JP6910884B2 - Toner and toner manufacturing method - Google Patents

Description

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

In recent years, with the increasing demand for energy saving in image formation, efforts have been taken to lower the fixing temperature of toner. 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, the toners may fuse with each other in a stationary state such as 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 a sharp melt property, in which the viscosity greatly decreases when the melting point is exceeded, has been proposed. However, when crystalline polyester, which is a crystalline resin, is used alone as the binder resin of the toner, there is a problem that the electric charge of the toner gradually escapes after triboelectric charging due to the low electric resistance of the crystalline polyester. was there.

Therefore, a toner has been proposed in which the amount of crystalline polyester added is reduced and a mixture of crystalline polyester and an amorphous resin having high compatibility is used (Patent Document 1).
A technique for using a low molecular weight 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 as an action similar to that of a crystalline polyester. Has been proposed (Patent Document 1).
Further, as a 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 a side chain has been proposed (Patent Document 2).

Japanese Unexamined Patent Publication No. 2008-281884 Japanese Unexamined Patent Publication No. 2013-68910

As in Patent Document 1, in the case of a toner containing an amorphous resin together with a crystalline polyester as a binder resin, when the resins having high compatibility are combined, the sharp melt property is good, but the chargeability and heat resistance are good. In some cases, the storage stability was not sufficient. Amorphous resin and crystalline polyester are present in the toner in a state of being compatible with each other when the toner is manufactured by heating and melting above the melting point of the crystalline polyester or a melting step with a solvent, and the amorphous resin and the crystalline polyester are present in the toner. This is because the plasticization of the sex resin (decrease in the glass transition temperature) is induced.

On the other hand, in the case of a toner in which a crystalline polyester and an amorphous resin having low compatibility are mixed and used, even after a step of heating and melting above the melting point of the crystalline polyester or a step of dissolving with a solvent at the time of manufacturing the toner. , Amorphous resin and crystalline polyester are phase-separated. Then, since the matrix-domain structure corresponding to the compatibility of the resin is spontaneously formed, the plasticization of the amorphous resin (decrease in the glass transition temperature) is not induced, and the chargeability and the 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 conventional toner containing a crystalline polyester and an amorphous resin, the compatibility contrast between the crystalline polyester and the amorphous resin before and after fixing (compatibility between a high temperature environment and a low temperature environment). It is difficult to make a difference). Therefore, the compatibility in a high temperature environment (compatibility at the time of fixing) and the compatibility in a low temperature environment (compatibility in the toner particles before fixing) correlate with each other. That is, when the low-temperature fixability is good, the chargeability and storage stability are insufficient due to the above-mentioned compatibilization, and conversely, when the low-temperature fixability is not sufficient, the charge is caused by the above-mentioned phase separation. There was a trade-off relationship between good sex and good storage. For this reason, it has been difficult to achieve both low-temperature fixability, chargeability, and storage stability at a high level.

As in Patent Document 1, instead of crystalline polyester, a low molecular weight 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. The same applies when it is contained. That is, in a high temperature and high humidity environment, the electric charge may gradually escape after triboelectric charging, and the chargeability is not sufficient especially in a high temperature and high humidity environment. This is because the low molecular weight 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 or styrene acrylic resin, the higher the polarity of the functional group, the more the amorphous resin and the low molecular crystallinity described above. The compatibility with the compound in a high temperature environment (compatibility at the time of fixing) is enhanced. 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 a side chain is a crystalline polyether as compared with a crystalline polyester having a glass transition temperature of the same degree. Low polarity. Due to this low polarity, the chargeability in a high temperature and high humidity environment is excellent, but the compatibility with the binder resin in a high temperature environment (compatibility at the time of fixing) is not sufficient. The low temperature fixability was not sufficient.
Therefore, an object of the present invention is to provide a toner having sharp meltability, achieving 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 diligent studies, the present inventors have obtained the recognition that the following is important.
-For low temperature fixability, the crystalline compound as a plasticizer and the binder resin must be a combination that is highly compatible with each other when fixed (in a high temperature environment).
-For storage stability, the crystalline compound and the binder resin form a phase-separated structure in the toner state (under a low temperature environment) before fixing.
-For chargeability, the crystalline compound and the binder resin form a phase-separated structure in the toner state (under a low temperature environment) before fixing, and the crystalline compound leaks the charge generated by triboelectric charging. Do not contain polar functional groups to prevent it.

In addition, as a result of diligent studies, the present inventors have obtained the following recognition.
The molecular weight of the crystalline compound that serves as a plasticizer during fixing greatly affects the contrast of compatibility 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 with the binder resin, which has low compatibility in a low temperature environment, in a high temperature environment. Further, the crystalline compound is contained in a combination of an ether structure having a relatively low polarity and an aromatic hydrocarbon structure to improve the compatibility with the binder resin, so that the crystal is crystallized while maintaining the compatibility. The leakage of electric charge due to the sex compound can be suppressed, and the chargeability is further improved.

Therefore, according to one aspect of the present invention, the toner contains a colorant, a binder resin, and a low molecular weight crystalline compound.
The low molecular weight crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton.
Toner having an SP value of the binder resin (SP1) and the SP value of the low-molecular crystalline compound (SP2) and satisfies the following formulas are provided.
0 (cal / mol) ≤ | SP1-SP2 | ≤3 (cal / mol)

Further, according to another aspect of the present invention.
The binder resin fine particle dispersion liquid in which the binder resin fine particles are dispersed and the colorant fine particle dispersion liquid in which the colorant fine particles are dispersed are mixed, and the binder resin fine particles and the colorant fine particles are agglomerated to form core agglomerated particles. The process of forming,
The binder resin and low-molecular crystalline compound is dissolved in an organic solvent, the resulting solution Ru is dispersed in an aqueous medium process,
C. in aqueous medium, and removing the organic solvent from the lysis solution, to obtain a composite fine particles containing the binder resin and the low molecular crystalline compound process,
An adhesion step of adhering the composite fine particles to the core agglomerated particles to form core-shell particles in the aqueous medium, and a fusion step of heating the core-shell particles to a temperature equal to or higher than the glass transition temperature of the binder resin to fuse them. ,
A method of manufacturing a toner have a,
The low molecular weight crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton.
Method for producing a toner having an SP value of the binder resin (SP1) and the SP value of the low-molecular crystalline compound (SP2) and satisfies the following formulas are provided.
0 (cal / mol) ≤ | SP1-SP2 | ≤3 (cal / mol)

According to the present invention, it is possible to provide a toner which has sharp melt property, has both low temperature fixability and storage stability, and has good chargeability even in a high temperature and high humidity environment.

First, a low molecular weight crystalline compound, which is a feature of the present invention, will be described.
The low molecular weight crystalline compound contained in the toner of the present invention is a low molecular weight 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 action of improving the compatibility between low temperature fixability and chargeability in the toner of the present invention are unknown, but it is considered as follows.

