JP6427426B2 - Method of producing aqueous dispersion of binder resin composition particles for toner for electrophotography - Google Patents

Description

  The present invention relates to a method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner used for developing a latent image formed in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to an aqueous dispersion of binder resin composition particles for electrophotographic toner obtained by the method, a method for producing a toner for electrophotography using the aqueous dispersion of the binder resin composition particles, and a toner for electrophotography obtained by the production method .

  From the viewpoint of speeding up the printing apparatus and energy saving, toners excellent in low-temperature fixability are required. However, if the softening point or the glass transition temperature of the toner is designed to be low in order to improve low temperature fixability, the storage stability is adversely affected. Therefore, in order to achieve both low temperature fixing ability and storage stability, development of toner using crystalline polyester has been conducted.

  Patent Document 1 describes a crystalline polyester obtained by using a raw material monomer containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms, and the total content of both is 80 mol% or more (1 -1), a raw material monomer of an amorphous condensation polymerization resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and a raw material monomer of the addition polymerization resin Amorphous condensation polymerization obtained by polymerizing a compound capable of reacting with 3 to 15 parts by weight of a raw material monomer of an amorphous condensation polymerization resin and a raw material monomer of an addition polymerization resin A toner for developing an electrostatic charge image, comprising a binder resin comprising an amorphous hybrid resin (2-1) comprising a base resin component and an addition polymerization resin component, which comprises the above-described binder. Ratio of crystalline polyester (1-1) to amorphous hybrid resin (2-1) (crystalline polyester (1-1) / amorphous hybrid resin (2-1)) is 1/99 to 40/60 A toner for developing an electrostatic charge image is disclosed.

JP, 2013-109237, A

In Patent Document 1, the compatibility of the crystalline polyester is improved by using the amorphous composite resin as the amorphous resin, and the dispersibility is improved, but it can not be said that it is sufficient yet. Further improvement such as heat resistant storage stability has been desired.
The present invention provides a method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner, which can obtain a toner for electrophotography which is excellent in low temperature fixability, heat resistant storage stability under high humidity, and durability. Aqueous dispersion of binder resin composition particles for electrophotographic toner obtained by the production method, method of producing toner for electrophotography using aqueous dispersion of the binder resin composition particles, and electrophotography obtained by the production method An object of the present invention is to provide a toner.

  The present inventors obtained from a specific raw material as a binder resin constituting binder resin composition particles in a method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner having a specific manufacturing process. Aqueous dispersion of binder resin composition particles for electrophotographic toner which can obtain a toner for electrophotography which is excellent in low temperature fixability, heat resistant storage stability under high humidity and durability by using a binder resin It has been found that the present invention can be completed.

That is, the present invention provides a method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner, an aqueous dispersion of binder resin composition particles for electrophotographic toner obtained by the production method, and the binding Provided are a method for producing a toner for electrophotography using an aqueous dispersion of resin composition particles, and a toner for electrophotography obtained by the method.
[1] A method for producing an aqueous dispersion of binder resin composition particles for an electrophotographic toner containing an amorphous composite resin (A) and a crystalline polyester resin (C),
A polycondensation resin component (A-1) obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms with an amorphous composite resin (A) And a resin containing a styrene resin component (A-2),
An alcohol component in which the crystalline polyester resin (C) contains 80 to 100 mol% of an aliphatic diol having 8 to 14 carbon atoms, and 80 mol% of an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms It is a resin obtained by polycondensing a carboxylic acid component containing at least 100 mol%,
A method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner, which comprises the following steps 1 to 3.
Step 1: Step of mixing amorphous composite resin (A) and crystalline polyester resin (C) to obtain a mixture Step 2: Step of mixing a neutralizing agent into the mixture obtained in Step 1 Step 3: Step A step of adding an aqueous medium to the mixture obtained in 2 and performing phase inversion emulsification [2] An aqueous dispersion of binder resin composition particles for electrophotographic toner obtained by the manufacturing method of the above [1].
[3] A process for producing a toner for electrophotography, which comprises the following steps A and B:
Step A: Step of obtaining aggregated particles by aggregating the binder resin composition particles for toner in the aqueous dispersion of the binder resin composition particles for toner obtained by the manufacturing method according to the above-mentioned [1] Step B: The toner for electrophotography obtained by the production method according to the process [4] above [3] of fusing the aggregated particles.

  According to the present invention, a method for producing an aqueous dispersion of binder resin composition particles for an electrophotographic toner capable of obtaining a toner for electrophotography which is excellent in low temperature fixability, heat resistant storage stability under high humidity, and durability. An aqueous dispersion of binder resin composition particles for electrophotographic toner obtained by the production method, a method for producing an electrophotographic toner using the aqueous dispersion of the binder resin composition particles, and the production method An electrophotographic toner can be provided.

[Method of producing aqueous dispersion of binder resin composition particles for electrophotographic toner]
The method for producing an aqueous dispersion (hereinafter, also simply referred to as “aqueous dispersion”) of binder resin composition particles for electrophotographic toner of the present invention comprises an amorphous composite resin (A) and a crystalline polyester resin (C) A method of producing an aqueous dispersion of binder resin composition particles for an electrophotographic toner containing
A polycondensation resin component (A-1) obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms with an amorphous composite resin (A) And a resin containing a styrene resin component (A-2),
An alcohol component in which the crystalline polyester resin (C) contains 80 to 100 mol% of an aliphatic diol having 8 to 14 carbon atoms, and 80 mol% of an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms It is a resin obtained by polycondensing a carboxylic acid component containing at least 100 mol%,
1 is a method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner, which includes the following steps 1 to 3.
Step 1: Step of mixing amorphous composite resin (A) and crystalline polyester resin (C) to obtain a mixture Step 2: Step of mixing a neutralizing agent into the mixture obtained in Step 1 Step 3: Step Adding an aqueous medium to the mixture obtained in 2 and performing phase inversion emulsification

A toner for electrophotography obtained from an aqueous dispersion of binder resin composition particles for electrophotographic toner (hereinafter, also simply referred to as "binder resin composition particles") obtained by the production method of the present invention (hereinafter simply referred to as "toner The reason why the toner is excellent in low-temperature fixability, heat-resistant storage stability under high humidity (hereinafter, also simply referred to as "storability"), and durability is not clear, but is considered as follows.
The crystalline polyester resin (C) contained in the toner of the present invention uses a long chain aliphatic monomer and is highly hydrophobic. Accordingly, the crystalline polyester resin (C) is easily crystallized and is considered to be excellent in low-temperature fixability and storage stability. However, since the crystallinity is high, the compatibility with the amorphous composite resin (A) is lowered, and the dispersibility in the amorphous composite resin (A) is deteriorated, so that the low temperature fixability and the low temperature fixability as originally expected. Preservability is not exhibited.
In the toner of the present invention, low temperature fixability and storage stability can be obtained by using a specific long chain aliphatic monomer as the polycondensation resin component of the amorphous composite resin (A) and using a specific manufacturing method. And the filming resistance could be improved.
The aqueous dispersion of the present invention can be achieved by using the production method of the present invention while enhancing the compatibility with the crystalline polyester resin (C) by using a specific long chain aliphatic monomer for the amorphous composite resin (A). The body is considered to have a fine morphology in which a crystalline polyester resin (C) having high hydrophobicity is encapsulated by the amorphous composite resin (A).
Thus, when a toner for electrophotography is produced by the production method of the present invention, the crystalline polyester resin (C) is finely dispersed in the toner, and the amorphous composite resin (A) and the crystalline polyester are produced. As a result of the increase in the contact area with the resin (C), the binder resin is likely to be melted near the melting point of the crystalline polyester, and the low-temperature fixability is considered to be improved. Further, since the crystalline polyester resin (C) has high crystallinity, it is considered that storage stability is improved without lowering the glass transition temperature of the toner. Furthermore, since the crystalline polyester resin (C) is contained in a finely dispersed form in the toner and is hardly precipitated on the toner surface, it is considered that the durability (filming resistance) of the toner also becomes good.

<Amorphous Composite Resin (A)>
The amorphous composite resin (A) is a polycondensation resin component (A-1) obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms. A resin containing a styrene resin component (A-2), a polycondensation resin component (A-1), a styrene resin component (A-2), and a polycondensation resin component (A-1) And the component derived from the bireactive monomer capable of reacting with any of the styrene resin component (A-2). In addition, components other than these three components may be included within the scope of the object of the present invention, but it is preferable not to include components other than three components.

In the present invention, the crystallinity of the resin is represented by the ratio of the softening point to the maximum peak temperature of endotherm by differential scanning calorimeter, that is, the crystallinity index defined by the value of [softening point / maximum peak temperature of endotherm]. .
The amorphous resin is a resin having a crystallinity index of more than 1.4 or less than 0.6, preferably more than 1.5 or less than 0.5, more preferably more than 1.6 It is 0.5 or less.
The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, and the production conditions (eg, reaction temperature, reaction time, cooling rate) and the like. The endothermic maximum peak temperature refers to the temperature of the highest end of the observed endothermic peaks. In the crystalline resin, the maximum peak temperature of the endotherm is taken as the melting point. The crystallinity index can be measured by the method described in the examples.

