corporation), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, a hybridization system (manufactured by Nara Machinery) Examples include a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), an automatic mortar, and the like.

  The developer of the present invention contains at least the toner, and other components appropriately selected such as a carrier. As the developer, either a one-component developer or a two-component developer is preferably used.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In the examples, “parts” is “parts by weight” unless otherwise specified. However, Examples 3, 8, and 11 are read as reference examples.

<Example of resin synthesis>
(Synthesis example 1 of amorphous polyester resin)
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 67 parts of a 2-mole addition product of ethylene oxide of bisphenol A, 84 parts of a 3-mole addition product of propion oxide of bisphenol A, 270 parts of terephthalic acid, 120 parts of isophthalic acid, and dibutyltin 2 parts of oxide was added and reacted at 270 ° C. under normal pressure for 8 hours. Next, it was made to react for 7 hours under the reduced pressure of 10-15 mmHg, and the polyester resin was synthesize | combined.
The obtained polyester resin R1 had an acid value of 19.8 mgKOH / g and a weight average molecular weight Mw of 4200.

(Production of crystalline resin C1)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet, 241 parts of sebacic acid, 55 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 75 parts was added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 3 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 1200.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts of ethyl acetate, 40 parts of hexamethylene diisocyanate (HDI) and 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C1 shown in Table 1.

(Production of crystalline resin C2)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet, 241 parts of sebacic acid, 55 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 75 parts was added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 5 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C2 shown in Table 1.

(Production of crystalline resin C3)
1. 241 parts of sebacic acid, 55 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. 25 parts were added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C. and reacting for 4 hours while distilling off generated water and 1,4-butanediol in a nitrogen stream, Mw (weight average) was further reduced under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the molecular weight reached about 3000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 250 parts of ethyl acetate, 15 parts of hexamethylene diisocyanate (HDI) and 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C3 shown in Table 1.

(Production of crystalline resin C4)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 25 parts were added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C. and reacting for 4 hours while distilling off generated water and 1,4-butanediol in a nitrogen stream, Mw (weight average) was further reduced under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 5 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C4 shown in Table 1.

(Production of crystalline resin C5)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 25 parts were added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C. and reacting for 4 hours while distilling off generated water and 1,4-butanediol in a nitrogen stream, Mw (weight average) was further reduced under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), and 7 parts of maleic anhydride were added. The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C5 shown in Table 1.

(Production of crystalline resin C6)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 25 parts were added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C. and reacting for 6 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, Mw (weight average) was further reduced under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred to a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI) and 50 parts of maleic anhydride were added. In addition, the reaction was carried out at 80 ° C. for 10 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C6 shown in Table 1.

(Production of crystalline resin C7)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 25 parts were added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C. and reacting for 6 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, Mw (weight average) was further reduced under a reduced pressure of 5 to 20 mmHg. The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI) and 50 parts of maleic anhydride were added. The reaction was carried out at 80 ° C. for 10 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C7 shown in Table 1.

(Production of crystalline resin C8)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 25 parts were added and reacted for 1 hour while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 175 ° C., the reaction was carried out for 3 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 600.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C8 shown in Table 1.

(Production of crystalline resin C9)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 5 parts were added and reacted for 1 hour while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 175 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream, and then Mw (weight average) under reduced pressure of 5 to 20 mmHg. The reaction was continued until the molecular weight reached about 750.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C9 shown in Table 1.

(Production of crystalline resin C10)
1. 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. 5 parts were added and reacted for 6 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 235 ° C., the reaction was carried out for 10 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under a reduced pressure of 5 to 20 mmHg, Mw (weight average The reaction was continued until the molecular weight reached about 7000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 8 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C10 shown in Table 1.

(Production of crystalline resin C11)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and 3 parts of titanium dihydroxybis (triethanolamate) as a condensation catalyst Was allowed to react for 6 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 235 ° C., the reaction was carried out for 11 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 8000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 8 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C11 shown in Table 1.

(Production of crystalline resin C12)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 200 parts of sebacic acid, 135 parts of adipic acid, 354 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 0. 75 parts was added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 5 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C12 shown in Table 1.

(Production of crystalline resin C13)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 220 parts of sebacic acid, 95 parts of adipic acid, 354 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 75 parts was added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 5 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C13 shown in Table 1.

(Production of crystalline resin C14)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 251 parts of sebacic acid, 35 parts of adipic acid, 274 parts of 1,4-hexanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 25 parts were added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 5 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C14 shown in Table 1.