First, since the low molecular weight crystalline compound which is a plasticizer is a low molecular weight compound having a lower molecular weight as compared with the conventional crystalline polyester, as described above, the crystalline compound and the binder resin before and after fixing are used. It is easy to get a contrast of compatibility with. Therefore, even if the binder resin and the small molecule crystalline compound are phase-separated in the toner, they are sufficiently compatible with each other at the time of fixing.
Secondly, the solubility parameter (SP2) is increased by containing the low molecular weight crystalline compound in combination with an ether structure having a relatively low polarity and an aromatic hydrocarbon structure, and the solubility parameter of the binder resin described later is increased. The difference from (SP1) is reduced. Therefore, it has a low dielectric constant and low moisture absorption while maintaining the same good compatibility as conventional low molecular weight crystalline compounds containing polar functional groups such as ester groups, carbonyl groups, and hydroxyl groups.

That is, the low-molecular-weight crystalline compound contained in the toner of the present invention is a conventional plastic agent because it has little adsorption of water molecules and has high insulating properties of the low-molecular-weight crystalline compound itself even under high temperature and high humidity. It is considered to have a charge retention property superior to that of the proposed crystalline compound.
The charge retention of the low molecular weight crystalline compound alone under high temperature and high humidity can be measured by the following method. 0.01 g of the low molecular weight crystalline compound is weighed in an aluminum pan and charged to -600 V using a strocon charging device. Subsequently, the change behavior of the surface potential is measured for 30 minutes using a surface electrometer (manufactured by Trek Japan Co., Ltd .: model347) in an atmosphere of a temperature of 30 ° C. and a relative humidity of 80%. By substituting the measurement result into the following formula, the charge retention rate can be calculated and the insulation property can be evaluated.
Charge retention after 30 minutes (%) = [Surface potential after 30 minutes] / [Initial surface potential] x 100

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

The weight average molecular weight of the low molecular weight crystalline compound of the present invention is preferably 1500 or less, more preferably 1000 or less, from the viewpoint of increasing the contrast of compatibility 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 is greater at higher temperature conditions. Therefore, in the case of high molecular weight crystalline polyester having a weight average molecular weight of more than 1500, which has been conventionally used as a plasticizer, it is difficult to obtain a contrast between the compatibility between the crystalline compound and the binder resin before and after fixing, and the low temperature fixing property is achieved. It is difficult to achieve both chargeability and storage stability. On the other hand, the low molecular weight crystalline compounds contained in the toner of the present invention are incompatible with each other in the above molecular weight range, and are incompatible with each other under high temperature conditions. That is, it is considered that the contrast between the compatibility between the crystalline compound and the binder resin before and after fixing is increased, so that low-temperature fixing property, chargeability and storage stability can be achieved at the same time.

The weight average molecular weight (Mw) of the low molecular weight crystalline compound is measured by gel permeation chromatography (GPC) as follows.
Special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added to o-dichlorobenzene for gel chromatograph so as to have a concentration of 0.10 wt / vol%, and the mixture is dissolved at room temperature. A low-molecular-weight crystalline compound and o-dichlorobenzene to which the above BHT is added 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. to obtain the low-molecular-weight crystalline compound. Dissolve. When the low molecular weight crystalline compound is dissolved, it is placed in a preheated filter unit and installed in the main body. A GPC sample that has passed through the filter unit is used. The sample solution is adjusted so that the concentration is about 0.15% by mass. This sample solution is used for measurement under the following conditions.

Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Column: TSKgel GMHHR-HHT 2 stations (manufactured by Tosoh Corporation)
Temperature: 135.0 ° C
Solvent: o-dichlorobenzene for gel chromatograph (BHT 0.10 wt / vol% added)
Flow velocity: 1.0 mL / min Injection volume: 0.4 mL

In calculating the molecular weight of the crystalline resin, a molecular weight calibration curve prepared using a standard polystyrene resin is used. Examples of the standard polystyrene resin include the following. 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.

Further, the weight average molecular weight (Mw) of the low molecular weight crystalline compound contained in the toner of the present invention is measured by isolating the low molecular weight crystalline compound component from the resin contained in the toner and measuring by the above method. Examples of the method for isolating the low molecular weight crystalline compound include the following methods.
The toner of the present invention preferably contains a mold release agent. When the toner of the present invention contains a mold release agent, the mold release agent is extracted from the toner by Soxhlet extraction using a hexane solvent, and then the obtained extraction residue is further extracted by Soxhlet extract with an ethyl acetate solvent to obtain low molecular weight 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 weight crystalline compound.

Further, the crystallinity of the low molecular weight crystalline compound contained in the toner of the present invention can be determined by the crystallinity measured by the wide-angle X-ray diffraction method, and when the crystallinity is 1% or more. Judged as a crystalline compound.
Further, the low molecular weight 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 required by a wide-angle X-ray diffraction method. When the crystallinity is 10% or more, the proportion of amorphous portions 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: Bruker AXS D8 ADVANCE
X-ray source: Cu-Kα ray (wavelength 0.15418 nm)
Output: 40kV, 40mA
Slit system: Slit DS, SS = 1 °, RS = 0.2 mm,
Measurement range: 2θ = 5 ° to 60 °
Step interval: 0.02 °
Scan speed: 1 ° / min From the measurement results, the X-ray diffraction profile of the sample can be separated into crystal peaks and amorphous scattering, and the area can be calculated by the following formula.
Crystallinity (%) = IC / (IC + IA) x 100
IC: Sum of peak areas of each crystal IA: Sum of amorphous scattering areas

In the low molecular weight 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 weight crystalline compound satisfy the following formula.
0 (cal / mol) ≤ | SP1-SP2 | ≤3 (cal / mol)
Here, the SP value is called a solubility parameter, and is a numerical value of how easily each other is chemically structurally soluble. It means that the compounds having similar SP values are easily mixed with each other and easily compatible with each other. There are various methods for calculating the SP value, but in the present invention, the commonly used Fedors method is used. Specifically, for example, it is described in detail in Polymer engineering and science, Vol. 14, pp. 147 to 154, and the SP value can be calculated by the following formula.
Formula: SP value = √ (Ev / v) = √ (ΣΔei / ΣΔvi)
(In the formula, 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)

If the absolute value of the difference between SP1 and SP2 is larger than 3 (cal / mol), the binder resin and the low molecular weight crystalline compound will be phase-separated even in a high temperature state and will not be compatible with each other at the time of fixing. It acts as a mold 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) or more and 2.5 (cal / mol) or less, and more preferably 0 (cal / mol) or more and 2.2 (cal / mol) or less. ..

