JP6519791B2 - Method for producing electrophotographic toner - Google Patents

Description

  The present invention relates to an electrophotographic toner and a method of manufacturing the same.

  From the viewpoint of speeding up and energy saving of an electrophotographic printing apparatus, a toner for electrophotography excellent in low-temperature fixability is required. However, if the softening point and the glass transition point of the toner are designed to be low in order to improve the low temperature fixability, a problem arises that the storage stability is lowered. In order to achieve both of the low temperature fixability and the storage stability, development of toner using crystalline polyester has been conducted.

  For example, in Patent Document 1, a polycondensation resin component obtained by polycondensation of an alcohol component containing an aliphatic diol having 2 to 10 carbon atoms and a carboxylic acid component containing an aromatic dicarboxylic acid, and a styrene resin A crystalline resin for toner, which is composed of a composite resin containing a resin component, is described.

Patent Document 2 describes a crystalline polyester (1-1) obtained 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,
Raw material monomer of amorphous condensation polymerization resin containing alcohol component and carboxylic acid component containing aromatic dicarboxylic acid compound, raw material monomer of addition polymerization resin, and 100 parts by weight of raw material monomer of addition polymerization resin An amorphous condensation polymerization resin component 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, which comprises a binder resin comprising an amorphous hybrid resin (2-1) comprising a polymerization resin component, is described.

  In Patent Document 3, after subjecting an alcohol component containing at least an aliphatic diol having 2 to 10 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms to a polycondensation reaction, 40 After cooling to a temperature of less than ° C, heat treatment is performed at a temperature exceeding 40 ° C and at "maximum peak temperature of endothermic (° C)-40 ° C" to "maximum peak temperature of endothermic (° C)-5 ° C" A process for producing a binder resin for toner, which has a step of obtaining a polyester, etc. is described.

JP, 2010-139659, A JP, 2013-109237, A JP, 2011-107341, A

In the case of an electrophotographic toner, the toner is fixed on a printing medium such as paper by heating with a heat roll or the like. However, energy consumption can be reduced by lowering the heating temperature, so low-temperature fixability is required. Be
On the other hand, when the low temperature fixability is enhanced, toner aggregation tends to occur when the toner is left under high humidity, and problems tend to occur from the viewpoint of storage stability. Furthermore, as the number of prints increases, problems occur in terms of printing durability, in which stains adhere to the printed matter.
The toners for electrophotography described in Patent Documents 1 to 3 are not necessarily satisfactory with regard to the above characteristics.
The present invention relates to an electrophotographic toner excellent in low-temperature fixability, storage stability under high humidity, and printing durability, and a method for producing the same.

The present invention relates to the following [1] to [2].
[1] A binder resin containing a crystalline resin (A) and an amorphous resin (B),
Polyester-based resin segment (A1) obtained by polycondensation of an alcohol component containing ethylene glycol with an acid component containing an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms, and a styrene resin Has a resin segment (A2),
A toner for electrophotography, wherein the mass ratio [(A1) / (A2)] of segment (A1) to segment (A2) is 60/40 or more and 96 or less.
A toner for electrophotography, which is obtained through a process of dispersing a resin containing a crystalline resin (A) in an aqueous medium.
[2] A binder resin containing a crystalline resin (A) and an amorphous resin (B),
Segment (A1) and styrene consisting of polyester resin obtained by polycondensation of the above-mentioned crystalline resin (A) with an alcohol component containing ethylene glycol and an acid component containing an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms A toner for electrophotography, having a segment (A2) made of a base resin and having a mass ratio of the segment (A1) to the segment (A2) [(A1) / (A2)] of 60/40 to 96/4. A manufacturing method,
A method for producing a toner for electrophotography, comprising the step of dispersing a resin containing the crystalline resin (A) in water.

  According to the present invention, it is possible to provide an electrophotographic toner excellent in low-temperature fixability, storage stability under high humidity, and printing durability, and a method for producing the same.

[Toner for electrophotography]
The toner for electrophotography of the present invention contains a binder resin containing a crystalline resin (A) and an amorphous resin (B).
The crystalline resin (A) is a polyester resin segment (A1) obtained by polycondensation of an alcohol component containing ethylene glycol and an acid component containing an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms, and a styrene resin It has a segment (A2), and the mass ratio [(A1) / (A2)] of the segment (A1) to the segment (A2) is 60/40 or more and 96/4 or less.
The toner for electrophotography of the present invention is obtained through the step of dispersing the resin containing the crystalline resin (A) in an aqueous medium.