  The total content of the polycondensation resin component (A-1), the styrene resin component (A-2), and the components derived from the both reactive monomers in the amorphous composite resin (A) is low temperature fixing From the viewpoint of the properties, storage stability and durability, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less, more preferably 100 It is mol%.

(Polycondensation resin component (A-1))
The polycondensation resin component (A-1) is a carboxylic acid component containing an alcohol component (hereinafter also referred to as “alcohol component (A-al)”) and an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms ( Hereinafter, it is also obtained by polycondensing with "a carboxylic acid component (A-ac)".
As a resin which comprises such a polycondensation type-resin component (A-1), a polyester resin is preferable.

[Alcohol component (A-al)]
Examples of the alcohol component (A-al) include aliphatic diols, aromatic diols, and trivalent or higher polyhydric alcohols.
The alcohol component (A-al) preferably contains an alkylene oxide adduct of bisphenol A represented by the following formula (I) from the viewpoint of low-temperature fixability, storage stability, and durability.

(Wherein, R ¹ O is an alkylene oxide, R ¹ is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers indicating the average addition mole number of the alkylene oxide, and the sum of x and y is , Preferably 1 or more, more preferably 1.5 or more, further preferably 2 or more, and preferably 16 or less, more preferably 5 or less, still more preferably 3 or less.)

As the alkylene oxide adduct of bisphenol A represented by the formula (I), a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane And polyoxyethylene adducts thereof.
These alcohol components (A-al) can be used alone or in combination of two or more.
The content of the alkylene oxide adduct of bisphenol A represented by the above-mentioned formula (I) in the alcohol component (A-al) is preferably 80% by mole from the viewpoint of low temperature fixability, storage stability and durability. The content is more preferably 85 mol% or more, further preferably 90 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.
The content of the polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane in the alcohol component (A-al) is preferably 50 in terms of low-temperature fixability, storage stability, and durability. The molar ratio is preferably at least 70 mol%, more preferably at least 85 mol%, and preferably at most 98 mol%, more preferably at most 95 mol%, further preferably at most 92 mol%.

[Carboxylic acid component (A-ac)]
The carboxylic acid component (A-ac) contains an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms from the viewpoint of low-temperature fixability, storage stability, and durability.
The carbon number of the aliphatic dicarboxylic acid compound is preferably 8 or more, more preferably 9 or more, and preferably 14 or less, more preferably 12 or less, from the viewpoint of low-temperature fixability, storage stability, and durability. More preferably, it is 11 or less, still more preferably 10 or less.
The carbon number of the aliphatic dicarboxylic acid compound is obtained by including the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.
Examples of aliphatic dicarboxylic acid compounds having 8 to 14 carbon atoms include suberic acid (8 carbon atoms), azeleic acid (9 carbon atoms), sebacic acid (10 carbon atoms), undecanedioic acid (11 carbon atoms), Examples thereof include dodecanedioic acid (carbon number 12), tridecanedioic acid (carbon number 13), tetradecanedioic acid (carbon number 14), and alkyl esters thereof having 1 or more and 3 or less carbon atoms. Among them, sebacic acid and dodecanedioic acid are preferable, and sebacic acid is more preferable, from the viewpoints of low-temperature fixing ability, storage ability and durability.

  The content of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms in the carboxylic acid component (A-ac) is preferably 20 mol% or more, more preferably from the viewpoint of low-temperature fixability, storage stability, and durability. It is preferably 30 mol% or more, more preferably 40 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less, still more preferably 50 mol% or less It is.

The carboxylic acid component (A-ac) may contain another carboxylic acid component other than an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms.
As another carboxylic acid component which a carboxylic acid component (A-ac) may contain, dicarboxylic acid compounds other than aliphatic dicarboxylic acid compounds having 8 to 14 carbon atoms, trivalent or higher polyvalent carboxylic acid compounds, and those Anhydride and those C1-C3 alkyl ester etc. are mentioned.
Examples of the dicarboxylic acid compounds include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds other than aliphatic dicarboxylic acid compounds having 8 to 14 carbon atoms, and alicyclic dicarboxylic acid compounds.
The carboxylic acid component (A-ac) includes not only the free acid but also an anhydride which is decomposed during the reaction to form an acid, and an alkyl ester having 1 to 3 carbon atoms of each carboxylic acid compound.
Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid and terephthalic acid. Among these, terephthalic acid is preferable from the viewpoint of low temperature fixing ability, storage ability and durability.
Examples of aliphatic dicarboxylic acid compounds other than aliphatic dicarboxylic acid compounds having 8 to 14 carbon atoms include malonic acid (3 carbon atoms), maleic acid (4 carbon atoms), fumaric acid (4 carbon atoms), citraconic acid (C5), itaconic acid (C5), glutaconic acid (C5), succinic acid (C4), adipic acid (C6), pentadecanedioic acid (C15), hexadecanedioic acid Examples thereof include (16 carbon atoms), an alkyl group having 12 to 20 carbon atoms, and a succinic acid substituted with an alkenyl group having 12 to 20 carbon atoms. Among them, aliphatic dicarboxylic acid compounds having 4 to 6 carbon atoms are preferable, and fumaric acid is more preferable, from the viewpoints of low-temperature fixability, storage stability, and durability.
Examples of trivalent or higher polyvalent carboxylic acid compounds include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid and pyromellitic acid. Among these, trimellitic acid is preferable from the viewpoint of low-temperature fixability, storage stability, and durability.

The content of the aromatic dicarboxylic acid compound in the carboxylic acid component (A-ac) is preferably 10 mol% or more, more preferably 20 mol% or more, from the viewpoint of low-temperature fixability, storage stability, and durability. And preferably 70 mol% or less, more preferably 60 mol% or less, still more preferably 50 mol% or less.
The content of the aliphatic dicarboxylic acid compound having 4 to 6 carbon atoms in the carboxylic acid component (A-ac) is preferably 5 mol% or more, more preferably from the viewpoint of low-temperature fixability, storage stability, and durability. Preferably, it is 10 mol% or more, and preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less.

  These carboxylic acid components (A-ac) can be used alone or in combination of two or more.

  From the viewpoint of adjusting physical properties, the alcohol component (A-al) may optionally contain a monohydric alcohol, and the carboxylic acid component (A-ac) may suitably contain a monovalent carboxylic acid compound. It may be

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (A-ac) to the alcohol component (A-al) is preferably 0.7 or more, more preferably from the viewpoint of low-temperature fixability, storage stability and durability. It is preferably 0.8 or more, more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, and still more preferably 1.1 or less.

(Styrene resin component (A-2))
The styrene resin component (A-2) is a segment made of a styrene resin.
Examples of styrene resins include polystyrene, polymers of styrene derivatives, styrene-acrylic copolymers and the like, and from the viewpoints of low-temperature fixability, storage stability and durability, polymers of polystyrene, styrene derivatives and styrene-acrylics One or more selected from copolymers are preferable, one or more selected from polystyrene and styrene-acrylic copolymers is more preferable, and styrene-acrylic copolymers are more preferable.

The content of the styrenic resin component in the amorphous composite resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably from the viewpoint of low-temperature fixability, storage stability, and durability. Is 30% by mass or more, more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 45% by mass or less.
In the above calculation of the content, the mass of the polycondensation resin component (A-1) is obtained by removing the dewatering amount at the condensation reaction from the total amount of the raw material monomers of the polycondensation resin component (A-1). In addition, the mass of the styrenic resin component (A-2) uses the total amount of the raw material monomer of the styrenic resin component (A-2) and the polymerization initiator. Moreover, the bireactive monomer used as needed is calculated as a mass of a polycondensation type-resin component (A-1).

From the viewpoint of low-temperature fixability, storage stability, and durability, the raw material monomer of the styrene resin component (A-2) is preferably at least one selected from styrene and a styrene derivative, and among these, the raw material price of the monomer From the viewpoint of low-temperature fixability, storage stability, and durability, styrene is more preferable, and using styrene and an alkyl (meth) acrylate in combination is more preferable.
The term "alkyl (meth) acrylate" means both alkyl acrylate and alkyl methacrylate. The same applies to the following.

  When styrene is used, the content of the structural unit derived from styrene in the styrene resin component (A-2) is preferably 50% by mass or more, more preferably 60% by mass or more from the viewpoint of low-temperature fixability and durability. , More preferably 70% by mass or more, still more preferably 75% by mass or more, and from the viewpoint of low temperature fixability and durability, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably It is 85 mass% or less.

  The styrene derivative is preferably one or more selected from methylstyrene, α-methylstyrene, β-methylstyrene, t-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrene sulfonic acid and salts thereof.

As the alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, (iso) palmityl (meth) acrylate, Examples include (iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate and the like. Among these, (iso) stearyl (meth) acrylate is preferable, and stearyl methacrylate is more preferable, from the viewpoint of low-temperature fixing ability and durability.
The carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 10 or more, more preferably 12 or more, and preferably 20 or less, more preferably 18 or less, from the viewpoint of low-temperature fixability and durability. is there.