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

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

The melting point can be measured using a differential scanning calorimeter (DSC). Specifically, 0.01 to 0.02 g of the sample is weighed in an aluminum pan, and the calorific value is measured while raising the temperature of the sample from room temperature at a heating rate of 10 ° C./min. Next, from the obtained DSC curve, the peak temperature of the endothermic peak is set as the melting point. Further, the melting point of the low molecular weight 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. To determine the melting point of the release agent and the melting point of the low molecular weight crystalline compound, the release agent is extracted from the toner by Soxhlet extraction using a hexane solvent, and the differential scanning calorimetry of the release agent alone is performed 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 weight crystalline compound is preferably contained in the toner in an amount of 10% by mass or more and 40% by mass or less. When the low molecular weight crystalline compound is contained in the toner in an amount of 10% by mass or more, the fixing temperature can be lowered at a high level. If it is 40% by mass or less, the low molecular weight crystalline compound is not exposed on the toner surface.

The low molecular weight 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. It is preferably a low-molecular-weight crystalline ether compound obtained by a nucleophilic substitution reaction between a halogenated aromatic hydrocarbon and a higher alcohol as described below.
-Halogenated aromatic hydrocarbons having one or more halogen groups such as chloro group and bromo group.
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 carbon atoms.

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

Further, the low molecular weight 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 later and can be lowered in melting point.

The aromatic hydrocarbon skeleton contained in the low molecular crystalline compound enhances 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 polar functional groups, it improves low-temperature fixability without deteriorating 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 later and can be lowered in melting point.

The long-chain hydrocarbon skeleton contained in the low-molecular-weight crystalline compound lowers SP1 of the low-molecular-weight crystalline compound, and makes the low-molecular-weight crystalline compound phase-separable from the binder resin under low temperature conditions (in toner). By improving and suppressing the plasticization of the binder resin, the storage stability and chargeability of the toner are improved. For example, if the number of carbon atoms in the long-chain hydrocarbon skeleton is too small, the low-molecular-weight crystalline compound is partially solubilized in the binder resin and functions as a plasticizer. Will decrease, resulting in poor storage stability. Further, even if the number of carbon atoms is the same, if it has a branched structure as compared with the case where it is linear, the melting point may be 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, but are not limited to, the following. 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, etc.
Further, a halogenated aromatic hydrocarbon having two or more halogen groups such as a chloro group and a bromo group may be used, and examples thereof include, but are not limited to, the following. 1,1'-dichlorobiphenyl, 2,2'-dichlorobiphenyl, 2,6-dichloronaphthalene, 1,4-dichloronaphthalene and the like.

Specific examples of higher alcohols 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), nonadecil alcohol (C = 19) ), Eikosyl alcohol (C = 20), behenyl alcohol (C = 22; 1-docosanol), ceryl alcohol (C = 26), mesilyl alcohol (C = 30) and the like.

Next, the binder resin in the present invention that is compatible with the low molecular weight 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 weight crystalline compound falls within the above range, and the combination is highly compatible with each other. If so, 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.
Monopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and its substitutions; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl ether copolymer, styrene-vinyl ethyl ether Styrene-based copolymers such as copolymers, styrene-vinylmethylketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenol resin, naturally modified phenol resin, natural resin modified maleic acid resin, acrylic resin , Methacrylic resin, polyvinyl acetate, silicone resin, amorphous polyester, crystalline polyester, polyurethane, polyamide, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, kumaron-inden resin, petroleum resin, etc. Among these, amorphous polyester which can achieve both low temperature fixability and mechanical strength is preferable because it has excellent strength even if it has a low molecular weight.

As the amorphous polyester, a polyester obtained by polycondensing an alcohol monomer and a carboxylic acid monomer is used.
Examples of the alcohol monomer include the following. 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 adduct 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, poly Tetramethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane Triol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 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 anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; alkyl groups or alkenyl having 6 to 18 carbon atoms. Succinic acid or an anhydride thereof substituted with a group; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

In addition, the following monomers can be used.
Polyhydric alcohols such as glycerin, sorbit, sorbitan, and oxyalkylene ethers of novolak type phenolic resins; polyvalent carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and its anhydrides.

Among them, the following amorphous polyesters are more preferable because the difference between the SP value (SP1) of the binder resin and the SP value (SP2) of the low molecular weight crystalline compound becomes small and the compatibility increases. ..
Contains 50 mol% or more of the propylene oxide adduct of bisphenol A as a divalent alcohol monomer component.
A carboxylic acid component consisting of a divalent or higher carboxylic acid or an acid anhydride thereof, or a 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 polycondensing 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, the storage stability is good, the decrease in electrical resistance due to the molecular motion of the resin is not induced in a high temperature and high humidity environment, and the chargeability does not deteriorate. On the other hand, when the glass transition temperature is 80 ° C. or lower, the fixability is good. Further, it is more preferable that the glass transition temperature is 40 ° C. or higher from the viewpoint of storage stability. Further, it is more preferable that the glass transition temperature is 70 ° C. or lower from the viewpoint of fixability.

The glass transition temperature (Tg) is measured using DSC (manufactured by METTLER TOLEDO Co., Ltd .: DSC822 / EK90). Specifically, 0.01 to 0.02 g of the sample is weighed in an aluminum pan, the temperature is raised to 200 ° C., and the sample cooled from that temperature to -100 ° C. at a temperature lowering rate of 10 ° C./min is heated to a temperature rising rate of 10. The calorific value is measured while raising the temperature at ° C / min. Next, from the obtained DSC curve, the temperature of the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the gradient of the curve of the stepwise change part of the glass transition is maximized. (So-called external 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. More preferred. When Tm is within the above temperature range, both blocking resistance and offset resistance are well achieved, and further, the toner melting component at the time of fixing at a high temperature is sufficiently permeated into the paper, which is good. Surface smoothness is obtained.

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

The melting temperature in the 1/2 method is calculated as follows.
First, find 1/2 of the difference between the piston descent amount at the end of the outflow (outflow end point, Smax) and the piston descent amount at the start of the outflow (minimum point, Smin). (This is referred to as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston is the sum of X and Smin was defined as the melting temperature in the 1/2 method.

The measurement sample is about 1.2 g of binder resin in an environment of 25 ° C. using a tablet molding compressor (for example, standard manual Newton Press NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa. Then, a columnar product having a diameter of about 8 mm is used, which is compression-molded for about 60 seconds. Specific operations in the measurement are performed according to the manual attached to the device.
The measurement conditions of CFT-500D are as follows.

Test mode: Hot compress start temperature: 60 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature rise 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: 1.0 mm

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. The acid value of the binder resin is preferably 3 to 35 mgKOH / g, more preferably 8 to 25 mgKOH / g. When 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 and the like contained in 1 g of the 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 for obtaining toner particles containing the binder resin, the low molecular weight crystalline compound, and a colorant. Granulation can be performed by a known toner production method such as a pulverization method, a suspension polymerization method, an emulsification / aggregation method, or a dissolution / suspension method.
Among them, the emulsification agglutination method is preferably used from the viewpoint that the toner particle size, the particle size distribution, and the toner shape can be easily controlled, and if necessary, the core shell can be easily formed.
Therefore, the emulsion aggregation method is exemplified below as a method for producing the toner of the present invention.