The toner for electrophotography of the present invention is excellent in low-temperature fixability, storage stability under high humidity, and printing durability. Although the reason is not clear, it is considered as follows.
The toner for electrophotography of the present invention is a polyester resin segment obtained by polycondensation of an alcohol component containing ethylene glycol and an acid component containing an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms as a binder resin. (A1) and a crystalline resin (A) having a styrene-based resin segment (A2) and having [(A1) / (A2)] of 60/40 or more and 96/4 or less.
The crystalline resin (A) has low compatibility with the amorphous resin contained in the toner, and the crystallization rate is fast, so that the crystalline resin (A) can be finely dispersed in the toner, and low temperature It is considered that coexistence of fixability and storage stability is possible. In particular, since the crystal size is reduced, the melting point is lowered and the low temperature fixability is excellent.
In the crystalline resin (A), as described above, it is possible to finely disperse crystals in the toner, and a toner excellent in storage stability can be obtained. However, due to the high hydrophilicity of the ethylene glycol-derived site of the crystalline resin (A), the storage stability under high humidity tends to be low. Therefore, by introducing a benzene ring by complexation with a styrene resin, the resin (A) is rendered hydrophobic to improve the storage stability under high humidity.
Since the low molecular weight component having a particularly high hydrophilicity and the remaining ethylene glycol are removed by the dispersion step in water, the low temperature fixability and the storage stability under high humidity are improved. In addition, since the remaining other monomers and oligomers are also removed, the shelf life is further improved. In particular, the removal of the remaining monomer by the underwater dispersing step increases the hardness of the surface and further improves the printing durability.

In the present invention, each term is defined as follows.
"Crystalline resin" is defined as the ratio of the softening point (° C) to the highest peak temperature (° C) of the endotherm by differential scanning calorimeter (DSC), that is, [(softening point) / (highest peak temperature of endotherm)] Refers to a resin having a crystallinity index of 0.6 or more and less than 1.4, preferably 0.8 or more and 1.2 or less.
The "amorphous resin" refers to a resin having a crystallinity index of 1.4 or more or less than 0.6.
The highest endothermic peak temperature refers to the temperature of the peak located on the highest temperature side among endothermic peaks observed under the conditions of the measurement method described in the examples. If the maximum peak temperature is the difference between the softening point and 20 ° C., it is regarded as the melting point of the crystalline resin, and the peak whose difference from the softening point exceeds 20 ° C. is regarded as the peak attributed to the glass transition point of the amorphous polyester.
In the present invention, when simply referred to as "resin", both crystalline resin and amorphous resin are meant.

[Binder resin]
The binder resin used in the toner for electrophotography of the present invention contains a crystalline resin (A) and an amorphous resin (B).
The mass ratio [(A) / (B)] of the crystalline resin (A) to the amorphous resin (B) is preferably 4/96 or more, more preferably 7 from the viewpoint of improving the low temperature fixability of the toner. / 93 or more, and preferably 40/60 or less, more preferably 30/70 or less, still more preferably 20/80 or less, still more preferably 15/85 or less from the viewpoint of improving the storage stability of the toner Even more preferably 10/90 or less.

<Crystalline resin (A)>
The crystalline resin (A) is a polyester resin segment (A1) (hereinafter referred to as, obtained by polycondensation of an alcohol component containing ethylene glycol and an acid component containing an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms). A mass ratio of the segment (A1) to the segment (A2) [(A1) having only the segment (A1)) and the styrenic resin segment (A2) (hereinafter, also simply referred to as the segment (A2)) / (A2)] is 60/40 or more and 96/4 or less.

(Polyester resin segment (A1))
The polyester resin segment (A1) is obtained by polycondensing an alcohol component containing ethylene glycol and an acid component containing an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms.

[Alcohol component]
Ethylene glycol is contained as an alcohol component which becomes a structural unit of a segment (A1) and becomes a raw material monomer (X).
The content of ethylene glycol in the alcohol component is preferably 70 mol% or more and 100 mol% or less, more preferably 80 mol% or more and 100 mol% or less in the alcohol component from the viewpoint of improving the low temperature fixability of the toner. It is preferably 90 mol% to 100 mol%, more preferably 95 mol% to 100 mol%, still more preferably substantially 100 mol%, and still more preferably 100 mol%.