  When an alkyl (meth) acrylate is used, the content of the alkyl (meth) acrylate in the styrenic resin component (A-2), that is, the constituent unit derived from (meth) acrylic acid alkyl ester, is low temperature fixability, storage stability, And from the viewpoint of durability, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less .

[Bi-reactive monomer]
The amorphous composite resin (A) preferably further contains a constituent unit derived from a bireactive monomer.
When a bireactive monomer is used as a raw material monomer of the amorphous composite resin (A), the bireactive monomer is both a polycondensation resin component (A-1) and a styrene resin component (A-2). By reacting, an amorphous composite resin (A) can be manufactured favorably.
That is, the amorphous composite resin (A) of the present invention comprises the raw material monomer of the polycondensation resin component (A-1), the raw material monomer of the styrene resin component (A-2), and the bireactive monomer. Those obtained by polymerization are preferred. As a result, in the amorphous composite resin (A), the polycondensation resin component (A-1) and the styrene resin component (A-2) are bonded through the constitutional unit derived from the bireactive monomer, and the weight is heavy. The condensation resin component (A-1) and the styrene resin component (A-2) are uniformly dispersed, and the low temperature fixability, the preservability, and the durability become excellent.

As the bireactive monomer, a compound having in the molecule one or more functional groups selected from a carboxy group, a hydroxyl group, an epoxy group, a primary amino group and a secondary amino group, and an ethylenically unsaturated bond And compounds having the formula: Among these, from the viewpoint of reactivity, preferably a compound having a hydroxyl group and / or a carboxy group and an ethylenically unsaturated bond, more preferably a compound having a carboxy group and an ethylenically unsaturated bond.
Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like can be mentioned as the bireactive monomer. From the viewpoint of the reactivity of the polycondensation reaction and the addition polymerization reaction, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable.

  The amount of the dual reactive monomer used is based on 100 parts by mole of the alcohol component (A-al), which is a raw material monomer of the polycondensation resin component (A-1), from the viewpoint of low-temperature fixability, storage stability and durability. Preferably, it is at least 1 molar part, more preferably at least 5 molar parts, further preferably at least 10 molar parts, and preferably at most 30 molar parts, more preferably at most 20 molar parts, further preferably at least 15 molar parts It is below.

  The amorphous composite resin (A) can be produced, for example, by any of the following methods (1) to (3). In addition, it is preferable that a bireactive monomer is supplied to a reaction system with the raw material monomer of a styrene resin component (A-2) from a reactive viewpoint. From the same viewpoint, a catalyst such as an esterification catalyst or an esterification co-catalyst may be used, and a polymerization initiator and a polymerization inhibitor may be used.

(1) After step (X) of polycondensation reaction by alcohol component (A-al) and carboxylic acid component (A-ac), raw material monomers of styrenic resin component (A-2) and both reactions as required Method of carrying out the step (Y) of the addition polymerization reaction with a reactive monomer.
In addition, in step (X), a portion of carboxylic acid component (A-ac) is subjected to a polycondensation reaction, and then step (Y) is carried out, and then the reaction temperature is raised again to obtain carboxylic acid component (A-ac). It is more preferable to add the remainder of the above to the polymerization system to further advance the reaction of the polycondensation reaction of step (X) and, if necessary, the reaction with the bireactive monomer.

(2) After the step (Y) of the addition polymerization reaction of the raw material monomer of the styrenic resin component (A-2) and the bireactive monomer, the polycondensation reaction of the raw material monomer of the polycondensation resin component (A-1) The method of performing a process (X).
The alcohol component (A-al) and the carboxylic acid component (A-ac) are allowed to be present in the reaction system at the time of the addition polymerization reaction, and the esterification catalyst and, if necessary, the ester at a temperature suitable for the polycondensation reaction. The polycondensation reaction can also be initiated by adding a copromoting agent, or the alcohol component (A-al) and the carboxylic acid component (A-ac) can be introduced into the reaction system at a temperature suitable for the polycondensation reaction. The polycondensation reaction can also be initiated by the addition of In the former case, the molecular weight and molecular weight distribution can be controlled by adding an esterification catalyst and, if necessary, an esterification promoter at a temperature suitable for the polycondensation reaction.

(3) Step (X) of the polycondensation reaction with alcohol component (A-al) and carboxylic acid component (A-ac) and addition polymerization with raw material monomer and bireactive monomer of styrenic resin component (A-2) A method of carrying out the reaction under conditions in which the reaction step (Y) proceeds in parallel.
In this method, step (X) and step (Y) are carried out under reaction temperature conditions suitable for addition polymerization reaction, reaction temperature is raised, and temperature conditions suitable for polycondensation reaction, if necessary, It is preferable to add a trivalent or higher raw material monomer or the like of the polycondensation resin component (A-1) as a crosslinking agent to the polymerization system, and further carry out the polycondensation reaction of the step (X). At that time, under the temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor may be added to proceed only with the polycondensation reaction. Both reactive monomers participate in the polycondensation reaction as well as the addition polymerization reaction. The methods (1) to (3) are preferably performed in the same container.

The temperature of the polycondensation reaction is preferably 120 ° C. or more, more preferably 160 ° C. or more, still more preferably 180 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less from the viewpoint of reactivity. is there.
The temperature of the addition polymerization reaction is preferably 120 ° C. or more, more preferably 130 ° C. or more, and preferably 200 ° C. or less, more preferably 180 ° C. or less from the viewpoint of reactivity.

[Esterification catalyst]
As an esterification catalyst suitably used for the polycondensation reaction, a titanium compound and a tin (II) compound not having a Sn-C bond may be mentioned, and these may be used alone or in combination of two or more. it can.
As a titanium compound, a titanium compound having a Ti-O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms in total, an alkenyloxy group or an acyloxy group is more preferable.
Examples of tin (II) compounds not having a Sn-C bond include tin (II) compounds having a Sn-O bond, tin (II) compounds having a Sn-X bond (where X represents a halogen atom), etc. Preferably, tin (II) compounds having a Sn-O bond are more preferable. Among them, di (2-ethylhexanoic acid) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous composite resin (A). ) Tin (II) is more preferred.
The amount of the esterification catalyst used is the total amount of the alcohol component (A-al) and the carboxylic acid component (A-ac) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous composite resin (A). The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 1.5 parts by mass or less, per 100 parts by mass. The amount is preferably 1.2 parts by mass or less, more preferably 1.0 parts by mass or less.

[Esterification promoter]
As the esterification promoter, pyrogallol compounds are preferred. The pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted by a hydroxyl group, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ' And benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; and catechin derivatives such as epigallocatechin and epigallocatechin gallate. Gallic acid is preferable from the viewpoint of reactivity.
The amount of the esterification co-catalyst used is a total of 100 of the alcohol component (A-al) and the carboxylic acid component (A-ac) from the viewpoint of reactivity, molecular weight adjustment and physical property adjustment of the amorphous composite resin (A). The amount is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, still more preferably 0.02 parts by mass or more, and preferably 0.15 parts by mass or less, more preferably, per part by mass. Is 0.12 parts by mass or less, more preferably 0.10 parts by mass or less.
The mass ratio of the esterification promoter to the esterification catalyst [esterification promoter / esterification catalyst] is preferably 0.001 or more, more preferably 0.01 or more, still more preferably 0. It is not less than 05, and preferably not more than 0.5, more preferably not more than 0.3, still more preferably not more than 0.15.
[Polymerization inhibitor]
It is preferable to use a polymerization inhibitor when polycondensation of a carboxylic acid component having a reactive unsaturated group, for example, fumaric acid or maleic acid. As a polymerization inhibitor, 4-t-butyl catechol etc. are mentioned. The amount of the polymerization inhibitor used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1 part by mass, per 100 parts by mass of the carboxylic acid component having a reactive unsaturated group. It is the above, Preferably it is 10 mass parts or less, More preferably, it is 5 mass parts or less, More preferably, it is 3 mass parts or less.

(Softening point)
The softening point of the amorphous composite resin (A) is preferably 60 ° C. or more, more preferably 75 ° C. or more, still more preferably 85 ° C. or more from the viewpoint of storage stability and durability, and low-temperature fixability Preferably it is 140 degrees C or less, More preferably, it is 120 degrees C or less, More preferably, it is 110 degrees C or less.
(Glass-transition temperature)
The glass transition temperature of the amorphous composite resin (A) is preferably 25 ° C. or more, more preferably 30 ° C. or more, still more preferably 35 ° C. or more, from the viewpoint of low temperature fixability, storage stability, and durability. And preferably 70 ° C. or less, more preferably 50 ° C. or less, further preferably 40 ° C. or less.
(Acid number)
The acid value of the amorphous composite resin (A) is preferably 0 mg KOH / g or more, more preferably 10 mg KOH / g or more, and still more preferably 20 mg KOH / g or more from the viewpoint of low temperature fixability, storage property and durability. And preferably 40 mg KOH / g or less, more preferably 35 mg KOH / g or less, still more preferably 30 mg KOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous composite resin (A) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate.