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

<Dispersion process>
-Aqueous dispersion of fine particles of the binder resin The aqueous dispersion of fine particles of the binder resin can be prepared by a known method. Known methods include an emulsification polymerization method, a self-emulsification method, a phase inversion emulsification method in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in an organic solvent, and an aqueous medium without using an organic solvent. There is 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 they are dissolved, and a surfactant or a basic compound is added. Subsequently, the aqueous medium is slowly added while stirring with a homogenizer or the like to precipitate the resin fine particles. Then, the solvent is removed by heating or reducing the pressure to prepare a resin fine particle dispersion liquid. As the organic solvent used for dissolution, any organic solvent that can dissolve the binder resin can be used, but it is possible to use an organic solvent that forms a uniform phase with water such as tetrahydrofuran. It is preferable from the viewpoint of suppressing the generation of coarse powder.

The surfactant used at the time of emulsification is not particularly limited, and examples thereof include the following. Anionic surfactants such as sulfate ester salt type, sulfonate type, carboxylate type, phosphoric acid ester type, soap type; 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. The surfactant may be used alone or in combination of two or more.

Examples of the basic compound used at the time of 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 50% particle size (d50) of the binding resin fine particles based on the volume distribution is 1.0 μm or less, toner particles having a volume-based median diameter of 4.0 to 7.0 μm suitable for the 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 type particle size distribution meter (Nanotrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).

-Aqueous dispersion of low molecular crystalline compound The aqueous dispersion of the low molecular crystalline compound can be prepared by the following known methods, but is not limited to these methods.
The aqueous dispersion of the low molecular weight crystalline compound heat-dissolves the low molecular weight crystalline compound in an organic solvent in which they are dissolved. The above-mentioned solution is added to an aqueous medium containing a surfactant, heated at a temperature at which the low-molecular-weight crystalline compound does not precipitate, and the oil phase is heated 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. Further, as the pressure discharge type disperser, for example, a "Gorin homogenizer" manufactured by Gorin Co., Ltd. can be mentioned.

By dispersing the oil phase in the form of particles and then evaporating and distilling off the organic solvent, fine particles containing the low molecular weight crystalline compound can be produced. As the organic solvent used for dissolution, any organic solvent that can dissolve the low molecular weight crystal can be used. However, it is preferable to use an organic solvent that forms an oil phase by phase separation from water such as toluene from the viewpoint of suppressing thickening of viscosity at the time of micronization and suppressing generation of coarse powder.

The dispersed particle size of the low molecular weight crystalline fine particles in the aqueous dispersion preferably has a volume-based median diameter of 1.0 μm or less, and more preferably 0.5 μm or less. Further, it is preferable that there are no coarse particles of 1 μm or more. When the dispersed particle size of the low-molecular-weight crystalline fine particles is within the above range, the low-molecular-weight crystalline compound is less likely to be exposed on the surface of the toner, and it is possible to suppress the occurrence of filming on the photoconductor. Further, the dispersed particle size of the low-molecular-weight crystalline fine particles is smaller because the smaller the dispersed particle size, the larger the contact area between the low-molecular-weight crystalline compound and the binder resin, and as a result, the rate of compatibility at the time of fixing increases. Is preferable. The dispersed particle size can be measured using a laser diffraction / scattering type 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 the colorant, the aqueous medium and the dispersant with a mixer such as a known stirrer, emulsifier, or disperser. As the dispersant used here, known ones such as a surfactant and a polymer dispersant 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, but from the viewpoint of cleaning efficiency, the surfactant is preferable, and among the surfactants, the anionic surfactant and the non-surfactant are not used. Ionic surfactants are more preferred. 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 is 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 the 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. Further, the dispersed particle size of the colorant fine particles in the aqueous dispersion is such that the 50% particle size (d50) based on the volume distribution is 0.5 μm or less from the viewpoint of the pigment dispersibility of the finally obtained toner. preferable. Further, for the same reason, it is preferable that the 90% particle size (d90) based on the volume distribution is 2 μm or less. The dispersed particle size of the colorant fine particles containing the pigment dispersed in the aqueous medium can be measured using a laser diffraction / scattering type particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.). ..

Known mixers such as stirrers, emulsifiers, and dispersers used to disperse colorants in aqueous media include ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint shakers. Can be mentioned. These may be used alone or in combination.

Examples of the surfactant include the following. Anionic surfactants such as sulfate ester salt type, sulfonate type, phosphoric acid 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 above-mentioned surfactant may be used alone or in combination of two or more. 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 mold release agent to an aqueous medium containing a surfactant, heating it above the melting point of the mold release agent, and dispersing it in the form of particles using a homogenizer or a 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. Further, as the pressure discharge type disperser, for example, a "Gorin homogenizer" manufactured by Gorin Co., Ltd. can be mentioned.

The dispersed particle size of the release agent fine particles in the aqueous dispersion preferably has a volume-based median diameter of 0.03 to 1.0 μm, more preferably 0.1 to 0.5 μm. Further, it is preferable that there are no coarse particles of 1 μm or more. When the dispersed particle size of the release agent fine particles is within the above range, the release of the release agent at the time of fixing becomes good, the hot offset temperature can be raised, and the filming on the photoconductor can be generated. It becomes possible to suppress. The dispersed particle size can be measured using a laser diffraction / scattering type particle size distribution measuring device (LA-920: manufactured by HORIBA, Ltd.).

<Aggregation process>
The agglomeration step is to prepare a mixed solution in which each of the following dispersions 1) to 3) or 1) to 4) below is mixed, and then the fine particles contained in the prepared mixed solution are aggregated for the purpose. This is a step of forming an agglomerate having a toner particle size.
1) Bound resin fine particle dispersion liquid in which fine particles of binder resin are dispersed 2) Low molecular crystal compound fine particle dispersion liquid in which fine particles of low molecular crystal compound are dispersed 3) Colorant fine particle dispersion liquid in which fine particles of colorant are dispersed 4) Mold release agent fine particle dispersion liquid in which fine particles of the mold release agent are dispersed By adding and mixing a flocculant to the above mixed liquid and appropriately applying heating and / or mechanical power as necessary, the following 1) to 3) or each of the following 1) to 4) fine particles is formed into a composite agglomerated particle.
1) Fine particles of binder resin 2) Fine particles of low molecular weight crystalline compound 3) Fine particles of colorant 4) Fine particles of release agent

As the coagulant, it is preferable to use a coagulant containing a metal ion having a divalent value or higher. Since the aggregating agent containing a monovalent metal ion has a weak cohesive force and needs to be added in a large amount in order to agglomerate the resin fine particles, 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 flocculant 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 can be added. Ionically neutralize. Then, the resin fine particles, the colorant fine particles, and the release agent fine particles are aggregated by the effects of salting out and ion cross-linking.