As long as the effects of the present invention are not impaired, other alcohol components other than ethylene glycol may be contained as the alcohol component. The other alcohol component is preferably at least one selected from aliphatic diols, aromatic diols, and polyhydric alcohols having a valence of 3 or more, and from the viewpoint of storage stability of the toner, aliphatic diols are preferable.
The aliphatic diol is preferably an aliphatic diol having 3 to 10 carbon atoms from the viewpoint of low temperature fixability and storage stability of the toner, and from the above viewpoint, an aliphatic diol having 3 to 6 carbon atoms is more preferable. Aliphatic diols having 4 to 6 carbon atoms are more preferable. Specifically, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol and hydrogenated bisphenol One or more selected from A is preferable, and 1,4-butanediol is more preferable.
The aliphatic diol is preferably an α, ω-aliphatic diol from the viewpoint of enhancing the crystallinity and improving the low temperature fixability and the storage stability of the toner.

As an aromatic diol, an alkylene (having 2 or more carbon atoms) of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane 3 or less) 1 or more types chosen from an oxide adduct (average added mole number 1 or more and 16 or less) are preferable.
As a polyhydric alcohol more than trivalence, 1 or more types chosen from glycerol, pentaerythritol, and trimethylol propane are preferable.

[Acid component]
As an acid component which becomes a structural unit of a segment (A1) and becomes a raw material monomer (X), C10-C14 aliphatic dicarboxylic acid is contained. The carbon number of the aliphatic dicarboxylic acid is 14 or less, preferably 12 or less, from the viewpoint of improving the low temperature fixability and storage stability of the toner, and the carbon number is 10 from the viewpoint of improving the storage stability of the toner. The carbon number is preferably 12 or more, more preferably 12 or more.
The aliphatic dicarboxylic acid having 10 to 14 carbon atoms can be used singly or in combination of two or more.
Specific examples of the aliphatic dicarboxylic acid having 10 to 14 carbon atoms include sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,13-tridecanedioic acid and 1,14-tetradecanediode. One or more selected from acids is preferable, and from the viewpoint of improving the low temperature fixability and storage stability of the toner, one selected from sebacic acid, 1,12-dodecanedioic acid and 1,14-tetradecanedioic acid. The above is more preferable, and from the viewpoint of improving the storage stability of the toner, 1,12-dodecanedioic acid is more preferable.
In the present invention, aliphatic dicarboxylic acid compounds having 10 to 14 carbon atoms also include anhydrides of these acids and esters having an alkyl group having 1 to 3 carbon atoms.

  The content of the aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms in the acid component is preferably 80 mol% to 100 mol%, more preferably 90 mol% or more, from the viewpoint of improving the storage stability of the toner. It is 100 mol% or less, more preferably 95 mol% or more and 100 mol% or less.

  As long as the effects of the present invention are not impaired, other acid components other than aliphatic carboxylic acid compounds having 10 to 14 carbon atoms may be included as the acid component. Other acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic acid; fumaric acid, maleic acid, adipic acid, succinic acid, succinic acid having one or more selected from alkyl groups and alkenyl groups, etc. Aliphatic dicarboxylic acids; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, decalindicarboxylic acid and tetrahydrophthalic acid; and one or more selected from trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid .

[Molar ratio of alcohol component to carboxylic acid component of polyester resin, etc.]
The molar ratio of the carboxylic acid component to the alcohol component of the polyester resin (carboxylic acid component / alcohol component) is preferably higher in alcohol component than in the carboxylic acid component when achieving high molecular weight of the crystalline resin. From the viewpoint that the molecular weight of the resin can be easily adjusted by distilling off the alcohol component during vacuum reaction, it is preferably 0.7 or more, more preferably 0.75 or more, still more preferably 0.8 or more, and preferably Is 1.2 or less, more preferably 1.1 or less, and still more preferably 1.0 or less.

