JP6740700B2 - Toner for developing electrostatic image and method for producing the same - Google Patents

Description

The present invention relates to an electrostatic charge image developing toner and a method for producing the same.

In recent years, reduction of heat energy at the time of fixing a toner image has been demanded for the purpose of increasing print speed, expanding paper types, and reducing environmental load. In order to reduce the thermal energy at the time of fixing the toner image, there is a demand for a technique capable of improving the low-temperature fixability of the toner for electrostatic image development (hereinafter, also simply referred to as a toner), and one of the means for achieving this is. As one of them, a method is known in which a crystalline resin such as crystalline polyester having excellent sharp melt property is used as a binder resin.

For example, Patent Document 1 proposes a toner containing a binder resin containing a crystalline polyester resin and an amorphous resin. By using a crystalline polyester resin and an amorphous resin as a binder resin in a mixture, the crystalline component melts when the melting point of the crystalline polyester resin exceeds the melting point during thermal fixing, and the crystalline component is compatible with the amorphous component. .. This accelerates the thermal melting of the amorphous resin and enables fixing at low temperature.

JP, 2006-251564, A JP, 2005-4962, A

However, in a system in which a crystalline polyester resin is mixed with an amorphous resin such as styrene-acrylic resin, the presence of the crystalline polyester resin in the toner particles causes a rapid decrease in the viscosity of the toner during heat fixing. If it occurs, there is a problem that the releasability becomes insufficient and the fixing support is easily wound around the fixing member, resulting in poor fixing separation. Further, in a system in which a crystalline polyester resin and an amorphous resin are mixed and used, toner particles sometimes aggregate when the toner is stored under heat exposure (for example, about 50° C.).

The present invention has been made in view of the above problems and circumstances, and an object of the present invention is to provide a toner for developing an electrostatic charge image, which is excellent in low-temperature fixability, and has improved heat-resistant storage property and fixing separation property. Is.

The present invention includes a mold releasing agent in a core portion composed of an amorphous resin and a crystalline polyester resin having a structural unit derived from a (meth)acrylic acid-based monomer having a long-chain alkyl group, and further, A toner for developing an electrostatic charge image, which comprises a hybrid amorphous resin in a shell portion that covers a core portion, and the release agent is a mixture of two specific waxes.

With the above-mentioned constitution, the toner for developing an electrostatic charge image has excellent low-temperature fixability and improved heat-resistant storage property and fixing separation property.

The first embodiment of the present invention is a toner for developing an electrostatic charge image containing a binder resin and a release agent, wherein the binder resin is an amorphous vinyl resin, a crystalline polyester resin, and an amorphous resin. A hybrid amorphous resin in which a polyester polymerized segment and an amorphous vinyl polymerized segment are chemically bonded, and a releasing agent is a fatty acid ester consisting of a glycerin condensate and a linear saturated fatty acid having 16 to 24 carbon atoms. A non-crystalline vinyl resin containing A and a fatty acid ester B composed of a linear saturated alcohol having 16 to 24 carbon atoms and a linear saturated fatty acid having 16 to 24 carbon atoms is represented by the following general formula (1):

[In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents an alkyl group having 8 to 22 carbon atoms. ] A structural unit derived from a (meth)acrylic acid alkyl ester-based monomer represented by, and a core portion containing an amorphous vinyl resin, a crystalline polyester resin, a fatty acid ester A and a fatty acid ester B, and a hybrid An electrostatic charge image developing toner having a core-shell structure having a shell portion containing an amorphous resin.

With the above-mentioned constitution, the toner for developing an electrostatic charge image has excellent low-temperature fixability and improved heat-resistant storage property and fixing separation property. Hereinafter, the fatty acid ester A and the fatty acid ester B are also referred to as a wax mixture or simply a wax.

Although the mechanism by which the toner of the first embodiment achieves the above effect is unknown, it is presumed as follows. The technical scope of the present invention is not limited by the mechanism described below.

First, the toner of the first embodiment, the general formula _(1): in _{H 2 C = CR 1 -COOR 2} [ wherein, _{R 1} represents a hydrogen atom or a methyl group. R ₂ represents an alkyl group having 8 to 22 carbon atoms. ] An amorphous vinyl resin having a structural unit derived from a (meth)acrylic acid alkyl ester-based monomer represented by As described in Patent Document 1 above, in order to improve low-temperature fixability, a combination of an amorphous vinyl resin and a crystalline polyester resin has been performed. The present inventors considered that the affinity between the crystalline polyester and the amorphous vinyl resin may be important in order to further improve the low-temperature fixability. That is, if the affinity between the two is low, it is difficult to make both coexist inside the toner particles, and it is assumed that the crystalline polyester resin is extruded from the toner particles during the manufacturing process. It was hypothesized that by enhancing the affinity with the non-crystalline vinyl resin, such discharge is suppressed and the low temperature fixability is enhanced. Based on these assumptions, as a result of earnest studies, it was found that the inclusion of a relatively long-chain alkyl group in the constituent unit that constitutes the amorphous vinyl resin improves the low-temperature fixability of the toner. This is because inclusion of a relatively long-chain alkyl group in the constituent units that make up the amorphous vinyl resin enhances the affinity between the amorphous vinyl resin and the crystalline polyester resin, and the crystalline polyester is produced at the time of production. It is considered that the resin can stay in the toner particles without being discharged, and as a result, the low temperature fixability is further improved.

Further, the toner of the first embodiment is a toner for developing an electrostatic charge image, which has further improved heat resistant storage property and fixing separation property. Generally, a high fixing separation property of toner particles is realized by the release agent quickly leaching from the toner particles during heat fixing. However, if it is attempted to accelerate the exudation of the release agent to the outside of the system to improve the fixing separation property, when the storage environment of the toner reaches a high temperature (for example, about 50° C.), the release agent stains are removed. Agglomeration of toner particles due to ejection is likely to occur. For this reason, it has been difficult to achieve both the improvement of the fixing separation property and the improvement of the heat resistant storage property.

In the toner of the first embodiment, the amorphous vinyl resin forming the core portion has a (meth)acrylic acid alkyl ester-based monomer having a long-chain alkyl group as a constitutional unit, and thus, can form a release agent. Since the compatibility is increased, it becomes possible to include the release agent in the core part. Furthermore, by providing the shell portion with the hybrid amorphous resin, it is possible to prevent the release agent from seeping out from the core portion even when the toner is stored under the condition of being exposed to heat.

Further, the crystalline polyester resin lowers the chargeability of the toner, and therefore, for the purpose of reducing the exposure of the crystalline polyester resin to the surface, for example, the crystalline polyester resin is used as the core part and the amorphous polyester is used as the shell part. The form of using a resin has been adopted. When the core contains an amorphous vinyl resin, it becomes incompatible with the amorphous polyester resin usually used for the shell, and it becomes difficult to form a uniform shell on the surface of the core. However, in the present embodiment, the shell portion contains the hybrid amorphous resin, and since the hybrid amorphous resin has the amorphous vinyl polymer segment, the partial phase at the interface between the shell portion and the core portion is Although the melting progresses, it becomes possible to form a more uniform shell portion with respect to the surface of the core portion while the binder resin as a whole is incompatible. Therefore, the toner of this exemplary embodiment can have improved low temperature fixability and heat resistant storage stability.

Furthermore, in this embodiment, a specific wax mixture is used as a release agent. When a wax composed of a fatty acid ester A which is a specific glycerin condensate ester and a fatty acid ester B which is a monoester is melted, its volume is significantly increased as compared with the case where each wax is used alone ( See Patent Document 2, Paragraph “0011”). The mechanism of action is not critical, but the fatty acid ester A, which is an ester composed of a specific glycerin condensate having a sterically bulky molecular structure, and the fatty acid ester B, which is a linear fatty acid ester, are mixed and melted to return to a solid state. In this case, the way in which the gaps formed in the crystal structure are formed changes in the process of crystallizing while mixing two kinds of waxes having different structures. In addition, it is assumed that the easiness of steric repulsion between molecules also changes, and the volume expansion rate becomes larger than that when each wax is used alone. Due to such an increase in volume, the wax quickly exudes from the toner particles due to the heat at the time of fixing, while the wax remains in the particles even when stored under high temperature conditions (for example, 50 to 60° C.). It is considered possible.

Therefore, the release agent is included in the core part, and the core part is covered with the shell part of the hybrid amorphous resin. Further, by using the specific wax mixture, the toner particle surface is fixed at the temperature necessary for fixing. The toner particles have excellent exudation to the surface and have high releasability from the roll, but also have excellent heat-resistant storage stability even when the toner is stored under heat exposure conditions (for example, about 50° C.).

The electrostatic image developing toner according to the first embodiment is configured to include at least a binder resin and a release agent.

The toner refers to an aggregate of toner base particles containing a binder resin and a release agent, or an aggregate of toner particles in which an external additive is added to the base particles.

In one embodiment of the present invention, the toner base particles include a core portion containing an amorphous vinyl resin, a crystalline polyester resin, a fatty acid ester A and a fatty acid ester B, an amorphous polyester polymerization segment, and an amorphous vinyl polymerization. And a shell portion containing a hybrid amorphous resin, which is chemically bonded to a segment, and has a core-shell structure. The toner base particles optionally contain a colorant.

The structure of the core portion is not particularly limited and may be a single-layer structure or a multi-layer structure, but is preferably a multi-layer structure. This is because by forming the wax into a plurality of layers, the wax can be contained in the inner layer which is not the outermost layer, and by suppressing the exposure of the wax to the surface, it is possible to suppress the decrease in heat resistant storage stability. Therefore, in a preferred embodiment of the present invention, the toner base particles have the above core-shell structure, and the core part is a fusion product of aggregates containing the multilayer resin particles, and the multilayer resin particles have inner layers than the outermost layer. The layer contains fatty acid ester A and fatty acid ester B. At this time, it is preferable that the outermost layer of the multilayer resin particles does not contain the fatty acid ester A and the fatty acid ester B.

Furthermore, an amorphous vinyl resin containing a fatty acid ester A and a fatty acid ester B, and a structural unit derived from a (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1) having a high affinity with them. The presence of and in the same layer can further improve the heat-resistant storage property and releasability. Therefore, in another preferred embodiment of the present invention, the toner base particles have the core-shell structure, and the core portion is a fusion product of aggregates containing the multilayer resin particles, and the multilayer resin particles are more than the outermost layer. The inner layer contains an amorphous vinyl resin containing a structural unit derived from the (meth)acrylic acid alkyl ester monomer represented by the general formula (1), a fatty acid ester A and a fatty acid ester B. At this time, it is preferable that the outermost layer of the multilayer resin particles does not contain the fatty acid ester A and the fatty acid ester B. Here, the number of layers in the case of forming a multilayer structure is not particularly limited, but considering productivity and effects, it is preferably 2 to 5 layers, and more preferably 2 to 3 layers. ..

The shell portion may not cover the entire surface of the core portion, or the core portion may be partially exposed. The cross section of the core-shell structure can be confirmed by a known observation means such as a transmission electron microscope (TEM) and a scanning probe microscope (SPM).

In the case of the core-shell structure, the characteristics such as the glass transition point, the melting point, and the hardness can be made different between the core portion and the shell portion, and the toner particles can be designed according to the purpose. For example, a resin having a relatively high glass transition point (Tg) is aggregated and fused on the surface of a core portion containing a binder resin, a colorant, a release agent, etc. and having a relatively low glass transition point (Tg). Can form a shell portion.

Further, the fact that the crystalline polyester resin and the wax are included in the core part can be confirmed by known observation means such as a transmission electron microscope (TEM) and a scanning probe microscope (SPM). , Can be confirmed.

Each material constituting the electrostatic image developing toner will be described below. The present invention is not limited to the following embodiments. Further, in the present specification, “X to Y” indicating a range means “X or more and Y or less”. Unless otherwise specified, the operation and measurement of physical properties are performed under the conditions of room temperature (20 to 25° C.)/relative humidity 40 to 50% RH. Furthermore, in the present specification, (meth)acrylic is a general term for acrylic and methacrylic.

<Binder resin>
The binder resin includes an amorphous vinyl resin, a crystalline polyester resin and a hybrid amorphous resin.

(Amorphous vinyl resin)
The amorphous vinyl resin has the following general formula (1):

[In General Formula (1), R ₁ represents a hydrogen atom or a methyl group, and R ₂ represents an alkyl group having 8 to 22 carbon atoms. ]
It has a structural unit derived from a (meth)acrylic acid alkyl ester-based monomer represented by.

Since the alkyl group represented by R ₂ is a long chain having 8 to 22 carbon atoms, it has a high affinity for a crystalline polyester resin and a highly hydrophobic resin such as wax which is a release agent. .. Due to the presence of the chain portion of the crystalline polyester resin and the amorphous vinyl resin having an alkyl group with a high affinity for wax, the crystallinity is significantly different from that of the amorphous vinyl resin in the amorphous vinyl resin. The polyester resin and the wax are not discharged from the resin during manufacturing, and the crystalline polyester resin and the wax can be included inside the toner base particles.

In the general formula (1), R ₂ represents an alkyl group having 8 to 22 carbon atoms. R ₂ preferably has 8 to 18 carbon atoms, and more preferably 8 to 12 carbon atoms. The alkyl group is preferably a linear alkyl group or a branched alkyl group. As the alkyl group represented by R ₂ , specifically, an n-octyl group, an n-nonyl group, an n-decyl group, an n-undecyl group, an n-dodecyl group, an n-tridecyl group, an n-tetradecyl group, Linear alkyl groups such as n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group and n-icosyl group; 1-methylheptyl group, 2-ethylhexyl group, 2- Methylheptyl group, 2-methyloctyl group, 2-methylnonyl group, 2-methyldecyl group, 2-methyldodecyl group, 2-methylhexadecyl group, 2-methylnonadecyl group, 2-ethylheptyl group, 2-ethyloctyl group, 2-ethylnonyl group, 2-ethyldecyl group, 2-ethyldodecyl group, 2-ethylpentadecyl group, 2-ethyloctadecyl group, 2-propylhexyl group, 2-propylheptyl group, 2-propyloctyl group, 2-propyl Nonyl group, 2-propyldecyl group, 2-propyldodecyl group, 2-propylheptadecyl group, 2-butylhexyl group, 2-pentylheptyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-heptylnonyl group , 2-octyldecyl group, 2-nonyldodecyl group, 3-methylheptyl group, 3-methyloctyl group, 3-methylnonyl group, 3-methyldecyl group, 3-methyldodecyl group, 3-methylhexadecyl group, 3- Methyl nonadecyl group, 3-ethylhexyl group, 3-ethylheptyl group, 3-ethyloctyl group, 3-ethylnonyl group, 3-ethyldecyl group, 3-ethyldodecyl group, 3-ethylpentadecyl group, 3-ethyloctadecyl group, 3 -Propylhexyl group, 3-propylheptyl group, 3-propyloctyl group, 3-propylnonyl group, 3-propyldecyl group, 3-propyldodecyl group, 3-propylheptadecyl group, 3-butylheptyl group, 3- Pentyloctyl group, 3-hexylnonyl group, 3-heptyldecyl group, 3-octyldodecyl group, 2,2-dimethylhexyl group, 2,2-methylethylheptyl group, 2,3-dimethylhexyl group, 2,4- Examples thereof include branched-chain alkyl groups such as dimethylhexyl group and 2,5-dimethylhexyl group.