Examples of the flocculant 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, the following. 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 either the form of a dry powder or an aqueous solution dissolved in an aqueous medium, but it is preferably added in the form of an aqueous solution in order to cause uniform agglomeration. Further, the addition / mixing of the flocculant is preferably performed at a temperature equal to or lower than the glass transition temperature of the resin contained in the mixed dispersion. By performing the mixing under this temperature condition, aggregation proceeds uniformly. The flocculant can be mixed with the mixed dispersion using a known mixing device such as a homogenizer or a mixer.

The average particle size of the agglomerated particles formed in the agglomeration step is not particularly limited, but it is usually preferable to control the average particle size to be about the same as the average particle size of the toner to be finally obtained. The particle size of the agglomerated particles can be easily controlled by appropriately adjusting the temperature, the solid content concentration, the concentration of the aggregating agent, and the stirring conditions.

Further, by going through the steps 1) and 2) below, it is possible to produce toner particles having a core-shell structure.
1) An adhesion step of adhering the resin fine particles to the surface of the agglomerated particles by further adding resin fine particles for forming a shell to the dispersion liquid of the agglomerated particles obtained in the above agglomeration step.
2) A fusion step in which aggregated particles (core-shell particles) having resin fine particles adhered to the surface are heated and fused.
The resin fine particles for forming the shell to be 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 shell resin 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 described above. Specifically, vinyl-based 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 may be used in combination of two or more. Above all, it is preferable that the shell near the surface layer of the toner contains the low molecular weight crystalline compound and the binder resin.

Generally, when the 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 paper), and the adhesion between the toners between the toner surfaces and the adhesion between the toner surface and the paper An image fixed on 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 surface of the toner can be quickly plasticized and fixed. However, in the conventional crystalline polyesters and crystalline compounds, when they are present or exposed in the vicinity of the surface, the electric resistance of each of them is low, so that the chargeability of the toner is deteriorated.

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

Specifically, the binder resin and the low molecular weight crystalline compound are heat-dissolved in an organic solvent in which they are dissolved. The above-mentioned solution is added to an aqueous medium containing a surfactant, heated at a temperature at which the low-molecular-weight crystalline compound does not precipitate, and in the form of particles using a homogenizer or a pressure discharge type disperser having a strong shearing ability. Disperse in.
Examples of the homogenizer include "Clearmix W Motion" manufactured by M-Technique Co., Ltd. Further, as the pressure discharge type disperser, for example, a "Gorin homogenizer" manufactured by Gorin Co., Ltd. can be mentioned.

By dispersing the organic solvent in the form of particles and then evaporating and distilling off the organic solvent, composite fine particles containing the binder resin and the low molecular weight crystalline compound can be produced. As the organic solvent used for dissolution, any organic solvent can be used as long as it can dissolve the binder resin and the low molecular weight crystalline compound. However, it is preferable to use an organic solvent that forms an oil phase by phase separation from water such as toluene from the viewpoint of suppressing thickening of viscosity at the time of micronization and suppressing generation of coarse powder.

The surfactant used at the time of emulsification is not particularly limited, and examples thereof include the following. Anionic surfactants such as sulfate ester salt type, sulfonate type, carboxylate type, phosphoric acid ester type, soap type; 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. The surfactant may be used alone or in combination of two or more.

<Fusion process>
In the fusion step, the aggregation terminator is added to the dispersion liquid containing the aggregated particles obtained in the aggregation step under the same stirring as in the aggregation step. Examples of the aggregation arresting agent include a basic compound that shifts the equilibrium of the acidic polar group of the binder resin fine particles to the dissociation side and stabilizes the aggregation particles, a chelating agent, and the like, but the aggregation arresting action is more effective. Large chelating agents are preferably used. The chelating agent stabilizes the agglomerated particles by partially dissociating the ion cross-linking between the acidic polar group of the binder resin fine particles and the metal ion which is the aggregating agent and forming a coordination bond between the metal ion and the chelating agent. To become.

After the dispersed state of the agglomerated particles in the dispersion liquid is stabilized by the action of the agglutination stop agent, the particles are heated to a temperature equal to or higher than the glass transition temperature of the binder resin to fuse the binder resins together to fuse the toner.
The chelating agent is not particularly limited as long as it is a known water-soluble chelating agent. Specifically, oxycarboxylic acids such as tartrate acid, citric acid and gluconic acid and their sodium salts, iminodic acid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA) and organic metal salts such as these sodium salts. Can be mentioned. By coordinating the chelating agent with the metal ions of the aggregating agent existing in the dispersion liquid of the agglomerated particles, the environment in the dispersion liquid is electrostatically unstable and easily aggregated. It can be changed to a state in which it is stable and less likely to cause further aggregation. As a result, further agglomeration of the agglomerated particles in the dispersion liquid can be suppressed, and the agglomerated particles can be stabilized. The chelating agent is preferably an organometallic salt having a trivalent or higher carboxylic acid because it is effective even if the amount added is small and toner particles having a sharp particle size distribution can be obtained. The amount of the chelating agent to be mixed is preferably 1 to 30 parts by mass, preferably 2.5 to 15 parts by mass, based on 100 parts by mass of the resin, from the viewpoint of achieving both stabilization from the aggregated state and cleaning efficiency of the toner. The portion is more preferable.

Toner can be obtained by washing, filtering, drying and the like the particles produced through the above steps. After that, it is dried, and if necessary, inorganic particles such as silica, alumina, titania, and calcium carbonate, and resin particles such as vinyl resin, polyester resin, and silicone resin are subjected to shearing force in a dry state. It may be added. These inorganic particles and resin particles function as an external additive such as a fluidity aid and a cleaning aid.
Subsequently, a colorant containing a pigment, which is a constituent material constituting the toner of the present invention, and a mold release agent will be described.

<Colorant containing pigment>
The colorant of the present invention contains at least a known organic pigment, a pigment such as carbon black. The colorant of the present invention may further contain a dye.
Examples of the cyan colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. Specifically, the following can be mentioned. 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. Specifically, the following can be mentioned. 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 and 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. Specifically, the following can be mentioned. 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 and C.I. I. Pigment Yellow 191 and C.I. I. Pigment Yellow 194.

Examples of the black colorant include carbon black, magnetic powder, and those colored black using the yellow colorant, magenta colorant, and cyan colorant.
These colorants can be used alone or in admixture, and even in the form of a solid solution. The colorant used in the present invention is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the cyan colorant, magenta colorant, yellow colorant or 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 which are the 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) by heating; Fatty acid amides such as oleic acid amide, erucic acid amide, ricinolic acid amide, stearic acid amide; Ester waxes such as stearyl stearate; Plant waxes such as carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil; animal waxes such as beeswax; 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 the resins constituting the toner. When it is 1 part by mass or more, sufficient fixability at high temperature is obtained, and when it is 25 parts by mass or less, it is not exposed on the toner surface layer.