The segment (A1) in the present invention, that is, the polyester resin, preferably contains an alcohol component and an acid component of the raw material monomer (X) in the presence of a catalyst, preferably 120 ° C. or more, more preferably 140 ° C. or more, still more preferably It is preferable to produce by carrying out a polycondensation reaction at a temperature of 150 ° C. or more, more preferably 160 ° C. or more, and preferably 240 ° C. or less, more preferably 235 ° C. or less.
As an esterification catalyst suitably used for the above-mentioned polycondensation, a titanium compound and a tin (II) compound which does not have a Sn-C bond are mentioned, and these are used individually by 1 type or in combination of 2 or more types can do.
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. More preferably, tin (II) compounds having a Sn-O bond are more preferable, and in particular, di (2-ethylhexanoic acid) tin (II) salt is further added from the viewpoints of reactivity, molecular weight adjustment and physical property adjustment of resin. preferable.
As an esterification co-catalyst suitably used for the above-mentioned polycondensation, a pyrogallol compound is mentioned. 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 ', Examples thereof include 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 catalyst is preferably 0.01 mol% or more, more preferably 0.02 mol%, based on 100 mol% of the total amount of alcohol components, from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the resin. It is the above, and preferably 2 mol% or less, more preferably 1 mol% or less, and still more preferably 0.6 mol% or less.
The amount of the esterification promoter is preferably 0.001 mol% or more, more preferably 0.005 mol%, based on 100 mol% of the total amount of alcohol components subjected to the polycondensation reaction, from the viewpoint of reactivity. The content is more preferably 0.01 mol% or more, and preferably 1 mol% or less, more preferably 0.4 mol% or less, and still more preferably 0.2 mol% or less.
It is preferable from the viewpoint of reactivity that an esterification catalyst and an esterification co-catalyst be used in combination, and the mass ratio of the esterification co-catalyst and the esterification catalyst (esterification co-catalyst / esterification catalyst) is in terms of reactivity Preferably, it is 0.01 or more, more preferably 0.02 or more, still more preferably 0.03 or more, and preferably 0.5 or less, more preferably 0.3 or less, still more preferably 0.2. It is below.

(Styrene-based resin segment (A2))
The styrene-based resin segment (A2) contained in the crystalline resin (A) is a segment composed of a styrene-based resin.
Examples of styrene resins include polystyrene, polymers of styrene derivatives, styrene-acrylic copolymers, etc. From the viewpoint of improving the storage stability of the toner, polystyrene, polymers of styrene derivatives and styrene-acrylic copolymers 1 or more types selected from is preferable, 1 or more types selected from a polystyrene and a styrene- acryl copolymer are more preferable, and a polystyrene is still more preferable.

From the viewpoint of improving the storage stability of the toner, at least one member selected from styrene and a styrene derivative is preferable as the raw material monomer (Y) to be a structural unit of the styrene resin, and among these, the raw material price of the monomer From the viewpoint of storage stability of the toner, styrene is more preferable, and styrene and (meth) acrylic acid ester can also be used in combination.
In addition, "(meth) acrylic acid ester" means methacrylic acid ester or acrylic acid ester. The same applies to the following.
When styrene is used, the content of the structural unit derived from styrene in the segment (A2) is preferably 50% by mass or more, more preferably 70% by mass or more, from the viewpoint of improving the storage stability of the toner. Preferably, it is 80% by mass or more, still more preferably 90% by mass or more, still more preferably substantially 100% by mass, and still more preferably 100% by mass.

The styrene derivative is preferably one or more selected from methylstyrene, α-methylstyrene, β-methylstyrene, t-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrene sulfonic acid or salts thereof.
The (meth) acrylic acid ester is preferably at least one selected from alkyl (meth) acrylate having 1 to 18 carbon atoms in the alkyl group, benzyl (meth) acrylate and dimethylaminoethyl (meth) acrylate. The alkyl group is more preferably an alkyl (meth) acrylate having 1 to 18 carbon atoms, the alkyl group having 4 to 12 carbon atoms, still more preferably an alkyl (meth) acrylate, and the alkyl group having 8 carbon atoms The alkyl (meth) acrylate having 12 or more and 12 or less is more preferable, and 2-ethylhexyl acrylate is more preferable.
When a (meth) acrylic ester is used, the content of the structural unit derived from the (meth) acrylic ester in the segment (A2) is preferably from the viewpoint of improving the low temperature fixability and the storage stability of the toner. It is 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less, further more Preferably it is 20 mass% or less.

The addition polymerization reaction of the raw material monomer (Y) of the styrenic resin segment (A2) can be carried out, for example, in the presence of a polymerization initiator, etc. in the presence of an organic solvent or in the absence of a solvent by a known method The conditions are preferably 120 ° C. or more, more preferably 150 ° C. or more, further preferably 155 ° C. or more, and preferably 180 ° C. or less, more preferably 170 ° C. or less, still more preferably 165 ° C. or less.
When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone or the like can be used. The amount of the organic solvent used is preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total amount of raw material monomers of the styrene resin.