Specific examples of the (meth)acrylic acid alkyl ester monomer represented by the general formula (1) include 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 1-methylheptyl acrylate, 2-propylheptyl acrylate, Examples thereof include (meth)acrylic acid alkyl esters such as 6-methylheptyl acrylate, isooctyl acrylate, isononyl acrylate, isodecyl acrylate, tridecyl acrylate, tridecyl methacrylate, and isostearyl acrylate.

The (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1) may be used alone or in combination of two or more.

The content of the structural unit derived from the (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1) is preferably 1.0 to 14.0 mass% in the toner base particles, and 2 It is more preferably from 0 to 10 mass %. Within such a range, the release agent is exuded from the toner particles well, and the fixing separation property is improved. On the other hand, both are efficiently encapsulated inside the toner particles, so that heat-resistant storage is possible. The property is improved.

Further, from the viewpoint of heat resistant storage property, the total content of the fatty acid ester A, the fatty acid ester B and the crystalline polyester resin in the core part is derived from the alkyl acrylate ester monomer represented by the general formula (1). It is preferably 120 times or less the content mass of the structural unit, and more preferably 10 times or less, since the heat resistant storage property and the fixing separability are further improved at the same time, and the fixing separability and low temperature fixing are good. From the viewpoint of sex, it is preferably 2 to 4 times.

The content of the structural unit derived from the monomer having the structure represented by the general formula (1) in the toner particles is determined by the charging of the monomer having the structure represented by the general formula (1) at the production stage. When the amount is known, the content of the monomer having the structure represented by the general formula (1) in the toner particles is calculated from the charged amount of the monomer having the structure represented by the general formula (1). Calculate by calculation.

Further, the content of the structural unit derived from the monomer having the structure represented by the general formula (1) in the toner particles is, for example, pyrolysis gas chromatography mass spectrometry (GC/MS: Gas Chromatography/Mass Spectrometry). ) Method.

Specifically, it can be quantified by the standard addition method using a column and a detector confirmed to be able to detect the monomer having the structure represented by the general formula (1). Detailed thermal decomposition conditions and GC/MS measurement conditions are as follows.
(Pyrolysis conditions)
Measuring device: PY-2020iD (made by Frontier Lab)
Measurement mass: 0.1mg
Heating temperature: 550°C
Heating time: 0.5 minutes (GC/MS measurement conditions)
Measuring device: QP2010 Shimadzu column: UltraALLOY-5 (inner diameter: 0.25 mm, length: 30 m, thickness: 0.25 μm, manufactured by Frontier Lab)
Temperature range: 40°C to 320°C (hold at 320°C)
Temperature rising rate: 20° C./min The above-mentioned amorphous vinyl resin, if it is obtained by polymerizing the (meth)acrylic acid alkyl ester-based monomer represented by the above general formula (1), the unit amount It may be a polymer of only the body or a copolymer of the monomer and another monomer. Other monomers include styrene-based monomers such as styrene and styrene derivatives; (meth)acrylic acid-based monomers other than the (meth)acrylic acid-based monomer represented by the general formula (1). Etc. can be used.

Examples of the styrene-based monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p. Examples thereof include -tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof. Of these, styrene is preferably used.

The (meth)acrylic acid-based monomer other than the (meth)acrylic acid-based monomer represented by the general formula (1) is preferably an alkyl group having 1 to 7 carbon atoms, more preferably 2 to 4 carbon atoms. The (meth)acrylate which it has is preferable, and, specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isopropyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth). ) Acrylate, phenyl (meth)acrylate and the like. Especially, it is preferable to use n-butyl (meth)acrylate. Here, (meth)acrylate is a general term for acrylate and methacrylate.

Other examples of other monomers include, for example, acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester, and 2-hydroxy. Ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , Polyethylene glycol mono(meth)acrylate and the like.

The other monomers may be used alone or in combination of two or more. Above all, it is preferable to include the styrene-based monomer as the other monomer because the plasticity at the time of heat fixing is good. That is, a preferred embodiment of the present invention is a form in which the amorphous vinyl resin contains a structural unit derived from a styrene-based monomer (the amorphous vinyl resin is a styrene-acrylic resin). The content of the structural unit derived from the styrene-based monomer in the amorphous polyester resin is preferably 1 to 95% by mass, more preferably 20 to 80% by mass.

The weight average molecular weight (Mw) of the amorphous vinyl resin is preferably 20,000 to 150,000, and more preferably 20,000 to 50,000 from the viewpoint of binding property.

In the present specification, as the weight average molecular weight (Mw), a value obtained from the molecular weight distribution measured by gel permeation chromatography (GPC) is adopted as follows.

The sample was added to tetrahydrofuran (THF) so as to have a concentration of 1 mg/mL, dispersed at room temperature for 5 minutes using an ultrasonic disperser, and then treated with a membrane filter having a pore size of 0.2 μm to prepare a sample solution. Prepare. Using a GPC device HLC-8120GPC (manufactured by Tosoh Corporation) and a column TSKguardcolumn+TSKgelSuperHZ-m3 (manufactured by Tosoh Corporation), tetrahydrofuran is flown at a flow rate of 0.2 mL/min as a carrier solvent while maintaining the column temperature at 40°C. 10 μL of the prepared sample solution was injected into a GPC device together with a carrier solvent, the sample was detected using a refractive index detector (RI detector), and a calibration curve measured using monodisperse polystyrene standard particles was used. Calculate the molecular weight distribution of the sample. Ten points are used as polystyrene for measuring the calibration curve.

The glass transition point (Tg) of the amorphous vinyl resin is preferably in the range of 20 to 70° C. from the viewpoint of both the fixability and the heat resistant storage stability.

The glass transition point (Tg) can be measured by the method described in the following examples according to the method (DSC method) defined in ASTM (American Society for Testing and Materials Standards) D3418-82.

In the present specification, the amorphous resin refers to a resin that does not have a clear endothermic peak in the DSC curve measured as described above.

Since the amorphous vinyl resin has a high degree of freedom in resin design and the charge control is easy, it is preferable to use it as the main component in the binder resin. It is preferably mass%.

(Crystalline polyester resin)
A crystalline polyester resin is used from the viewpoint of achieving both low temperature fixability and heat resistant storage stability of the toner. The “crystalline polyester resin” is a known polyester obtained by a polycondensation reaction of a divalent or higher carboxylic acid (polyvalent carboxylic acid) and its derivative with a divalent or higher valent alcohol (polyhydric alcohol) and its derivative. Among the resins, it refers to a resin having a clear endothermic peak instead of a stepwise endothermic change in differential scanning calorimetry (DSC). The definite endothermic peak specifically means that the half-value width of the endothermic peak is within 15° C. when measured at a temperature rising rate of 10° C./min in differential scanning calorimetry (DSC) described in the following examples. It means a certain peak. Examples of polyvalent carboxylic acid derivatives include alkyl esters of polyvalent carboxylic acids, acid anhydrides and acid chlorides, and examples of polyhydric alcohol derivatives include ester compounds of polyhydric alcohols and hydroxycarboxylic acids.

The polycarboxylic acid is a compound containing two or more carboxyl groups in one molecule. Among these, a divalent carboxylic acid is a compound containing two carboxyl groups in one molecule, and examples thereof include oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, sebacic acid, azelaic acid, and n-dodecyl. Succinic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (dodecanedioic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid (tetradecanedioic acid), 1,13-tri Saturated aliphatic dicarboxylic acids such as decanedicarboxylic acid and 1,14-tetradecanedicarboxylic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid; Examples thereof include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid. Examples of the polyvalent carboxylic acid other than the divalent carboxylic acid include trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid. Examples of the polycarboxylic acid derivative include anhydrides of these carboxylic acid compounds and alkyl esters having 1 to 3 carbon atoms. These may be used alone or in combination of two or more.

Polyhydric alcohol is a compound containing two or more hydroxyl groups in one molecule. Among them, the divalent polyol (diol) is a compound containing two hydroxy groups in one molecule, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol and 1,4-butane. Diol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12- Aliphatic diols such as dodecane diol, neopentyl glycol and 1,4-butene diol can be mentioned. Examples of the polyol other than the divalent polyol include trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol. These may be used alone or in combination of two or more.

Further, depending on the valency of the polyhydric carboxylic acid and the valency of the polyhydric alcohol, it may have some branching or crosslinking.

The method for forming the crystalline polyester resin using the above monomer is not particularly limited, and by polycondensing (esterifying) the above polyvalent carboxylic acid and polyhydric alcohol using a known esterification catalyst. The resin can be formed. Esterification catalysts that can be used include titanium acetate, titanium propionate, titanium hexanoate, titanium monocarboxylic acid aliphatic such as titanium octanoate, titanium oxalate, titanium succinate, titanium maleate, titanium adipate, sebacic acid. Aliphatic carboxylic acids such as titanium aliphatic dicarboxylates such as titanium, titanium hexane tricarboxylate, titanium titanium tricarboxylates such as isooctane tricarboxylic acid, titanium octane tetracarboxylates, titanium titanium polycarboxylates such as titanium decane tetracarboxylates, etc. Aromatic titanium monocarboxylic acid such as titanium oxide and titanium benzoate, titanium phthalate, titanium terephthalate, titanium isophthalate, titanium naphthalene dicarboxylate, titanium biphenyldicarboxylate, titanium anthracenedicarboxylate and the like; Aromatic titanium carboxylates such as titanium trimellitate and titanium naphthalene tricarboxylate; titanium aromatic tetracarboxylates such as titanium benzenetetracarboxylate and titanium naphthalene tetracarboxylate; Titanium compounds of titanium and titanium aromatic carboxylates and their alkali metal salts, titanium halides such as dichlorotitanium, trichlorotitanium, tetrachlorotitanium and tetrabromotitanium, tetrabutoxytitanium (titanium tetrabutoxide), tetra Examples thereof include titanium-containing catalysts such as tetraalkoxytitaniums such as octoxytitanium and tetrastearyloxytitanium, titanium acetylacetonate, titanium diisopropoxide bisacetylacetonate, and titanium triethanolaminate.

The content of the crystalline polyester resin in the toner base particles is preferably in the range of 1 to 20% by mass, and in the range of 5 to 15% by mass, from the viewpoint of obtaining sufficient low-temperature fixability and heat-resistant storage property. Is more preferable. With the above-mentioned amorphous vinyl resin, the crystalline polyester resin having a content within this range can be uniformly dispersed in the toner particles, and crystallization can be sufficiently suppressed.

The melting point (Tm) of the crystalline polyester resin is preferably in the range of 50 to 90° C., and in the range of 60 to 80° C. from the viewpoint of obtaining sufficient low temperature fixability and heat resistant storage stability. preferable. As the melting point (Tm) of the crystalline polyester resin, the value measured by the method described in Examples is adopted.

The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 5,000 to 50,000, and more preferably 5,000 to 30,000 from the viewpoint of low temperature fixability and gloss stability. preferable.

(Hybrid amorphous resin)
The hybrid amorphous resin (hereinafter, also simply referred to as hybrid amorphous resin) contained in the shell portion is a resin in which an amorphous polyester polymerized segment and an amorphous vinyl polymerized segment are chemically bonded.

In the above, the amorphous polyester polymerized segment refers to a portion derived from the amorphous polyester resin. That is, it refers to a molecular chain having the same chemical structure as that of the amorphous polyester resin. Further, the amorphous vinyl polymer segment refers to a portion derived from the amorphous vinyl resin. That is, it refers to a molecular chain having the same chemical structure as that of the amorphous vinyl resin.

The hybrid amorphous resin may be in any form such as a block copolymer or a graft copolymer as long as it contains an amorphous polyester polymerized segment and an amorphous vinyl polymerized segment. It is preferable that they are united. By using the graft copolymer, the finally obtained toner has improved heat-resistant storage stability and mold releasability while maintaining good low-temperature fixability.

Furthermore, from the above viewpoint, it is preferable that the amorphous polyester polymerized segment has a structure in which the amorphous vinyl polymerized segment has a main chain and is grafted. That is, the hybrid amorphous resin is preferably a graft copolymer having an amorphous vinyl polymer segment as a main chain and an amorphous polyester polymer segment as a side chain. With such a configuration, the finally obtained toner has improved heat-resistant storage property and release separation property while maintaining good low-temperature fixability.

<<Amorphous polyester polymerized segment>>
The amorphous polyester polymerized segment is a portion derived from a known polyester resin obtained by a polycondensation reaction between a divalent or higher carboxylic acid (polyvalent carboxylic acid component) and a divalent or higher valent alcohol (polyhydric alcohol component). That is, the polymerized segment in which a clear endothermic peak is not observed in the differential scanning calorimetry (DSC) of the toner.

The amorphous polyester polymerized segment is not particularly limited as long as it is as defined above. For example, regarding a resin having a structure in which the main chain of the amorphous polyester polymerized segment is copolymerized with another component, or a resin having a structure in which the amorphous polyester polymerized segment is copolymerized with the main chain of the other component, If the toner containing the resin does not have a clear endothermic peak as described above, the resin corresponds to the hybrid amorphous resin having the amorphous polyester polymerized segment in the present invention.

Examples of the polyvalent carboxylic acid component include oxalic acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, Fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid, tartaric acid, mucus acid, phthalic acid, Isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, Diphenyl acids such as diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, dodecenylsuccinic acid And trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid and the like. These polyvalent carboxylic acids can be used alone or in admixture of two or more.

Among these, from the viewpoint of easily obtaining the effects of the present invention, fumaric acid, maleic acid, aliphatic unsaturated dicarboxylic acids such as mesaconic acid, and aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid, succinic acid, and trimellitate It is preferable to use an acid.

Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, dodecanediol, an ethylene oxide adduct of bisphenol A, and propylene oxide of bisphenol A. Divalent alcohols such as adducts; trihydric or higher polyols such as glycerin, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, and tetraethylolbenzoguanamine. These polyhydric alcohol components may be used alone or in admixture of two or more.

Among these, dihydric alcohols such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A are preferable from the viewpoint of easily obtaining the effect of the present invention.

The use ratio of the polyhydric carboxylic acid component and the polyhydric alcohol component is the equivalent ratio [OH]/[COOH] of the hydroxyl group [OH] of the polyhydric alcohol component and the carboxyl group [COOH] of the polyhydric carboxylic acid component. ], 1.5/1 to 1/1.5 is preferable, and 1.2/1 to 1/1.2 is more preferable. When the use ratio of the polyhydric alcohol component and the polycarboxylic acid component is within the above range, it becomes easier to control the acid value and the molecular weight of the amorphous polyester resin.

The method for forming the amorphous polyester polymerized segment is not particularly limited, and the unit is obtained by polycondensing (esterifying) the polyvalent carboxylic acid component and the polyhydric alcohol component using a known esterification catalyst. Can be formed.

Since the catalyst that can be used in the production of the amorphous polyester polymerized segment is the same as the catalyst described in the above section (Crystalline polyester resin), the description thereof is omitted here.

The polymerization temperature is not particularly limited, but it is preferably 150 to 250°C. The polymerization time is not particularly limited, but it is preferably 0.5 to 10 hours. During the polymerization, the pressure inside the reaction system may be reduced if necessary.

The content of the amorphous polyester polymerized segment in the hybrid amorphous resin is preferably 50 to 99.9 mass% with respect to the total amount of the hybrid amorphous resin, and 70 to 95 mass%. More preferable. When the content is in the above range, the coating of the core portion is good and the chargeability of the toner particles is good. The constituent components and the content ratio of each unit in the hybrid amorphous resin can be specified by, for example, NMR measurement and methylation reaction P-GC/MS measurement.

The hybrid amorphous resin may further have a substituent such as a sulfonic acid group, a carboxyl group or a urethane group introduced therein. The introduction of the above-mentioned substituent may be carried out in the amorphous polyester polymerized segment or in the amorphous vinyl polymerized segment which will be described in detail below.

<<Amorphous vinyl polymerization segment>>
The amorphous vinyl polymer segment is an essential unit for controlling the affinity between the amorphous vinyl resin forming the core of the binder resin and the hybrid amorphous resin. Due to the presence of the amorphous vinyl polymerization segment, the compatibility between the amorphous vinyl resin contained in the core part and the hybrid amorphous resin contained in the shell part is high, and the amorphous vinyl resin is contained in the toner particles. It can be dispersed uniformly.

The inclusion of the amorphous vinyl polymer segment in the hybrid amorphous resin (and further in the toner) can be achieved by specifying the chemical structure by using, for example, NMR measurement or methylation reaction P-GC/MS measurement. You can check.

In addition, the amorphous vinyl polymerized segment has no melting point and a relatively high glass transition temperature (Tg) when subjected to differential scanning calorimetry (DSC) on a resin having the same chemical structure and molecular weight as the unit. It is a polymerized segment having. At this time, the glass transition temperature (Tg) of the resin having the same chemical structure and molecular weight as that of the unit is preferably 30 to 70°C, and particularly preferably 35 to 65°C.

The amorphous vinyl polymer segment is not particularly limited as long as it is as defined above. For example, for a resin having a structure in which the main chain of the amorphous vinyl polymerization segment is copolymerized with another component, or for a resin having a structure in which the amorphous vinyl polymerization segment is copolymerized with the main chain of the other component, If the toner containing the resin has the amorphous polymerized segment as described above, the resin corresponds to the hybrid amorphous resin having the amorphous polymerized segment in the present invention.

The amorphous vinyl polymerization segment is not particularly limited as long as it is obtained by polymerizing a vinyl compound, and examples thereof include an acrylic acid ester polymerization segment, a styrene-acrylic acid ester polymerization segment, and an ethylene/vinyl acetate polymerization segment. These may be used alone or in combination of two or more.

Among the above vinyl polymerized segments, a styrene-acrylic acid ester polymerized segment (styrene acrylic polymerized segment) is preferable in consideration of plasticity at the time of heat fixing. Further, since the preferred form of the amorphous vinyl resin is styrene-acrylic resin, the amorphous vinyl polymer segment is also preferably styrene-acrylic resin. With such a form, the affinity between the hybrid amorphous resin and the amorphous vinyl resin is further improved, and a more uniform shell portion can be easily formed. The unit of styrene-acrylic resin means a resin portion derived from styrene-acrylic resin, that is, a molecular chain having the same chemical structure as that of styrene-acrylic resin.

Below, the styrene acrylic polymer segment as an amorphous vinyl polymer segment is demonstrated.

The styrene acrylic polymer segment is formed by addition-polymerizing at least a styrene monomer and a (meth)acrylic acid ester monomer. The styrene monomer mentioned here includes, in addition to styrene represented by the structural formula of CH ₂ ═CH—C ₆ H ₅ , those having a known side chain or functional group in the styrene structure. Further, the (meth)acrylic acid ester monomer referred to here is, in addition to the acrylic acid ester compound and the methacrylic acid ester compound represented by CH ₂ ═CHCOOR (R is an alkyl group), the acrylic acid ester derivative and the methacrylic acid ester. It includes an ester compound having a known side chain or functional group in the structure such as an ester derivative.

Specific examples of the styrene monomer and (meth)acrylic acid ester monomer capable of forming the styrene acrylic polymer segment are shown below, but those usable for forming the styrene acrylic polymer segment used in the present invention are shown. Is not limited to those shown below.

First, as specific examples of the styrene monomer, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4- Examples thereof include dimethyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene and pn-dodecyl styrene. These styrene monomers may be used alone or in combination of two or more.

Further, specific examples of the (meth)acrylic acid ester monomer include, for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, isobutyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate. Acrylic acid ester monomers such as stearyl acrylate, lauryl acrylate, and phenyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, Examples thereof include methacrylic acid ester monomers such as stearyl methacrylate, lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate and dimethylaminoethyl methacrylate.

These acrylic acid ester monomers or methacrylic acid ester monomers can be used alone or in combination of two or more. That is, a copolymer is formed by using a styrene monomer and two or more kinds of acrylic acid ester monomers, and a copolymer is formed by using a styrene monomer and two or more kinds of methacrylic acid ester monomers. It is possible to form a combination or to form a copolymer by using a styrene monomer and an acrylic acid ester monomer and a methacrylic acid ester monomer in combination.

The content of the structural unit derived from the styrene monomer in the amorphous vinyl polymer segment is preferably 60 to 85 mass% with respect to the total amount of the amorphous vinyl polymer segment. The content of the structural unit derived from the (meth)acrylic acid ester monomer in the amorphous vinyl polymer segment is preferably 10 to 35 mass% with respect to the total amount of the amorphous vinyl polymer segment. .. By setting it in such a range, it becomes easy to control the plasticity of the hybrid amorphous resin.

In addition to the styrene monomer and the (meth)acrylic acid ester monomer, the amorphous vinyl polymer segment may also be addition polymerized with a compound for chemically bonding to the amorphous polyester polymer segment. Is preferred. Specifically, it is preferable to use a compound contained in the amorphous polyester polymerized segment and having an ester bond with a hydroxyl group [-OH] derived from a polyhydric alcohol or a carboxyl group [-COOH] derived from a polyvalent carboxylic acid. Therefore, the amorphous vinyl polymer segment is addition-polymerizable with the styrene monomer and the (meth)acrylic acid ester monomer, and has a carboxyl group [—COOH] or a hydroxyl group [—OH]. It is preferable to further polymerize the compound.

Examples of such a compound include a compound having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, cinnamic acid, fumaric acid, maleic acid monoalkyl ester, itaconic acid monoalkyl ester; 2-hydroxy. Ethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , A compound having a hydroxyl group such as polyethylene glycol mono(meth)acrylate.

The content of the constituent unit derived from the compound for chemically bonding to the amorphous polyester polymerized segment in the amorphous vinyl polymerized segment is 0.1 to 15 mass with respect to the total amount of the amorphous polymerized segment. % Is preferable.

The method for forming the styrene acrylic polymer segment is not particularly limited, and examples thereof include a method of polymerizing a monomer using a known oil-soluble or water-soluble polymerization initiator. Specific examples of the oil-soluble polymerization initiator include azo-based or diazo-based polymerization initiators and peroxide-based polymerization initiators shown below.

Examples of the azo or diazo polymerization initiator include 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile and 1,1′-azobis(cyclohexane-1). -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like.

As the peroxide type polymerization initiator, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4 -Dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis-(4,4-t-butylperoxycyclohexyl)propane, tris-(t-butylperoxy)triazine and the like can be mentioned.

Further, when the resin particles are formed by the emulsion polymerization method, a water-soluble radical polymerization initiator can be used. Examples of the water-soluble polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, azobisaminodipropaneacetate, azobiscyanovaleric acid and its salts, hydrogen peroxide and the like.

The content of the amorphous vinyl polymerized segment in the hybrid amorphous resin is preferably 0.1 to 50% by mass, and 5 to 30% by mass based on the total amount of the hybrid amorphous resin. Is more preferable. When the content is in the above range, the affinity with the amorphous resin contained in the core portion becomes higher, and the toner finally obtained has both improved heat-resistant storability while maintaining good low-temperature fixability. Will be things.

<<Method for producing hybrid amorphous resin>>
The method for producing the hybrid amorphous resin is particularly limited as long as it is a method capable of forming a polymer having a structure in which the amorphous polyester polymerization segment and the amorphous vinyl polymerization segment are molecularly bonded. Not a thing. Specific methods for producing the hybrid amorphous resin include, for example, the following methods.

(1) A method for producing a hybrid amorphous resin by preliminarily polymerizing an amorphous vinyl polymer segment and performing a polymerization reaction to form an amorphous polyester polymer segment in the presence of the amorphous vinyl polymer segment. In this method, first, a monomer (preferably a vinyl monomer such as a styrene monomer and a (meth)acrylic acid ester monomer) constituting the above-mentioned amorphous vinyl polymerized segment is subjected to an addition reaction to give a non-polymerized product. Form crystalline polymerized segments. Next, in the presence of the amorphous polymerized segment, the polyvalent carboxylic acid component and the polyhydric alcohol component are polymerized to form an amorphous polyester polymerized segment. At this time, a polymorphic carboxylic acid and a polyhydric alcohol are subjected to a condensation reaction, and at the same time, a polyvalent carboxylic acid or a polyhydric alcohol is subjected to an addition reaction with respect to the amorphous polymerized segment to form a hybrid amorphous resin. ..

In the above-mentioned method, it is preferable to incorporate sites capable of reacting with each other in the amorphous polyester polymerized segment or the amorphous vinyl polymerized segment. Specifically, at the time of forming the amorphous vinyl polymer segment, in addition to the monomer constituting the amorphous vinyl polymer segment, a carboxy group [—COOH] or a hydroxyl group [—COOH] remaining in the amorphous polyester polymer segment A compound having a site capable of reacting with —OH] and a site capable of reacting with an amorphous polymer segment is also used. That is, this compound reacts with a carboxy group [—COOH] or a hydroxyl group [—OH] in the amorphous polyester polymerized segment to chemically bond the amorphous polyester polymerized segment with the amorphous vinyl polymerized segment. can do.

Alternatively, when forming the amorphous polyester polymerized segment, a compound which can react with the polyhydric alcohol component or the polycarboxylic acid component and has a site capable of reacting with the amorphous vinyl polymerized segment may be used. ..

By using the above method, it is possible to form a hybrid amorphous resin having a structure (a graft structure) in which an amorphous vinyl polymer segment is molecularly bonded to an amorphous polyester polymer segment.

(2) A method for producing a hybrid amorphous resin by forming an amorphous polyester polymer segment and an amorphous polymer segment, respectively, and combining them to each other. In this method, first, a polyvalent carboxylic acid component and a polycarboxylic acid component are added. An amorphous polyester polymerized segment is formed by condensation reaction with a polyhydric alcohol component. Separately from the reaction system for forming the amorphous polyester polymerized segment, the above-mentioned monomer constituting the amorphous vinyl polymerized segment is subjected to addition polymerization to form the amorphous vinyl polymerized segment. At this time, it is preferable to incorporate a site where the amorphous polyester polymerized segment and the amorphous vinyl polymerized segment can react with each other. Since the method of incorporating such a reactive site is as described above, detailed description thereof will be omitted.

Next, by reacting the amorphous polyester unit formed above and the amorphous vinyl polymer segment, a hybrid amorphous structure having a structure in which the amorphous polyester polymer segment and the amorphous vinyl polymer segment are molecularly bonded. Resin can be formed.

Further, when the above-mentioned reactive site is not incorporated in the amorphous polyester polymerized segment and the amorphous vinyl polymerized segment, a system in which the amorphous polyester polymerized segment and the amorphous vinyl polymerized segment coexist is formed. Alternatively, a method may be adopted in which a compound having a site capable of binding to the amorphous polyester polymerized segment and the amorphous vinyl polymerized segment is added thereto. Then, a hybrid amorphous resin having a structure in which the amorphous polyester polymerized segment and the amorphous vinyl polymerized segment are molecularly bonded can be formed through the compound.

(3) A method for producing a hybrid amorphous resin by forming an amorphous polyester polymerized segment in advance and performing a polymerization reaction to form an amorphous vinyl polymerized segment in the presence of the amorphous polyester polymerized segment. In this method, first, a polyvalent carboxylic acid component and a polyhydric alcohol component are subjected to a condensation reaction to carry out polymerization to form an amorphous polyester polymerized segment. Next, in the presence of the amorphous polyester polymerized segment, the monomers constituting the amorphous vinyl polymerized segment are polymerized to form the amorphous vinyl polymerized segment. At this time, similarly to the above (1), it is preferable to incorporate sites capable of reacting with each other in the amorphous polyester polymerized segment or the amorphous vinyl polymerized segment. Since the method of incorporating such a reactive site is as described above, detailed description thereof will be omitted.

By using the above method, a hybrid amorphous resin having a structure (graft structure) in which an amorphous vinyl polymer segment is molecularly bonded to an amorphous polyester polymer segment can be formed.

Among the formation methods (1) to (3), the method (1) facilitates formation of a hybrid amorphous resin having a structure in which an amorphous vinyl resin chain is grafted with an amorphous polyester resin chain, It is preferable because the production process can be simplified.

In addition to the above hybrid amorphous resin, the shell portion may contain other resin such as non-hybridized amorphous resin.