(Production of crystalline resin C15)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 261 parts of sebacic acid, 15 parts of adipic acid, 274 parts of 1,4-hexanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 25 parts were added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 5 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 12 parts of hexamethylene diisocyanate (HDI), 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C15 shown in Table 1.

(Production of crystalline resin C16)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet, 241 parts of sebacic acid, 55 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 75 parts was added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 5 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, 250 parts of ethyl acetate and 12 parts of hexamethylene diisocyanate (HDI) were added, and the mixture was heated at 80 ° C. under a nitrogen stream. The reaction was allowed for 5 hours. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C16 shown in Table 1.

(Production of crystalline resin C17)
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet, 241 parts of sebacic acid, 55 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 75 parts was added and reacted for 4 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 2 hours while distilling off the water and 1,4-butanediol produced under a nitrogen stream, and under a reduced pressure of 5 to 20 mmHg, Mw (weight average The reaction was continued until the molecular weight reached about 1000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, and 250 parts of ethyl acetate, 50 parts of hexamethylene diisocyanate (HDI) and 25 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C17 shown in Table 1.

(Production of crystalline resin C18)
2. 231 parts of sebacic acid, 65 parts of adipic acid, 314 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst in a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet. 5 parts were added and reacted for 6 hours while distilling off the water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 235 ° C., the reaction was carried out for 11 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 8000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 250 parts of ethyl acetate, 15 parts of hexamethylene diisocyanate (HDI), 6 parts of maleic anhydride were added, The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C18 shown in Table 1.

(Production of crystalline resin C19)
1. In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 200 parts of sebacic acid, 135 parts of adipic acid, 354 parts of 1,4-butanediol and titanium dihydroxybis (triethanolaminate) as a condensation catalyst 5 parts were added and reacted for 4 hours while distilling off water produced at 180 ° C. under a nitrogen stream. Next, while gradually raising the temperature to 225 ° C., the reaction was carried out for 5 hours while distilling off the generated water and 1,4-butanediol in a nitrogen stream, and then under reduced pressure of 5 to 20 mmHg, the Mw (weight average The reaction was continued until the molecular weight reached about 4000.
218 parts of the obtained crystalline resin was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 250 parts of ethyl acetate, 15 parts of hexamethylene diisocyanate (HDI) and 10 parts of maleic anhydride were added. The reaction was carried out at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain a crystalline resin C19 shown in Table 1.
The crystalline resin is shown in Table 1.

<Synthesis of ketimine compound (active hydrogen group-containing compound)>
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (active hydrogen group-containing compound).
The amine value of the obtained ketimine compound was 418.

(Preparation of monoester waxes W1 to W13)
A four-necked flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator was charged with 1740 parts by weight of benzene, 1300 parts by weight of a long-chain alkyl carboxylic acid component, 1200 parts by weight of a long-chain alkyl alcohol component, and p-toluenesulfonic acid. 120 parts by weight was added, and the mixture was sufficiently stirred and dissolved. After refluxing for 5 hours, the water separator valve was opened and azeotropic distillation was performed. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain a monoester wax.
Each ester wax was prepared as a monoester wax having the characteristics shown in Table 2 by changing the type and amount of the long-chain alkyl carboxylic acid and the type and amount of the long-chain alkyl alcohol.

[Manufacture of colorant masterbatch]
After mixing 100 parts of amorphous resin A and 100 parts of cyan pigment (CI Pigment blue 15: 3) with a Henschel mixer (Mitsui Mining Co., Ltd.) at 1000 rpm for 5 minutes, an open roll kneader (Mitsui Mine) was used. And 2 mm large pigment dispersion powder was prepared with a rotoplex pulverizer to prepare a master batch.

[Production of Wax Dispersion 1]
Add 20 parts of wax W1 shown in Table 2, 80 parts of amorphous resin A and 120 parts of ethyl acetate, heat to 78 ° C. to dissolve sufficiently, cool to 30 ° C. with stirring for 1 hour, and then further Ultravisco Using a mill (manufactured by Imex), heating to 40 ° C., liquid feeding speed 1.0 Kg / hr, disk peripheral speed: 10 m / sec, 0.5 mm zirconia bead filling volume 80 volume%, conditions of 6 passes And a wax dispersion 1 was prepared.