(Bi-reactive monomer (Z))
The crystalline resin (A) in the present invention is a composite resin having the polyester resin segment (A1) and the styrene resin segment (A2), and the segment (A1) and the segment (A2) are directly or linked It is linked via a group. Examples of the linking group include compounds derived from a bireactive monomer (Z) described later, a chain transfer agent, and the like, and other resins.

  The crystalline resin (A) in the present invention preferably further has a structural unit derived from the bireactive monomer (Z), from the viewpoint of improving the low temperature fixability and storage stability of the toner, and the polyester resin segment (A1). A raw material monomer (X), a raw material monomer (Y) of a styrenic resin segment (A2), and a bireactive monomer (Z) capable of reacting with both the raw material monomer (X) and the raw material monomer (Y) It is more preferable that it is a resin obtained by polymerizing. The bireactive monomer (Z) is a monomer capable of both addition polymerization reaction and polycondensation reaction, whereby the segment (A1) and the segment (A2) are derived from the bireactive monomer (Z). The polyester resin and the styrenic resin are more finely and uniformly dispersed.

The dual reactive monomer (Z) is a compound having a functional group capable of reacting with the raw material monomer (X) of the polyester resin or the carboxy group or hydroxyl group of the polyester resin, and an ethylenically unsaturated bond. Preferably, it is a compound having in the molecule one or more selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group, and an ethylenically unsaturated bond, more preferably a hydroxyl group It is a compound having one or more selected from a carboxy group and an ethylenically unsaturated bond, and more preferably a compound having a carboxy group and an ethylenically unsaturated bond. By using such a direactive monomer (Z), the dispersibility of the crystalline resin (A) to be the dispersed phase can be further improved.
The bireactive monomer (Z) having a carboxy group and an ethylenically unsaturated bond is preferably one or more selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride, and a polycondensation reaction and From the viewpoint of the reactivity of the addition polymerization reaction, it is more preferably one or more selected from acrylic acid, methacrylic acid and fumaric acid, and still more preferably acrylic acid. However, when used together with a polymerization inhibitor, a polyvalent carboxylic acid such as fumaric acid may function as a polycondensation monomer.

  The content of the structural unit derived from the dual reactive monomer (Z) is preferably 1 molar part from the viewpoint of improving the low-temperature fixability of the toner with respect to the total of 100 molar parts of the alcohol component of the polyester resin segment (A1). The amount is more preferably 2 parts by mol or more, further preferably 3 parts by mol or more, and preferably 15 parts by mol or less, more preferably 12 parts by mol or less, and further preferably 10 parts by mol or less.

(Method for producing crystalline resin (A))
The crystalline resin (A) is preferably produced, for example, by the following method.
The bireactive monomer (Z) is preferably used for the polymerization reaction together with the raw material monomer (Y) of the styrene resin.

Method (I): Step (A) of the polycondensation reaction of raw material monomer (X) of polyester resin, and after step (A), raw material monomer (Y) of styrenic resin and bireactive monomer (Z) A method comprising the step (B) of addition polymerization reaction.
In this method, it is preferable to carry out step (A) under reaction temperature conditions suitable for the polycondensation reaction, to lower the reaction temperature, and to carry out step (B) under the temperature conditions suitable for the addition polymerization reaction. It is preferable to add the raw material monomer (Y) of the styrene resin and the bireactive monomer (Z) into the reaction system at a temperature suitable for the addition polymerization reaction. The bireactive monomer (Z) reacts with the polyester resin together with the addition polymerization reaction.
After the step (B), the reaction temperature is raised again, and if necessary, a raw material monomer (X) or the like of a polyester resin having a valence of 3 or higher to be a crosslinking agent is added to the polymerization system, and polycondensation of the step (A) It is preferable to have a step (C) of carrying out the reaction or the reaction with the bireactive monomer (Z).

Method (II): Step (B) of addition polymerization reaction of styrene-based resin raw material monomer (Y) and bireactive monomer (Z), and raw material monomer (X) of polyester-based resin after the step (B) And a method comprising the step (A) of the polycondensation reaction according to
In this method, step (B) is carried out under reaction temperature conditions suitable for addition polymerization reaction, reaction temperature is increased, and polycondensation reaction of step (A) is carried out under temperature conditions suitable for polycondensation reaction. Both reactive monomers (Z) participate in the polycondensation reaction as well as the addition polymerization reaction.
The raw material monomer (X) of the polyester resin may be present in the reaction system during the addition polymerization reaction, or may be added to the reaction system under temperature conditions suitable for the polycondensation reaction. In the former case, the molecular weight and molecular weight distribution can be controlled by adding an esterification catalyst at a temperature suitable for the polycondensation reaction.