<Example>
Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but these are not intended to limit the present invention.

<Production of low molecular weight crystalline compound 1>
Halogenated aromatic hydrocarbon component; 2-chloronaphthalene 1.0 mol parts Higher alcohol component; Stearyl alcohol 1.1 mol parts Put 1000 parts by mass of acetone into a fully dried two-necked flask and add the above compound. The mixture was stirred and mixed, and sufficiently heated and dissolved 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 above reactive compound and refluxed for 2 hours. Further, when 0.5 mol parts of potassium carbonate was added to the reaction product and refluxed for 5 hours, the reaction proceeded by 90% or more, and a crude product of octadecylnaphthyl ether was obtained. After that, acetone was evaporated and distilled off, and recrystallization using hexane was repeated a plurality of times to obtain octadecylnaphthyl ether (SP: 9.7, melting point: 67 ° C.), which is the target low molecular weight crystalline compound 1. Obtained.

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

<Evaluation of charge retention of a single substance>
The charge retention of the simple substances of the low molecular weight crystalline compounds 1 to 7 produced above under high temperature and high humidity was measured by the following method. Then, it was compared and verified with crystalline polyester A, docosanol, stearic acid, stearic acid amide, and terphenyl, which are conventionally used crystalline compounds.
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) = 15,500, main Peak molecular weight (Mp) = 11,400, Mw / Mn = 2.8, melting point = 78 ° C., acid value = 13 mgKOH / g]

0.01 g of the measurement sample was weighed in an aluminum pan and charged to −600 V using a strocon charging device. Subsequently, the change behavior of the surface potential was measured for 30 minutes using a surface electrometer (manufactured by Trek Japan Co., Ltd .: model347) in an atmosphere of a temperature of 30 ° C. and a relative humidity of 80%. The measurement result was substituted into the following formula to calculate the charge retention rate, and its insulating property (charge retention property) was evaluated. The evaluation results are shown in Table 4.
Charge retention after 30 minutes (%) = [Surface potential after 30 minutes] / [Initial surface potential] x 100
(Evaluation criteria)
◯: The triboelectric retention rate of the crystalline compound after 30 minutes is 80% or more Δ: The triboelectric retention rate of the crystalline compound after 30 minutes is less than 80% and 60% or more.
X: The triboelectric retention rate of the crystalline compound after 30 minutes is less than 60%.

<Manufacturing of binding resin fine particles 1>
To 200 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), 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 the ultrafast stirrer T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix Corporation). Further, 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Then, tetrahydrofuran was removed using an evaporator to obtain binder resin fine particles 1.
The 50% particle size (d50) of the obtained binder resin fine particles 1 based on the volume distribution was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.13 μm. there were.

<Manufacturing of binding resin fine particles 2>
Bound resin fine particles 2 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 B. The 50% particle size (d50) of the obtained binder resin fine particles 2 based on the volume distribution was 0.12 μm.
-The composition (molar ratio) and physical properties of the polyester resin B are as shown in Table 2.

<Manufacturing of binding resin fine particles 3>
The 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 50% particle size (d50) of the obtained binder resin fine particles 3 based on the volume distribution was 0.12 μm.
-The composition (molar ratio) and physical characteristics of the polyester resin C are as shown in Table 2.

<Manufacturing of binding resin fine particles 4>
Bound resin fine particles 4 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 D. The 50% particle size (d50) of the obtained binder resin fine particles 4 based on the volume distribution was 0.12 μm.
-The composition (molar ratio) and physical characteristics of the polyester resin D are as shown in Table 2.

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

Next, the ultrafast stirrer T.I. K. While stirring at 4000 rpm using Robomix (manufactured by Primix Corporation), 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) of the binder resin fine particles 5 based on the volume distribution was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm. ..

<Production of fine particle dispersion of low molecular weight crystalline compound 1>
120 g of the low molecular weight crystalline compound 1 was added to 200 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), the mixture was heated to near the melting point of the low molecular weight crystalline compound, and then stirred for 12 hours to dissolve the low molecular weight crystalline compound 1. Next, an aqueous solution prepared by dissolving 3 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 6 g of an anionic surfactant (sodium lauryl sulfate) in 360 g of ion-exchanged water was added to the toluene solution. , Ultra-high speed stirrer T.I. K. A suspension solution was obtained by stirring at 4000 rpm using Robomix (manufactured by Primix Corporation). Then, 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 remove low molecular weight crystalline compounds. A fine particle dispersion of 1 was obtained.
The 50% particle size (d50) of the low molecular weight crystalline compound 1 based on the volume distribution was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.21 μm. Met.

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

<Manufacturing of fine particle dispersion of docosanol>
A fine particle dispersion of docosanol was obtained in the same manner as in the production of the fine particle dispersion of the low molecular crystalline compound 1 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 the volume distribution was 0.33 μm.

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

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

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

<Manufacturing of fine particle dispersion of crystalline polyester A>
To 200 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), 120 g of crystalline polyester A and 0.6 g of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) are added, heated to 50 ° C. and stirred for 3 hours to dissolve. rice field.
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) = 15,500, 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 the ultrafast stirrer T.I. K. The mixture was stirred at 4000 rpm using Robomix (manufactured by Primix Corporation). Further, 360 g of ion-exchanged water was added at a rate of 1 g / min to precipitate resin fine particles. Then, tetrahydrofuran was removed using an evaporator to obtain a fine particle dispersion of crystalline polyester A.
The 50% particle size (d50) of the crystalline polyester A fine particles based on the volume distribution was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and found to be 0.30 μm. rice field.

<Production of composite fine particle dispersion of polyester resin A and low molecular weight crystalline compound 1>
To 200 g of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), 96 g of polyester resin A and 24 g of low molecular weight crystalline compound 1 are added, heated to near the melting point of the low molecular weight crystalline compound, and then stirred for 12 hours to obtain the polyester resin A and the low molecular weight crystalline compound. The low molecular weight crystalline compound 1 was dissolved.
Next, an aqueous solution prepared by dissolving 3 g of an anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen RK) and 6 g of an anionic surfactant (sodium lauryl sulfate) in 360 g of ion-exchanged water was added to the toluene solution. After that, the ultra-high speed agitator T.I. K. A suspension solution was obtained by stirring at 4000 rpm using Robomix (manufactured by Primix Corporation).
Then, 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 remove the toluene to the polyester resin A. A dispersion of composite fine particles of the molecular crystalline compound 1 was obtained.
The 50% particle size (d50) of the composite fine particles of the polyester resin A and the low molecular weight crystalline compound 1 based on the volume distribution was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.). , 0.20 μm.

