JP2019032492A - Toner and method for manufacturing toner - Google Patents

Abstract

To provide a toner that achieves both low-temperature fixability and storage stability and has good chargeability even in a high-temperature and high-humidity environment.SOLUTION: A toner contains a colorant, a binder resin, and a low molecular weight crystalline compound. The low molecular weight crystalline compound is an ether compound having a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms, inclusive and an aromatic hydrocarbon skeleton; the SP value of the binder resin (SP1) and the SP value of the crystalline compound (SP2) satisfy the following formula: 0(cal/mol)≤|SP1-SP2|≤3(cal/mol).SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic image forming method and a toner manufacturing method.

  In recent years, with increasing demands for energy saving in image formation, efforts have been made to lower the toner fixing temperature. As one of them, it has been proposed to further lower the fixing temperature by using polyester having a low softening temperature. However, since the softening temperature is low, toner may be fused with each other in a stationary state during storage or transportation, and blocking may occur.

  Therefore, as a means for achieving both blocking resistance and low-temperature fixability, a technique using a crystalline resin having sharp melt properties in which the viscosity greatly decreases when the melting point is exceeded has been proposed. However, when a crystalline polyester, which is a crystalline resin, is used alone as a binder resin for a toner, the toner charge gradually escapes after frictional charging due to the low electrical resistance of the crystalline polyester. was there.

Therefore, a toner has been proposed in which the amount of crystalline polyester added is reduced and an amorphous resin having a high compatibility with the crystalline polyester is mixed (Patent Document 1).
In addition, a technique using a low molecular crystalline compound containing a polar functional group such as an alcohol compound, an ester compound, an amide compound or the like having a long-chain hydrocarbon skeleton having 16 or more carbon atoms as one having the same action as a crystalline polyester Has been proposed (Patent Document 1).
As means for achieving both low-temperature fixability and chargeability, a crystalline polyether having a long-chain hydrocarbon skeleton having 16 or more carbon atoms in the side chain has been proposed (Patent Document 2).

JP 2008-28184 A JP 2013-68910 A

  As in Patent Document 1, in the case of a toner containing an amorphous resin together with a crystalline polyester as a binder resin, a combination of highly compatible resins can provide a good sharp melt property, but can be charged and heat resistant. In some cases, the storage stability was not sufficient. When the toner is manufactured, it is present in the toner in a state where the amorphous resin and the crystalline polyester are in a compatible state when heated and melted to a temperature higher than the melting point of the crystalline polyester, or through a dissolution step with a solvent. This is because plasticization of the conductive resin (reduction in glass transition temperature) is induced.

  On the other hand, in the case of a toner using a mixture of a crystalline polyester and an amorphous resin having a low compatibility, the toner is heated and melted at a temperature higher than the melting point of the crystalline polyester, or after a dissolution process using a solvent. The amorphous resin and the crystalline polyester are phase-separated. And since the matrix-domain structure corresponding to the compatibility of the resin is spontaneously formed, the plasticization of the amorphous resin (reduction in the glass transition temperature) is not induced, and the chargeability and heat-resistant storage stability are improved. However, the low-temperature fixability was not sufficient due to the low compatibility.

  That is, in the case of a toner containing a conventional crystalline polyester and an amorphous resin, the compatibility contrast between the crystalline polyester and the amorphous resin before and after fixing (the compatibility between the high temperature environment and the low temperature environment). It is difficult to make a difference. Therefore, the compatibility under a high temperature environment (compatibility during fixing) and the compatibility under a low temperature environment (compatibility in toner particles before fixing) are correlated. That is, when the low-temperature fixability is good, the above-mentioned compatibilization causes insufficient chargeability and storage stability. Conversely, when the low-temperature fixability is not sufficient, the above-described phase separation causes charge. The trade-off relationship is that the stability and storage stability are improved. For this reason, it has been difficult to achieve both low-temperature fixability, chargeability, and storage stability at a high level.

  A low molecular crystalline compound containing a polar functional group such as an alcohol compound, an ester compound or an amide compound having a long chain hydrocarbon skeleton having 16 or more carbon atoms is used as a toner instead of the crystalline polyester as in Patent Document 1. The same applies when it is contained. That is, in a high-temperature and high-humidity environment, the charge may gradually escape after frictional charging, and the chargeability in a high-temperature and high-humidity environment is not sufficient. This is due to the fact that the low molecular crystalline compound contains a highly polar functional group in order to enhance the compatibility with the amorphous resin. That is, when the amorphous resin is a resin generally used as a binder resin for toner such as polyester and styrene acrylic resin, the higher the polarity of the functional group, the more the amorphous resin and the low molecular crystallinity described above. Compatibility with the compound in a high temperature environment (compatibility at the time of fixing) increases. For this reason, the low-temperature fixability is good, but there is a trade-off relationship that the chargeability in a high-temperature and high-humidity environment deteriorates due to the high polarity of the functional group.

On the other hand, as in Patent Document 2, a crystalline polyether having a long-chain hydrocarbon skeleton having 16 or more carbon atoms in the side chain is more crystalline than a crystalline polyester having a comparable glass transition temperature. Low polarity. And due to this low polarity, although it has excellent chargeability in a high temperature and high humidity environment, the compatibility with the binder resin in a high temperature environment (compatibility at the time of fixing) is not sufficient, Low temperature fixability was not sufficient.
Accordingly, an object of the present invention is to provide a toner having sharp melt properties, having both low-temperature fixability and storage stability, and having good chargeability even in a high-temperature and high-humidity environment, and a method for producing the same.

As a result of intensive studies, the present inventors have recognized that the following is important.
-For low-temperature fixability, the crystalline compound that serves as a plasticizer and the binder resin must be a highly compatible combination at the time of fixing (in a high temperature environment).
-For storage stability, the crystalline compound and the binder resin form a phase separation structure in the toner state (under a low temperature environment) before fixing.
-For chargeability, the crystalline compound and the binder resin form a phase separation structure in the state of the toner before fixing (under a low temperature environment), and the crystalline compound leaks the charge generated by frictional charging. Do not contain polar functional groups.

In addition, as a result of intensive studies, the present inventors have obtained the following recognition.
The molecular weight of the crystalline compound that becomes a plasticizer during fixing greatly affects the compatibility contrast between the crystalline compound and the binder resin before and after fixing. That is, the smaller the molecular weight of the crystalline compound, the higher the compatibility in a high temperature environment with respect to a binder resin having a low compatibility in a low temperature environment. Further, the crystalline compound contains a combination of a relatively low polarity ether structure and an aromatic hydrocarbon structure to improve the compatibility with the binder resin, thereby maintaining the compatibility with the crystalline state. It is possible to suppress the leakage of charges due to the conductive compound, and the chargeability is further improved.

Therefore, according to one embodiment of the present invention, a toner containing a colorant, a binder resin, and a low molecular crystalline compound,
The low molecular crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton;
There is provided a toner in which the SP value (SP1) of the binder resin and the SP value (SP2) of the low molecular crystalline compound satisfy the following formula.
0 (cal / mol) ≦ | SP1-SP2 | ≦ 3 (cal / mol)

According to another aspect of the invention,
The binder resin fine particle dispersion in which the fine particles of the binder resin are dispersed and the colorant fine particle dispersion in which the fine particles of the colorant are dispersed are mixed to aggregate the binder resin fine particles and the colorant fine particles, thereby forming the core aggregated particles. Forming step,
Composite fine particles containing the binder resin and the low molecular crystalline compound obtained by dissolving the binder resin and the low molecular crystalline compound in an organic solvent and dispersing in water and then removing the organic solvent Attaching to the core agglomerated particles to form core-shell particles, and a fusion step of fusing the core-shell particles by heating to a temperature equal to or higher than the glass transition temperature of the binder resin.
The low molecular crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton;
There is provided a toner production method in which the SP value (SP1) of the binder resin and the SP value (SP2) of the crystalline compound satisfy the following formula.
0 (cal / mol) ≦ | SP1-SP2 | ≦ 3 (cal / mol)

  According to the present invention, it is possible to provide a toner having sharp melt properties, having both low-temperature fixability and storability, and good chargeability even in a high-temperature and high-humidity environment.

First, the low molecular crystalline compound that is a feature of the present invention will be described.
The low molecular crystalline compound contained in the toner of the present invention is a low molecular crystalline compound containing an ether bond, an aromatic hydrocarbon skeleton, and a long chain hydrocarbon skeleton having 12 to 26 carbon atoms. The details of the effect of improving the compatibility between the low-temperature fixability and the chargeability in the toner of the present invention are unknown, but are considered as follows.