From the viewpoint of achieving both low temperature fixability and heat resistant storage stability, the weight average molecular weight (Mw) of the hybrid amorphous resin is preferably 10,000 to 100,000, and preferably 20,000 to 90,000. Is more preferable.

The glass transition point (Tg) of the hybrid amorphous resin is preferably in the range of 20 to 70°C. The glass transition point (Tg) can be measured in the same manner as in the case of the amorphous vinyl resin.

The content of the hybrid amorphous resin in the toner base particles is preferably in the range of 1 to 50% by mass, and preferably 5 to 30% by mass from the viewpoint of fixability and environmental stability of charging. Is more preferable.

<Release agent>
The release agent is a fatty acid ester A composed of a glycerin condensate and a linear saturated fatty acid having 16 to 24 carbon atoms, and a fatty acid ester composed of a linear saturated alcohol having 16 to 24 carbon atoms and a linear saturated fatty acid having 16 to 24 carbon atoms. Contains B. The release agent may contain a substance other than the fatty acid esters A and B, but preferably the release agent contains only the fatty acid ester A and the fatty acid ester B.

The content mass ratio of the fatty acid ester A and the fatty acid ester B in the core portion is preferably 1:0.2 to 1:5, and is 1:0.5 to 1:2 (2:1 to 1:2). 2) is more preferable. With such a range, the volume expansion coefficient when the wax melts becomes high, and it becomes possible to obtain good thin paper separability while maintaining the low temperature fixing property and heat resistant storage property.

The content of the release agent in the toner base particles is preferably 7 to 16 mass% with respect to the toner base particles.

(Fatty acid ester A)
The fatty acid ester A is an ester composed of a glycerin condensate and a linear saturated fatty acid having 16 to 24 carbon atoms.

The glycerin condensate, which is a raw material alcohol for the fatty acid ester A, has an average degree of polymerization of preferably 10 or less, more preferably 6 or less, and further preferably 2 to 6. When the average degree of polymerization is 10 or less, the gloss of the image obtained by printing the toner is suppressed, which is preferable.

Specific examples of the glycerin condensate include diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, dipentaerythritol, tripentaerythritol and the like.

The raw material fatty acid of the fatty acid ester A is a linear saturated fatty acid having 16 to 24 carbon atoms, preferably 16 to 22 carbon atoms. If the number of carbon atoms is less than 16, the wax may melt at low temperature and the stability of the toner during storage at high temperature may decrease. When the carbon number is more than 24, the wax cannot be exuded quickly during fixing, and the fixability and the peeling property may be deteriorated especially at high speed printing.

Specific examples of the raw material fatty acids include palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, tetracosanoic acid and the like. Of these, behenic acid is particularly preferable.

The fatty acid ester A preferably has an acid value of 3 mgKOH/g or lower (lower limit 0 mgKOH/g), more preferably 1 mgKOH/g or lower (lower limit 0 mgKOH/g). When the acid value is 3 mgKOH/g or less, the chargeability, blocking resistance and storage stability of the toner are further improved, which is preferable.

Further, the fatty acid ester A is preferably one in which all the hydroxyl groups of the glycerin condensate are esterified. Further, the fatty acid ester A preferably has a hydroxyl value of 10 mgKOH/g or less (lower limit 0 mgKOH/g), and more preferably 7 mgKOH/g or less (lower limit 0 mgKOH/g). When the hydroxyl value is 10 mgKOH/g or less, it is preferable because the charging property, blocking resistance and storage stability of the toner are further improved.

The fatty acid ester A can be synthesized by the method described in JP-A-2015-4962.

(Fatty acid ester B)
The fatty acid ester B is an ester composed of a linear saturated alcohol having 16 to 24 carbon atoms and a linear saturated fatty acid having 16 to 24 carbon atoms.

The raw material alcohol of the fatty acid ester B has 16 to 24 carbon atoms, and preferably 16 to 22 carbon atoms. When the number of carbon atoms is less than 16, the melting of the wax starts at a low temperature, which may reduce the stability of the toner during high temperature storage. When the carbon number is more than 24, the wax cannot be exuded quickly during fixing, and the fixability and peeling property may be deteriorated especially at high speed printing.

Specific examples of the raw material alcohol include palmityl alcohol, heptacosanol, stearyl alcohol, nonadecanol, eicosanol, heneicosanol, behenyl alcohol, triacosanol, tetracosanol and the like.

The raw material fatty acid of the fatty acid ester B is a linear saturated fatty acid having 16 to 24 carbon atoms, preferably 16 to 22 carbon atoms. When the number of carbon atoms is less than 16, the wax starts to melt at a low temperature, which may lower the stability of the toner during high temperature storage. When the carbon number is more than 24, the wax cannot be exuded quickly during fixing, and the fixability and the peeling property may be deteriorated especially at high speed printing.

Specific examples of the raw material fatty acids include palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, behenic acid, tricosanoic acid, tetracosanoic acid and the like.

The fatty acid ester B preferably has an acid value of 3 mgKOH/g or lower (lower limit 0 mgKOH/g), more preferably 1 mgKOH/g or lower (lower limit 0 mgKOH/g). When the acid value is 3 mgKOH/g or less, the chargeability, blocking resistance and storage stability of the toner are further improved, which is preferable.

The fatty acid ester B preferably has a hydroxyl value of 5 mgKOH/g or lower (lower limit 0 mgKOH/g), more preferably 3 mgKOH/g or lower (lower limit 0 mgKOH/g). When the hydroxyl value is 5 mgKOH/g or less, the charging property, blocking resistance and storage stability of the toner are further improved, which is preferable.

<Colorant>
As the colorant, known dyes, pigments and the like can be used.

Examples of the dye include C.I. I. Solvent Red 1, 49, 52, 58, 63, 111, 122, C.I. I. Solvent Yellow 19, the same 44, the same 77, the same 79, the same 81, the same 82, the same 93, the same 98, the same 103, the same 104, the same 112, the same 162, C.I. I. Solvent Blue 25, the same 36, the same 60, the same 70, the same 93, the same 95 and the like.

Examples of the pigment include C.I. I. Pigment Red 5, Same 48:1, Same 48:3, Same 53:1, Same 57:1, Same 81:4, Same 122, Same 139, Same 144, Same 149, Same 150, Same 166, Same 177, 178, 222, 238, 269, C.I. I. Pigment Orange 31, the same 43, C.I. I. Pigment Yellow 14, the same 17, the same 74, the same 93, the same 94, the same 138, the same 155, the same 156, the same 158, the same 180, the same 185, C.I. I. Pigment Green 7, C.I. I. Pigment Blue 15:3, 60 and the like.

Further, carbon black such as channel black, furnace black, acetylene black, thermal black and lamp black, black iron oxide such as magnetite, hematite and titanium trioxide can also be used.

In order to obtain a toner of a desired color, one kind of the above-mentioned plural kinds of materials can be used alone or in combination of two or more kinds.

The content of the colorant in the toner base particles is preferably in the range of 1 to 10 mass% from the viewpoint of obtaining a toner having sufficient color reproducibility.

The toner base particles may contain other internal additives such as a charge control agent.

<External additive>
From the viewpoint of improving the charging performance, fluidity, or cleaning property of the toner, known inorganic fine particles, organic fine particles and the like, and a lubricant can be added to the surface of the toner particles as an external additive.

Preferred examples of the inorganic fine particles include inorganic fine particles made of silica, titania (titanium oxide), alumina, strontium titanate and the like.

If necessary, these inorganic fine particles may be subjected to a hydrophobic treatment.

As the organic fine particles, spherical organic fine particles having a number average primary particle diameter of about 10 to 2000 nm can be used. Specifically, it is possible to use homopolymers of styrene, methyl methacrylate, etc., and organic fine particles made of copolymers thereof.

The lubricant is used for the purpose of further improving the cleaning property and the transfer property, and examples of the lubricant include zinc stearate, salts of aluminum, copper, magnesium, calcium and the like, zinc oleate. , Salts of manganese, iron, copper, magnesium, etc., salts of zinc palmitate, copper, magnesium, calcium etc., salts of linoleic acid zinc, calcium etc., higher fatty acids such as salts of ricinoleic acid zinc, calcium etc. Metal salts may be mentioned. As these external additives, various kinds may be used in combination.

The addition amount of the external additive is preferably 0.1 to 10.0 mass% with respect to 100 mass% of the toner particles.

Examples of the method of adding the external additive include a method of adding using various known mixing devices such as a Turbuler mixer, a Henschel mixer, a Nauter mixer, and a V-type mixer.

[Characteristics of electrostatic image developing toner]
(Glass transition point)
The toner for developing an electrostatic image of the present invention preferably has a glass transition point (Tg) in the range of 50 to 70°C, more preferably 55 to 65°C.

When the glass transition point is within the above range, sufficient low-temperature fixing property and heat-resistant storage property can both be achieved. Further, the heat resistance (thermal strength) of the toner can be maintained, and sufficient heat resistant storage stability and hot offset resistance can be obtained.

The glass transition point (Tg) can be measured in the same manner as the amorphous vinyl resin.

(Melting point)
The toner for developing an electrostatic image of the present invention preferably has a melting point (Tm) of 60 to 90°C, more preferably 65 to 80°C.

When the melting point is within the above range, sufficient low temperature fixing property and heat resistant storage property can both be achieved. Further, good heat resistance (thermal strength) of the toner can be maintained, and sufficient heat resistant storage stability can be obtained.

The melting point (Tm) can be measured in the same manner as the above crystalline polyester resin.

(Particle size of toner particles)
In the toner for developing an electrostatic image of the present invention, the volume-based median diameter of toner particles is preferably in the range of 3.0 to 8.0 μm, more preferably in the range of 5.0 to 8.0 μm. is there.

If the volume-based median diameter is within the above range, 1200 dpi level high-resolution dots can be accurately reproduced.

The volume-based median diameter can be controlled by the concentration of the aggregating agent used during production, the amount of the organic solvent added, the fusion time, the composition of the binder resin, and the like.

The volume-based median diameter can be measured by using a measuring device in which a computer system equipped with Multisizer 3 (manufactured by Beckman Coulter, Inc.) equipped with data processing software Software V3.51 is connected.

Specifically, 0.02 g of the sample (toner) is added to 20 mL of a surfactant solution (for the purpose of dispersing the toner particles, for example, a neutral detergent containing a surfactant component diluted with pure water ten times After being added to the solution) and blended, an ultrasonic dispersion treatment is performed for 1 minute to prepare a toner dispersion. This toner dispersion is pipetted into a beaker containing ISOTONII (manufactured by Beckman Coulter, Inc.) in a sample stand until the indicated concentration on the measuring device reaches 8%. With this concentration, reproducible measurement values can be obtained.

Then, in the measuring device, the number of particles to be measured was set to 25,000, the aperture diameter was set to 100 μm, the frequency value was calculated by dividing the range of 2 to 60 μm, which is the measurement range, into 256, and the frequency value was calculated from the larger volume cumulative fraction to 50. The particle diameter of% is determined as the volume-based median diameter.

(Average circularity of toner particles)
In the toner for developing an electrostatic charge image, the average circularity of the toner particles is preferably in the range of 0.930 to 1.000, more preferably 0.950 to 0.995.

When the average circularity is within the above range, crushing of toner particles can be suppressed, contamination of the triboelectrification imparting member can be suppressed, and the chargeability of the toner can be stabilized. Further, the image formed by the toner has high image quality.

The average circularity of the toner can be measured as follows.

A toner dispersion is prepared in the same manner as in the case of measuring the median diameter. An FPIA-2100, an FPIA-3000 (both manufactured by Sysmex) or the like is used to take an image of the toner dispersion liquid in an HPF (high-magnification imaging) mode in an appropriate concentration range of 3,000 to 10,000 HPF detections. The circularity of the toner particles is calculated by the following formula (y). The average circularity is calculated by adding the circularity of each toner particle and dividing the sum of circularity by the number of each toner particle. Sufficient reproducibility can be obtained when the HPF detection number is within the above-mentioned proper concentration range.

Formula (y): Circularity=(perimeter of a circle having the same projected area as the particle image)/(perimeter of the particle projected image)
<Developer>
The toner for developing an electrostatic image of the present invention can be used as a magnetic or non-magnetic one-component developer, or may be mixed with a carrier and used as a two-component developer.

When the toner is used as a two-component developer, as the carrier, magnetic particles made of conventionally known materials such as metals such as iron, ferrite and magnetite, alloys of these metals with metals such as lead and lead are used. It can be used and ferrite particles are particularly preferable.

Further, as the carrier, a coated carrier in which the surface of magnetic particles is coated with a coating agent such as silicone resin, or a dispersion type carrier in which fine magnetic powder is dispersed in a binder resin may be used.

The average particle size of the carrier is preferably in the range of 20 to 100 μm, and more preferably in the range of 25 to 80 μm in terms of volume-based median diameter.

The volume-based median diameter of the carrier can be typically measured by a laser diffraction particle size distribution analyzer HELOS (manufactured by SYMPATEC) equipped with a wet disperser.

<Method of manufacturing toner for developing electrostatic image>
The method for producing the toner base particles is not particularly limited, and known methods such as a kneading and pulverizing method, a suspension polymerization method, an emulsion aggregation method, a solution suspension method, a polyester elongation method and a dispersion polymerization method can be mentioned.

Among these, it is preferable to employ the emulsion aggregation method from the viewpoints of uniformity of particle size, controllability of shape, and ease of forming the core-shell structure. The emulsion aggregation method will be described below.

The emulsion aggregation method mixes the binder resin particle dispersion obtained by dispersing the binder resin in an aqueous medium and the colorant particle dispersion obtained by dispersing the colorant in the aqueous medium. By so doing, the binder resin particles and the colorant particles are aggregated and fused in an aqueous medium to form toner particles.

Further, toner particles having a core-shell structure can also be obtained by an emulsion aggregation method. Specifically, the toner particles having a core-shell structure are obtained by first aggregating the binder resin particles for the core particles and the colorant (the fusion bonding). ) To prepare core particles, and then add the binder resin particles for the shell part to the dispersion liquid of the core particles to aggregate and fuse the binder resin particles for the shell part on the surface of the core particles. It can be obtained by forming a shell portion that covers the surface of the core particle.