<Example of toner production>
[Example 1: Production of toner 1]
In a container equipped with a thermometer and a stirrer, 20 parts of crystalline resin C1 and 24 parts of ethyl acetate are placed and heated to a temperature equal to or higher than the melting point of the resin to dissolve well, and a 50% ethyl acetate solution of amorphous resin A is added to 102 parts. 66 parts of [Wax Dispersion 1] and 10 parts of the colorant master batch were added and stirred at 50 ° C. with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 10,000 rpm to uniformly dissolve and disperse. To obtain [Oil Phase 1]. The temperature of [Oil Phase 1] was maintained within 50 ° C., and was used within 5 hours from preparation so as not to crystallize.
Next, in another container set with a stirrer and a thermometer, 90 parts of ion exchange water, 3 parts of a 5% aqueous solution of polyoxyethylene lauryl ether type nonionic surfactant (NL450, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), And 10 parts of ethyl acetate were mixed and stirred at 40 ° C. to prepare an aqueous phase solution, and 50 parts of [Oil Phase 1] maintained at 50 ° C. was added, and the temperature was maintained at 50 ° C., and a TK homomixer (Special Machine Industries, Ltd.) was added. Manufactured for 1 minute at a rotational speed of 13,000 rpm to obtain [Slurry 1].
Next, 100 parts of [Composite Particle Slurry 1] of the obtained toner base particles was filtered under reduced pressure, and then the following washing treatments (1) to (4) were performed.
(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filtered.
(2) 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (rotation speed: 6,000 rpm for 10 minutes), and then filtered under reduced pressure.
(3) 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 6,000 rpm for 5 minutes), and then filtered.
(4) Add 300 parts of ion exchanged water to the filter cake of (3) above, mix with a TK homomixer (5 minutes at a rotation speed of 6,000 rpm), and then filter twice to perform [Filter cake 1]. Obtained.
The obtained [Filter cake 1] was dried at 45 ° C. for 48 hours by a circulating dryer. Thereafter, the mixture was sieved with a mesh having an opening of 75 μm to produce [Toner Base Particles 1].
Next, 1.0 part of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) is mixed with 100 parts of the obtained [toner base particle 1] using a Henschel mixer to obtain a volume average particle diameter of 5. 6 μm of [Toner 1] was produced.

[Example 2: Production of toner 2]
Toner 2 was prepared in the same manner as toner 1 except that C2 was used as the crystalline resin.

[Example 3: Production of toner 3]
Toner 3 was produced in the same manner as toner 1 except that C3 was used as the crystalline resin.

[Example 4: Production of toner 4]
Toner 4 was produced in the same manner as toner 2, except that 35 parts by weight of crystalline resin C2 and 72 parts by weight of a 50% solution of amorphous resin A were used.

[Example 5: Production of toner 5]
Toner 5 was produced in the same manner as toner 2 except that 30 parts by weight of crystalline resin C2 and 82 parts by weight of a 50% solution of amorphous resin A were used.

[Example 6: Production of toner 6]
Toner 6 was produced in the same manner as toner 2 except that 5 parts by weight of crystalline resin C2 and 132 parts by weight of a 50% solution of amorphous resin A were used.

[Example 7: Production of toner 7]
Toner 7 was produced in the same manner as Toner 2, except that 4 parts by weight of crystalline resin C2 and 134 parts by weight of a 50% solution of amorphous resin A were used.

[Example 8: Production of toner 8]
Toner 8 was produced in the same manner as toner 1 except that C4 was used as the crystalline resin.

[Example 9: Production of toner 9]
A toner 9 was produced in the same manner as the toner 1 except that C5 was used as the crystalline resin.

[Example 10: Production of toner 10]
Toner 10 was prepared in the same manner as toner 1 except that C6 was used as the crystalline resin.

[Example 11: Production of toner 11]
Toner 11 was prepared in the same manner as toner 1 except that C7 was used as the crystalline resin.

[Example 12: Production of toner 12]
Toner 12 was prepared in the same manner as toner 1 except that C8 was used as the crystalline resin.

[Example 13: Production of toner 13]
Toner 13 was produced in the same manner as toner 1 except that C9 was used as the crystalline resin.

[Example 14: Production of toner 14]
A toner 14 was produced in the same manner as the toner 1 except that C10 was used as the crystalline resin.

[Example 15: Production of toner 15]
A toner 15 was produced in the same manner as the toner 1 except that C11 was used as the crystalline resin.

[Example 16: Production of toner 16]
Toner 16 was produced in the same manner as toner 1 except that C12 was used as the crystalline resin.