<Crystalline polyester resin (C)>
The crystalline polyester resin (C) comprises an alcohol component (hereinafter also referred to as "alcohol component (C-al)") containing 80 mol% to 100 mol% of an aliphatic diol having 8 to 14 carbon atoms, and carbon Resin obtained by polycondensing a carboxylic acid component (hereinafter, also referred to as "carboxylic acid component (C-ac)") containing 80 mol% to 100 mol% of aliphatic dicarboxylic acid compounds of number 8 to 14 It is.
The crystalline polyester resin (C) is a resin having a crystallinity index of 0.6 or more and 1.4 or less, preferably 0.7 or more and 1.2 or less, more preferably 0.9 or more and 1.2 or less. is there.

(Alcohol component (C-al))
The alcohol component (C-al) contains 80% by mole or more and 100% by mole or less of an aliphatic diol having 8 to 14 carbon atoms.
The carbon number of the aliphatic diol is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, and preferably 14 or less, more preferably, from the viewpoint of low-temperature fixability, storage stability, and durability. Is 12 or less, more preferably 12.
Examples of the aliphatic diol having 8 to 14 carbon atoms include 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, etc. are mentioned. Among them, preferred is 1,12-dodecanediol from the viewpoint of low-temperature fixability, storage stability, and durability.

  The content of the aliphatic diol having 8 to 14 carbon atoms in the alcohol component (C-al) is 80 mol% to 100 mol% from the viewpoint of low-temperature fixability, storage stability, and durability, Preferably it is 85 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 100 mol%.

The alcohol component (C-al) may contain an alcohol other than an aliphatic diol having 8 to 14 carbon atoms.
As other alcohol components that the alcohol component (C-al) may contain, aliphatic diols other than aliphatic diols having 8 to 14 carbon atoms, aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, Or the alkylene oxide (average added mole number 1 or more and 16 or less) adduct etc. of those C2 or more and 4 or less are mentioned.
Specific examples of the other alcohol which the alcohol component (C-al) may contain include aliphatic diols such as 1,5-pentanediol, 1,6-hexanediol, aromatic diols such as bisphenol A, or alkylene oxides thereof (Average addition mole number 1 or more and 16 or less) adduct, alicyclic diol such as hydrogenated bisphenol A, or alkylene oxide (average addition mole number 2 or more and 12 or less) adduct thereof, glycerin, Examples thereof include trivalent or higher polyhydric alcohols such as pentaerythritol, trimethylolpropane and sorbitol, and adducts thereof having an alkylene oxide (average addition mole number is 1 or more and 16 or less) carbon number of 2 or more and 4 or less.

  These alcohol components (C-al) can be used alone or in combination of two or more.

(Carboxyl acid component (C-ac))
A carboxylic acid component (C-ac) contains 80 mol% or more and 100 mol% or less of aliphatic dicarboxylic acid compounds each having 8 to 14 carbon atoms.
The carbon number of the aliphatic dicarboxylic acid compound is preferably 8 or more, more preferably 9 or more, and preferably 14 or less, more preferably 12 or less, from the viewpoint of low-temperature fixability, storage stability, and durability. More preferably, it is 11 or less, still more preferably 10 or less.
Examples of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms include the same as the carboxylic acid component (A-ac). Among these, sebacic acid is preferred.
The content of the aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms in the carboxylic acid component (C-ac) is 80 mol% to 100 mol% from the viewpoint of low-temperature fixing ability, storage stability, and durability. Preferably it is 85 mol% or more, More preferably, it is 90 mol% or more, More preferably, it is 100 mol%.

  The carboxylic acid component (C-ac) may contain another carboxylic acid component other than an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms, and as a specific example thereof, the carboxylic acid component (A-ac) The same as those mentioned above.

  These carboxylic acid components (C-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (C-ac) to the alcohol component (C-al) is preferably 0.6 or more, more preferably from the viewpoint of low-temperature fixing ability, storage stability and durability. Preferably it is 0.7 or more, More preferably, it is 0.8 or more, Preferably it is 1.2 or less, More preferably, it is 1.1 or less, More preferably, it is 1.0 or less.

The crystalline polyester resin (C) contains an alcohol component (C-al) and a carboxylic acid component (C-ac) in an inert gas atmosphere and, if necessary, an esterification catalyst, an esterification co-catalyst, a polymerization inhibitor It can manufacture by polycondensing using etc.
As the esterification catalyst, the esterification co-catalyst, and the polymerization inhibitor, those similar to those which can be used for the production of the amorphous composite resin (A) can be mentioned, and preferred embodiments are also the same.

  The amount of the esterification catalyst used is a total of 100 mass of the alcohol component (C-al) and the carboxylic acid component (C-ac) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the crystalline polyester resin (C) The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, and preferably 2.0 parts by mass or less, more preferably It is 1.5 parts by mass or less, more preferably 1.0 parts by mass or less.

  The temperature of the polycondensation reaction is preferably 120 ° C. or more, more preferably 160 ° C. or more, still more preferably 180 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less, still more preferably 230 ° C. or less It is.

(Softening point)
The softening point of the crystalline polyester resin (C) is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 80 ° C. or more, from the viewpoint of storage stability and durability. From the viewpoint, it is preferably 120 ° C. or less, more preferably 100 ° C. or less, still more preferably 90 ° C. or less.
(Melting point)
The melting point of the crystalline polyester resin (C) is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 80 ° C. or more, from the viewpoint of low temperature fixability, storage stability and durability. Is 120 ° C. or less, more preferably 100 ° C. or less, still more preferably 90 ° C. or less.
(Acid number)
The acid value of the crystalline polyester resin (C) is preferably 0 mg KOH / g or more, more preferably 0.5 mg KOH / g or more, still more preferably 1 mg KOH / g or more from the viewpoint of low-temperature fixability, storage stability and durability. And preferably 20 mg KOH / g or less, more preferably 10 mg KOH / g or less, still more preferably 5 mg KOH / g or less.
The softening point, the melting point and the acid value of the crystalline polyester resin (C) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time and the cooling rate. The softening point, the melting point and the acid value are determined by the methods described in the examples.
Next, steps 1 to 3 in the production method of the present invention will be described.

The process for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner according to the present invention includes the following steps 1 to 3.
Step 1: Step of mixing amorphous composite resin (A) and crystalline polyester resin (C) to obtain a mixture Step 2: Step of mixing a neutralizing agent into the mixture obtained in Step 1 Step 3: Step Adding an aqueous medium to the mixture obtained in 2 and performing phase inversion emulsification

<Step 1>
Step 1 is a step of mixing the amorphous composite resin (A) and the crystalline polyester resin (C) to obtain a mixture.
The method of mixing the amorphous composite resin (A) and the crystalline polyester resin (C) is not particularly limited, but a method of dissolving in an organic solvent and mixing is preferable.

(Organic solvent)
As the organic solvent, from the viewpoint of solubility, alcohol solvents such as isopropanol and isobutanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether and dioxane; ethyl acetate Preferred are acetic acid ester solvents such as isopropyl acetate and the like. Among these, ketone solvents are more preferable, and methyl ethyl ketone is more preferable.
The amount of the organic solvent used is preferably 30 parts by mass or more in terms of low-temperature fixability, storage stability, and durability, based on 100 parts by mass in total of the amorphous composite resin (A) and the crystalline polyester resin (C). More preferably, it is 40 parts by mass or more, more preferably 50 parts by mass or more, and preferably 200 parts by mass or less, more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less, still more preferably 80 parts by mass It is below.

(Mass ratio of crystalline polyester resin (C) to amorphous composite resin (A))
The mass ratio of the crystalline polyester resin (C) to the amorphous composite resin (A) [crystalline polyester resin (C) / amorphous composite resin (A)] is from the viewpoint of low temperature fixability and durability. It is preferably 5/95 or more, more preferably 10/90 or more, more preferably 20/80 or more, still more preferably 30/70 or more, and preferably 70/30 or less from the viewpoint of storage stability and durability. More preferably, it is 60/40 or less, more preferably 50/50 or less, still more preferably 45/55 or less.

(Optional ingredient)
In addition, in this step, a known resin used for the toner, for example, polyester other than the crystalline polyester resin (C), styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like may be contained.
The total content of the amorphous composite resin (A) and the crystalline polyester resin (C) in the binder resin to be subjected to Step 1 is preferably 80% by mass from the viewpoint of low temperature fixability, storage stability and durability. % Or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and preferably 100% by mass or less, more preferably 100% by mass.

Also, in this step, optional components such as a coloring agent, a charge control agent, a mold release agent, a surfactant, a conductive regulator, a reinforcing filler such as a fibrous substance, an antioxidant, and an antiaging agent are added. May be
The additives such as the colorant and the charge control agent may be mixed with the binder resin in advance, and in that case, it is preferable to melt-knead the binder resin and the additive.
It is preferable to use an open roll type twin-screw kneader for melt kneading. The open-roll type twin-screw kneader is a kneader in which two rolls are disposed in parallel and in close proximity, and a heating function or a cooling function can be provided by passing a heat medium through each roll. Therefore, the open-roll type twin-screw kneader has a part to be melt-kneaded as an open type, and is provided with a heating roll and a cooling roll, so unlike an ordinary twin-screw kneader, it occurs during melt kneading. The heat of kneading can be dissipated easily.