When the toner is produced by the emulsion aggregation method, the method for producing the toner according to a preferred embodiment includes a step of preparing a crystalline polyester resin particle dispersion liquid, an amorphous vinyl resin particle dispersion liquid, and a hybrid amorphous resin particle dispersion liquid. (Hereinafter, also referred to as a preparation step) A step of mixing (a) with the crystalline polyester resin particle dispersion and the amorphous vinyl resin particle dispersion and aggregating and fusing them to obtain a core particle dispersion (hereinafter, (Aggregating/fusing step) (b) and a step (c) of mixing the core particle dispersion liquid and the hybrid amorphous resin particle dispersion liquid and aggregating and fusing them to obtain a toner particle dispersion liquid.

Furthermore, the fatty acid ester A and the fatty acid ester B are preferably present in the amorphous vinyl resin particles. As described above, the amorphous vinyl resin particles have the (meth)acrylic acid alkyl ester-based monomer represented by the formula (1), which has a high affinity with wax, and thus has such a form. As a result, the wax can be included in the toner base particles, and both heat-resistant storage property and releasability can be improved. As a method for producing such particles, it is preferable to produce an amorphous vinyl resin particle dispersion liquid containing an amorphous vinyl resin, a fatty acid ester A, and a fatty acid ester B.

Therefore, as a preferred embodiment of the method for producing a toner for developing an electrostatic image of the present invention, a non-crystalline vinyl resin, a glycerin condensate, and a fatty acid ester A composed of a linear saturated fatty acid having 16 to 24 carbon atoms, and A step of obtaining an amorphous vinyl resin particle dispersion liquid containing a fatty acid ester B composed of a linear saturated alcohol having 16 to 24 carbon atoms and a linear saturated fatty acid having 16 to 24 carbon atoms (hereinafter, also referred to as step (1)) A step of obtaining a crystalline polyester resin particle dispersion, and a step of aggregating the amorphous vinyl resin particle dispersion and the crystalline polyester resin particle dispersion, and heat-fusing the obtained aggregate to obtain core particles. A core-shell structure having a core part and a shell part, wherein a shell part containing a hybrid amorphous resin in which an amorphous polyester polymerized segment and an amorphous vinyl polymerized segment are chemically bonded is formed on the core particle surface. And a step of producing a toner for developing an electrostatic charge image.

Hereinafter, each of the steps (a) to (c) and each of the steps (d) to (f) optionally performed other than these steps will be described in detail.

(A) Preparation Step The step (a) includes a step of preparing a crystalline polyester resin particle dispersion liquid, an amorphous vinyl resin particle dispersion liquid, and a hybrid amorphous resin particle dispersion liquid, and if necessary, , A colorant dispersion liquid preparation step and the like.

(A-1) Amorphous vinyl resin particle dispersion liquid preparation step For the amorphous vinyl resin particle dispersion liquid, for example, a method of performing dispersion treatment in an aqueous medium without using a solvent, or using an amorphous vinyl resin with acetic acid Examples thereof include a method in which the solution is dissolved in a solvent such as ethyl, the solution is emulsified and dispersed in an aqueous medium using a disperser, and then the solvent is removed. Preferably, the amorphous vinyl resin is dispersed in an aqueous medium to prepare an amorphous vinyl resin particle dispersion liquid.

The aqueous medium means a medium having a water content of 50% by mass or more. Examples of components other than water include organic solvents that are soluble in water, such as methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran. Of these, alcohol-based organic solvents such as methanol, ethanol, isopropanol, butanol, which are organic solvents that do not dissolve the resin, are particularly preferable. Preferably only water is used as the aqueous medium.

Furthermore, a dispersion stabilizer may be dissolved in the aqueous medium, and a surfactant, resin fine particles and the like may be added for the purpose of improving the dispersion stability of oil droplets.

As the dispersion stabilizer, known ones can be used, for example, it is preferable to use one that is soluble in an acid or an alkali such as tricalcium phosphate, or from the viewpoint of the environment, an enzyme can be used. It is preferable to use a degradable one.

As the surfactant, known anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants can be used.

Examples of resin fine particles for improving dispersion stability include polymethylmethacrylate resin fine particles, polystyrene resin fine particles, and polystyrene-acrylonitrile resin fine particles.

The dispersion treatment is preferably carried out under stirring, and can be carried out by utilizing mechanical energy. The disperser is not particularly limited, and includes a homogenizer, a low speed shearing type disperser, and a high speed shearing type. Examples thereof include a disperser, a friction disperser, a high-pressure jet disperser, an ultrasonic disperser, a high-pressure impact disperser Ultimizer, and an emulsifying disperser.

The method for producing an amorphous vinyl resin is not particularly limited, but an emulsion polymerization method in which a resin monomer is added to an aqueous medium together with a polymerization initiator, and the monomer is polymerized to obtain a dispersion liquid of resin particles. Can be used.

In the emulsion polymerization method, the following seed polymerization is preferable. Specifically, a monomer for obtaining an amorphous vinyl resin is added to an aqueous medium together with a polymerization initiator and polymerized to obtain basic particles. Next, in the dispersion liquid in which the resin particles are dispersed, a radical polymerizable monomer and a polymerization initiator for obtaining an amorphous vinyl resin are added, and the radical polymerizable monomer is added to the basic particles. It is preferable to use a technique of seed polymerization.

Further, for example, in the case of carrying out the polymerization reaction in three stages, a dispersion liquid of resin particles is prepared by the first stage polymerization, and the monomer of the resin and the polymerization initiator are further added to this dispersion liquid to carry out the second stage polymerization. Let A resin monomer and a polymerization initiator are further added to the dispersion prepared by the second stage polymerization to carry out the third stage polymerization. During the second and third stages of polymerization, the resin particles in the dispersion liquid produced by the previous polymerization can be used as seeds to further polymerize the monomer newly added to the resin particles, It is possible to make the particle diameter of the resin particles uniform. In addition, by using different monomers during the polymerization reaction at each stage, the structure of the resin particles can be a multi-layered structure, and resin particles having the desired characteristics can be easily obtained.

When the amorphous vinyl resin is produced by the multistage polymerization reaction described above, the monomer having the structure represented by the general formula (1) may be added at any stage.

As described above, since it is preferable that the multilayer resin particles contain the fatty acid ester A and the fatty acid ester B in the innermost layer than the outermost layer, the fatty acid ester A and the fatty acid ester B are used before the final polymerization in the multi-step polymerization. Preferably contained in Furthermore, in the multilayer resin particle, it is preferable that the layer inside the outermost layer contains the (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1), the fatty acid ester A and the fatty acid ester B. Therefore, the polymerization of the (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1) is preferably performed at least before the final polymerization, and the polymerization step of the (meth)acrylic acid alkyl ester-based monomer is performed. It is preferable that the fatty acid ester A and the fatty acid ester B are contained in the monomer solution. In addition, if the fatty acid ester A and the fatty acid ester B are not included, the (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1) may be polymerized to form the outermost layer.

That is, in another preferred embodiment of the step (1), the alkyl (meth)acrylate represented by the formula (1) or the alkyl (meth)acrylate represented by the formula (1) is used. The first polymerizable monomer mixture containing an ester-based monomer, the fatty acid ester A and the fatty acid ester B are added to an aqueous medium to give a (meth)acrylic acid alkyl ester-based compound represented by the formula (1). Step (A) of preparing a resin particle dispersion by polymerizing a monomer or a first polymerizable monomer mixture, and resin particles obtained in the step (A) of a second polymerizable monomer And a step (B) of preparing a resin particle dispersion liquid by adding the dispersion liquid to the dispersion liquid and polymerizing the second polymerizable monomer.

Here, before the step (A), there is a step (A′) in which a monomer for obtaining an amorphous vinyl resin is added together with a polymerization initiator into an aqueous medium and polymerized to obtain basic particles. Preferably.

In the step (A), in order to improve the dispersibility of the wax, it is preferable to add the wax and the polymerizable monomer (mixture) to the aqueous medium, and then apply mechanical energy to stir the mixture. It is preferable to use a disperser such as a low speed shearing disperser, a high speed shearing disperser, a friction disperser, a high pressure jet disperser, an ultrasonic disperser, a high pressure impact disperser, and an optimizer. As the disperser, a commercially available product may be used, and for example, "CLEARMIX (registered trademark)" (manufactured by M Technique Co., Ltd.), HJP30006 (manufactured by Sugino Machine Co., Ltd.), ultrasonic homogenizer US-150T. (Manufactured by Nippon Seiki Seisakusho) or the like can be used.

During dispersion, it is preferable to heat the solution. The heating condition is not particularly limited, but is usually about 60 to 100°C.

(Polymerization initiator)
As the polymerization initiator that can be used in the polymerization reaction, known ones can be used, for example, persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, 2,2′-azobis(2-aminodipropane). ) Hydrochloride, 2,2'-azobis-(2-aminodipropane) nitrate, 4,7'-azobis-4-cyanovaleric acid, poly(tetraethylene glycol-2,2'-azobisisobutyrate) Examples thereof include azo compounds such as, and peroxides such as hydrogen peroxide.

The addition amount of the polymerization initiator varies depending on the target molecular weight and the molecular weight distribution, but is specifically 0.1 to 5.0 mass% with respect to the addition amount of the polymerizable monomer. it can.

(Chain transfer agent)
During the polymerization reaction, a chain transfer agent can be added from the viewpoint of controlling the molecular weight of the resin particles. Examples of chain transfer agents that can be used include mercaptans such as octyl mercaptan, dodecyl mercaptan, and t-dodecyl mercaptan; chain transfer agents such as n-octyl-3-mercaptopropionate and stearyl-3-mercaptopropionate. Mercaptopropionic acid; and styrene dimer can be used. These can be used alone or in combination of two or more.

The addition amount of the chain transfer agent varies depending on the target molecular weight and the molecular weight distribution, but can be within the range of 0.1 to 5.0 mass% with respect to the addition amount of the polymerizable monomer.

(Surfactant)
During the polymerization reaction, a surfactant can be added from the viewpoint of preventing the resin particles in the dispersion liquid from aggregating and maintaining a good dispersion state.

Examples of the surfactant include cationic surfactants such as dodecyl ammonium bromide and dodecyl trimethyl ammonium bromide, sodium stearate, sodium lauryl sulfate (sodium dodecyl sulfate), sodium polyoxyethylene dodecyl ether sulfate, sodium dodecylbenzenesulfonate, etc. Known surfactants such as anionic surfactants, nonionic surfactants such as dodecyl polyoxyethylene ether, and hexadecyl polyoxyethylene ether can be used. One of these may be used alone or in combination of two or more.

The particle diameter of the amorphous vinyl resin particles (oil droplets) in the thus prepared amorphous vinyl resin particle dispersion is a volume-based median diameter of preferably 60 to 1000 nm, more preferably 80 to 500 nm. preferable. The volume-based median diameter is measured by the method described in Examples. The volume-based median diameter of the oil droplets can be controlled by the magnitude of mechanical energy during emulsion dispersion.

(A-2) Crystalline polyester resin particle dispersion liquid preparation step As a method of dispersing the crystalline polyester resin in an aqueous medium, the crystalline polyester resin is dissolved or dispersed in an organic solvent (solvent) to obtain an oil phase liquid. Is prepared, the oil phase liquid is dispersed in an aqueous medium by phase inversion emulsification or the like to form oil droplets in a state where the particle size is controlled to a desired particle size, and then the organic solvent is removed.

As the organic solvent (solvent) used in the preparation of the oil phase liquid, those having a low boiling point and low solubility in water are preferable from the viewpoint of easy removal treatment after formation of oil droplets, Specific examples thereof include methyl acetate, ethyl acetate, methyl ethyl ketone, isopropyl alcohol, methyl isobutyl ketone, toluene and xylene. These can be used alone or in combination of two or more.

The amount of the organic solvent (solvent) used (the total amount used when two or more types are used) is preferably 1 to 300 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 100 parts by mass of the resin. Is 25 to 100 parts by mass.

Further, ammonia, sodium hydroxide or the like may be added to the oil phase liquid in order to ionically dissociate the carboxyl group and stably emulsify the water phase to promote smooth emulsification.

The amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, and more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the oil phase liquid. When the amount of the aqueous medium used is within the above range, the oil phase liquid can be emulsified and dispersed in the aqueous medium to have a desired particle size.

A dispersion stabilizer may be dissolved in the aqueous medium, and a surfactant, resin fine particles, or the like may be added for the purpose of improving the dispersion stability of oil droplets. Specific examples and suitable examples of the dispersion stabilizer, the surfactant and the resin fine particles are as described in the above section (a-1).

The emulsification and dispersion of such an oil phase liquid can be performed by utilizing mechanical energy, and the disperser for performing the emulsification and dispersion is not particularly limited, and includes a low speed shearing disperser and a high speed shearing machine. Type dispersers, friction type dispersers, high pressure jet type dispersers, ultrasonic dispersers such as ultrasonic homogenizers, high pressure impact dispersers ultimizer, and the like.

The removal of the organic solvent after the formation of oil droplets is carried out by gradually raising the temperature of the entire dispersion liquid in which the crystalline polyester resin particles/amorphous resin particles are dispersed in the aqueous medium in a stirring state at a constant temperature. It can be carried out by an operation such as desolvation after giving strong stirring in the zone. Alternatively, it can be removed under reduced pressure using a device such as an evaporator.

The average particle diameter of the crystalline polyester resin particles (oil droplets) (oil droplets) in the thus prepared crystalline polyester resin particle dispersion is preferably 60 to 1000 nm in terms of volume-based median diameter, and 80 More preferably, it is about 500 nm. The average particle size is measured by the method described in the examples. The average particle size of the oil droplets can be controlled by the magnitude of mechanical energy during emulsion dispersion.

(A-3) Hybrid amorphous resin particle dispersion liquid preparation step In the hybrid amorphous resin particle dispersion liquid preparation step, a hybrid amorphous resin that constitutes toner particles is synthesized, and this hybrid amorphous resin is used as an aqueous medium. It is a step of preparing a dispersion liquid of hybrid amorphous resin particles by dispersing it in the form of fine particles.

Since the method for producing the hybrid amorphous resin is as described above, the details are omitted.

The hybrid amorphous resin particle dispersion is, for example, a method of performing a dispersion treatment in an aqueous medium without using a solvent (A), or an oil obtained by dissolving or dispersing a hybrid amorphous resin in an organic solvent (solvent). A method of preparing a phase liquid, dispersing the oil phase liquid in an aqueous medium by phase inversion emulsification, etc. to form oil droplets in a state where the particle size is controlled to a desired particle size, and then removing the organic solvent (I) And so on.

The aqueous medium and the dispersing method in the method (a) are as described in the above section (a-1). Details of the method (i) are as described in the above section (a-2).