[Example 17: Production of toner 17]
Toner 17 was produced in the same manner as toner 1 except that C13 was used as the crystalline resin.

[Example 18: Production of toner 18]
A toner 18 was produced in the same manner as the toner 1 except that C14 was used as the crystalline resin.

[Example 19: Production of toner 19]
A toner 19 was produced in the same manner as the toner 1 except that C15 was used as the crystalline resin.

[Example 20: Production of toner 20]
[Production of Wax Dispersion 2]
A wax dispersion 2 was produced in the same manner as the wax dispersion 1 except that the wax was paraffin wax (HNP-9: manufactured by Nippon Seiki Co., Ltd.).
A toner 20 was produced in the same manner as the toner 2 except that the wax dispersion 2 was used instead of the wax dispersion 1.

[Example 21: Production of toner 21]
Toner 21 was produced in the same manner as toner 2 except that 134 parts by weight of 50% ethyl acetate solution of amorphous resin A and 22 parts by weight of wax dispersion 1 were used.

[Example 22: Production of toner 22]
Toner 22 was produced in the same manner as toner 2, except that 118 parts by weight of 50% ethyl acetate solution of amorphous resin A and 44 parts by weight of wax dispersion 1 were used.

[Example 23: Production of toner 23]
Toner 23 was produced in the same manner as toner 2 except that 86 parts by weight of 50% ethyl acetate solution of amorphous resin A and 88 parts by weight of wax dispersion 1 were used.

[Example 24: Production of toner 24]
Toner 24 was produced in the same manner as toner 2, except that 54 parts by weight of 50% ethyl acetate solution of amorphous resin A and 132 parts by weight of wax dispersion 1 were used.

[Example 25: Production of toner 25]
[Production of Wax Dispersion 3]
A wax dispersion 3 was prepared in the same manner as the wax dispersion 1 except that the monoester wax W2 was used.
A toner 25 was produced in the same manner as the toner 2 except that the wax dispersion 3 was used instead of the wax dispersion 1.

[Example 26: Production of toner 26]
[Production of Wax Dispersion 4]
A wax dispersion 4 was prepared in the same manner as the wax dispersion 1 except that the monoester wax W3 was used.
A toner 26 was produced in the same manner as the toner 2 except that the wax dispersion 4 was used instead of the wax dispersion 1.

[Example 27: Production of toner 27]
[Production of wax dispersion 5]
A wax dispersion 5 was prepared in the same manner as the wax dispersion 1 except that W4 was used.
A toner 27 was produced in the same manner as the toner 2 except that the wax dispersion 5 was used instead of the wax dispersion 1.

[Example 28: Production of toner 28]
[Production of Wax Dispersion 6]
A wax dispersion 6 was prepared in the same manner as the wax dispersion 1 except that W5 was used.
A toner 28 was produced in the same manner as the toner 2 except that the wax dispersion 6 was used instead of the wax dispersion 1.

[Example 29: Production of toner 29]
[Production of Wax Dispersion 7]
A wax dispersion 7 was prepared in the same manner as the wax dispersion 1 except that W6 was used.
A toner 29 was produced in the same manner as the toner 2 except that the wax dispersion 7 was used instead of the wax dispersion 1.

[Example 30: Production of toner 30]
[Production of Wax Dispersion 8]
A wax dispersion 8 was prepared in the same manner as the wax dispersion 1 except that W7 was used.
A toner 30 was produced in the same manner as the toner 2 except that the wax dispersion 8 was used instead of the wax dispersion 1.

[Example 31: Production of toner 31]
[Production of Wax Dispersion 9]
A wax dispersion 9 was prepared in the same manner as the wax dispersion 1 except that W8 was used.
A toner 31 was produced in the same manner as the toner 2 except that the wax dispersion 9 was used instead of the wax dispersion 1.

[Example 32: Production of toner 32]
[Production of Wax Dispersion 10]
A wax dispersion 10 was prepared in the same manner as the wax dispersion 1 except that W9 was used.
A toner 32 was produced in the same manner as the toner 2 except that the wax dispersion 10 was used instead of the wax dispersion 1.

[Example 33: Production of toner 33]
[Production of Wax Dispersion 11]
A wax dispersion 11 was prepared in the same manner as the wax dispersion 1 except that W10 was used.
A toner 33 was produced in the same manner as the toner 2 except that the wax dispersion 11 was used instead of the wax dispersion 1.