Method (III): Step (A) of polycondensation reaction by raw material monomer (X) of polyester resin, and step (B) of addition polymerization reaction by raw material monomer (Y) of styrene resin and bireactive monomer (Z) ) And how to do in parallel.
In this method, step (A) and step (B) are carried out under reaction temperature conditions suitable for addition polymerization reaction, reaction temperature is increased, and crosslinking is carried out under temperature conditions suitable for polycondensation reaction, if necessary. It is preferable to add to the polymerization system a raw material monomer (X) of a polyester resin having a valence of 3 or higher, which is an agent, and to further carry out the polycondensation reaction of step (A). 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 (Z) participate in the polycondensation reaction as well as the addition polymerization reaction.
In the above method (I), a polyester resin polymerized in advance may be used instead of the step (A) in which the polycondensation reaction is performed. When the step (A) and the step (B) are carried out in parallel in the above method (III), the raw material monomer (Y of styrene resin) is contained in the mixture containing the raw material monomer (X) of polyester resin. The mixture containing) can also be reacted dropwise. The methods (I) to (III) are preferably performed in the same container. Method (II) is preferred in that the degree of freedom of the reaction temperature of the polycondensation reaction is high.

The mass ratio [(A1) / (A2)] of the segment (A1) to the segment (A2) in the crystalline resin (A) is 60/40 or more, preferably 70 or more, from the viewpoint of improving the low temperature fixability of the toner. / 30 or more, more preferably 75/25 or more, and from the same viewpoint, 96/4 or less, preferably 90/10 or less, more preferably 85/15 or less.
Here, the mass of the segment (A1) is the total amount of the raw material monomer (X) of the polyester resin and the bireactive monomer (Z) used if necessary, and the mass of the styrene resin segment (A2) is It is the total amount of the raw material monomer (Y) of a styrene resin and the amount of a polymerization initiator.
In order for the resin to have crystallinity, it is preferable that the segment (A1) be present in a larger amount than the segment (A2).

(Physical properties of crystalline resin (A), etc.)
The number average molecular weight of the crystalline resin (A) is preferably 1,500 or more, more preferably 2,000 or more from the viewpoint of improving the low-temperature fixability and storage stability of the toner, and the crystalline resin From the viewpoint of productivity, it is preferably 10,000 or less, more preferably 9,000 or less, and still more preferably 8,000 or less.
The weight average molecular weight of the crystalline resin (A) is preferably 4000 or more, more preferably 6,000 or more, still more preferably 8,000 or more, from the viewpoint of improving the low temperature fixability and storage stability of the toner. And preferably it is 1,000,000 or less, more preferably 750,000 or less, further preferably 500,000 or less, still more preferably 200,000 or less, still more preferably 100,000 or less.

The acid value of the crystalline resin (A) is preferably 1 mg KOH / g or more, more preferably 5 mg KOH / g or more, and still more preferably 10 mg KOH / g or more from the viewpoint of dispersion stability of the crystalline resin (A). And, preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, further preferably 20 mg KOH / g or less.
The hydroxyl value of the crystalline resin (A) is preferably 1 mg KOH / g or more, more preferably 5 mg KOH / g or more, and still more preferably 10 mg KOH / g or more from the viewpoint of dispersion stability of the crystalline resin (A). And it is preferably 50 mg KOH / g or less, more preferably 40 mg KOH / g or less, still more preferably 30 mg KOH / g or less.

The melting point of the crystalline resin (A) is preferably 60 ° C. or more, more preferably 65 ° C. or more, still more preferably 70 ° C. or more, still more preferably 75 ° C. or more from the viewpoint of improving the storage stability of the toner. And, from the viewpoint of improving the low-temperature fixability of the toner, it is preferably 110 ° C. or less, more preferably 100 ° C. or less, still more preferably 90 ° C. or less.
The softening point of the crystalline resin (A) is preferably 70 ° C. or more, more preferably 80 ° C. or more, still more preferably 90 ° C. or more from the viewpoint of improving the storage stability of the toner, and low temperature fixing of the toner From the viewpoint of improving the properties, it is preferably 120 ° C. or less, more preferably 110 ° C. or less, still more preferably 100 ° C. or less.