(Colorant)
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned and it can select suitably according to the objective. Specifically, carbon black, inorganic complex oxide, chromium yellow, Hansa yellow, benzidine yellow, Sureren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, Vulcan orange, watch young red, permanent red, permanent anchor 3B, Brylly anchor Min 6B, Dupont oil red, pyrazolone red, lisole red, rhodamine B lake, lake red C, bengal, aniline blue, ultramarine blue, chalco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate etc Pigments of acridine type, xanthene type, azo type, benzoquinone type, azine type, anthraquinone type, indigo type, Indigo dyes, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
The content of the colorant is preferably 0.1 parts by mass with respect to 100 parts by mass in total of the amorphous composite resin (A) and the crystalline polyester resin (C) from the viewpoint of improving the image density of the toner. The content is more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass or less .

(Charge control agent)
Examples of charge control agents include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. You may use these individually or in combination of 2 or more types.
The content of the charge control agent is preferably 0.01 parts by mass with respect to a total of 100 parts by mass of the amorphous composite resin (A) and the crystalline polyester resin (C) from the viewpoint of toner charge stability. The content is more preferably 0.1 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, still more preferably 1. It is 5 parts by mass or less.

(Release agent)
As a mold release agent, polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc .; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant-based waxes such as oil; Animal-based waxes such as beeswax; Waxes such as mineral and petroleum-based waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, Fischer-Tropsch wax, etc. These may be used alone or in combination of two or more Can be mixed and used.

(Surfactant)
Surfactants include nonionic surfactants, anionic surfactants and cationic surfactants. Among these, from the viewpoint of the dispersibility of binder resin composition particles, nonionic surfactants and / or anionic surfactants are preferable, and anionic surfactants are more preferable.
As nonionic surfactants, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Polyethylene glycol monostearate, polyoxyethylene fatty acid esters such as polyethylene glycol monooleate, oxyethylene / oxypropylene block copolymer, etc. are mentioned, among them, polyoxyethylene alkyl ethers from the viewpoint of the emulsion stability of the resin Is preferred.
Examples of the anionic surfactant include alkyl benzene sulfonates such as sodium alkyl benzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, etc. From the viewpoint of emulsion stability, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, and alkyl ether sulfate is preferable.
Examples of the cationic surfactant include alkyl trimethyl ammonium chloride and dialkyl dimethyl ammonium chloride.
Among these, from the viewpoint of the emulsion stability of the binder resin, polyoxyethylene alkyl ethers and alkyl ether sulfates are preferable, and alkyl ether sulfates are more preferable.

<Step 2>
Step 2 is a step of mixing a neutralizing agent into the mixture obtained in step 1.

As the neutralizing agent used in the present invention, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia; trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine etc. And organic bases of Among these, ammonia is preferable.
The degree of neutralization of the binder resin by the neutralizing agent is controlled by adjusting the volume median particle size to the weighted average value of the acid value of the amorphous composite resin (A) and the crystalline polyester resin (C). From the viewpoint of improving fixability, storage stability and durability, it is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and from the same viewpoint, preferably 150. It is at most mol%, more preferably at most 120 mol%, further preferably at most 100 mol%, even more preferably at most 80 mol%.
The degree of neutralization (mol%) of the resin can be determined by the following equation.
Degree of neutralization = {[mass of neutralizing agent (g) / equivalent of neutralizing agent] / [acid value of resin (mg KOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

<Step 3>
Step 3 is a step of adding an aqueous medium to the mixture obtained in step 2 and performing phase inversion emulsification.
In the phase inversion emulsification step, by adding an aqueous medium to the mixture, the W / O phase is formed first, and then phase inversion is performed to the O / W phase. Whether or not phase inversion is occurring can be confirmed, for example, by visual inspection or conductivity.
The phase inversion step can be adjusted by the addition rate and amount of the aqueous medium as described later.

The aqueous medium is preferably one containing water as a main component. The water content is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, from the viewpoint of improving the emulsion stability of the resin in the aqueous medium. It is 100 mass% or less, more preferably 100 mass%. The water is preferably deionized water or distilled water.
As components other than water, an organic solvent which is dissolved in water such as methanol, ethanol, acetone, cyclic ether such as tetrahydrofuran, etc. may be mentioned.

  The temperature at which the aqueous medium is added is preferably 20 ° C. or more, more preferably 40 ° C. or more, still more preferably 50 ° C. or more, and preferably 90 ° C. or less from the viewpoint of improving the emulsion stability of the resin. More preferably, it is 85 degrees C or less, More preferably, it is 80 degrees C or less.

  The addition rate of the aqueous medium is from the viewpoint of obtaining resin particles having a small particle diameter, to 100 parts by mass in total of the amorphous composite resin (A) and the crystalline polyester resin (C) until phase inversion is completed. Is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, still more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and preferably The content is 50 parts by mass or less, more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less. There is no limitation on the addition rate of the aqueous medium after phase inversion.

  The amount of the aqueous medium used is preferably 100, relative to the total 100 parts by mass of the amorphous composite resin (A) and the crystalline polyester resin (C), from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. The content is at least 200 parts by mass, preferably at least 200 parts by mass, more preferably at least 300 parts by mass, and still more preferably at least 400 parts by mass, and preferably at most 2000 parts by mass, more preferably at most 1500 parts by mass, more preferably Is 1000 parts by mass or less, more preferably 600 parts by mass or less.

When the mixture after phase inversion emulsification contains an organic solvent, it is preferable to carry out the following step 4 after step 3.
Step 4: Step of removing the organic solvent from the mixture subjected to phase inversion emulsification in step 3 The method of removing the organic solvent is not particularly limited, and any method may be used, but it is dissolved in water and distilled. Is preferred. Also, the organic solvent may not be completely removed but may remain in the aqueous dispersion. In this case, the residual amount of the organic solvent in the aqueous dispersion is preferably 1% by mass or less, more preferably 0.5% by mass or less, and substantially more preferably 0%.
When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature above the boiling point of the organic solvent to be used and to distill it off while stirring. Further, from the viewpoint of maintaining the dispersion stability of the binder resin composition particles, it is more preferable that the temperature is raised to a temperature equal to or higher than the boiling point of the organic solvent to be used under reduced pressure. Note that the temperature may be raised after depressurization, or may be reduced after raising the temperature. From the viewpoint of maintaining the dispersion stability of the binder resin composition particles, it is preferable to distill off with the temperature and pressure kept constant.

Furthermore, after step 3 or step 4, step 5 may be carried out in which a surfactant is mixed with the obtained aqueous dispersion.
The amount of surfactant added in step 5 is preferably 50% by mass or more and 100% by mass or less, more preferably 60% by mass of the total addition amount of the surfactant added to the aqueous dispersion of binder resin composition particles. % Or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, still more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less.
The amount of surfactant added in step 5 is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 1.5 parts by mass with respect to 100 parts by mass of binder resin composition particles. The amount is preferably at least 6 parts by mass, more preferably at most 5 parts by mass, and still more preferably at most 4.5 parts by mass.
At the time of surfactant addition, it is preferable to stir with a generally used mixing and stirring apparatus such as an anchor wing, an external circulation stirring apparatus and the like.
In the case of using a mixing and stirring apparatus such as an anchor wing, the peripheral speed of stirring is preferably 20 m / min or more, more preferably 40 m / min or more, still more preferably 60 m / min or more, further preferably from the viewpoint of dispersibility Is 80 m / min or more, and preferably 200 m / min or less, more preferably 150 m / min or less, and still more preferably 100 m / min or less.
The temperature at the time of surfactant addition is preferably 5 ° C. or more, more preferably 10 ° C. or more, still more preferably 20 ° C. or more, from the viewpoint of the dispersibility of the surfactant in water, etc., and preferably 50 C. or less, more preferably 40 ° C. or less, still more preferably 35 ° C. or less.

  The solid content concentration of the aqueous dispersion of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably by adding water as appropriate from the viewpoint of the stability and easy handling of the aqueous dispersion. The content is preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The volume median particle diameter (D ₅₀ ) of the binder resin composition particles contained in the aqueous dispersion of the present invention is preferably 30 nm or more, more preferably from the viewpoint of low temperature fixability, storage stability and durability of the toner. Is 50 nm or more, more preferably 80 nm or more, still more preferably 100 nm or more, still more preferably 130 nm or more, and from the same viewpoint, preferably 700 nm or less, more preferably 500 nm or less, still more preferably 300 nm or less Still more preferably, it is 200 nm or less.
In the present specification, the volume median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by volume fraction is 50% as calculated from the smaller particle size.