The particle diameter of the hybrid amorphous resin particles (oil droplets) in the thus prepared hybrid amorphous resin particle dispersion is a volume-based median diameter of preferably 60 to 1000 nm, more preferably 80 to 500 nm. The volume-based median diameter is measured by the method described in Examples. The volume-based median diameter of the oil droplets can be controlled by the magnitude of mechanical energy during emulsion dispersion.

(A-4) Step of preparing colorant particle dispersion liquid A colorant particle dispersion liquid is prepared by dispersing a colorant in an aqueous medium.

In order to improve the dispersion stability of the colorant particles even when the colorant particle dispersion liquid is prepared, the above-mentioned surfactant can be added. Further, the mechanical energy described above can be used for the dispersion processing.

The volume-based median diameter of the colorant particles in the dispersion is preferably within the range of 10 to 300 nm, more preferably within the range of 100 to 200 nm, and further preferably within the range of 100 to 150 nm. ..

(B) Aggregation/Fusing Step The prepared amorphous vinyl resin particle dispersion liquid, crystalline polyester resin particle dispersion liquid and, if necessary, colorant particle dispersion liquid are mixed, and the amorphous vinyl resin particles are mixed in an aqueous medium. The crystalline polyester resin particles and the colorant particles are aggregated. Further, the particles are fused by heating the mixed liquid to form core particles (core portion). At the time of aggregation and fusion, the aggregation and fusion may be promoted by adding a flocculant having a critical aggregation concentration or higher and heating the mixed solution to the glass transition point (Tg) or higher of the amorphous resin.

More specifically, after mixing the amorphous vinyl resin particle dispersion liquid and the crystalline polyester resin particle dispersion liquid, in order to impart cohesiveness, a base such as an aqueous sodium hydroxide solution is added to the mixed liquid in advance, It is preferable to adjust the pH to 9-12.

Next, it is preferable to add a colorant particle dispersion liquid, if necessary, and to add an aggregating agent such as an aqueous solution of magnesium chloride with stirring at 25 to 35° C. for 5 to 15 minutes. The amount of the aggregating agent used is preferably 5 to 20 mass% with respect to the total solid content of the binder resin particles and the colorant particles. After that, it is preferable that the temperature is generally left for 30 minutes or less, preferably 10 minutes or less, more preferably 1 to 6 minutes, and the temperature is raised to 70 to 95°C over 30 to 90 minutes. The resin particles and the colorant particles aggregated by such a method can be fused.

In the aggregating step, it is preferable that the standing time after the coagulant is added (time until heating is started) be as short as possible. That is, it is preferable to start heating of the dispersion liquid for aggregation as soon as possible after adding the aggregating agent. The standing time is usually 30 minutes or less, preferably 10 minutes or less. The temperature at which the aggregating agent is added is not particularly limited, but is preferably not higher than the glass transition temperature of the amorphous resin that is the core portion.

In addition, in the aggregating step, it is preferable to quickly raise the temperature by heating after adding the aggregating agent, and it is preferable that the temperature raising rate is 0.8° C./min or more. The upper limit of the temperature rising rate is not particularly limited, but it is preferably 15° C./minute or less from the viewpoint of suppressing the generation of coarse particles due to the rapid progress of fusion. Further, after the dispersion liquid for aggregation reaches a temperature of the glass transition temperature or higher, the temperature of the dispersion liquid for aggregation is maintained for a certain period of time, preferably until the volume-based median diameter becomes 4.5 to 7.0 μm. Therefore, it is important to continue the fusion bonding (first aging step).

(Flocculant)
The aggregating agent that can be used is not particularly limited, and examples thereof include metal salts such as alkali metal salts and Group 2 metal salts.

Examples of the metal salt include monovalent metal salts such as sodium chloride, potassium chloride and lithium chloride, divalent metal salts such as calcium chloride, magnesium chloride, copper sulfate and magnesium sulfate, and trivalent metals such as iron and aluminum. Salt etc. are mentioned. Among them, a divalent metal salt is preferable because it can be aggregated in a smaller amount.

(C) Step of Mixing Core Particle Dispersion Liquid and Hybrid Amorphous Resin Particle Dispersion Liquid and Aggregating and Fusing to Obtain Toner Particle Dispersion Liquid In order to obtain the binder resin having the core-shell structure of the present invention, After the first aging step, an aqueous dispersion of hybrid amorphous resin particles forming a shell portion is further added to form a shell portion on the surface of the binder resin particles (core particles) obtained above. The amorphous resin is aggregated and fused. As a result, a binder resin having a core-shell structure is obtained (shell forming step). Then, when the size of the aggregated particles reaches the target size, a salt such as an aqueous sodium chloride solution is added to stop the aggregation. Then, it is better to further heat-treat the reaction system until the aggregation and fusion of the shell portion on the surface of the core particle are strengthened and the shape of the particle becomes a desired shape (second aging step). This second ripening step may be performed until the average circularity of the toner particles having the core-shell structure falls within a desired average circularity (preferably within the above-mentioned preferable range).

As a result, particle growth (aggregation of crystalline resin particles, amorphous vinyl resin particles, hybrid amorphous resin, and optionally colorant particles) and fusion (disappearance of interface between particles) The toner particles can be effectively advanced, and the durability of the finally obtained toner particles can be improved.

(D) Cooling Step The toner particle dispersion obtained in the toner particle forming step, aging step or shelling step is cooled.

The cooling rate can be in the range of 1 to 20° C./minute. The cooling method is not particularly limited, and a cooling medium may be introduced from the outside of the reaction vessel for cooling, or cold water may be directly added to the reaction system for cooling.

(E) Filtration, Washing, and Drying Step The toner particle dispersion after cooling is filtered to solid-liquid separate the toner particles, and the obtained wet toner cake (referred to as a cake-shaped aggregate of toner particles). Are washed to remove surfactants, flocculants and the like.

As the solid-liquid separation method, a centrifugal separation method, a vacuum filtration method using a Nutsche or the like, a filtration method using a filter press, or the like can be used.

At the time of washing, for example, the filtrate can be washed with water until the electric conductivity of the filtrate becomes 10 μS/cm or less.

The toner cake after filtration and washing is dried.

For drying, a spray dryer, a vacuum freeze dryer, a vacuum dryer, a stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, a rotary dryer, a stirring dryer, etc. can be used.

The water content of the dried toner particles is preferably 5% by mass or less, more preferably 2% by mass or less.

When the toner particles after drying are aggregated by a weak attractive force between the particles, the aggregate may be crushed. A jet mill, a Henschel mixer, a coffee mill, a food processor or the like can be used as the disintegration treatment device.

(F) Step of Adding External Additive When the external additive is added to the toner particles, the external additive is added to the dried toner particles and mixed.

A Henschel mixer, a coffee mill, or the like can be used as a mixing device for the external additive.

The effects of the present invention will be described using the following examples and comparative examples, but the present invention is not limited to these embodiments. In the examples, "parts" or "%" may be used, but unless otherwise specified, "parts by mass" or "% by mass" is shown. Unless otherwise specified, each operation is performed at room temperature (25°C).

(Melting point (Tm) of crystalline polyester resin and glass transition temperature (Tg) of amorphous resin)
The melting point (Tm) of the crystalline polyester resin and the glass transition temperature (Tg) of the amorphous resin were obtained using a differential scanning calorimeter (manufactured by Shimadzu Corporation: DSC-60A) in accordance with ASTM D3418. The melting point of indium and zinc was used to correct the temperature of the detection part of this device (DSC-60A), and the heat of fusion of indium was used to correct the amount of heat. An aluminum pan was used as a sample, an empty pan was set as a control, the temperature was raised at a heating rate of 10° C./min, and the temperature was held from room temperature to 150° C. for 5 minutes, and liquid nitrogen was used from 150° C. to 0° C. Then, the temperature was lowered at −10° C./min, the temperature was held at 0° C. for 5 minutes, and the temperature was raised again from 0° C. to 200° C. at 10° C./min. The onset temperature was set to Tg for the amorphous resin, and the peak top temperature of the endothermic peak was set to the melting point for the crystalline polyester resin by analyzing the endothermic curve during the second heating.

(Volume average particle size of resin particles, colorant particles, etc.)
The volume average particle diameters of the resin particles, the colorant particles, the release agent and the like were measured by a laser diffraction/scattering particle size distribution measuring device (Microtrac particle size distribution measuring device “UPA-150” (manufactured by Nikkiso Co., Ltd.)).

(Preparation of fatty acid ester A and fatty acid ester B)
By the method described in paragraphs “0030” to “0032” of JP-A-2015-4962, the fatty acid esters A-1 to A-3, which are fatty acid esters A, are prepared using the raw material alcohols and fatty acids shown in Table 2 below. And fatty acid ester B-1 to B-4 which is fatty acid ester B were produced.

[Example 1]
(Preparation of crystalline polyester resin particle dispersion)
315 parts by mass of 1,10-decanedicarboxylic acid (dodecanedioic acid) and 252 parts by mass of 1,9-nonanediol were placed in a reaction vessel equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introducing pipe. After replacing the inside of this reaction vessel with dry nitrogen gas, 0.1 parts by mass of titanium tetrabutoxide was added, and a polymerization reaction was carried out for 8 hours while stirring at 180° C. under a nitrogen gas stream. Further, 0.2 parts by mass of titanium tetrabutoxide was added, the temperature was raised to 220° C., and the polymerization reaction was carried out for 6 hours while stirring. Then, the pressure in the reaction vessel was reduced to 10 mmHg, and the reaction was performed under reduced pressure to obtain crystalline polyester resin particles. The obtained crystalline polyester resin had a weight average molecular weight (Mw) of 14,000 and a melting point (Tm) of 72°C.

After dissolving 200 parts by mass of the crystalline polyester resin obtained above in 200 parts by mass of ethyl acetate heated to 70° C., sodium polyoxyethylene lauryl ether sulfate was added to 800 parts by mass of ion-exchanged water to a concentration of 1% by mass. The mixture was mixed with an aqueous solution that had been dissolved, and dispersed using an ultrasonic homogenizer. After removing ethyl acetate from this solution under reduced pressure, the solid content concentration was adjusted to 20% by mass. As a result, a crystalline polyester resin particle dispersion liquid in which particles of the crystalline polyester resin were dispersed in the aqueous medium was prepared. The volume average particle diameter (Mv) of the crystalline polyester resin particles was 200 nm.

(Preparation of amorphous vinyl resin particle dispersion)
(First stage polymerization)
A 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube and a nitrogen introducing device was charged with 8 parts by mass of sodium dodecylsulfate and 3000 parts by mass of ion-exchanged water, while stirring at a stirring rate of 230 rpm under a nitrogen stream, while stirring. The temperature was raised to 80°C. After the temperature was raised, a solution prepared by dissolving 10 parts by mass of potassium persulfate in 200 parts by mass of ion-exchanged water was added, the liquid temperature was again set to 80° C., and a mixed liquid of the following monomers was added dropwise over 1 hour.

Styrene 480.0 parts by mass n-Butyl acrylate 250.0 parts by mass Methacrylic acid 68.0 parts by mass After dropping, polymerization was performed by heating and stirring at 80° C. for 2 hours to prepare a basic particle dispersion liquid.
(Second-stage polymerization)
A 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe and a nitrogen introducing device was charged with a solution prepared by dissolving 7.8 parts by mass of sodium polyoxyethylene (2) dodecyl ether sulfate in 2429 parts by mass of deionized water. , Heated to 98°C. After heating, 55 parts by mass of the amorphous vinyl resin particle dispersion liquid prepared by the above-mentioned first-stage polymerization, in terms of solid content, and the following monomers, chain transfer agents and mold releasing agents were dissolved at 90° C. and mixed. And liquid were added.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester A-1 (release agent) 53.3 parts by mass Fatty acid ester B-1 (release agent) 90.7 parts by mass A mechanical dispersion machine CLEARMIX (registered trademark) (manufactured by M Technique Co., Ltd.) having a circulation path was subjected to a mixing dispersion treatment for 1 hour to prepare a dispersion liquid containing emulsified particles (oil droplets). To this dispersion, a solution of a polymerization initiator in which 5.4 parts by mass of potassium persulfate was dissolved in 103 parts by mass of ion-exchanged water was added, and the system was heated and stirred at 84° C. for 1 hour to carry out polymerization. Then, an amorphous vinyl resin particle dispersion liquid was prepared.

(Third stage polymerization)
400 parts by mass of ion-exchanged water was further added to the amorphous vinyl resin particle dispersion liquid obtained by the second-stage polymerization and mixed well, and then 7.3 parts by mass of potassium persulfate was added to 138 parts by mass of ion-exchanged water. The dissolved solution was added. Furthermore, under a temperature condition of 82° C., a mixed liquid of the following monomer and chain transfer agent was added dropwise over 1 hour.

Styrene (St) 367 parts by mass Butyl acrylate (BA) 165 parts by mass 80% methacrylic acid aqueous solution (MAA80) 42.5 parts by mass (methacrylic acid solid content 34.0 parts by mass)
Methyl methacrylate (MMA) 52.45 parts by mass n-octyl-3-mercaptopropionate 8.0 parts by mass After completion of dropping, polymerization is carried out by heating and stirring for 2 hours, followed by cooling to 28° C., An amorphous vinyl resin dispersion was prepared.

The amorphous vinyl resin particles in the dispersion had a volume-based median diameter of 220 nm, a weight average molecular weight (Mw) of 32000, and a glass transition point (Tg) of 44.5°C.

(Preparation of hybrid amorphous resin particle dispersion for shell layer)
A mixture liquid of the following styrene-acrylic resin monomer, a monomer (acrylic acid) having a substituent that reacts with both the amorphous polyester resin and the styrene-acrylic resin, and a polymerization initiator was placed in a dropping funnel.

Styrene 80.0 parts by mass n-butyl acrylate 20.0 parts by mass Acrylic acid 10.0 parts by mass Di-t-butyl peroxide (polymerization initiator) 16.0 parts by mass In addition, a single amount of the following amorphous polyester resin The body was placed in a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170° C. to be dissolved.

Bisphenol A Propylene oxide 2 mol adduct 285.7 parts by mass Terephthalic acid 66.9 parts by mass Fumaric acid 47.4 parts by mass With stirring, the mixed solution placed in the dropping funnel was added dropwise to the four-necked flask over 90 minutes. After aging for 60 minutes, unreacted monomer was removed under reduced pressure (8 kPa). After that, 0.4 parts by mass of Ti(OBu) ₄ as an esterification catalyst was added, the temperature was raised to 235° C., and the pressure was raised under normal pressure (101.3 kPa) for 5 hours, and further under reduced pressure (8 kPa) for 1 hour. , The reaction was carried out.