First, since the low molecular weight crystalline compound as a plasticizer is a low molecular weight compound having a low molecular weight compared to the conventional crystalline polyester, as described above, the crystalline compound and the binder resin before and after fixing. The compatibility contrast with is easy. Therefore, even if the binder resin and the low molecular crystalline compound are phase-separated in the toner, they are sufficiently compatible during fixing.
Second, the low molecular crystalline compound contains a combination of a relatively low polarity ether structure and an aromatic hydrocarbon structure, thereby increasing the solubility parameter (SP2), and the solubility parameter of the binder resin described later. The difference from (SP1) is reduced. Therefore, it has a low dielectric constant and low hygroscopicity while maintaining good compatibility similar to that of conventional low molecular crystalline compounds containing polar functional groups such as ester groups, carbonyl groups, and hydroxyl groups.

That is, the low molecular crystalline compound contained in the toner of the present invention is a conventional plasticizer because it has low water molecule adsorption and high insulation of the low molecular crystalline compound itself even under high temperature and high humidity. It is considered to have charge retention superior to that of the crystalline compound that has been proposed.
In addition, the charge retention property under high temperature and high humidity of a low molecular crystalline compound can be measured by the following method. 0.01 g of a low molecular crystalline compound is weighed into an aluminum pan and charged to -600 V using a strocolon charging device. Subsequently, the change behavior of the surface potential is measured for 30 minutes using a surface potentiometer (manufactured by Trek Japan Co., Ltd .: model 347) in an atmosphere of a temperature of 30 ° C. and a relative humidity of 80%. The charge retention is calculated by substituting the measurement result into the following formula, and the insulation can be evaluated.
Charge retention (%) after 30 minutes = [surface potential after 30 minutes] / [initial surface potential] × 100

  The charge retention (%) after 30 minutes of the low molecular crystalline compound alone is preferably more than 80%, more preferably more than 90%. The charge retention satisfies the above range because the low molecular crystalline compound contains a chemical structure described later.

  The weight average molecular weight of the low molecular crystalline compound of the present invention is preferably 1500 or less, and more preferably 1000 or less, from the viewpoint of increasing the compatibility contrast between the crystalline compound and the binder resin before and after the fixing. In general, the compatibility when two kinds of compounds are mixed is greatly influenced by the structural affinity (difference in solubility parameter: ΔSP value) of the two kinds of compounds and the molecular weight of each compound. The smaller the molecular weight, the higher the compatibility of the two compounds, but the effect becomes more significant at higher temperature conditions. For this reason, a crystalline polyester having a weight average molecular weight of more than 1500, which has been used as a plasticizer in the past, is less likely to have a compatible contrast between the crystalline compound and the binder resin before and after fixing, and has low-temperature fixability. It is difficult to achieve both chargeability and storage stability. On the other hand, the low molecular crystalline compounds contained in the toner of the present invention are in the above molecular weight range, so that they are incompatible and phase separated at low temperature conditions, and are compatible with each other at high temperature conditions. That is, it is considered that the compatibility contrast between the crystalline compound and the binder resin before and after fixing is increased, so that low-temperature fixing property, charging property and storage property can be compatible.

Moreover, the weight average molecular weight (Mw) of the said low molecular crystalline compound is measured as follows using gel permeation chromatography (GPC).
To o-dichlorobenzene for gel chromatography, special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added so that the concentration becomes 0.10 wt / vol%, and dissolved at room temperature. A low molecular weight crystalline compound and the above-mentioned BHT-added o-dichlorobenzene are placed in a sample bottle and heated above the melting point of the low molecular weight crystalline compound on a hot plate set at 100 ° C. Dissolve. When the low molecular crystalline compound is dissolved, it is put in a preheated filter unit and installed in the main body. The sample that has passed through the filter unit is used as a GPC sample. The sample solution is adjusted so that the concentration is about 0.15% by mass. Using this sample solution, measurement is performed under the following conditions.

Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-H HT 2 series (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatograph (BHT added at 0.10 wt / vol%)
Flow rate: 1.0 mL / min Injection amount: 0.4 mL

  In calculating the molecular weight of the crystalline resin, a molecular weight calibration curve created using a standard polystyrene resin is used. As standard polystyrene resin, the following are mentioned, for example. Product name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation.

The weight average molecular weight (Mw) of the low molecular crystalline compound contained in the toner of the present invention is measured by the above method after isolating the low molecular crystalline compound component from the resin contained in the toner. Examples of the method for isolating the low molecular crystalline compound include the following methods.
The toner of the present invention preferably contains a release agent. When the toner of the present invention contains a release agent, after extracting the release agent from the toner by Soxhlet extraction using a hexane solvent, the obtained extraction residue is further subjected to Soxhlet extraction with an ethyl acetate solvent to obtain low molecular crystallinity. The compound is isolated as a residue. It can be confirmed by NMR spectrum measurement that the molecular structure of the extraction residue is a low molecular crystalline compound.

Further, the crystallinity of the low molecular crystalline compound contained in the toner of the present invention can be judged by the crystallinity measured using the wide-angle X-ray diffraction method, and when the crystallinity is 1% or more. Judged as crystalline compound.
Further, the low molecular crystalline compound contained in the toner of the present invention preferably has a crystallinity of 10% or more, more preferably 20% or more, which is obtained by a wide angle X-ray diffraction method. When the degree of crystallinity is 10% or more, the ratio of the amorphous part does not increase, and the storage stability does not deteriorate.

The crystallinity using the wide angle X-ray diffraction method can be measured under the following conditions.
X-ray diffractometer: D8 ADVANCE made by Bruker AXS
X-ray source: Cu-Kα ray (wavelength: 0.15418 nm)
Output: 40 kV, 40 mA
Slit system: Slit DS, SS = 1 °, RS = 0.2 mm,
Measurement range: 2θ = 5 ° -60 °
Step interval: 0.02 °
Scanning speed: 1 ° / min From the measurement result, the X-ray diffraction profile of the sample is separated into a crystal peak and amorphous scattering, and can be calculated from the area by the following formula.
Crystallinity (%) = IC / (IC + IA) × 100
IC: Sum of respective crystal peak areas IA: Sum of amorphous scattering areas

In the low molecular crystalline compound contained in the toner of the present invention, the SP value (SP1) of the binder resin described later and the SP value (SP2) of the low molecular crystalline compound satisfy the following formula.
0 (cal / mol) ≦ | SP1-SP2 | ≦ 3 (cal / mol)
Here, the SP value is referred to as a solubility parameter, and is a numerical value of how easily each other is soluble in terms of chemical structure. The closer the SP values are, the easier it is to mix with each other and the more compatible. There are various SP value calculation methods. In the present invention, a commonly used Fedors method is used. Specifically, for example, it is described in detail in Polymer Engineering and Science, Vol. 14, pages 147 to 154, and the SP value can be calculated by the following formula.
Formula: SP value = √ (Ev / v) = √ (ΣΔei / ΣΔvi)
(Wherein Ev: evaporation energy (cal / mol), v: molar volume (cm ³ / mol), Δei: evaporation energy of each atom or atomic group, Δvi: molar volume of each atom or atomic group)

When the absolute value of the difference between SP1 and SP2 is greater than 3 (cal / mol), the binder resin and the low molecular crystalline compound are phase-separated even at a high temperature, and are not compatibilized at the time of fixing. It acts as a release agent rather than as a plasticizer that imparts low temperature fixability.
The absolute value of the difference between SP1 and SP2 is preferably 0 (cal / mol) to 2.5 (cal / mol), more preferably 0 (cal / mol) to 2.2 (cal / mol). .

  The difference between SP1 and SP2) is that the monomer structure or monomer composition ratio of the binder resin described later is changed, the number of aromatic hydrocarbons or ether groups contained in the low molecular crystalline compound, or the long chain hydrocarbon It can be controlled by changing the length of the skeleton hydrocarbon.

  The melting point of the low molecular crystalline compound contained in the toner of the present invention is preferably 50 ° C. or higher and 100 ° C. or lower from the viewpoints of low temperature fixability and storage stability. When the melting point is 100 ° C. or lower, low temperature fixing becomes possible. Further, the melting point is preferably 90 ° C. or lower from the viewpoint of lower temperature fixing. On the other hand, when the melting point is 50 ° C. or higher, the storage stability does not deteriorate.

  In addition, the said melting | fusing point can be measured using a scanning scanning calorimeter (DSC). Specifically, 0.01 to 0.02 g of the sample is weighed into an aluminum pan, and calorimetric measurement is performed while heating the sample from room temperature at a heating rate of 10 ° C./min. Then, from the obtained DSC curve, the peak temperature of the endothermic peak is defined as the melting point. Further, the melting point of the low molecular crystalline compound present in the toner can be measured by the same method. At that time, the melting point due to the release agent present in the toner may be observed. The melting point of the release agent and the melting point of the low molecular weight crystalline compound are determined by extracting the release agent from the toner by Soxhlet extraction using a hexane solvent, and performing the scanning scanning calorimetry of the release agent alone by the above method, This is done by comparing the obtained melting point with the melting point of the toner.

  In the present invention, the low molecular crystalline compound is preferably contained in the toner in an amount of 10% by mass to 40% by mass. By including 10% by mass or more of the low molecular crystalline compound in the toner, the fixing temperature can be lowered at a high level. When the content is 40% by mass or less, the low molecular crystalline compound is not exposed on the toner surface.