<Manufacturing of colorant fine particles>
-Colorant 10.0 parts by mass (Cyan pigment manufactured by Dainichiseika Kogyo Co., Ltd .: CI Pigment Blue 15: 3)
・ Anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts by mass ・ Ion-exchanged water 88.5 parts by mass Mix and dissolve each of the above materials to create a high-pressure impact disperser nanomizer ( An aqueous dispersion of colorant fine particles prepared by dispersing the colorant was prepared by dispersing the colorant using Yoshida Kikai Kogyo Co., Ltd. for about 1 hour. The 50% particle size (d50) of the obtained colorant fine particles based on the volume distribution was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and was 0.20 μm.

<Manufacturing of mold 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 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.0 part by mass・ 79.0 parts by mass of ion-exchanged water After putting each of the above materials into a mixing container equipped with a stirrer, heat to 90 ° C. and circulate to Claremix W Motion (manufactured by M-Technique Co., Ltd.) outside the rotor. At a shear stirring site having a diameter of 3 cm and a clearance of 0.3 mm, the mixture was stirred under the following conditions and subjected to dispersion treatment.
・ Rotor rotation speed 19000r / min ・ Screen rotation speed 19000r / min ・ Dispersion time 60 minutes After that, rotor rotation speed 1000r / min, screen rotation speed 0r / min, cooling speed up to 40 ° C. By cooling, an aqueous dispersion of the release agent fine particles was obtained. The 50% particle size (d50) of the release agent fine particles based on the volume distribution was measured using a dynamic light scattering type particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.) and was 0.15 μm.

<Toner manufacturing example 1>
-Ion exchange 400 parts by mass of water

After putting each of the above materials into a round stainless steel flask and mixing them, 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. Then, it was dispersed at 5000 r / min for 10 minutes using a homogenizer (manufactured by IKA: Ultratarax T50). Then, using a stirring blade in a water bath for heating, the mixture was heated to 58 ° C. while appropriately adjusting the rotation speed at which the mixture was stirred. After holding 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 Co., Ltd .: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that agglomerated particles having a volume average particle diameter of about 6.0 μm were formed.

An aqueous solution prepared by dissolving 20 parts by mass of trisodium citrate in 380 parts by mass of ion-exchanged water was added to the dispersion liquid of the agglomerated particles obtained in the agglomeration step, and then heated to 85 ° C. After holding at 85 ° C. for 2 hours, the volume average particle size and average circularity of the obtained particles were measured using a flow-type particle image analyzer (manufactured by Sysmex Co., Ltd .: FPIA-3000) in the operation manual of the device. Measured according to. As a result, a well-fused toner having a volume average particle size of about 5.8 μm and an average circularity of 0.968 was obtained. The aqueous dispersion of the obtained toner is cooled to 25 ° C. while maintaining stirring, filtered and separated into solid and liquid, and then the filtrate is thoroughly washed with ion-exchanged water and dried using a vacuum drier. As a result, toner particles 1 having a volume-based median diameter of 5.4 μm were obtained.

<Toner manufacturing examples 2 to 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 liquid of the binder resin fine particles 1 was changed to the dispersion liquid of the binder resin fine particles 2 to 3. rice field. The volume-based median diameter of the obtained toner particles was 5.5 μm.

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

<Toner manufacturing 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 volume-based median diameter of the obtained toner particles was 5.5 μm.

<Toner manufacturing example 10>
-Ion exchange 400 parts by mass of water

After putting each of the above materials into a round stainless steel flask and mixing them, an aqueous solution in which 2 parts by mass of magnesium sulfate is dissolved is added to 98 parts by mass of ion-exchanged water, and a homogenizer (manufactured by IKA: Ultratarax) is added. Using T50), the mixture was dispersed at 5000 r / min for 10 minutes. Then, using a stirring blade in a water bath for heating, the mixture was heated to 58 ° C. while appropriately adjusting the rotation speed at which the mixture was stirred. After holding at 58 ° C. for 1 hour, the volume average particle diameter of the formed core agglomerated particles was measured using a flow-type particle image analyzer (manufactured by Sysmex Co., Ltd .: FPIA-3000) according to the operation manual of the apparatus. .. As a result, it was confirmed that core agglomerated particles having a volume average particle diameter of about 5.0 μm were formed.

200 parts by mass of a composite fine particle dispersion liquid of the above polyester resin A and the low molecular weight crystalline compound 1 was added dropwise to the obtained core agglomerated particles, and further treated at 58 ° C. for 1 hour to be composited with the core agglomerated particles. Fine particles were attached. 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 colorless and transparent, and it was confirmed that all the composite fine particles of the added polyester resin A and the low molecular weight crystalline compound 1 were attached.

An aqueous solution prepared by dissolving 20 parts by mass of trisodium citrate 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 holding at 85 ° C. for 2 hours, the volume average particle size and average circularity of the obtained particles were measured using a flow-type particle image analyzer (manufactured by Sysmex Co., Ltd .: FPIA-3000) in the operation manual of the device. Measured according to. As a result, a well-fused toner having a volume average particle size of about 5.8 μm and an average circularity of 0.968 was obtained.
The aqueous dispersion of the obtained toner is cooled to 25 ° C. while maintaining stirring, filtered and separated into solid and liquid, and then the filtrate is thoroughly washed with ion-exchanged water and dried using a vacuum drier. As a result, the toner particles 10 having a volume-based median diameter of 5.4 μm were obtained.

<Toner manufacturing example 11>
-Ion exchange 400 parts by mass of water

After putting each of the above materials into a round stainless steel flask and mixing them, an aqueous solution in which 2 parts by mass of magnesium sulfate is dissolved is added to 98 parts by mass of ion-exchanged water, and a homogenizer (manufactured by IKA: Ultratarax) is added. Using T50), the mixture was dispersed at 5000 r / min for 10 minutes. Then, using a stirring blade in a water bath for heating, the mixture was heated to 58 ° C. while appropriately adjusting the rotation speed at which the mixture was stirred. After holding 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 Co., Ltd .: FPIA-3000) according to the operation manual of the apparatus. As a result, it was confirmed that agglomerated particles having a volume average particle diameter of about 6.0 μm were formed.

An aqueous solution prepared by dissolving 20 parts by mass of trisodium citrate in 380 parts by mass of ion-exchanged water was added to the dispersion liquid of the agglomerated particles obtained in the agglomeration step, and then heated to 85 ° C. After holding at 85 ° C. for 2 hours, the volume average particle size and average circularity of the obtained particles were measured using a flow-type particle image analyzer (manufactured by Sysmex Co., Ltd .: FPIA-3000) in the operation manual of the device. Measured according to. As a result, a well-fused toner having a volume average particle size of about 5.8 μm and an average circularity of 0.968 was obtained. The aqueous dispersion of the obtained toner is cooled to 25 ° C. while maintaining stirring, filtered and separated into solid and liquid, and then the filtrate is thoroughly washed with ion-exchanged water and dried using a vacuum drier. As a result, the toner particles 11 having a volume-based median diameter of 5.4 μm were obtained.