Then, the mixture was cooled to 200° C., and the reaction was performed under reduced pressure (20 kPa), followed by solvent removal, and the amorphous polyester polymer segment was grafted with a styrene-acrylic resin as a main chain to form a hybrid amorphous resin. Got The weight average molecular weight (Mw) of the obtained hybrid amorphous resin was 25,000, and the glass transition point (Tg) was 60°C. The weight average molecular weight (Mw) was measured in the same manner as the crystalline polyester resin described above, and the glass transition point (Tg) was measured in the same manner as the amorphous vinyl resin.

100 parts by mass of the obtained hybrid amorphous resin was dissolved in 400 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Inc.) to prepare 638 parts by mass of a 0.26% by mass concentration aqueous sodium lauryl sulfate solution prepared in advance. Mixed. While stirring the mixed solution, an ultrasonic homogenizer US-150T (manufactured by Nippon Seiki Seisakusho Co., Ltd.) was used to perform ultrasonic dispersion treatment for 30 minutes at 300 μA of V-LEVEL. Then, while heating to 40° C., a diaphragm vacuum pump V-700 (manufactured by BUCHI) was used to completely remove ethyl acetate while stirring under reduced pressure for 3 hours to obtain a solid content of 13.5 mass. % Hybrid amorphous resin particle dispersion was prepared. The volume-based median diameter of the hybrid amorphous resin particles in the dispersion was 160 nm.

(Preparation of colorant particle dispersion)
While stirring a solution prepared by adding 90 parts by mass of sodium dodecyl sulfate to 1600 parts by mass of ion-exchanged water, 420 parts by mass of copper phthalocyanine (CI Pigment Blue 15:3) was gradually added. A colorant particle dispersion was prepared by performing a dispersion treatment using a stirrer Clearmix (manufactured by M Technique Co., Ltd.).

The colorant particles in the dispersion had a volume-based median diameter of 110 nm.

(Production of Toner 1)
In a reaction vessel equipped with a stirrer, a temperature sensor and a cooling pipe, 480 parts by mass of the amorphous vinyl resin particle dispersion liquid (solid content conversion), 60 parts by mass of the crystalline polyester resin particle dispersion liquid (solid content conversion), ion exchange 332 parts by mass of water was added. The pH was adjusted to 10 by adding 5 mol/L sodium hydroxide aqueous solution at room temperature (25° C.).

Further, 31 parts by mass of the colorant particle dispersion (converted to solid content) was added, and a solution prepared by dissolving 72.5 parts by mass of an aqueous magnesium chloride solution in 72.5 parts by mass of ion-exchanged water was stirred at 30° C. for 10 days. Added over minutes. After standing for 3 minutes, the temperature was raised to 80° C. over 60 minutes, and after reaching 80° C., the stirring speed was adjusted so that the particle size growth rate was 0.01 μm/min, and the Coulter Multisizer 3( It was grown until the volume-based median diameter measured by Coulter Beckman Co., Ltd. was 6.0 μm.

Next, 60 parts by mass of the hybrid amorphous resin particle dispersion liquid (solid content conversion) was added over 30 minutes, and when the supernatant of the reaction liquid became transparent, 94.6 parts by mass of sodium chloride was added to 378 ion-exchanged water. An aqueous solution dissolved in 4 parts by mass was added to stop the growth of the particle size. Next, the temperature is raised and the mixture is agitated at a temperature of 80° C., whereby the fusion of the particles proceeds, and when the average circularity of the toner particles reaches 0.970, the cooling rate is 2.5° C./min. Cooled to 30°C. The average circularity was measured by using a measuring device FPIA-3000 (manufactured by Sysmex) with the number of HPF detections being 4000.

Next, solid-liquid separation and dehydration of the toner cake are redispersed in ion-exchanged water, and solid-liquid separation is repeated three times for washing. After washing, the toner base particles were obtained by drying at 40° C. for 24 hours.

To 100 parts by mass of the obtained toner base particles, 0.6 parts by mass of hydrophobic silica particles (number average primary particle size: 12 nm, hydrophobicity: 68) and hydrophobic titanium oxide particles (number average primary particle size: 20 nm) , Hydrophobicity: 63) 1.0 part by mass, and sol-gel silica (number average primary particle size=110 nm,) 1.0 part by mass were added, and a rotor blade peripheral speed was obtained by a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.). It mixed at 35 mm/sec and 32 degreeC for 20 minutes. After mixing, coarse particles were removed using a sieve having an opening of 45 μm to obtain Toner 1.

(Example 2/Toner 2)
In the production of Toner 1 described above, in the mixed liquid of the monomers used in the second-stage polymerization, the alkyl acrylate monomer was changed from 2-ethylhexyl acrylate (2EHA) to 2-propylheptyl acrylate, and the following composition was used. Toner 2 was manufactured in the same manner as Toner 1 except that the above was adopted.

Styrene (St) 256.4 parts by mass 2-propylheptyl acrylate 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester A-1 (release agent) 53.3 parts by mass Fatty acid ester B-1 (release agent) 90.7 parts by mass (Example 3/Toner 3)
In the production of Toner 1, the ratio of the fatty acid ester A-1 and the fatty acid ester B-1 in the mixed liquid of the monomers used in the second stage polymerization was changed from 1:1.7 to 1:2. Toner 3 was manufactured in the same manner as Toner 1, except that the following composition was used.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester A-1 (release agent) 48 parts by mass Fatty acid ester B-1 (release agent) 96 parts by mass (Example 4) /Toner 4)
In the production of Toner 1, the release agent contained in the mixed liquid of the monomers used in the second-stage polymerization is changed to fatty acid ester A-2 and fatty acid ester B-3, and the mixing ratio is 1:1.7. Toner 4 was manufactured in the same manner as Toner 1, except that the composition was changed from 1:3 to 1:3.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-Octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester A-2 (release agent) 36 parts by mass Fatty acid ester B-3 (release agent) 108 parts by mass (Example 5) / Toner 5)
In the production of Toner 1, the release agent contained in the mixed liquid of the monomers used in the second-stage polymerization is changed to fatty acid ester A-3 and fatty acid ester B-4, and the mixing ratio is 1:1.7. Toner 5 was manufactured in the same manner as Toner 1, except that the composition was changed to 2:1 to 2:1.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester A-3 (release agent) 96 parts by mass Fatty acid ester B-4 (release agent) 48 parts by mass (Example 6) / Toner 6)
In the production of Toner 1, the mixing ratio of the fatty acid ester A-1 and the fatty acid ester B-1 in the mixed liquid of the monomers used in the second-stage polymerization was changed from 1:1.7 to 3:1. Toner 6 was manufactured in the same manner as Toner 1, except that the following composition was used.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass fatty acid ester A-1 (release agent) 108 parts by mass fatty acid ester B-1 (release agent) 36 parts by mass (Example 7) /Toner 7)
In the same manner as in Toner 1 except that the composition of the mixed liquid used in the second-stage polymerization was changed to the following in the production of Toner 1 and the composition of the mixed liquid used in the third-stage polymerization was changed to the following. To produce toner 7.

(Second-stage polymerization)
Styrene (St) 238.0 parts by mass 2-ethylhexyl acrylate (2EHA) 88.4 parts by mass 80% methacrylic acid aqueous solution (MAA80) 35.5 parts by mass (methacrylic acid solid content 28.4 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.70 parts by mass Fatty acid ester A-1 (release agent) 80.0 parts by mass Fatty acid ester B-1 (release agent) 136 parts by mass (No. (3-step polymerization)
Styrene (St) 340.8 parts by mass Butyl acrylate (BA) 153.1 parts by mass 80% methacrylic acid aqueous solution (MAA80) 39.5 parts by mass (methacrylic acid solid content 31.6 parts by mass)
Methyl methacrylate (MMA) 48.7 parts by mass n-octyl-3-mercaptopropionate (chain transfer agent) 7.7 parts by mass In addition, amorphous vinyl resin particle dispersion liquid at the time of association charging 480 parts by mass (solid) Toner 7 was manufactured in the same manner except that the amount (in terms of solid content) was changed to 468 parts by weight and the amount of the crystalline polyester resin particle dispersion liquid (in terms of solid content) was changed to 60 parts by weight (in terms of solid content) to 72 parts by weight (in terms of solid content).

(Example 8/Toner 8)
In the same manner as in Toner 1 except that the composition of the mixed liquid used in the second-stage polymerization was changed to the following in the production of Toner 1 and the composition of the mixed liquid used in the third-stage polymerization was changed to the following. To produce Toner 8.

(Second-stage polymerization)
Styrene (St) 228.5 parts by mass Butyl acrylate (BA) 49.0 parts by mass 2-ethylhexyl acrylate (2EHA) 49.0 parts by mass Methacrylic acid 80% aqueous solution (MAA80) 35.5 parts by mass (methacrylic acid solid content) 28.4 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.93 parts by mass Fatty acid ester A-1 (release agent) 80.0 parts by mass Fatty acid ester B-1 (release agent) 136 parts by mass (No. (3-step polymerization)
Styrene (St) 340.8 parts by mass Butyl acrylate (BA) 153.1 parts by mass Methyl methacrylate (MMA) 48.7 parts by mass Methacrylic acid 80% aqueous solution (MAA80) 39.5 parts by mass (methacrylic acid solid content 31 .6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 7.7 parts by mass Further, 480 parts by mass of the amorphous vinyl resin particle dispersion liquid at the time of association charging (solid content conversion) to 450 parts by mass and crystallinity Toner 8 was produced in the same manner except that the polyester resin particle dispersion liquid was changed from 60 parts by mass (solid content conversion) to 90 parts by mass (solid content conversion).

(Example 9/Toner 9)
In the production of Toner 1, a mixture of the monomers used in the third-stage polymerization was used to adjust the content of butyl acrylate to 0 parts by mass and the content of 2-ethylhexyl acrylate to 0 to 139.9 parts by mass to prepare a monomer composition. Toner 9 was manufactured in the same manner as Toner 1, except that the following was changed.

Styrene (St) 389.1 parts by mass 2-ethylhexyl acrylate (2EHA) 139.9 parts by mass Methyl methacrylate (MMA) 55.6 parts by mass 80% methacrylic acid aqueous solution (MAA80) 42.5 parts by mass (methacrylic acid solid content 34.0 parts by mass)
8.5 parts by mass of n-octyl-3-mercaptopropionate (chain transfer agent) (Example 10/toner 10)
Toner 10 was produced in the same manner as in Toner 1, except that the composition of the mixed liquid used in the second-stage polymerization was changed to the following in the above-mentioned production of Toner 1.

Styrene (St) 234.1 parts by mass Butyl acrylate (BA) 114.1 parts by mass 2-ethylhexyl acrylate (2EHA) 3.56 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 4.51 parts by mass Fatty acid ester A-1 (release agent) 53.3 parts by mass Fatty acid ester B-1 (release agent) 90.7 parts by mass (Example 11/Toner 11)
Toner 11 was produced in the same manner as Toner 9 except that the composition of the mixed liquid used in the third-stage polymerization was changed to the following in the production of Toner 9 described above.

Styrene (St) 392.5 parts by mass Butyl acrylate (BA) 16.0 parts by mass 2 Ethylhexyl acrylate (2EHA) 120 parts by mass Methyl methacrylate (MMA) 56.1 parts by mass 80% methacrylic acid aqueous solution (MAA80) 42. 5 parts by mass (methacrylic acid solid content 34.0 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 7.7 parts by mass (Comparative Example 1/Toner 12)
In the production of the toner 1, the release agent in the mixed liquid of the monomers used in the second-stage polymerization is changed from the mixed system of the fatty acid ester A and the fatty acid ester B to the fatty acid ester A alone, and 2-ethylhexyl acrylate is used. Toner 12 was manufactured in the same manner except that (2EHA) was changed to butyl acrylate (BA) and the monomer composition was changed to the following.

Styrene (St) 233.2 parts by mass Butyl acrylate (BA) 118.5 parts by mass 80% aqueous methacrylic acid solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 4.53 parts by mass Fatty acid ester A-1 (release agent) 144 parts by mass (Comparative Example 2/Toner 13)
In the production of the toner 12, the butyl acrylate (BA) contained in the mixed liquid of the monomers used in the second-stage polymerization was changed to 2-ethylhexyl acrylate (2EHA), and the monomer composition was changed as follows. A toner 13 was manufactured in the same manner except for the above.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-Octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester A-1 (release agent) 144 parts by mass (Comparative Example 3/Toner 14)
Toner 14 was produced in the same manner as in the production of Toner 13, except that the release agent in the mixed liquid of the monomers used in the second-stage polymerization was changed from fatty acid ester A-1 to fatty acid ester B-1. ..

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-Octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester B-1 (release agent) 144 parts by mass (Comparative Example 4/Toner 15)
Toner 15 was produced in the same manner as in the production of Toner 13, except that the composition of the mixed liquid used in the second-stage polymerization was changed to the following.

Styrene (St) 238.4 parts by mass 2-ethylhexyl acrylate (2EHA) 88.4 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.70 parts by mass Fatty acid ester A-1 (release agent) 216 parts by mass (Comparative Example 5/Toner 16)
In the production of Toner 13 described above, the release agent in the mixed liquid of the monomers used in the second-stage polymerization was changed in the same manner except that the fatty acid ester A-1 alone system was changed to the combined use system with the fatty acid ester A-2. To produce toner 16.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester A-1 (release agent) 53.3 parts by mass Fatty acid ester A-2 (release agent) 90.7 parts by mass (Comparative Example 6/Toner 17)
In the production of the toner 16, the release agent in the mixed liquid of the monomers used for the second-stage polymerization is a combination system of the fatty acid ester A-1 and the fatty acid ester A-2, and the fatty acid ester B-1 and the fatty acid ester are used. Toner 17 was manufactured in the same manner except that the system was changed to the combined use with B-2.