The low molecular crystalline compound contained in the toner of the present invention is an ether compound having an aromatic hydrocarbon skeleton and a long-chain hydrocarbon skeleton. A low molecular crystalline ether compound obtained by a nucleophilic substitution reaction between a halogenated aromatic hydrocarbon and a higher alcohol as described below is preferred.
-Halogenated aromatic hydrocarbons having one or more halogen groups such as chloro and bromo groups.
A higher alcohol having a linear or branched long-chain hydrocarbon skeleton having 12 or more carbon atoms, preferably 14 to 30, more preferably 14 to 22.

  The nucleophilic substitution reaction for obtaining an ether compound having an aromatic hydrocarbon skeleton and a long-chain hydrocarbon skeleton is not particularly limited. For example, a halogenated aromatic compound and a higher alcohol are mixed with a basic compound in a suitable solvent. It may be reacted under conditions. Alternatively, an aromatic alcohol compound and a halogenated long chain aliphatic hydrocarbon may be reacted.

  The low molecular crystalline compound contained in the toner of the present invention may be a monoether compound or a polyvalent ether compound such as a diether compound. However, it is preferably a monoether compound because it falls within the melting point range described below and can lower the melting point.

  The aromatic hydrocarbon skeleton contained in the low molecular crystalline compound increases the SP1 of the low molecular crystalline compound and improves the compatibility of the low molecular crystalline compound with the binder resin under high temperature conditions (at the time of fixing). Unlike the polar functional group, the low temperature fixability is improved without deteriorating the chargeability. Among the aromatic hydrocarbon skeletons, a benzene ring structure, a naphthalene ring structure, and a biphenyl ring structure are preferable because they fall within the melting point range described below and can lower the melting point.

  The long-chain hydrocarbon skeleton contained in the low-molecular crystalline compound lowers the SP1 of the low-molecular crystalline compound and improves the phase separation of the low-molecular crystalline compound from the binder resin under low temperature conditions (in the toner). This improves the storage stability and chargeability of the toner by suppressing the plasticization of the binder resin. For example, if the number of carbon atoms in the long-chain hydrocarbon skeleton is too small, the low-molecular crystalline compound is partially solubilized in the binder resin and functions as a plasticizer, so the glass transition temperature of the binder resin Decreases, resulting in a toner having poor storage stability. In addition, even if the number of carbon atoms is the same, if it has a branched structure as compared with a straight chain, the melting point is too low, or it may function as a plasticizer for the binder resin. The long chain hydrocarbon skeleton is preferably linear because the storage stability is deteriorated.

Specific examples of the halogenated aromatic hydrocarbon include the following, but are not limited thereto. Benzene skeleton compounds such as chlorobenzene and bromobenzene, biphenyl skeleton compounds such as 4-chlorobiphenyl and 2-chlorobiphenyl, naphthalene skeleton compounds such as 1-chloronaphthalene and 2-chloronaphthalene.
Moreover, the halogenated aromatic hydrocarbon which has 2 or more halogen groups, such as a chloro group and a bromo group, may be mentioned, for example, Although the following are mentioned, it is not limited to this. 1,1'-dichlorobiphenyl, 2,2'-dichlorobiphenyl, 2,6-dichloronaphthalene, 1,4-dichloronaphthalene and the like.

  Specific examples of the higher alcohol having 12 or more carbon atoms include the following. Dodecyl alcohol (C = 12), pentadecyl alcohol (C = 15), cetyl alcohol (C = 16), heptadecyl alcohol (C = 17), stearyl alcohol (C = 18), nonadecyl alcohol (C = 19) ), Eicosyl alcohol (C = 20), behenyl alcohol (C = 22; 1-docosanol), seryl alcohol (C = 26), mesyl alcohol (C = 30) and the like.

Next, the binder resin in the present invention that is compatible with the low molecular crystalline compound will be described in detail below.
In the present invention, the binder resin is a resin in which the difference between the SP value (SP1) of the binder resin and the SP value (SP2) of the low molecular crystalline compound falls within the above range and is highly compatible with each other. If it is, it is possible to use a known polymer usually used for toner.

Specifically, the following polymers can be used, and two or more of these may be used in combination.
Styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, and homopolymers thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrene copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resins, natural modified phenol resins, natural resin modified maleic resins, acrylic resins , Methacrylic tree , Polyvinyl acetate, silicone resin, amorphous polyester, a crystalline polyester, polyurethane, polyamide, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone - indene resins, and petroleum resins. Among these, amorphous polyesters that can achieve both low-temperature fixability and mechanical strength are preferable because they are excellent in strength even at a low molecular weight.

As the amorphous polyester, a polycondensation product of an alcohol monomer and a carboxylic acid monomer is used.
The following are mentioned as an alcohol monomer. Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, neopentyl glycol, 1,4-butenediol 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, 1,2 , 3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropane Triol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene.

  On the other hand, examples of the carboxylic acid monomer include the following. Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; alkyl group or alkenyl having 6 to 18 carbon atoms Group-substituted succinic acid or anhydride; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

In addition, the following monomers can be used.
Glycerin, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ethers of novolac-type phenol resins; polyhydric carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and anhydrides thereof.

Among them, the following amorphous polyesters are particularly preferable because the difference between the SP value (SP1) of the binder resin and the SP value (SP2) of the low molecular crystalline compound is reduced and compatibility is increased. .
Containing 50 mol% or more of propylene oxide adduct of bisphenol A as a dihydric alcohol monomer component,
Carboxylic acid component consisting of divalent or higher carboxylic acid or acid anhydride thereof, or lower alkyl ester thereof (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. ) As an acid monomer component,
Amorphous polyester obtained by condensation polymerization of these polyester unit components.

  The glass transition temperature of the binder resin of the present invention is preferably 30 ° C. or higher and 80 ° C. or lower. When the glass transition temperature is 30 ° C. or higher, storage stability is good, and a decrease in electrical resistance due to the molecular motion of the resin is not induced in a high-temperature and high-humidity environment, and chargeability is not deteriorated. On the other hand, when the glass transition temperature is 80 ° C. or lower, the fixability is good. The glass transition temperature is more preferably 40 ° C. or more from the viewpoint of storage stability. In addition, the glass transition temperature is more preferably 70 ° C. or less from the viewpoint of fixability.

  In addition, the said glass transition temperature (Tg) is measured using DSC (Mettler Toledo Co., Ltd. product: DSC822 / EK90). Specifically, 0.01 to 0.02 g of the sample was weighed in an aluminum pan, heated to 200 ° C., and the sample cooled from the temperature to −100 ° C. at a temperature decreasing rate of 10 ° C./min was heated to 10 ° C. Calorimetry is performed while raising the temperature at a rate of ° C / min. Next, from the obtained DSC curve, the temperature at the intersection of a straight line obtained by extending the base line on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the stepped change portion of the glass transition becomes maximum. The so-called extrapolated glass transition start temperature is defined as the glass transition temperature.

  In the present invention, the softening temperature (Tm) of the binder resin is preferably 70 ° C. or higher and 150 ° C. or lower, more preferably 80 ° C. or higher and 140 ° C. or lower, and 80 ° C. or higher and 130 ° C. or lower. Further preferred. If Tm is within the above temperature range, both anti-blocking and anti-offset properties can be achieved, and further, the toner melt component can be soaked into the paper at the time of fixing at a high temperature. Surface smoothness is obtained.

In the present invention, the measurement of the softening temperature of the binder resin was performed using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation). The CFT-500D melts while raising the temperature of the measurement sample filled in the cylinder while applying a constant load with the piston from the top and pushes it out from the narrow tube hole at the bottom of the cylinder. It is an apparatus that can graph a flow curve from temperature (° C.).
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is defined as the softening temperature (Tm).

The melting temperature in the 1/2 method is calculated as follows.
First, ½ of the difference between the piston descent amount (outflow end point, Smax) when the outflow is completed and the piston descent amount (lowest point, Smin) when the outflow starts is obtained. (This is assumed to be X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of piston descent becomes the sum of X and Smin was taken as the melting temperature in the 1/2 method.

The measurement sample was about 1.2 g of binder resin in a 25 ° C. environment using a tablet molding compressor (for example, standard manual Newton press NT-100H, manufactured by NP System Co., Ltd.). Then, compression molding is performed for about 60 seconds, and a cylindrical shape having a diameter of about 8 mm is used. The specific operation in the measurement is performed according to the manual attached to the device.
The measurement conditions of CFT-500D are as follows.

Test mode: Temperature rising start temperature: 60 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 5.0 kgf
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

  The binder resin preferably has an ionic group such as a carboxylic acid group, a sulfonic acid group, or an amino group in the resin skeleton, and more preferably has a carboxylic acid group. Moreover, it is preferable that the acid value of the said binder resin is 3-35 mgKOH / g, and it is more preferable that it is 8-25 mgKOH / g. If the acid value of the binder resin is within the above range, a good charge amount can be obtained in both a high humidity environment and a low humidity environment. The acid value is the number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids, etc. contained in 1 g of a sample. The measuring method is measured according to JIS-K0070.