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

<Toner manufacturing examples 13-18>
Toner except that the dispersion liquid of the binder resin fine particles 4 was changed to the dispersion liquid of the binder resin fine particles 1 and the fine particle dispersion liquid of the low molecular weight crystalline compound 1 was changed to the fine particle dispersion liquid of the compounds shown in Table 3. Toner particles 13 to 18 were obtained in the same manner as in Production Example 11. The volume-based median diameter of the obtained toner particles 13 to 18 was 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 storage stability>
1.8 parts by mass of silica fine particles hydrophobized with silicone oil having a specific surface area of 200 m ^{2 / g measured by the BET method are dry-mixed with 100 parts by mass of toner particles using a Henschel mixer (manufactured by Mitsui Mine).} Toners to which an external additive was added were prepared. The amount of toner remaining on the sieve when the toner is allowed to stand 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 determined by the following criteria. Evaluated at. The evaluation results are shown in Table 5.

(Evaluation criteria)
◯: The amount of toner remaining on the sieve is 10% or less when sieving after standing in a constant temperature and humidity chamber at a temperature of 55 ° C. and a humidity of 10% for 3 days. The amount of toner remaining on the sieve is 10% or more when sieving after standing in a wet tank for 3 days, but after sieving in a constant temperature and constant humidity bath with a temperature of 50 ° C and a humidity of 10% for 3 days. The amount of toner remaining on the sieve is 10% or less ×: The amount of toner remaining on the sieve is 10 when the sieve is processed after standing in a constant temperature and humidity chamber at a temperature of 50 ° C. and a humidity of 10% for 3 days. %that's all

<Evaluation of low temperature fixability>
Toner particles of 100 parts by mass have a specific surface area of 200 m ² / g measured by the BET method, and 1.8 parts by mass of silica fine powder hydrophobized with silicone oil is dry-mixed with a Henschel mixer (manufactured by Mitsui Mine). Then, 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 copier (CLC1100, manufactured by Canon Inc.) to form an unfixed toner image (0.6 mg / cm ^{2 ) on image receiving paper (64 g / m 2).} did. The fixing unit removed from a commercially available full-color digital copying machine (imageRUNNER ADVANCE C5051, manufactured by Canon Inc.) was modified so that the fixing temperature could be adjusted, and a fixing test of an unfixed image was performed using this. The process speed was set to 246 mm / sec under normal temperature and humidity, and the state when the unfixed image was fixed was visually evaluated. The evaluation results are shown in Table 5.

(Evaluation criteria)
5: Can be fixed in a temperature range of 130 ° C or lower 4: Can be fixed in a temperature range higher than 130 ° C and 135 ° C or lower 3: Can be fixed in a temperature range higher than 135 ° C and 140 ° C or lower 2: 140 ° C Higher and can be fixed in the temperature range of 150 ° C or less 1: There is a fixable area only in the temperature range higher than 150 ° C

<Evaluation of chargeability>
Toner particles of 100 parts by mass have a specific surface area of 200 m ² / g measured by the BET method, and 1.8 parts by mass of silica fine powder hydrophobized with silicone oil is dry-mixed with a Henschel mixer (manufactured by Mitsui Mine). Then, 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 amount of charge of the toner particles was measured by an Espart analyzer manufactured by Hosokawa Micron Co., Ltd. The Espart analyzer is a device that introduces sample particles into a detection unit (measurement unit) that simultaneously forms an electric field and an acoustic field, measures the moving speed of the particles by the laser Doppler method, and measures the particle size and the amount of charge. .. The sample particles that have entered the measuring unit of the device are affected by the acoustic field and the electric field, and fall while being biased in the horizontal direction, and the beat frequency of this horizontal velocity is counted. The count value is input to the computer by an interrupt, and the particle size distribution or the charge amount distribution per unit particle size is displayed on the computer screen in real time. Then, when a predetermined number of charge amounts are measured, the screen stops, and then the three-dimensional distribution of the charge amount and the particle size, the charge amount distribution by particle size, the average charge amount (coulomb / weight), etc. are displayed on the screen. Is displayed in. By introducing the above-mentioned developer as sample particles into the measuring unit of the Espart analyzer, the amount of charge of the toner can be measured.

After measuring the triboelectric charge 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. and humidity 80%) for one week, and the triboelectric charge was measured again.
By substituting the measurement results into the following formula, the retention rate of the triboelectric charge was calculated and evaluated according to the following criteria. The evaluation results are shown in Table 5.
Formula: Toner triboelectric retention rate (%) = [Toner triboelectric charge after one week] / [Initial triboelectric charge] x 100

(Evaluation criteria)
◯: The triboelectric retention of the toner after 1 week is 80% or more Δ: The triboelectric retention of the toner after 1 week is less than 80% and 60% or more ×: The triboelectric 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 to 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 weight crystalline compound.
The low molecular weight crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton.
Toner having an SP value of the binder resin (SP1) and the SP value of the low-molecular crystalline compound (SP2) and is characterized by satisfying the following expression.
0 (cal / mol) ≤ | SP1-SP2 | ≤3 (cal / mol) The toner according to claim 1, wherein the low molecular weight crystalline compound has a melting point of 50 ° C. or higher and 100 ° C. or lower. The binder resin, toner according to claim 1 or 2 is an amorphous polyester is a condensation polymer of an alcohol component and a carboxylic acid component comprising propylene oxide adduct of bisphenol A 50 mol% or more. Claims 1 to 3 are toners having a core-shell structure, wherein the toner has a shell containing the binder resin and the low molecular weight crystalline compound on the surface of a core containing the binder resin and the colorant. The toner according to any one of the above. The binder resin fine particle dispersion liquid in which the binder resin fine particles are dispersed and the colorant fine particle dispersion liquid in which the colorant fine particles are dispersed are mixed, and the binder resin fine particles and the colorant fine particles are agglomerated to form core agglomerated particles. The process of forming,
The binder resin and low-molecular crystalline compound is dissolved in an organic solvent, the resulting solution Ru is dispersed in an aqueous medium process,
C. in aqueous medium, and removing the organic solvent from the lysis solution, to obtain a composite fine particles containing the binder resin and the low molecular crystalline compound process,
An adhesion step of adhering the composite fine particles to the core agglomerated particles to form core-shell particles in the aqueous medium, and a fusion step of heating the core-shell particles to a temperature equal to or higher than the glass transition temperature of the binder resin to fuse them. ,
A method of manufacturing a toner have a,
The low molecular weight crystalline compound is an ether compound containing a long-chain hydrocarbon skeleton having 12 to 26 carbon atoms and an aromatic hydrocarbon skeleton.
Method for producing a toner, wherein the SP value of the binder resin (SP1) and the SP value of the low-molecular crystalline compound (SP2) and satisfies the following expression.
0 (cal / mol) ≤ | SP1-SP2 | ≤3 (cal / mol)