The number average molecular weight, weight average molecular weight, acid value, hydroxyl value, melting point and softening point can be easily adjusted by adjusting the raw material monomer composition, molecular weight, catalyst amount and the like or selecting reaction conditions.
Moreover, the said crystalline resin (A) can be used individually by 1 type or in combination of 2 or more types. When two or more types are used in combination, the softening point is a value determined by the method described in the examples for the mixture.

<Amorphous resin (B)>
The toner for electrophotography of the present invention contains an amorphous resin (B) from the viewpoint of low temperature fixability of the toner, storage stability under high humidity, and printing durability. It is more preferable that it is mixed with the crystalline resin (A) and contained as a binder resin. The amorphous resin is preferably an amorphous polyester obtained by polycondensation of an alcohol component and a carboxylic acid component.

(Alcohol component)
The alcohol component as a raw material monomer of the amorphous resin (B) is selected from aromatic diols, aliphatic diols and polyhydric alcohols having a valency of 3 or more from the viewpoint of improving the low temperature fixability and storage stability of the toner. It is preferable to contain a species or more, and it is more preferable to include one or more selected from an aromatic diol and an aliphatic diol, and further preferable to include one or more selected from an aromatic diol.
The aromatic diol is preferably a diol having a 2,2-bis (4-hydroxyphenyl) propane structure, from the viewpoint of improving the low temperature fixability and storage stability of the toner, and 2,2-bis (4-hydroxyphenyl). More preferred are alkylene oxide adducts of propane). In the present invention, the alkylene oxide adduct means the entire structure in which an alkyleneoxy group is added to 2,2-bis (4-hydroxyphenyl) propane.
Specifically, the alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane is preferably a compound represented by the following general formula (1).

[Wherein, R ^a and R ^{b each} represent an alkylene group having 2 or 3 carbon atoms, x and y each represent a positive number, and the sum of x and y is 1 or more and 16 or less, preferably 1.5 or more and 5 or less] . ]

The x pieces of R ^a O or y pieces of R ^b O in the general formula (1) may be identical to or different from each other, but are preferably the same, and more preferably they are propyleneoxy groups preferable.
The alkylene oxide adducts of 2,2-bis (4-hydroxyphenyl) propane may be used singly or in combination of two or more, and propylene of 2,2-bis (4-hydroxyphenyl) propane It is further preferred to use a mixture of an oxide adduct and an ethylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane. The mixing molar ratio of the propylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane and the ethylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane is preferably 50/50 or more, more preferably Preferably, it is 60/40 or more, and preferably 99/1 or less, more preferably 90/10 or less, and still more preferably 80/20 or less.

The content of the aromatic diol is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95 mol% or more in the alcohol component of the amorphous resin (B) from the viewpoint of improving the low temperature fixability of the toner. It is at least mol%, more preferably substantially 100 mol%, still more preferably 100 mol%.
The content of the alkylene oxide adduct of 2,2-bis (4-hydroxyphenyl) propane is preferably 80 mol% in the alcohol component of the amorphous polyester (B) from the viewpoint of improving the printing durability of the toner. The content is more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably substantially 100 mol%, still more preferably 100 mol%.

As an aliphatic diol, C2-C6 aliphatic diol is preferable. Specific examples thereof include ethylene glycol, 1,2-propanediol, 1,4-butanediol and 2,3-butanediol from the viewpoint of increasing the ester value, and from the viewpoint of improving the low temperature fixability and storage stability of the toner. At least one selected from neopentyl glycol and 1,6-hexanediol, more preferably at least one selected from 1,2-propanediol and 1,4-butanediol, and 1,2-propanediol More preferable.
As a polyhydric alcohol more than trivalence, 1 or more types chosen from glycerol, pentaerythritol, trimethylol propane, and sorbitol are preferable.
The alcohol components may be used alone or in combination of two or more.

  The content of the aliphatic diol having 2 to 6 carbon atoms is preferably 80 mol% or more, more preferably 90 moles, in the alcohol component of the amorphous resin (B) from the viewpoint of improving the low-temperature fixability of the toner. %, More preferably 95 mol% or more, still more preferably substantially 100 mol%, still more preferably 100 mol%.