The toner production method of the present invention is not particularly limited as long as it is a method by which toner particles containing the binder resin, the low molecular crystalline compound, and the colorant can be obtained. Granulation can be performed by a known toner production method such as a pulverization method, a suspension polymerization method, an emulsion aggregation method, or a dissolution suspension method.
Among these, the emulsion aggregation method is preferably used from the viewpoint of easy control of the toner particle size, particle size distribution, and toner shape, and easy core-shell formation as necessary.
Then, the emulsion aggregation method is illustrated below as a manufacturing method of the toner of this invention.

<Emulsion aggregation method>
In the emulsion aggregation method, a fine particle dispersion composed of a toner constituent material, which is sufficiently small with respect to a target particle size, is prepared in advance, and the fine particles are aggregated in an aqueous medium until the toner particle size is reached. This is a method for producing a toner by fusing a binder resin. That is, in the emulsion aggregation method, a dispersion step for producing a fine particle dispersion composed of toner constituent materials, an aggregation step for controlling the particle size until the toner particle size is reached, a fusion step for fusing a binder resin to obtain a toner, And a toner is manufactured through a subsequent cooling step.

<Dispersing process>
-Aqueous dispersion of fine particles of binder resin The aqueous dispersion of fine particles of the binder resin can be prepared by a known method. Known methods include emulsion polymerization, self-emulsification, phase inversion emulsification in which an aqueous medium is added to a resin solution dissolved in an organic solvent, and in an aqueous medium without using an organic solvent. And a forced emulsification method in which the resin is forcibly emulsified by high-temperature treatment. However, it is not limited to these methods.

  Specifically, the binder resin is dissolved in an organic solvent in which these are dissolved, and a surfactant or a basic compound is added. Subsequently, while stirring with a homogenizer or the like, the aqueous medium is slowly added to precipitate resin fine particles. Thereafter, the solvent is removed by heating or decompression to prepare a resin fine particle dispersion. Any organic solvent can be used as long as it can dissolve the binder resin, but it is possible to use an organic solvent that forms a homogeneous phase with water, such as tetrahydrofuran, It is preferable from the viewpoint of suppressing the generation of coarse powder.

  Although it does not specifically limit as surfactant used at the time of the said emulsification, For example, the following are mentioned. Anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type, alkylphenol Nonionic surfactants such as ethylene oxide adducts and polyhydric alcohols. These surfactants may be used alone or in combination of two or more.

  Examples of the basic compound used during emulsification include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more.

  The 50% particle size (d50) of the binder resin fine particles based on the volume distribution is preferably 0.05 to 1.0 μm, more preferably 0.05 to 0.4 μm. When the volume distribution standard 50% particle size (d50) of the binder resin fine particles is 1.0 μm or less, toner particles having a volume standard median diameter of 4.0 to 7.0 μm suitable as toner particles are obtained. It becomes easy. The 50% particle size (d50) based on the volume distribution can be measured by using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).

-Aqueous dispersion liquid of low molecular crystalline compound The aqueous dispersion liquid of the low molecular crystalline compound can be prepared by the following known methods, but is not limited to these methods.
In the aqueous dispersion of the low molecular crystalline compound, the low molecular crystalline compound is heated and dissolved in an organic solvent in which the low molecular crystalline compound is dissolved. The solution is added to an aqueous medium containing a surfactant and heated at a temperature at which the low molecular crystalline compound does not precipitate, and at the same time, an oil phase is obtained using a homogenizer or a pressure discharge type disperser having a strong shearing ability. Is dispersed in the form of particles.
Examples of the homogenizer include “CLEARMIX W-Motion” manufactured by M Technique Co., Ltd. Examples of the pressure discharge type disperser include “Gorin homogenizer” manufactured by Gorin.

  After the oil phase is dispersed in the form of particles, the organic solvent is evaporated and distilled off, whereby fine particles containing the low molecular crystalline compound can be produced. Any organic solvent can be used as long as it can dissolve the low-molecular crystals. However, it is preferable to use an organic solvent that forms an oil phase by phase separation with water, such as toluene, from the viewpoint of suppressing the increase in viscosity at the time of micronization and suppressing the generation of coarse powder.

  The dispersion particle diameter of the low molecular crystalline fine particles in the aqueous dispersion is preferably a volume-based median diameter of 1.0 μm or less, and more preferably 0.5 μm or less. Moreover, it is preferable that coarse particles of 1 μm or more do not exist. When the dispersed particle diameter of the low molecular crystalline fine particles is within the above range, the low molecular crystalline compound is hardly exposed on the toner surface, and filming on the photoreceptor can be suppressed. In addition, the dispersion particle size of the low molecular crystalline fine particles is smaller because the contact area between the low molecular crystalline compound and the binder resin increases as the finer, and as a result, the speed of compatibilization during fixing increases. Is preferred. The dispersed particle size can be measured using a laser diffraction / scattering particle size distribution measuring device (LA-920: manufactured by Horiba, Ltd.).

-Aqueous dispersion of colorant fine particles The aqueous dispersion of colorant fine particles can be prepared by the following known methods, but is not limited to these methods. The colorant preferably has a pigment.
It can be prepared by mixing a colorant, an aqueous medium, and a dispersant with a known mixer such as a stirrer, an emulsifier and a disperser. As the dispersant used here, known ones such as surfactants and polymer dispersants may be used, or those newly synthesized for the present invention may be used. Both the surfactant and the polymer dispersant can be removed in the toner cleaning step described later. However, from the viewpoint of cleaning efficiency, the surfactant is preferable, and among the surfactants, anionic surfactants, non-surfactants are preferable. An ionic surfactant is more preferable. The amount of the dispersant to be mixed is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the colorant, and 2 to 10 parts by mass from the viewpoint of achieving both dispersion stability and toner cleaning efficiency. More preferably. The content of the colorant in the aqueous dispersion of colorant fine particles is not particularly limited, but is preferably 1 to 30% by mass with respect to the total mass of the aqueous dispersion of the colorant. The dispersion particle diameter of the colorant fine particles in the aqueous dispersion is such that the 50% particle diameter (d50) based on volume distribution is 0.5 μm or less from the viewpoint of pigment dispersibility of the finally obtained toner. preferable. For the same reason, the 90% particle size (d90) based on volume distribution is preferably 2 μm or less. The dispersed particle diameter of the colorant fine particles containing the pigment dispersed in the aqueous medium can be measured using a laser diffraction / scattering particle size distribution measuring device (LA-920: manufactured by Horiba, Ltd.). .

  Known mixers used to disperse the colorant in the aqueous medium include mixers such as an ultrasonic homogenizer, jet mill, pressure homogenizer, colloid mill, ball mill, sand mill, and paint shaker. Can be mentioned. These may be used alone or in combination.

  Examples of the surfactant include the following. Anionic surfactants such as sulfate ester type, sulfonate type, phosphate ester type and soap type; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type, alkylphenol ethylene oxide adduct type Nonionic surfactants such as polyhydric alcohols. Among these, nonionic surfactants or anionic surfactants are preferable. Further, a nonionic surfactant and an anionic surfactant may be used in combination. The said surfactant may be used individually by 1 type, and may use 2 or more types together. The concentration of the surfactant in the aqueous medium is preferably 0.5 to 5% by mass.

-Aqueous dispersion of release agent fine particles The aqueous dispersion of release agent fine particles can be prepared by the following known methods, but is not limited to these methods.
After adding a release agent to an aqueous medium containing a surfactant, heating it above the melting point of the release agent, and dispersing it into particles using a homogenizer or pressure discharge type disperser having a strong shearing ability Cool to below melting point.
Examples of the homogenizer include “CLEARMIX W-Motion” manufactured by M Technique Co., Ltd. Examples of the pressure discharge type disperser include “Gorin homogenizer” manufactured by Gorin.

  The dispersion particle diameter of the release agent fine particles in the aqueous dispersion is preferably 0.03 to 1.0 μm, more preferably 0.1 to 0.5 μm, based on the volume median diameter. Moreover, it is preferable that coarse particles of 1 μm or more do not exist. When the dispersion particle size of the release agent fine particles is within the above range, release of the release agent at the time of fixing is improved, the hot offset temperature can be increased, and filming on the photosensitive member can be prevented. It becomes possible to suppress. The dispersed particle size can be measured using a laser diffraction / scattering particle size distribution measuring device (LA-920: manufactured by Horiba, Ltd.).