[Example 34: Production of toner 34]
[Production of Wax Dispersion 12]
A wax dispersion 12 was prepared in the same manner as the wax dispersion 1 except that W11 was used.
A toner 34 was produced in the same manner as the toner 2 except that the wax dispersion 12 was used instead of the wax dispersion 1.

[Example 35: Production of toner 35]
[Production of Wax Dispersion 13]
A wax dispersion 13 was prepared in the same manner as the wax dispersion 1 except that W12 was used.
A toner 35 was produced in the same manner as the toner 2 except that the wax dispersion 13 was used instead of the wax dispersion 1.

[Example 36: Production of toner 36]
[Production of Wax Dispersion 14]
A wax dispersion 14 was prepared in the same manner as the wax dispersion 1 except that W13 was used.
A toner 36 was produced in the same manner as the toner 2 except that the wax dispersion 14 was used instead of the wax dispersion 1.

[Comparative Example 1: Production of Comparative Toner 1]
Comparative toner 1 was prepared in the same manner as toner 1 except that C16 was used as the crystalline resin.

[Comparative Example 2: Production of Comparative Toner 2]
Comparative toner 2 was prepared in the same manner as toner 1 except that C17 was used as the crystalline resin.

[Comparative Example 3: Production of Comparative Toner 3]
Comparative toner 3 was prepared in the same manner as toner 1 except that C18 was used as the crystalline resin.

[Comparative Example 4: Production of Comparative Toner 4]
Comparative toner 4 was prepared in the same manner as toner 1 except that C19 was used as the crystalline resin.
Table 3 summarizes the prescriptions of the toners of Examples and Comparative Examples.

[Fixability evaluation]
(Low-temperature fixability evaluation)
The two-component developer obtained above was used to produce an unfixed image with an adhesion amount of 4.0 g / m ^{2 using} a copying machine manufactured by Ricoh Co. (Imagio Neo C355), and then a copying machine manufactured by Ricoh Co., Ltd. (Imagio Neo C355) Fixing device (oilless system) modified by using an external fixing machine that can freely set the roller temperature, fixing the paper feed at 120 mm / sec and increasing the temperature from 100 ° C to 140 ° C in 1 ° C increments changed. At this time, the offset phenomenon in which the image was not fully melted and the image was retransferred to the non-image portion was observed on the fixing roller and the paper, and the temperature at which the image was not retransferred was defined as the low-temperature non-offset temperature. At this time, a non-offset temperature of less than 110 ° C. was marked with ◎, 110 ° C. or more and less than 120 ° C. with ○, 120 ° C. or more and less than 130 ° C. with Δ, and 130 ° C. or more with x.
The evaluation results are shown in Table 4.

(High temperature offset evaluation)
Similarly to the above, an unfixed image was prepared, and the temperature was increased from 170 ° C. by 1 ° C. using an external fixing machine under the same conditions. At this time, the offset phenomenon in which the image was not sufficiently melted and the image was retransferred to the non-image area was observed on the fixing roller and the paper, and the temperature at which the image was not retransferred was defined as the high temperature non-offset temperature. At this time, the non-offset temperature was 200 ° C. or higher, ◎, 185 ° C. or higher and lower than 195 ° C., 175 ° C. or higher and lower than 185 ° C., and 170 ° C. or lower.
The evaluation results are shown in Table 4.

(Preservation evaluation)
10 g of the above toner was weighed into a 200 CC screw vial and allowed to stand in a 35 ° C./80% environment for 1 month to obtain an evaluation toner. The toner for evaluation was sprayed on an opening of 75 μm and shaken with a sieve for 1 minute, and the state of the toner remaining on the sieve was observed.
The case where a large amount of the aggregated toner was scattered was indicated as x, the case where it was slightly observed as Δ, and the case where it was not observed at all as ○.
The evaluation results are shown in Table 4.

(Evaluation of back dirt after fixing)
Toners 1 to 36 and Comparative toners 1 to 4 produced above and a ferrite carrier having a particle diameter of 50 μm are added to a toner concentration of 8%, and stirred for 1 hour with a Nauta mixer (manufactured by Hosokawa Micron). A developer for evaluation was prepared. This developer is mounted on an image forming apparatus RICOH C901 (manufactured by Ricoh Co., Ltd.) having a two-component developing device, and 50% images are continuously printed on 2000 sheets in a 35 ° C. and 80% environment, and the printed matter is stored on a paper discharge tray. I left it.
After printing 2000 sheets, 2000 printed materials were taken out, and it was confirmed whether each sheet was melted and adhered to the upper paper. If the number of adhering printed materials was 5 or less out of 2000 sheets, ◎ if 5 to 20 sheets, ◯, 20 to 50 sheets, △, if more than 50 sheets, X.
The evaluation results are shown in Table 4.