[Method for producing electrophotographic toner]
The process for producing a toner for electrophotography of the present invention includes the following steps A and B.
Step A: The binder resin composition particles for toner in the aqueous dispersion of binder resin composition particles for toner obtained by the method for producing the aqueous dispersion of binder resin composition particles for toner according to the present invention are aggregated Step of obtaining agglomerated particles Step B: Step of fusing the agglomerated particles

<Step A>
Step A aggregates the binder resin composition particles for toner in an aqueous dispersion of binder resin composition particles for toner obtained by the method for producing an aqueous dispersion of binder resin composition particles for toner according to the present invention It is a process of obtaining the aggregated particles.
In this step, it is preferable to add a coagulant in order to efficiently carry out the aggregation.

As the coagulant, a cationic surfactant of a quaternary salt, an organic coagulant such as polyethylene imine, and an inorganic coagulant such as an inorganic metal salt and an inorganic ammonium salt are used. From the viewpoint of the particle size distribution of the toner and the storage stability, inorganic coagulants are preferable, and inorganic metal salts are more preferable.
Examples of inorganic metal salts include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and the like. The valence of the central metal of the inorganic metal salt is preferably divalent or higher from the viewpoint of the particle size distribution of the toner and the storage stability.
When a coagulant is added, the addition amount thereof is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, further preferably 0 with respect to 100 parts by mass in total of binder resin composition particles. 1 part by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less.
The coagulant is preferably dissolved in an aqueous medium and added, and it is preferable to sufficiently stir the addition of the coagulant and after completion of the addition.

In the aggregation step, the solid concentration in the system is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably, in order to cause uniform aggregation. It is 40% by mass or less, more preferably 30% by mass or less.
In the aggregation step, the temperature at the time of addition of the coagulant is preferably 10 ° C. or more, more preferably 15 ° C. or more, still more preferably 18 ° C. or more, from the viewpoint of uniformly dispersing the coagulant and causing uniform aggregation. And preferably 40 ° C. or less, more preferably 35 ° C. or less, still more preferably 30 ° C. or less.
The holding temperature after addition of the coagulant is preferably 40 ° C. or more, more preferably 45 ° C. or more, still more preferably 47 ° C. or more, and preferably 65 ° C. or less, more preferably 60 ° C. or less, more preferably Is 55 ° C. or less.

In step A, additives such as colorants, charge control agents, mold release agents, conductivity modifiers, reinforcing fillers such as fibrous substances, antioxidants, and antioxidants are added and then aggregated. May be
The colorant, the charge control agent and the release agent may be the same as those usable in the method for producing an aqueous dispersion of binder resin composition particles of the present invention, and preferred types and amounts thereof are also the same.
Additives such as colorants, charge control agents, and mold release agents are dispersions in which the respective additives are separately dispersed in a dispersion medium such as water, that is, colorant dispersions containing colorant fine particles, charge control agent fine particles The charge control agent dispersion containing the above, and the release agent dispersion containing the release agent fine particles may be prepared and subjected to the aggregation step.
The volume median particle size (D ₅₀ ) of the colorant fine particle is preferably 50 nm or more, more preferably 100 nm or more, and preferably 200 nm or less, more preferably 150 nm or less.
The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 800 nm or less, more preferably 500 nm or less.

<Step B>
Process B is a process of fusing the aggregated particles obtained in Process A.
In step B, after adding an aggregation terminator to the aqueous dispersion of aggregated particles obtained in step A as necessary, fused particles are obtained by heating as necessary.
The temperature in the system in step B is an amorphous composite from the viewpoints of target toner particle size, particle size distribution, shape control and particle fusion property, and low temperature fixing property, storage property and durability. The softening point of the resin (A) is preferably -30 ° C or more, more preferably the softening point -25 ° C or more, still more preferably the softening point -20 ° C or more, and preferably the softening point + 10 ° C or less, more preferably the softening point or less A softening point of −5 ° C. or less is more preferable, and a softening point of −10 ° C. or less is still more preferable.
Specifically, it is preferably 70 ° C. or more, more preferably 75 ° C. or more, and preferably 100 ° C. or less, more preferably 90 ° C. or less.
Moreover, it is preferable to carry out this process under stirring, and the stirring speed is preferably a speed at which the aggregated particles do not settle.

  In addition, when using an aggregation terminator, it is preferable to use surfactant as an aggregation terminator, and it is more preferable to use an anionic surfactant. Among the anionic surfactants, it is more preferable to use one or more selected from alkyl ether sulfates, alkyl sulfates, and linear alkyl benzene sulfonates, and it is further preferable to use alkyl ether sulfates.

<Post process>
By appropriately applying the fused particles obtained in the step B to a solid-liquid separation step such as filtration, a washing step, and a drying step, a toner for electrophotography can be suitably obtained.
In the washing step, the added nonionic surfactant is also preferably completely removed by washing, and washing with an aqueous solution at a cloud point or less of the nonionic surfactant is preferred. It is preferable to carry out washing several times.
In the drying step, any method such as vibration type fluid drying method, spray drying method, freeze drying method, flash jet method, etc. can be adopted. The water content after drying of the toner is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of chargeability.

In the toner of the present invention, an external additive may be used to improve transferability. As the external additive, inorganic fine particles are preferably used. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide and zinc oxide. Among these, silica is preferable. As the silica, from the viewpoint of the transferability of the toner, hydrophobicized hydrophobic silica is preferable.
Examples of hydrophobizing agents for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), methyltriethoxysilane, etc. Among these, hexamethyldisilazane is preferred.

The average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoint of toner chargeability, flowability, and transferability. More preferably, it is 100 nm or less, still more preferably 50 nm or less.
The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass with respect to 100 parts by mass of the toner before being treated with the external additive. The amount is preferably at least 5 parts by mass, more preferably at most 4 parts by mass, and still more preferably at most 3 parts by mass.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3.0 μm or more, more preferably 3.5 μm or more, and still more preferably 4. from the viewpoint of low temperature fixability, storage stability and durability. The thickness is 0 μm or more, more preferably 4.5 μm or more, and preferably 9.0 μm or less, more preferably 8.5 μm or less, still more preferably 8.0 μm or less, still more preferably 7.5 μm or less.

  The toner for electrophotography obtained by the production method of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  The properties of the resin, binder resin composition particles, toner and the like were measured and evaluated by the following methods.

[Acid number of resin]
The acid value of the resin was measured based on the method of JIS K 0070. However, only the measurement solvent was changed to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)) from a mixed solvent of ethanol and ether defined in JIS K 0070.

[Softening point, melting point, crystallinity index, and glass transition temperature of resin]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa is applied by a plunger to obtain a diameter It extruded from the nozzle of 1 mm and length 1 mm. The plunger drop of the flow tester was plotted against temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

(2) Maximum endothermic peak temperature, melting point, crystallinity index,
A sample cooled from room temperature (20 ° C) to 0 ° C at a temperature decrease rate of 10 ° C / min using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Ltd.) for 1 minute The sample was allowed to stand and then measured while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. Of the observed endothermic peaks, the temperature of the peak located on the highest temperature side was taken as the maximum endothermic peak temperature. Moreover, in crystalline resin, the maximum peak temperature of this heat of fusion was made into melting | fusing point.
The crystallinity index was determined from the ratio [softening point / endothermic maximum peak temperature] between the softening point and the maximum endothermic peak obtained above.

(3) Glass transition temperature Measure 0.01 to 0.02 g of a sample on an aluminum pan using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 200 ° C. The temperature was raised up, and the temperature was cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min. Next, measurement was performed while raising the temperature to 150 ° C. at a heating rate of 10 ° C./min. The temperature at the intersection point of the extension of the baseline below the maximum endothermic peak temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak was taken as the glass transition temperature.

[Volume median particle size of aggregated particles (D ₅₀ )]
The volume median particle size of the agglomerated particles was measured as follows.
・ Measurement machine: "Coulter Multisizer III" (made by Beckman Coulter Inc.)
・ Aperture diameter: 50μm
Analysis software: "Multisizer III version 3.51" (manufactured by Beckman Coulter Inc.)
-Electrolyte: "Isoton II" (manufactured by Beckman Coulter)
Dispersion: Polyoxyethylene lauryl ether "Emulgen 109P" (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion conditions: 10 mg of a sample (in terms of solid content) is added to 5 mL of the dispersion, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolyte is added, and 1 minute with an ultrasonic disperser. The sample was dispersed to prepare a sample dispersion.
Measurement conditions: The particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, and then 30,000 particles are measured, and the particle size distribution thereof The volume median particle size (D ₅₀ ) was determined from

Binder resin composition particles, colorant particles, a volume-median particle size of the charge control agent particles (D _50)]
(1) Measuring device: Laser diffraction particle size measuring device "LA-920" (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water was added to the cell for measurement, and the volume median particle size (D ₅₀ ) was measured at a concentration at which the absorbance falls within the appropriate range.