<Aggregation process>
The agglomeration step is to prepare a mixed solution in which the following dispersions 1) to 3) or 1) to 4) below are mixed, and then agglomerate fine particles contained in the prepared mixed solution. This is a step of forming an aggregate having a toner particle size of
1) Binder resin fine particle dispersion in which fine particles of binder resin are dispersed 2) Low molecular crystal compound fine particle dispersion in which fine particles of low molecular crystalline compound are dispersed 3) Colorant fine particle dispersion in which fine particles of colorant are dispersed 4) Release agent fine particle dispersion in which fine particles of release agent are dispersed By adding an aggregating agent to the above mixed solution and adding heating and / or mechanical power as needed, the following 1) to Aggregated particles in which the fine particles of 3) or 1) to 4) below are combined are formed.
1) Fine particles of binder resin 2) Fine particles of low molecular crystalline compound 3) Fine particles of colorant 4) Fine particles of release agent

  As the flocculant, it is preferable to use a flocculant containing divalent or higher metal ions. The aggregating agent containing monovalent metal ions has a weak aggregating force and needs to be added in a large amount in order to agglomerate the resin fine particles, so that the particle size distribution of the obtained agglomerated particles tends to be broad. Further, by adding a large amount of the flocculant, the flocculant tends to remain in the toner. On the other hand, a coagulant containing a divalent or higher metal ion has a high cohesive force. Therefore, by adding a small amount, the acidic polar group of the resin fine particles and the ionic surfactant contained in the aqueous dispersion of the resin fine particles, the aqueous dispersion of the colorant fine particles, and the aqueous dispersion of the release agent fine particles are added. Neutralizes ionically. Then, the resin fine particles, the colorant fine particles, and the release agent fine particles are aggregated by the effects of salting out and ionic crosslinking.

  Examples of the aggregating agent containing a divalent or higher metal ion include a divalent or higher metal salt or a polymer of a metal salt. Specific examples include, but are not limited to: Divalent inorganic metal salts such as calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, zinc chloride; trivalent metal salts such as iron (III) chloride, iron (III) sulfate, aluminum sulfate, aluminum chloride, and poly Inorganic metal salt polymers such as aluminum chloride, polyaluminum hydroxide and calcium polysulfide. These may be used alone or in combination of two or more.

  The flocculant may be added in the form of a dry powder or an aqueous solution dissolved in an aqueous medium, but is preferably added in the form of an aqueous solution in order to cause uniform aggregation. Moreover, it is preferable to add and mix the said flocculant at the temperature below the glass transition temperature of resin contained in the said mixed dispersion liquid. By performing the mixing under this temperature condition, the aggregation proceeds uniformly. Mixing of the flocculant into the mixed dispersion can be performed using a known mixing apparatus such as a homogenizer or a mixer.

  The average particle diameter of the aggregated particles formed in the aggregation process is not particularly limited, but it is usually preferable to control the average particle diameter of the toner to be finally obtained to be approximately the same. The particle size control of the aggregated particles can be easily performed by appropriately adjusting the temperature, the solid content concentration, the concentration of the aggregating agent, and the stirring conditions.

In addition, toner particles having a core-shell structure can be produced through the following steps 1) and 2).
1) An adhesion step of attaching resin fine particles to the surface of the aggregated particles by adding resin fine particles for forming a shell to the dispersion of the aggregated particles obtained in the aggregation step.
2) A fusion process in which the agglomerated particles (core-shell particles) with the resin fine particles attached to the surface are fused by heating.
The resin fine particles for forming the shell added here may be resin fine particles having the same structure as the resin contained in the aggregated particles, or may be resin fine particles having a different structure.

  The resin for shell contained in the resin fine particles for forming such a shell is not particularly limited, and a known resin can be used in the same manner as the binder resin. Specifically, vinyl polymers such as styrene-acrylic copolymers, polyester resins, epoxy resins, polycarbonate resins, and polyurethane resins can be used. In the present invention, the shell resin may be used alone or in combination of two or more. In particular, the low molecular crystalline compound and the binder resin are preferably contained in a shell that is in the vicinity of the surface layer of the toner.

  In general, when toner is fixed, the toner particles are hardly deformed at a temperature near the minimum fixing temperature (the lowest temperature at which the toner can be fixed on the paper). The image fixed on the paper is formed by the adhesion of. Therefore, in order to further improve the low-temperature fixability, it is preferable that the vicinity of the toner surface is quickly plasticized and fixed. However, in conventional crystalline polyesters and crystalline compounds, if they are present in the vicinity of the surface or exposed, the electric resistance of the single substance is low, and the chargeability of the toner is deteriorated.

The low-molecular crystalline compound contained in the toner of the present invention has high insulating properties even in a high-temperature and high-humidity environment as a single compound as described above, and the chargeability deteriorates even if it is present or exposed near the surface of the toner. do not do. For this reason, the toner containing the low molecular crystalline compound in the shell can realize both low-temperature fixability and chargeability at a higher level. As a shell particle for forming a shell containing the binder resin and the low molecular crystalline compound, an aqueous dispersion of fine particles that are individually finely divided by the above method may be used.
However, it is preferable to form composite fine particles containing the binder resin and the low molecular crystalline compound and use an aqueous dispersion of the composite fine particles. Formation of the composite fine particles can be prepared by the following known methods, but is not limited to these methods.

Specifically, the binder resin and the low molecular crystalline compound are dissolved by heating in an organic solvent in which they are dissolved. The solution is added to an aqueous medium containing a surfactant and heated at a temperature at which the low-molecular crystalline compound does not precipitate, and in the form of particles using a homogenizer or pressure discharge type disperser having a strong shearing ability. To disperse.
Examples of the homogenizer include “CLEARMIX W-Motion” manufactured by M Technique Co., Ltd. Examples of the pressure discharge type disperser include “Gorin homogenizer” manufactured by Gorin.

  After being dispersed in the form of particles, the organic solvent is evaporated and evaporated to produce composite fine particles containing the binder resin and the low molecular crystalline compound. Any organic solvent can be used as long as it can dissolve the binder resin and the low molecular crystalline compound. However, it is preferable to use an organic solvent that forms an oil phase by phase separation with water, such as toluene, from the viewpoint of suppressing the increase in viscosity at the time of micronization and suppressing the generation of coarse powder.

  Although it does not specifically limit as surfactant used at the time of the said emulsification, For example, the following are mentioned. Anionic surfactants such as sulfate ester, sulfonate, carboxylate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol type, alkylphenol Nonionic surfactants such as ethylene oxide adducts and polyhydric alcohols. These surfactants may be used alone or in combination of two or more.

<Fusion process>
In the fusion step, an aggregation terminator is added to the dispersion containing the aggregated particles obtained in the aggregation step under the same stirring as in the aggregation step. Examples of the aggregation terminator include a basic compound that stabilizes the aggregated particles by moving the acidic polar group of the binder resin fine particles to the dissociation side, and a chelating agent. Large chelating agents are preferably used. The chelating agent stabilizes the agglomerated particles by partially dissociating the ionic bridge between the acidic polar group of the binder resin fine particles and the metal ion, which is an aggregating agent, and forming a coordinate bond between the metal ion and the chelating agent. Turn into.

After the aggregation state of the aggregated particles in the dispersion is stabilized by the action of the aggregation terminator, the toner is fused by heating the binder resin to a temperature higher than the glass transition temperature and fusing the binder resins together.
The chelating agent is not particularly limited as long as it is a known water-soluble chelating agent. Specifically, oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid and their sodium salts, organometallic salts such as iminodic acid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and sodium salts thereof Is mentioned. The chelating agent coordinates to the metal ions of the flocculant present in the dispersion liquid of the aggregated particles, so that the environment in the dispersion liquid is electrostatically unstable and easily aggregated. It is possible to change to a state that is stable and hardly causes further aggregation. Thereby, further aggregation of the aggregated particles in the dispersion can be suppressed, and the aggregated particles can be stabilized. The chelating agent is effective even when added in a small amount, and toner particles having a sharp particle size distribution can be obtained. Therefore, an organic metal salt having a trivalent or higher carboxylic acid is preferable. Further, the addition amount of the chelating agent to be mixed is preferably 1 to 30 parts by mass, and 2.5 to 15 parts by mass with respect to 100 parts by mass of the resin, from the viewpoint of achieving both stabilization from the aggregation state and toner cleaning efficiency. Part is more preferred.

Toner can be obtained by washing, filtering, drying, etc. the particles produced through the above steps. Then, drying is performed, and if necessary, shearing force is applied in a dry state to inorganic particles such as silica, alumina, titania, calcium carbonate, and resin particles such as vinyl resin, polyester resin, and silicone resin. It may be added. These inorganic particles and resin particles function as external additives such as fluidity aids and cleaning aids.
Subsequently, a colorant containing a pigment, which is a constituent material constituting the toner of the present invention, and a release agent will be described.

<Colorant containing pigment>
The colorant of the present invention contains at least a known organic pigment, pigment such as carbon black. The colorant of the present invention may further contain a dye.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

Examples of the black colorant include carbon black, magnetic powder, and those prepared in a black color using the yellow colorant, magenta colorant, and cyan colorant.
These colorants can be used alone or in combination, and further in a solid solution state. The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the cyan colorant, the magenta colorant, the yellow colorant, or the black colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the amorphous resin and the crystalline resin that are resins constituting the toner. .