(Charger dirt evaluation)
White stripe evaluation was performed as charger dirt evaluation. The white streak evaluation was performed by printing three continuous images in A3 length after printing 2000 sheets of the back stain after fixing.
◎ No streak observed ◎ Three out of three streaks observed ◯ Three or all streaks observed or two or more streaks △ Three In each case, two or more streaks were observed as x.
The evaluation results are shown in Table 4.

As can be seen from the above results, the toners of the examples had good results, although their levels differed.
On the other hand, since the toner of Comparative Example 1 does not have a urethane bond, sufficient results with respect to the high temperature offset property were not obtained. In the toner of Comparative Example 2, in the diffraction spectrum obtained by the X-ray diffractometer, the integrated intensity of the spectrum derived from the crystal structure is (C), and the integrated intensity of the spectrum derived from the amorphous structure is (A). The ratio (C) / (A) is smaller than 0.04. That is, since the crystallinity was low, sufficient results were not obtained in the low-temperature fixability. In the toner of Comparative Example 3, in the diffraction spectrum obtained by the X-ray diffractometer, the integrated intensity of the spectrum derived from the crystal structure is (C), and the integrated intensity of the spectrum derived from the amorphous structure is (A). The ratio (C) / (A) is greater than 0.15. That is, since the ratio of the crystalline resin is high and it takes time to recrystallize after heating, sufficient results were not obtained with respect to image back-staining after fixing. In the toner of Comparative Example 4, in the diffraction spectrum obtained by the X-ray diffractometer after heating, the integrated intensity of the spectrum derived from the crystal structure is (C), and the integrated intensity of the spectrum derived from the amorphous structure is (A). Since the ratio (C) / (A) at the time was larger than 0.02, there was a crystalline resin that could not be compatible with the amorphous resin, and sufficient results in storage stability were not obtained.

JP 2005-234046 A JP 2013-050578 A JP 2005-227672 A

Claims (10)

In an electrophotographic toner containing at least a binder resin and a release agent,
The binder resin includes a crystalline polyester resin having a urethane group and / or a urea group bond,
The acid value of the crystalline polyester resin having a urethane group and / or urea group bond is 5 to 60 mgKOH / g,
In the diffraction spectrum obtained by the X-ray diffractometer of the toner, the ratio before heating when the integrated intensity of the spectrum derived from the crystal structure is (C) and the integrated intensity of the spectrum derived from the amorphous structure is (A) (C) / (A) is 0.05 or more and 0.14 or less,
An electrophotographic toner, wherein (C) / (A) after heating and cooling the toner to 120 ° C. is 0.02 or less. The urethane Ri groups and / or acid number from 5 to 27.6 mg KOH / g der of the crystalline polyester resin having a urea group bonds, the proportion of pre-heating (C) / (A) is 0.05 or more 0. the toner for electrophotography according to claim 1, 12 or less, wherein the der Rukoto.   3. The toner for electrophotography according to claim 1, wherein the crystalline polyester resin having a urethane group and / or urea group bond is contained in 5 to 30 parts by weight in 100 parts by weight of the toner.   4. The toner for electrophotography according to claim 1, wherein the polyester resin having crystallinity having a urethane group and / or urea group bond has a weight average molecular weight of 3000 to 30000.   The electrophotographic toner according to claim 1, wherein the crystalline polyester resin having a urethane group and / or urea group bond has a melting point of 50 ° C. to 70 ° C. 6.   6. The electrophotographic toner according to claim 1, wherein the release agent is a monoester wax.   7. The electrophotographic toner according to claim 1, wherein the amount of the releasing agent added is 3 to 10 parts by weight per 100 parts by weight of the toner.   The electrophotographic toner according to claim 6 or 7, wherein the monoester wax has a melting point of 55 to 85 ° C.   The toner for electrophotography according to any one of claims 6 to 8, wherein the C44 component in the monoester wax contains 45% to 55%.   The electrophotographic toner according to any one of claims 6 to 9, wherein the monoester wax has a C38 or less component of 4.0% or less.

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