Styrene (St) 256.4 parts by mass 2-ethylhexyl acrylate (2EHA) 95.3 parts by mass 80% methacrylic acid aqueous solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 3.99 parts by mass Fatty acid ester B-1 (release agent) 53.3 parts by mass Fatty acid ester B-2 (release agent) 90.7 parts by mass (Comparative Example 7/Toner 18)
Toner 18 was manufactured in the same manner as in Toner 13 except that the composition of the mixed solution used in the second-stage polymerization was changed to the following and the composition of the mixed solution used in the third-stage polymerization was changed to the following. Was produced (second-stage polymerization)
Styrene (St) 268.8 parts by mass 2-ethylhexyl acrylate (2EHA) 99.9 parts by mass 80% methacrylic acid aqueous solution (MAA80) 40.1 parts by mass (methacrylic acid solid content 32.1 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 4.19 parts by mass Fatty acid ester A-1 (release agent) 96 parts by mass (third stage polymerization)
Styrene (St) 384.8 parts by mass Butyl acrylate (BA) 172.9 parts by mass Methyl methacrylate (MMA) 55.0 parts by mass Methacrylic acid 80% aqueous solution (MAA80) 44.6 parts by mass (methacrylic acid solid content 36 .6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 8.80 parts by mass (Comparative Example 8/Toner 19)
Toner 19 was manufactured in the same manner as in the above toner 12, except that the releasing agent in the mixed liquid of the monomers used in the second-stage polymerization was changed to a mixed system of fatty acid esters A and B.

Styrene (St) 233.2 parts by mass Butyl acrylate (BA) 118.5 parts by mass 80% aqueous methacrylic acid solution (MAA80) 38.2 parts by mass (methacrylic acid solid content 30.6 parts by mass)
n-octyl-3-mercaptopropionate (chain transfer agent) 4.53 parts by mass Fatty acid ester A-1 (release agent) 53.3 parts by mass Fatty acid ester B-1 (release agent) 90.7 parts by mass (Comparative Example 9/Toner 20)
Preparation of Amorphous Polyester Resin Particle Dispersion The following amorphous polyester resin monomers are placed in a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and heated to 170° C. to dissolve them. Let

Bisphenol A Propylene oxide 2 mol adduct 285.7 parts by mass Terephthalic acid 66.9 parts by mass Fumaric acid 47.4 parts by mass Then, 0.1 part by mass of Ti(OBu) ₄ is added, and under nitrogen gas flow, about 180 parts by mass. Stirring reaction was carried out at 8° C. for 8 hours. Furthermore, after 0.2 part by mass of Ti(OBu) ₄ was added and the temperature was raised to about 220° C. to carry out a stirring reaction for 6 hours, the pressure in the reaction vessel was reduced to 1.33 kPa (10 mmHg), and the reaction was performed under reduced pressure. The amorphous polyester resin (2) was obtained.

100 parts by mass of the obtained amorphous polyester resin was dissolved in 400 parts by mass of ethyl acetate (manufactured by Kanto Chemical Co., Inc.) and 638 parts by mass of a 0.26% by mass aqueous sodium lauryl sulfate solution prepared in advance. Mixed. While stirring the mixed solution, an ultrasonic homogenizer US-150T (manufactured by Nippon Seiki Seisakusho Co., Ltd.) was used to perform ultrasonic dispersion treatment for 30 minutes at 300 μA of V-LEVEL. Then, while heating to 40° C., a diaphragm vacuum pump V-700 (manufactured by BUCHI) was used to completely remove ethyl acetate while stirring under reduced pressure for 3 hours to obtain a solid content of 13.5 mass. % Amorphous polyester resin particle dispersion liquid (2) was prepared.

In the production of the toner 1, except that the amorphous polyester resin particle dispersion liquid (1) used in the shelling step was changed to the amorphous polyester resin particle dispersion liquid (2) while maintaining 60 parts by mass in terms of solid content. Toner 20 was manufactured in the same manner.

<Method for producing developers (1) to (20)>
<<Preparation of developer>>
To the toners (1) to (20), a ferrite carrier coated with a silicone resin and having a volume average particle diameter of 60 μm is added and mixed so that the toner particle concentration becomes 6% by mass. )-(20) were manufactured respectively.

<Evaluation method>
(Heat resistant storage)
0.5 g of the toner was placed in a 10 ml glass bottle having an inner diameter of 21 mm, the lid was closed, and the mixture was shaken 600 times at room temperature with Tap Denser KYT-2000 (manufactured by Seishin Enterprise Co., Ltd.), and then the lid was removed at 57.5° C. at 35° C. It was left for 2 hours in the environment of %RH. Then, the toner is placed on a 48-mesh sieve (opening 350 μm), being careful not to crush the toner aggregates, set in a powder tester (manufactured by Hosokawa Micron Co., Ltd.), and fixed with a holding bar and a knob nut. After adjusting the vibration strength of the feed width of 1 mm and applying vibration for 10 seconds, the ratio (% by mass) of the amount of toner remaining on the sieve was measured.

The toner aggregation rate is a value calculated by the following formula.

Toner aggregation rate (%)=residual toner mass on the screen (g)/0.5 (g)×100
The heat-resistant storage stability of the toner was evaluated according to the criteria described below and used as an index of storage stability.

The toner aggregation rate is preferably less than 35% by mass, more preferably less than 25% by mass, and further preferably less than 15% by mass.

⊚: Toner aggregation rate is less than 15 mass% (heat resistant storage property of toner is extremely good)
◯: Toner aggregation rate is 15% by mass or more and less than 25% by mass (heat resistant storage stability of toner is good)
Δ: Agglomeration rate of toner is 25% by mass or more and less than 35% by mass (heat resistant storage property of toner is slightly inferior but acceptable level)
X: The toner aggregation rate is 35% by mass or more (the toner has poor heat-resistant storage stability and cannot be used).

(Low temperature fixability (under offset property))
Under-offset refers to an image defect in which the toner layer is insufficiently melted by heat applied when passing through a fixing device, and thus is peeled off from a transfer material such as recording paper.

The image evaluation was carried out by sequentially loading the developing device of a commercially available color composite machine "bizhub PRO (registered trademark) C6500 (manufactured by Konica Minolta Co., Ltd.)" with the toner and the developer prepared above. The fixing temperature, the toner adhesion amount, and the system speed were modified so that they could be freely set. Using NPI 128 g/m ² (manufactured by Nippon Paper Industries) as an evaluation paper, a solid image having a toner adhesion amount of 11.3 g/m ² is fixed at a fixing speed of 300 mm/sec, the temperature of the upper fixing belt is 110 to 200° C., and the temperature of the lower fixing roller is Was set to 100° C. and fixed at a level of every 5° C., the lower limit fixing temperature of the upper fixing belt at which under-offset did not occur was evaluated and used as an index of low-temperature fixability. The lower the lower limit fixing temperature, the better the fixability. The under-offset property is preferably less than 140°C, more preferably less than 135°C, and even more preferably less than 130°C.

◯: Less than 130° C. Δ: 130° C. or more and less than 135° C. ×: 135° C. or more (low temperature fixing property/fold fixing property evaluation)
In the copying machine "bizPRO PRO (registered trademark) C6501" (manufactured by Konica Minolta Co., Ltd.), the fixing device is modified so that the surface temperature of the fixing heat roller can be changed within the range of 100 to 210°C. The above developers (1) to (20) were loaded in the respective cartridges. "NPi high-quality paper (128 g/m ² )" (manufactured by Nippon Paper Industries Co., Ltd.) was used as the evaluation paper, and a solid image with a toner adhesion amount of 8 mg/10 cm ² was fixed at normal temperature and normal temperature (temperature 20° C., relative humidity 55%). The fixing experiment to be carried out was repeated up to 200° C. while changing the set fixing temperature from 95° C. in increments of 5° C.

Next, the printed matter obtained in the fixing experiment at each fixing temperature was folded by a folding machine so as to apply a load to the solid image, and compressed air of 0.35 MPa was blown to this, and the creases are shown in the following evaluation criteria. The stages were ranked, and the temperature reaching the rank 3 was used as the index of the deviation between the folding fixing temperature and the under-offset temperature. The folding fixability is preferably under offset (UO) plus 15° C. or more and less than 20° C., more preferably plus 12° C. or more and less than 15° C., and even more preferably plus 12° C. or less.

⊚: Under offset (UO) plus less than 12° C. ○: Under offset (UO) plus 12° C. or more and less than 15° C. Δ: Under offset (UO) plus 15° C. or more and less than 20° C. (Fixing separation)
Fixation separability evaluation: Kindo 85 g/m, which was conditioned using a modified "bizhub (registered trademark) C6500 (manufactured by Konica Minolta)" at room temperature and normal humidity environment (NN environment: 25°C, 50% RH). ^{At the 2nd} T (Oji Paper Co., Ltd.), the tip margin is 5 mm, and the fixing temperature is 195°C/120°C. All solid images are printed by changing the adhesion amount, and the solid image just before the paper jam (jam) occurs The amount (g/m ² ) was measured and taken as the separation limit adhesion amount, which was used as a measure of the fixing separation performance. The larger this value, the better the separation performance. In addition, it carries out in normal temperature and normal humidity environment (NN environment: 25 degreeC, 50%RH). The fixing separability is preferably 2.5 g/m ² or more, more preferably 3.0 g/m ² or more, and further preferably 3.5 g/m ² or more.

⊚: 3.5 g/m ² or more O: 3.0 g/m ² or more and less than 3.5 g/m ² Δ: 2.5 g/m ² or more and less than 3.0 g/m ² ×: 2.5 g/m ² or less The properties of each toner and the evaluation results are shown below.

In each table, the content of the structural unit derived from the (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1) in the toner base particles is “the toner base particles of the general formula (1)”. Medium content (%)".

Further, in Example 1, the content (%) of the structural unit derived from the (meth)acrylic acid alkyl ester monomer represented by the general formula (1) in the toner base particles, the crystal in the toner base particles Of the reactive polyester resin (%), the content of the shell resin in the toner base particles (%), and the content of the wax in the toner base particles (%) were calculated as follows.

Content (%) of 2-ethylhexyl acrylate (alkyl (meth)acrylate monomer represented by general formula (1)) in the amorphous vinyl resin dispersion=95.3/{55+(256 .4+95.3+30.6+53.3+90.7)+(367+165+34.0+52.45)}×100=7.94%
Content (%) of the structural unit derived from the (meth)acrylic acid alkyl ester-based monomer represented by the general formula (1) in the toner base particles={(480×0.0794)/(480+60+31+60)} ×100=6.0
Content of crystalline polyester resin in toner base particles (%)=(60/631)×100=9.5
Shell resin content (%) in toner base particles=(60/631)×100=9.5
Wax content in toner base particles (%)=(53.3+90.7)/{55+(256.4+95.3+30.6+53.3+90.7)+(367+165+34.0+52.45)}×480/631×100 =9.1
Similarly, Examples 2 to 11 and Comparative Examples 1 to 9 were calculated.

As is apparent from the table, the toner of the present invention is superior to the toners of Comparative Examples in low-temperature fixing property, heat-resistant storage property, and fixing separation property.

On the other hand, Comparative Examples 1 and 8 in which the amorphous resin does not have a structural unit derived from the (meth)acrylic acid alkyl ester-based monomer represented by the formula (1) have low temperature fixability (U.V. O avoidance temperature) was bad. Comparative Examples 2, 3 and 7 containing only one type of wax and Comparative Examples 5 and 6 containing only one type of fatty acid ester A or B had poor fixability. Further, Comparative Example 4, which contained only one type of wax and contained a larger amount of wax than Comparative Example 2, had poor heat-resistant storage properties and low-temperature fixability. Furthermore, in Comparative Example 9 in which the hybrid amorphous resin was not used in the shell part, the heat resistant storage property was poor.

Further, by comparing Examples 1 and 3 to 6, it can be seen that fixing separability is further improved by setting fatty acid ester A:fatty acid ester B=2:1 to 1:2. Further, by comparing Examples 1, 9, and 11, the content of the structural unit derived from the (meth)acrylic acid alkyl ester-based monomer was 1.0 in the toner base particles containing the binder resin and the release agent. It can be seen that the heat-resistant storage property and the fixing separation property are further improved when the content is ˜14.0 mass %.

Claims (5)

A toner for developing an electrostatic charge image containing a binder resin and a release agent,
The binder resin contains an amorphous vinyl resin, a crystalline polyester resin, and a hybrid amorphous resin in which an amorphous polyester polymer segment and an amorphous vinyl polymer segment are chemically bonded,
The release agent is a fatty acid ester A composed of a glycerin condensate and a linear saturated fatty acid having 16 to 24 carbon atoms, and a fatty acid composed of a linear saturated alcohol having 16 to 24 carbon atoms and a linear saturated fatty acid having 16 to 24 carbon atoms. Containing ester B,
The amorphous vinyl resin has the following general formula (1):
[In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents an alkyl group having 8 to 22 carbon atoms. ]
Having a structural unit derived from a (meth)acrylic acid alkyl ester monomer represented by
A core-shell structure having a core portion containing the amorphous vinyl resin, the crystalline polyester resin, the fatty acid ester A and the fatty acid ester B, and a shell portion containing the hybrid amorphous resin;
The content of the structural unit derived from the (meth)acrylic acid alkyl ester-based monomer is 1.0% by mass or more and 14.0% by mass or less in the toner base particles containing the binder resin and the release agent. Toner for charge image development. The electrostatic charge image developing toner according to claim 1, wherein a content mass ratio of the fatty acid ester A and the fatty acid ester B in the core portion is 2:1 to 1:2. In the core part, the total mass of the fatty acid ester A, the fatty acid ester B, and the crystalline polyester resin is 10 times or less the mass of the structural unit derived from the (meth)acrylic acid alkyl ester-based monomer. The toner for developing an electrostatic charge image according to claim 1, which is The content of the amorphous vinyl resin in the binder resin, 50 to 90 wt%, the electrostatic charge image developing toner according to any one of claims 1-3. Amorphous vinyl resin, glycerin condensate and fatty acid ester A consisting of straight chain saturated fatty acid having 16 to 24 carbon atoms, and straight chain saturated alcohol having 16 to 24 carbon atoms and straight chain saturated fatty acid having 16 to 24 carbon atoms A step of obtaining an amorphous vinyl resin particle dispersion liquid containing a fatty acid ester B,
A step of obtaining a crystalline polyester resin particle dispersion,
A step of aggregating the amorphous vinyl resin particle dispersion and the crystalline polyester resin particle dispersion, and heat-fusing the obtained aggregate to obtain core particles;
A shell portion containing a hybrid amorphous resin in which an amorphous polyester polymer segment and an amorphous vinyl polymer segment are chemically bonded is formed on the core particle surface, and a core-shell structure having a core portion and a shell portion is formed. And a step of
The amorphous vinyl resin has the following general formula (1):
[In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents an alkyl group having 8 to 22 carbon atoms. ]
Having a structural unit derived from a (meth)acrylic acid alkyl ester-based monomer represented by
The content of the structural unit derived from the (meth)acrylic acid alkyl ester-based monomer is 1.0% by mass or more and 14.0% by mass or less in the toner base particles containing the binder resin and the release agent. A method for producing a toner for developing a charge image.