<Release agent>
Examples of the release agent contained in the toner of the present invention include the following. Low molecular weight polyolefins such as polyethylene; silicones having a melting point (softening point) upon heating; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; ester waxes such as stearyl stearate; Plant waxes such as carnauba wax, rice wax, candelilla wax, tree wax, jojoba oil; animal waxes such as beeswax; montan wax, ozokerite, ceresin wax, microcrystalline wax, Fischer-Tropsch wax, ester wax, etc. Mineral and petroleum waxes; and their modified products.

  The content of the release agent is preferably 1 to 25 parts by mass with respect to 100 parts by mass of the amorphous resin and the crystalline resin which are resins constituting the toner. When the amount is 1 part by mass or more, sufficient fixability at a high temperature can be obtained, and when the amount is 25 parts by mass or less, the toner surface layer is not exposed.

<Example>
EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example and a comparative example, these do not limit this invention at all.

<Production of low molecular crystalline compound 1>
Halogenated aromatic hydrocarbon component; 2-chloronaphthalene 1.0 mol part higher alcohol component; stearyl alcohol 1.1 mol part To a well-dried two-necked flask, 1000 parts by mass of acetone is added, and the above compound is added. The mixture was stirred and mixed, and sufficiently dissolved by heating in a water bath heated to 60 ° C.

  After confirming that it was sufficiently dissolved, 1.75 mol parts of potassium carbonate was added to the reactive compound and refluxed for 2 hours. Furthermore, when 0.5 mol part of potassium carbonate was added to the reaction product and refluxed for 5 hours, the reaction proceeded by 90% or more to obtain a crude product of octadecylnaphthyl ether. Thereafter, acetone is evaporated and distilled off, and recrystallization using hexane is repeated a plurality of times to obtain octadecyl naphthyl ether (SP: 9.7, melting point: 67 ° C.) which is the target low molecular crystalline compound 1. Obtained.

<Production of low molecular crystalline compounds 2-7>
The low molecular crystalline compound 1 except that the types and amounts of the halogenated aromatic hydrocarbon components, the types and amounts of the higher alcohol components, and the input amounts of potassium carbonate (first and second times) are changed as shown in Table 1. Low molecular crystalline compounds 2 to 7 were produced in the same manner as in the above. Table 1 shows the SP values and melting points of the produced low molecular crystalline compounds 2-7.

<Evaluation of single charge retention>
The charge retention of the low molecular weight crystalline compounds 1 to 7 produced as described above under high temperature and high humidity was measured by the following method. Then, comparison was made with crystalline polyester A, docosanol, stearic acid, stearamide, and terphenyl, which have been conventionally used.
Crystalline polyester A [composition (molar ratio) [1,9-nonanediol: sebacic acid = 100: 100], number average molecular weight (Mn) = 5,500, weight average molecular weight (Mw) = 15,000, main Peak molecular weight (Mp) = 11,400, Mw / Mn = 2.8, melting point = 78 ° C., acid value = 13 mgKOH / g]

A measurement sample (0.01 g) was weighed into an aluminum pan and charged to −600 V using a strocolon charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface potentiometer (manufactured by Trek Japan Co., Ltd .: model 347) in an atmosphere at a temperature of 30 ° C. and a relative humidity of 80%. The charge retention was calculated by substituting the measurement results into the following formula, and the insulation (charge retention) was evaluated. The evaluation results are shown in Table 4.
Charge retention (%) after 30 minutes = [surface potential after 30 minutes] / [initial surface potential] × 100
(Evaluation criteria)
◯: The triboelectric charge retention of the crystalline compound after 30 minutes is 80% or more Δ: The triboelectric charge retention of the crystalline compound after 30 minutes is less than 80% and 60% or more
X: The triboelectric charge retention of the crystalline compound after 30 minutes is less than 60%

<Manufacture of Binder Resin Fine Particles 1>
To 200 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries), 120 g of polyester resin A and 0.6 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) were added and stirred for 12 hours to dissolve.
The composition (molar ratio) and physical properties of the polyester resin A are as shown in Table 2.

Next, 2.7 g of N, N-dimethylaminoethanol was added, and an ultra-high speed stirring device T.A. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primemics). Furthermore, 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain binder resin fine particles 1.
When the 50% particle diameter (d50) based on the volume distribution of the obtained binder resin fine particles 1 was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.), it was 0.13 μm. there were.

<Manufacture of binder resin fine particles 2>
Binder resin fine particles 2 were obtained in the same manner as the production of the resin fine particles 1 except that the polyester resin A was changed to the polyester resin B. The obtained binder resin fine particles 2 had a volume distribution standard 50% particle size (d50) of 0.12 μm.
The composition (molar ratio) and physical properties of the polyester resin B are as shown in Table 2.

<Manufacture of Binder Resin Fine Particles 3>
Binder resin fine particles 3 were obtained in the same manner as in the production of the resin fine particles 1 except that the polyester resin A was changed to the polyester resin C. The obtained binder resin fine particles 3 had a 50% particle size (d50) based on volume distribution of 0.12 μm.
The composition (molar ratio) and physical properties of the polyester resin C are as shown in Table 2.

<Manufacture of Binder Resin Fine Particles 4>
Binder resin fine particles 4 were obtained in the same manner as the production of the resin fine particles 1 except that the polyester resin A was changed to the polyester resin D. The obtained binder resin fine particles 4 had a 50% particle size (d50) based on volume distribution of 0.12 μm.
The composition (molar ratio) and physical properties of the polyester resin D are as shown in Table 2.

<Manufacture of binder resin fine particles 5>
To 200 g of toluene (manufactured by Wako Pure Chemical Industries), 120 g of styrene acrylic resin A, 3 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 6 g of an anionic surfactant (sodium laurate) were added and stirred for 12 hours. , Dissolved.
The composition (molar ratio) and physical properties of styrene acrylic resin A are as shown in Table 2.

Next, an ultra-high speed stirring device T.I. K. While stirring at 4000 rpm using Robomix (manufactured by Primemics), 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Then, after dispersing for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), toluene was removed using an evaporator to obtain binder resin fine particles 5.
The 50% particle size (d50) based on the volume distribution of the binder resin fine particles 5 was measured using a dynamic light scattering particle size distribution size (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.15 μm. .

<Production of Fine Particle Dispersion of Low Molecular Crystalline Compound 1>
120 g of low molecular crystalline compound 1 was added to 200 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), heated to near the melting point of the low molecular crystalline compound, and then stirred for 12 hours to dissolve the low molecular crystalline compound 1. Next, after adding an aqueous solution in which 3 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 6 g of an anionic surfactant (sodium laurate) in 360 g of ion-exchanged water is added to the toluene solution. Ultra-high speed stirring device T.A. K. The suspension was obtained by stirring at 4000 rpm using Robomix (manufactured by Primics Co., Ltd.). After that, the obtained suspension solution was dispersed for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), and then toluene was removed using an evaporator to obtain a low molecular crystalline compound. 1 fine particle dispersion was obtained.
The 50% particle size (d50) of the low molecular crystalline compound 1 based on the volume distribution of the fine particles was measured using a dynamic light scattering particle size distribution size (Nanotrack: manufactured by Nikkiso Co., Ltd.). Met.

<Manufacture of fine particle dispersion of low molecular crystalline compounds 2-7>
A fine particle dispersion of low molecular weight crystalline compound 2 was obtained in the same manner as the production of the fine particle dispersion of low molecular weight crystalline compound 1 except that low molecular weight crystalline compound 1 was changed to low molecular weight crystalline compounds 2-7. . The 50% particle size (d50) based on volume distribution of the obtained fine particles of the low molecular crystalline compounds 2 to 7 was as follows.
・ Low molecular crystalline compound 2 0.19μm
・ Low molecular crystalline compound 3 0.20μm
・ Low molecular crystalline compound 4 0.24μm
・ Low molecular crystalline compound 5 0.29μm
・ Low molecular crystalline compound 6 0.35μm
・ Low molecular crystalline compound 7 0.17μm

<Production of fine particle dispersion of docosanol>
A docosanol fine particle dispersion was obtained in the same manner as the production of the low molecular weight crystalline compound 1 fine particle dispersion except that the low molecular crystalline compound 1 was changed to docosanol. The 50% particle size (d50) of the obtained docosanol fine particles based on volume distribution was 0.33 μm.

<Production of fine particle dispersion of stearic acid>
A fine particle dispersion of stearic acid was obtained in the same manner as the production of the fine particle dispersion of low molecular weight crystalline compound 1 except that the low molecular crystalline compound 1 was changed to stearic acid. The 50% particle size (d50) of the obtained stearic acid fine particles based on volume distribution was 0.35 μm.

<Production of fine particle dispersion of stearamide>
A fine particle dispersion of stearic acid amide was obtained in the same manner as the production of the fine particle dispersion of low molecular weight crystalline compound 1 except that low molecular weight crystalline compound 1 was changed to stearic acid amide. The 50% particle size (d50) of the obtained stearamide fine particles based on volume distribution was 0.31 μm.