[Solid Content Concentration of Colorant Dispersion, Charge Control Agent Dispersion, and Aqueous Dispersion of Binder Resin Composition Particles]
Using an infrared moisture meter “FD-230” (manufactured by Ketto Science Research Institute Co., Ltd.), under the conditions of a drying temperature of 150 ° C. and a measurement mode 96 (monitoring time 2.5 minutes / a fluctuation range 0.05%), using a 5 g sample The sample was dried and the water content (mass%) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (mass%) = 100-M
M: Moisture of sample (mass%)

[Minimum fixing temperature of toner]
The toner was mounted on an apparatus in which the fixing device of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so as to enable fixing outside the apparatus, and a printed matter was obtained in an unfixed state (printing area: 2 cm) X 12 cm, adhesion amount: 0.5 mg / cm ² ). Thereafter, using a fixing device (fixing speed 300 mm / sec) adjusted so that the total fixing pressure is 40 kgf, the temperature of the fixing roll is gradually raised from 80 ° C. to 240 ° C. by 5 ° C. while unfixed at each temperature The fixing test of the printed matter of the state was done. A cellophane adhesive tape "UNICEF Cellophane" (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) was attached to the image portion of the obtained printed matter, passed through a fixing roller set at 30 ° C, and then the tape was peeled off. . The optical reflection density before and after sticking the tape is measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth), and the ratio of both (after peeling / before sticking × 100) is 90% first. The temperature of the fixing roller which exceeded the above was taken as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability.

[Heat-resistant storage stability under high humidity of toner]
5 g of the toner was put in a 25 mL container (about 3 cm in diameter), and was left for 72 hours under the environment of temperature 55 ° C. and humidity 90%. The degree of toner aggregation was visually observed every 12 hours, and the heat resistant storage stability under high humidity was evaluated according to the following evaluation criteria. The longer the time when no aggregation is observed, the better the heat-resistant storage stability under high humidity.
(Evaluation criteria)
A: No aggregation was observed even after 72 hours.
B: No aggregation was observed after 60 hours, but aggregation was observed after 72 hours.
C: No aggregation was observed after 36 hours, but aggregation was observed after 48 hours.
D: No aggregation was observed after 24 hours, but aggregation was observed after 36 hours.
E: Cohesion is observed after 24 hours.

[Toner printing capacity]
A toner is mounted on a non-magnetic one-component development printer "OKI Microline 18" (Oki Data Co., Ltd.), and a diagonal stripe pattern with a blackening ratio of 5.5% under the conditions of temperature 30 ° C and humidity 80%. Printing test was conducted. On the way, a black solid image was printed every 500 sheets, and the streaks on the image were confirmed. The number of printed sheets up to the point when streaks were visually observed on the image was taken as the number of printing sheets. The larger the number of printing proofs, the better the durability.

[Production of amorphous resin]
Production Examples 1 to 3 and 5 to 6
(Production of Amorphous Composite Resins A to C, E to F)
BPA-PO, BPA-EO, terephthalic acid, esterification catalyst and esterification co-catalyst shown in Table 1, 5 liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a downflow condenser and a nitrogen inlet tube And the temperature was raised to 235 ° C. in a mantle heater in a nitrogen atmosphere over 2 hours. After that, it confirmed that the reaction rate reached 95% or more at 235 ° C, cooled to 160 ° C, mixed solution of raw material monomer of styrenic resin component shown in Table 1, bireactive monomer and radical polymerization initiator It dripped over 1 hour. Thereafter, the temperature is maintained at 160 ° C. for 30 minutes, the temperature is raised to 200 ° C., and reaction is further performed under a reduced pressure of 8 kPa for 1 hour, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor and the remaining carboxylic acid component were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting for 1 hour at 210 ° C., the reaction was carried out at 40 kPa until the softening point described in Table 1 was reached, to obtain amorphous composite resins A to C and E to F. Physical properties of the resin are shown in Table 1. Incidentally, the reaction rate in the present invention means a value of generation reaction water amount (mol) / theoretical generation water amount (mol) × 100.

Production Example 4
(Manufacture of amorphous polyester resin D)
BPA-PO, BPA-EO, terephthalic acid, esterification catalyst and esterification co-catalyst shown in Table 1, 5 liter four-necked flask equipped with a thermometer, a stainless steel stir bar, a downflow condenser and a nitrogen inlet tube And the temperature was raised to 235 ° C. in a mantle heater in a nitrogen atmosphere over 2 hours. After that, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Then, it cooled to 190 degreeC, the radical polymerization inhibitor and the remaining carboxylic acid component were added, and it heated up to 210 degreeC over 2 hours. Then, after reacting for 1 hour at 210 ° C., the reaction was carried out at 40 kPa until the softening point described in Table 1 was reached, to obtain an amorphous polyester resin D. Physical properties of the resin are shown in Table 1.

[Production of crystalline resin]
Production Examples 7-9
(Crystalline polyester resin GI)
The raw material monomers and the esterification catalyst shown in Table 2 are placed in a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a downflow condenser and a nitrogen inlet tube, and 135 in a mantle heater under a nitrogen atmosphere. The temperature was raised to 210 ° C. over 10 hours. The mixture was further reacted under a reduced pressure of 8 kPa for 2 hours to obtain crystalline polyester resins G to I. Physical properties of the resin are shown in Table 2.

[Production of Colorant Dispersion]
Preparation Example 1
Mix 50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (polyoxyethylene lauryl ether, manufactured by Kao Corporation), and 200 g of ion-exchanged water, The mixture was dispersed for 10 minutes using a homogenizer to obtain a colorant dispersion containing colorant fine particles. The volume median particle size (D ₅₀ ) of the colorant fine particles was 120 nm, and the solid content concentration was 22% by mass.

[Production of Charge Control Agent Dispersion]
Preparation Example 2
Mix 50 g of a salicylic acid compound "Bontron E-84" (manufactured by Orient Chemical Industries, Ltd.) as a charge control agent, 5 g of "Emulgen 150" (manufactured by Kao Corporation) as a nonionic surfactant, and 200 g of ion-exchanged water, The glass beads were used and dispersed for 10 minutes using a sand grinder to obtain a charge control agent dispersion containing charge control agent microparticles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles was 400 nm, and the solid content concentration was 22% by mass.

[Production of Aqueous Dispersion of Binder Resin Composition Particles and Toner for Electrophotography]
Example 1
(Production of Aqueous Dispersion of Binder Resin Composition Particles)
60 g of crystalline polyester resin G, 90 g of amorphous composite resin B, and 90 g of methyl ethyl ketone are introduced into a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction pipe, and at 73 ° C. It was allowed to dissolve for 2 hours (step 1). A 20% by mass aqueous ammonia solution was added to the obtained solution so as to have a neutralization degree of 70 mol% with respect to the acid value of the resin, and stirred for 30 minutes (step 2).
While maintaining the temperature at 73 ° C., 675 g of ion exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral velocity 88 m / min) to perform phase inversion emulsification (Step 3). The methyl ethyl ketone was distilled off under reduced pressure while keeping the temperature continuously at 70 ° C. (step 4). Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at a rate of 280 r / min (peripheral velocity 88 m / min), and then anionic surfactant “Emar E27C” (sodium polyoxyethylene lauryl ether sulfate, manufactured by Kao Corporation ) Was mixed and completely dissolved (Step 5). Thereafter, the solid content concentration of the dispersion is measured, and ion-exchanged water is added so as to be 20% by mass, whereby aqueous dispersion of binder resin composition particles in which binder resin composition particles are dispersed in an aqueous medium I got a body. The volume median particle diameter of the obtained binder resin composition particles was 162 nm.

(Manufacture of electrophotographic toner)
300 g of the aqueous dispersion of binder resin composition particles obtained above, 8 g of a colorant dispersion, 2 g of a charge control agent dispersion, and 52 g of deionized water are placed in a 2 L container, and 100 r with an anchor type stirrer. 150 g of a 0.1 mass% aqueous solution of calcium chloride was added dropwise over 30 minutes at 20 ° C. while stirring for 1 minute (peripheral velocity 31 m / minute). Then, it heated up to 50 degreeC, stirring. It was kept at 50 ° C. until the volume median particle size was 5 μm. After 3 hours, the volume median particle size reached 5 μm. Thereafter, a dilution liquid obtained by diluting 4.2 g of an anionic surfactant "Emar E27C" (manufactured by Kao Corporation, solid content 28% by mass) as an aggregation stopper with 37 g of deionized water was added. Then, the temperature was raised to 80 ° C., and after 80 ° C. was maintained for 1 hour, the heating was ended. After forming fused particles by this, it was gradually cooled to 20 ° C., filtered with a 150 mesh (150 μm mesh) wire mesh, suction filtered, washed and dried to obtain toner particles. .

  1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter 40 nm) relative to 100 parts by mass of the toner particles, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd.) 10 L Henschel mixer equipped with ST, A0 stirring blade (number average particle diameter 16 nm) 0.6 parts by mass, titanium oxide “JMT-150 IB” (manufactured by Tayca Co., Ltd., number average particle diameter 15 nm) 0.5 parts by mass The mixture was introduced into Japan Coke Industry Co., Ltd. and stirred at 3000 rpm for 2 minutes to obtain a toner. The evaluation results of the toner are shown in Table 3.