<Production of terphenyl fine particle dispersion>
A terphenyl fine particle dispersion was obtained in the same manner as the production of the low molecular weight crystalline compound 1 fine particle dispersion except that the low molecular crystalline compound 1 was changed to terphenyl. The 50% particle size (d50) based on volume distribution of the obtained terphenyl fine particles was 0.39 μm.

<Manufacture of fine particle dispersion of crystalline polyester A>
To 200 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries), 120 g of crystalline polyester A and 0.6 g of anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) are added, heated to 50 ° C., stirred for 3 hours and dissolved. It was.
Crystalline polyester A [composition (molar ratio) [1,9-nonanediol: sebacic acid = 100: 100], number average molecular weight (Mn) = 5,500, weight average molecular weight (Mw) = 15,000, main Peak molecular weight (Mp) = 11,400, Mw / Mn = 2.8, melting point = 78 ° C., acid value = 13 mgKOH / g]

Next, 2.7 g of N, N-dimethylaminoethanol was added, and an ultra-high speed stirring device T.A. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primemics). Furthermore, 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain a fine particle dispersion of crystalline polyester A.
The volume distribution standard 50% particle size (d50) of the fine particles of crystalline polyester A was measured using a dynamic light scattering particle size distribution size (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.30 μm. It was.

<Production of Composite Fine Particle Dispersion of Polyester Resin A and Low Molecular Crystalline Compound 1>
After adding 96 g of polyester resin A and 24 g of low molecular crystalline compound 1 to 200 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), heating to near the melting point of the low molecular crystalline compound, stirring for 12 hours, Low molecular crystalline compound 1 was dissolved.
Next, an aqueous solution prepared by dissolving 3 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 6 g of an anionic surfactant (sodium laurate) in 360 g of ion-exchanged water was added to the toluene solution. Thereafter, an ultra-high speed stirring device T.I. K. The suspension was obtained by stirring at 4000 rpm using Robomix (manufactured by Primics Co., Ltd.).
Thereafter, the obtained suspension solution was dispersed for about 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.), and then the toluene was removed using an evaporator, and the polyester resin A and low A dispersion of composite fine particles of molecular crystalline compound 1 was obtained.
The volume distribution standard 50% particle size (d50) of the composite fine particles of the polyester resin A and the low molecular crystalline compound 1 was measured using a dynamic light scattering particle size distribution size (Nanotrack: manufactured by Nikkiso Co., Ltd.). 0.20 μm.

<Manufacture of colorant fine particles>
Colorant 10.0 parts by mass (Cyan Pigment Dainichi Seika Kogyo Co., Ltd .: CI Pigment Blue 15: 3)
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts by mass-Ion-exchanged water 88.5 parts by mass The above materials are mixed, dissolved, and a high-pressure impact disperser Nanomizer ( An aqueous dispersion of colorant fine particles was prepared by dispersing the colorant for about 1 hour using Yoshida Kikai Kogyo Co., Ltd.). The volume-based 50% particle size (d50) of the obtained colorant fine particles was measured using a dynamic light scattering particle size distribution (Nanotrack: Nikkiso Co., Ltd.) and found to be 0.20 μm.

<Manufacture of release agent fine particles>
Release agent (HNP-51, melting point 78 ° C., manufactured by Nippon Seiwa Co., Ltd.) 20.0 parts by mass Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 parts by mass・ Ion-exchanged water 79.0 parts by mass Each of the above materials was added to a mixing vessel equipped with a stirrer, then heated to 90 ° C and circulated to Claremix W Motion (M Technique Co., Ltd.) outside the rotor. The mixture was stirred and dispersed under the following conditions at a shearing stirring site having a diameter of 3 cm and a clearance of 0.3 mm.
・ Rotor speed 19000r / min ・ Screen speed 19000r / min ・ Dispersion time 60 minutes Then, rotor speed 1000r / min, screen speed 0r / min, cooling rate 10 ℃ / min. By cooling, an aqueous dispersion of release agent fine particles was obtained. The 50% particle size (d50) based on the volume distribution of the release agent fine particles was measured using a dynamic light scattering particle size distribution size (Nanotrack: manufactured by Nikkiso Co., Ltd.), and was 0.15 μm.

<Toner Production Example 1>
-Binder resin fine particle 1 dispersion 320 parts by mass-Low molecular weight crystalline compound 1 fine particle dispersion 80 parts by mass-Colorant fine particle dispersion 50 parts by mass-Release agent fine particle dispersion 50 parts by mass-Ion exchange 400 parts by weight of water

  After each material was put into a round stainless steel flask and mixed, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved in 98 parts by mass of ion-exchanged water was added. And it disperse | distributed for 10 minutes at 5000 r / min using the homogenizer (the product made by IKA: Ultra Talux T50). Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixed solution was stirred. After maintaining at 58 ° C. for 1 hour, the volume average particle diameter of the formed aggregated particles was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that aggregated particles having a volume average particle diameter of about 6.0 μm were formed.

  An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the dispersion of aggregated particles obtained in the aggregation process, and then heated to 85 ° C. After maintaining at 85 ° C. for 2 hours, the volume average particle diameter and average circularity of the obtained particles were measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000). Measured according to As a result, a sufficiently fused toner having a volume average particle diameter of about 5.8 μm and an average circularity of 0.968 was obtained. The obtained aqueous dispersion of toner is cooled to 25 ° C. while maintaining stirring, filtered and solid-liquid separated, and the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer. As a result, toner particles 1 having a volume-based median diameter of 5.4 μm were obtained.

<Toner Production Examples 2-3>
As shown in Table 3, toner particles 2 to 3 were obtained in the same manner as in Toner Production Example 1 except that the dispersion of the binder resin fine particles 1 was changed to the dispersion of the binder resin fine particles 2 to 3. It was. The resulting toner particles had a volume-based median diameter of 5.5 μm.

<Toner Production Examples 4 to 8>
As shown in Table 3, toner particles 4 were obtained in the same manner as in Toner Production Example 1, except that the fine particle dispersion of low molecular crystalline compound 1 was changed to the fine particle dispersion of low molecular crystalline compounds 2-6. ~ 8 was obtained. The resulting toner particles had a volume-based median diameter of 5.5 μm.

<Toner Production Example 9>
As shown in Table 3, toner particles 9 were obtained in the same manner as in Toner Production Example 1 except that the dispersion liquid of the binder resin fine particles 1 was changed to the dispersion liquid of the binder resin fine particles 5. The resulting toner particles had a volume-based median diameter of 5.5 μm.

<Toner Production Example 10>
-Dispersion liquid of binder resin fine particles 320 parts by mass-Fine particle dispersion liquid of low molecular crystalline compound 1 80 parts by mass-Dispersion liquid of colorant fine particles 75 parts by mass-Dispersion liquid of release agent fine particles 75 parts by mass-Ion exchange 400 parts by weight of water

  After the above materials were put into a round stainless steel flask and mixed, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved was added to 98 parts by mass of ion-exchanged water, and a homogenizer (manufactured by IKA: Ultra Turrax) was added. For 10 minutes at 5000 r / min. Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixed solution was stirred. After maintaining at 58 ° C. for 1 hour, the volume average particle diameter of the formed core aggregated particles was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. . As a result, it was confirmed that core aggregated particles having a volume average particle diameter of about 5.0 μm were formed.

  To the obtained core aggregated particles, 200 parts by mass of a composite fine particle dispersion of the above-described polyester resin A and low molecular crystalline compound 1 is dropped, and further treated at 58 ° C. for 1 hour to be composited with the core aggregated particles. Fine particles were allowed to adhere. As a result, it was confirmed that core-shell particles having a volume average particle diameter of about 5.6 μm were formed. At this stage, a small amount was sampled and filtered through a filter having a pore size of 1 μm. As a result, it was clear and colorless, and it was confirmed that all of the added fine particles of polyester resin A and low molecular crystalline compound 1 were adhered.

An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the obtained dispersion of core-shell particles, and then heated to 85 ° C. After maintaining at 85 ° C. for 2 hours, the volume average particle diameter and average circularity of the obtained particles were measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000). Measured according to As a result, a sufficiently fused toner having a volume average particle diameter of about 5.8 μm and an average circularity of 0.968 was obtained.
The obtained aqueous dispersion of toner is cooled to 25 ° C. while maintaining stirring, filtered and solid-liquid separated, and the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer. As a result, toner particles 10 having a volume-based median diameter of 5.4 μm were obtained.

<Toner Production Example 11>
-Binder resin fine particle 4 dispersion liquid 320 parts by mass-Low molecular weight crystalline compound 1 fine particle dispersion liquid 80 parts by mass-Colorant fine particle dispersion liquid 50 parts by mass-Release agent fine particle dispersion liquid 50 parts by mass-Ion exchange 400 parts by weight of water

  After the above materials were put into a round stainless steel flask and mixed, an aqueous solution in which 2 parts by mass of magnesium sulfate was dissolved was added to 98 parts by mass of ion-exchanged water, and a homogenizer (manufactured by IKA: Ultra Turrax) was added. For 10 minutes at 5000 r / min. Thereafter, the mixture was heated to 58 ° C. using a stirring blade in a heating water bath while appropriately adjusting the number of revolutions so that the mixed solution was stirred. After maintaining at 58 ° C. for 1 hour, the volume average particle diameter of the formed aggregated particles was measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that aggregated particles having a volume average particle diameter of about 6.0 μm were formed.

  An aqueous solution in which 20 parts by mass of trisodium citrate was dissolved in 380 parts by mass of ion-exchanged water was added to the dispersion of aggregated particles obtained in the aggregation process, and then heated to 85 ° C. After maintaining at 85 ° C. for 2 hours, the volume average particle diameter and average circularity of the obtained particles were measured using a flow type particle image analyzer (manufactured by Sysmex Corporation: FPIA-3000). Measured according to As a result, a sufficiently fused toner having a volume average particle diameter of about 5.8 μm and an average circularity of 0.968 was obtained. The obtained aqueous dispersion of toner is cooled to 25 ° C. while maintaining stirring, filtered and solid-liquid separated, and the filtrate is sufficiently washed with ion-exchanged water and dried using a vacuum dryer. As a result, toner particles 11 having a volume-based median diameter of 5.4 μm were obtained.

<Toner Production Example 12>
Toner particles 12 were obtained in the same manner as in Toner Production Example 11 except that the fine particle dispersion of low molecular crystalline compound 1 was changed to the fine particle dispersion of low molecular crystalline compound 6. The resulting toner particles had a volume-based median diameter of 5.5 μm.

<Toner Production Examples 13 to 18>
Toner except that the dispersion of the binder resin fine particles 4 is changed to the dispersion of the binder resin fine particles 1 and the fine particle dispersion of the low molecular crystalline compound 1 is changed to the fine particle dispersion of the compounds shown in Table 3. In the same manner as in Production Example 11, toner particles 13 to 18 were obtained. The toner particles 13 to 18 thus obtained had a volume-based median diameter of 5.5 μm.

<Example 1>
The toner particles 1 were evaluated for storage stability, low-temperature fixability and chargeability by the following methods. The results are shown in Table 5.

<Evaluation of preservability>
To 100 parts by mass of toner particles, 1.8 parts by mass of silica fine particles having a specific surface area measured by the BET method of 200 m ² / g and hydrophobized with silicone oil are dry-mixed with a Henschel mixer (Mitsui Mine). Thus, a toner to which an external additive was added was prepared. The amount of toner remaining on the sieve when the toner is left in a constant temperature and humidity chamber for 3 days and sieved for 300 seconds with a shaking width of 1 mm using a sieve having an opening of 75 μm is based on the following criteria. Evaluated. The evaluation results are shown in Table 5.

(Evaluation criteria)
○: The amount of toner remaining on the sieve is 10% or less after sieving after standing in a constant temperature and humidity chamber at a temperature of 55 ° C. and a humidity of 10% for 3 days. Δ: A constant temperature and constant temperature of 55 ° C. and a humidity of 10%. The amount of toner remaining on the sieve is 10% or more after sieving after standing in a wet tank for 3 days. The amount of toner remaining on the sieve was 10% or less x: The amount of toner remaining on the sieve was 10% after standing in a constant temperature and humidity chamber with a temperature of 50 ° C. and a humidity of 10% for 3 days. %that's all

<Evaluation of low-temperature fixability>
100 parts by mass of toner particles having a specific surface area measured by the BET method of 200 m ² / g and 1.8 parts by mass of silica fine powder hydrophobized with silicone oil are dry-mixed with a Henschel mixer (Mitsui Mine). Thus, a toner to which an external additive was added was prepared. The toner and a ferrite carrier (average particle size 42 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 8% by mass to prepare a two-component developer. The two-component developer is filled in a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.) to form an unfixed toner image (0.6 mg / cm ² ) on the image receiving paper (64 g / m ² ). did. A fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon Inc.) was remodeled so that the fixing temperature could be adjusted, and a fixing test for unfixed images was performed using the fixing unit. Under normal temperature and humidity, the process speed was set to 246 mm / sec, and the state when the unfixed image was fixed was visually evaluated. The evaluation results are shown in Table 5.

(Evaluation criteria)
5: Fixing is possible in a temperature range of 130 ° C. or lower 4: Fixing is possible in a temperature range higher than 130 ° C. and 135 ° C. or lower 3: Fixing is possible in a temperature range higher than 135 ° C. and 140 ° C. or lower 2: 140 ° C. Fixing is possible in a higher temperature range of 150 ° C. or lower. 1: There is a fixing possible region only in a temperature range higher than 150 ° C.

<Evaluation of electrification>
100 parts by mass of toner particles having a specific surface area measured by the BET method of 200 m ² / g and 1.8 parts by mass of silica fine powder hydrophobized with silicone oil are dry-mixed with a Henschel mixer (Mitsui Mine). Thus, a toner to which an external additive was added was prepared. The toner and a ferrite carrier (average particle size 42 μm) surface-coated with a silicone resin were mixed so that the toner concentration was 8% by mass to prepare a two-component developer.

  Here, the charge amount of the toner particles was measured with an Espart analyzer manufactured by Hosokawa Micron Corporation. The Espart analyzer is a device that measures the particle size and the charge amount by introducing sample particles into a detection unit (measurement unit) in which an electric field and an acoustic field are simultaneously formed, and measuring the moving speed of the particles by a laser Doppler method. . The sample particles entering the measuring unit of the apparatus are affected by the acoustic field and the electric field, fall while being biased in the horizontal direction, and the beat frequency of the horizontal speed is counted. The count value is input by interruption to the computer, and the particle size distribution or the charge amount distribution per unit particle size is shown on the computer screen in real time. The screen stops when a predetermined number of charge amounts are measured, and then the three-dimensional distribution of charge amount and particle diameter, charge amount distribution by particle size, average charge amount (coulomb / weight), etc. are displayed on the screen. Is displayed. By introducing the developer as sample particles into the measurement part of the Espart analyzer, the charge amount of the toner can be measured.

After measuring the triboelectric charge amount of the initial toner by the above method, the two-component developer was allowed to stand in a constant temperature and humidity chamber (temperature 30 ° C., humidity 80%) for one week, and the triboelectric charge amount was measured again.
The measurement result was substituted into the following formula to calculate the triboelectric charge retention rate and evaluated according to the following criteria. The evaluation results are shown in Table 5.
Formula: Toner triboelectric charge retention ratio (%) = [triboelectric triboelectric charge after one week] / [triboelectric triboelectric charge of initial toner] × 100

(Evaluation criteria)
○: The triboelectric charge retention of the toner after 1 week is 80% or more. Δ: The triboelectric charge retention of the toner after 1 week is less than 80% and 60% or more. X: The triboelectric charge retention of the toner after 1 week is 60. %Less than

<Examples 2 to 11>
The toner particles 2 to 10 were evaluated in the same manner as the toner particles 1. The results are shown in Table 5.
<Comparative Examples 1-10>
The toner particles 11 to 18 were evaluated in the same manner as the toner particles 1. The results are shown in Table 5.

Claims (5)

A toner containing a colorant, a binder resin, and a low molecular crystalline compound,
The low molecular crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton;
A toner wherein the SP value (SP1) of the binder resin and the SP value (SP2) of the crystalline compound satisfy the following formula:
0 (cal / mol) ≦ | SP1-SP2 | ≦ 3 (cal / mol)   The toner according to claim 1, wherein the low molecular crystalline compound has a melting point of 50 ° C. or higher and 100 ° C. or lower.   The toner according to claim 1, wherein the binder resin is an amorphous polyester obtained by polycondensing an alcohol component containing 50 mol% or more of a propylene oxide adduct of bisphenol A and a carboxylic acid component.   4. The toner having a core-shell structure in which the toner has a shell containing the binder resin and the low molecular crystalline compound on the surface of the core containing the binder resin and the colorant. The toner according to any one of the above. The binder resin fine particle dispersion in which the fine particles of the binder resin are dispersed and the colorant fine particle dispersion in which the fine particles of the colorant are dispersed are mixed to aggregate the binder resin fine particles and the colorant fine particles, thereby forming the core aggregated particles. Forming step,
Composite fine particles containing the binder resin and the low molecular crystalline compound obtained by dissolving the binder resin and the low molecular crystalline compound in an organic solvent and dispersing in water and then removing the organic solvent Attaching to the core agglomerated particles to form core-shell particles, and a fusion step of fusing the core-shell particles by heating to a temperature equal to or higher than the glass transition temperature of the binder resin,
The low molecular crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton;
A toner production method, wherein the SP value (SP1) of the binder resin and the SP value (SP2) of the crystalline compound satisfy the following formula:
0 (cal / mol) ≦ | SP1-SP2 | ≦ 3 (cal / mol)