Examples 2-5, 9-12, comparative examples 1-4
A water system of binder resin composition particles is carried out in the same manner as in Example 1 except that the kind of resin used in step 1, the compounding ratio, and the phase inversion emulsification conditions in Example 1 are changed as shown in Table 3. A dispersion was obtained.
Subsequently, using the aqueous dispersion of binder resin composition particles obtained, a toner was obtained in the same manner as in Example 1. The volume median particle diameter of the binder resin composition particles and the evaluation results of the toner are shown in Table 3.

Example 6
In Example 1, 16.7 g of the anionic surfactant "Emar E27C" (manufactured by Kao Corporation) is not mixed in Step 5, and the anionic surfactant "Emar E27C" (manufactured by Kao Corporation) is not mixed in Step 1. An aqueous dispersion of binder resin composition particles was obtained in the same manner as in Example 1 except that 16.7 g of the resin composition was mixed.
Subsequently, using the aqueous dispersion of binder resin composition particles obtained, a toner was obtained in the same manner as in Example 1. The volume median particle diameter of the binder resin composition particles and the evaluation results of the toner are shown in Table 3.

Examples 7 and 8
Example 1 except that the 20% by mass aqueous ammonia solution was changed to a neutralization degree of 120 mol% in Example 7 and a neutralization degree of 30 mol% in Example 8 with respect to the acid value of the resin. In the same manner as Example 1, an aqueous dispersion of binder resin composition particles was obtained.
Subsequently, using the aqueous dispersion of binder resin composition particles obtained, a toner was obtained in the same manner as in Example 1. The volume median particle diameter of the binder resin composition particles and the evaluation results of the toner are shown in Table 3.

Comparative example 5
An aqueous dispersion of binder resin composition particles was obtained in the same manner as in Example 1 except that the neutralizing agent was not used in step 2 in Example 1. Subsequently, using the aqueous dispersion of binder resin composition particles obtained, a toner was obtained in the same manner as in Example 1. The volume median particle diameter of the binder resin composition particles and the evaluation results of the toner are shown in Table 3.

Comparative example 6
(Manufacture of crushed toner)
A total of 200 parts by mass of the crystalline polyester resin G and the amorphous composite resin B in a mass ratio shown in Table 3 and 2.0 mass of a negatively chargeable charge control agent "Bontron E-81" (manufactured by Orient Chemical Industries, Ltd.) Parts, 1 part by mass of a coloring agent "Regal 330R" (Cabt Co., carbon black), and 4.0 parts by mass of a release agent "Mitsui High Wax NP055" (Mitsui Chemical Co., Ltd., polypropylene wax, melting point: 125 ° C) After adding and thoroughly mixing with a Henschel mixer, melt kneading was performed using a co-rotating twin-screw extruder at a roll rotational speed of 200 r / min and a heating temperature of 80 ° C. in the roll. The obtained melt-kneaded product was cooled, roughly pulverized, pulverized by a jet mill, and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of about 5 μm.

  1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter 40 nm) relative to 100 parts by mass of the toner particles, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd.) 10 L Henschel mixer equipped with ST, A0 stirring blade (number average particle diameter 16 nm) 0.6 parts by mass, titanium oxide “JMT-150 IB” (manufactured by Tayca Co., Ltd., number average particle diameter 15 nm) 0.5 parts by mass The mixture was introduced into Japan Coke Industry Co., Ltd. and stirred at 3000 rpm for 2 minutes to obtain a toner. The evaluation results of the toner are shown in Table 3.

From Table 3, it can be seen that the toners of Examples 1 to 12 of the present invention are superior in balance between low-temperature fixability, storage stability, and durability as compared with the toners of Comparative Examples 1 to 6.
Comparing Examples 1 and 2 and Comparative Example 1, the toner of Example 1 using an amorphous composite resin (A) using an aliphatic dicarboxylic acid compound having 10 carbon atoms as a raw material monomer of a polycondensation resin component However, it is understood that the low temperature fixability, the preservability, and the durability are excellent.
Comparing Example 1 with Example 3, the toner of Example 1 using the amorphous composite resin (A) having a styrene resin component content of 40% by mass has low-temperature fixability, storage stability, And it turns out that it is excellent in durability.
When Example 1 and Example 4 are compared, it can be seen that the toner of Example 1 using styrene and alkyl (meth) acrylate as the raw material monomers of the styrene resin component is excellent in low-temperature fixability and durability.
When Example 1 and Example 5 are compared, in Step 1, 60 parts by mass of an organic solvent was used for a total of 100 parts by mass of the amorphous composite resin (A) and the crystalline polyester resin (C). It is understood that the toner of Example 1 obtained from the aqueous dispersion of binder resin composition particles is excellent in low-temperature fixability, preservability, and durability.
Comparing Examples 1, 7 and 8, the neutralization degree of the binder resin is 70 mol%, and the volume median particle size of the aqueous dispersion of binder resin composition particles is 173 nm. It is understood that the toner is excellent in low-temperature fixability, storage stability and durability.
Comparing Examples 1 and 9 to 12, the mass ratio [crystalline polyester resin (C) / amorphous composite resin (A)] of crystalline polyester resin (C) and amorphous composite resin (A) It is understood that the toner of Example 1 having 40/60 is excellent in low-temperature fixability, storage stability, and durability.
On the other hand, in the toner of Comparative Example 1, the long chain aliphatic dicarboxylic acid compound is not used as a raw material monomer of the polycondensation resin component of the amorphous composite resin (A). It can be seen that the properties and durability decrease.
Since the toner of Comparative Example 2 uses an amorphous polyester resin instead of the amorphous composite resin (A), it can be seen that the low-temperature fixability, the storage stability, and the durability decrease.
The toner of Comparative Example 3 has a low carbon number of the alcohol component of the crystalline polyester resin, and Comparative Example 4 has a low carbon number of the carboxylic acid component of the crystalline polyester resin, so low temperature fixability, storage stability, and durability Is found to decrease.
It can be seen that the toner of Comparative Example 6, which is a pulverized toner, has reduced low-temperature fixability, storage stability, and durability.

Claims (8)

A method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner, comprising an amorphous composite resin (A) and a crystalline polyester resin (C),
A polycondensation resin component (A-1) obtained by polycondensation of an alcohol component and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms with an amorphous composite resin (A) And a resin containing a styrene resin component (A-2),
An alcohol component in which the crystalline polyester resin (C) contains 80 to 100 mol% of an aliphatic diol having 8 to 14 carbon atoms, and 80 mol% of an aliphatic dicarboxylic acid compound having 8 to 14 carbon atoms It is a resin obtained by polycondensing a carboxylic acid component containing at least 100 mol%,
A method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner, which comprises the following steps 1 to 3.
Step 1: Step of mixing amorphous composite resin (A) and crystalline polyester resin (C) to obtain a mixture Step 2: Step of mixing a neutralizing agent into the mixture obtained in Step 1 Step 3: Step Adding an aqueous medium to the mixture obtained in 2 and performing phase inversion emulsification   Amorphous composite resin (A) is a raw material monomer of polycondensation resin component (A-1), a raw material monomer of styrene resin component (A-2), and polycondensation resin component (A-1) The binder resin composition for an electrophotographic toner according to claim 1, which is a resin obtained by polymerizing both a raw material monomer and a bireactive monomer capable of reacting with any of the raw material monomers of the styrene resin component (A-2). Method of producing an aqueous dispersion of particulates.   The binder resin for electrophotographic toner according to claim 1 or 2, wherein the content of the styrene resin component (A-2) in the amorphous composite resin (A) is 10% by mass or more and 60% by mass or less. Method for producing an aqueous dispersion of composition particles.   The binder resin for electrophotographic toner according to any one of claims 1 to 3, wherein the content of the structural unit derived from styrene in the styrene resin component (A-2) is 50% by mass or more and 95% by mass or less. Method for producing an aqueous dispersion of composition particles.   The mass ratio of the crystalline polyester resin (C) to the amorphous composite resin (A) [crystalline polyester resin (C) / amorphous composite resin (A)] is 5/95 or more and 70/30 or less A method for producing an aqueous dispersion of binder resin composition particles for electrophotographic toner according to any one of claims 1 to 4. The volume average particle diameter of the aqueous dispersion (D ₅₀₎ is at 30nm or more 700nm or less, a method of manufacturing an aqueous dispersion of an electrophotographic toner binder resin composition particles according to any one of claims 1 to 5. The step 1 is a step of mixing an amorphous composite resin (A), a crystalline polyester resin (C), and an organic solvent to obtain a mixture, and further comprising the following step 4 The manufacturing method of the aqueous dispersion of the binder resin composition particle for electrophotographic toners in any one.
Step 4: A step of removing the organic solvent from the mixture subjected to phase inversion emulsification in Step 3 A manufacturing method of toner for electrophotography including the following processes A and B.
Step A: aggregating binder resin composition particles for electrophotographic toner in an aqueous dispersion of binder resin composition particles for electrophotographic toner obtained by the manufacturing method according to any one of claims 1 to 7 Step of obtaining aggregated particles Step B: Step of fusing the aggregated particles