(Carboxylic acid component)
As a carboxylic acid component used as a raw material monomer of amorphous resin (B), 1 or more types chosen from a dicarboxylic acid compound and the trivalent or more polyvalent carboxylic acid compound are preferable. Aliphatic dicarboxylic acid compounds such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, azelaic acid and the like as dicarboxylic acid compounds; Aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid and terephthalic acid; alicyclic dicarboxylic acid compounds such as cyclohexanedicarboxylic acid; 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid It is preferable to use one or more selected from an acid, a furandicarboxylic acid compound such as 3,4-furandicarboxylic acid, and an anhydride of these acids, an alkyl (having 1 to 3 carbon atoms) ester, and the like.
Among these, from the viewpoint of improving the low temperature fixability and storage stability of the toner, at least one selected from aliphatic dicarboxylic acid compounds, aromatic dicarboxylic acid compounds, and furandicarboxylic acid compounds is preferable, and aromatic dicarboxylic acids are preferable. One or more selected from compounds are more preferable. Specifically, one or more kinds selected from alkenyl succinic anhydrides such as fumaric acid and dodecenyl succinic anhydride, phthalic acid, isophthalic acid and terephthalic acid are preferable, and fumaric acid, alkenyl succinic anhydride, isophthalic acid and terephthalic acid are preferable. One or more selected is more preferable, one or more selected from isophthalic acid and terephthalic acid is more preferable, and terephthalic acid is still more preferable.

Examples of trivalent or higher polyvalent carboxylic acid compounds include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and the like, and One or more selected from derivatives such as acid anhydrides and alkyl (having 1 to 3 carbon atoms) esters are preferable.
Other carboxylic acid compounds include unrefined rosin, purified rosin, and rosin modified with fumaric acid, maleic acid, acrylic acid and the like.

  The carboxylic acid component of the amorphous resin (B) preferably contains an aromatic dicarboxylic acid compound from the viewpoint of improving the low temperature fixability and storage stability of the toner. The content of the aromatic dicarboxylic acid compound in the carboxylic acid component is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol from the viewpoint of improving the low temperature fixability and storage stability of the toner. % Or more, and preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.

  The carboxylic acid component of the amorphous resin (B) increases the molecular weight of the amorphous polyester (B), promotes amorphization, and improves the storage stability of the toner. A carboxylic acid compound, preferably a trimellitic acid compound, more preferably one containing trimellitic anhydride. From the same viewpoint, the content of the trivalent or higher polyvalent carboxylic acid compound is preferably 0.1 mol% or more, more preferably 1 mol% or more, still more preferably 5 mol% or more, in the carboxylic acid component. More 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.

[Molar ratio of alcohol component to carboxylic acid component of amorphous resin (B)]
The molar ratio of the carboxylic acid component to the alcohol component of the amorphous resin (B) (carboxylic acid component / alcohol component) is preferably 0.7 or more, more preferably 0. It is 75 or more, and preferably 1.2 or less, more preferably 1.1 or less, and still more preferably 1.0 or less.

(Physical properties of amorphous resin (B))
The softening point of the amorphous resin (B) is preferably 70 ° C. or more, more preferably 80 ° C. or more, still more preferably 85 ° C. or more, still more preferably from the viewpoint of improving the low temperature fixability and storage stability of the toner. Is 90 ° C. or higher, and preferably 150 ° C. or lower, more preferably 140 ° C. or lower, and still more preferably 135 ° C. or lower.

The amorphous resin (B) may be used in combination of an amorphous polyester having a high softening point and an amorphous polyester having a low softening point, from the viewpoint of improving the low-temperature fixability of the toner. A combination of an amorphous polyester having a softening point of less than 120 ° C. (hereinafter also referred to as a low softening point polyester) and an amorphous polyester having a softening point of 120 ° C. or more (hereinafter also referred to as a high softening point polyester). Is preferred. The softening point of the high softening point polyester is preferably 120 ° C. or more and 150 ° C. or less, more preferably 130 ° C. or more and 150 ° C. or less, and still more preferably 140 ° C. or more and 150 ° C. or less. The softening point of the low softening point polyester is preferably 80 ° C. or more and less than 120 ° C., more preferably 80 ° C. or more and 110 ° C. or less, and still more preferably 80 ° C. or more and 100 ° C. or less. It is preferable to use two types whose softening points differ preferably by 10 ° C. or more, more preferably by 20 ° C. or more.
The mass ratio of low softening point polyester to high softening point polyester (low softening point polyester / high softening point polyester) is preferably 30/70 or more, more preferably 40/60 or more, and preferably 70/30 or less And more preferably 60/40 or less.

The content of the low softening point polyester in the amorphous resin (B) is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of improving the low temperature fixability of the toner, and From the viewpoint of the properties, it is preferably 100% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.
The content of the high softening point polyester in the amorphous resin (B) is preferably 30% by mass or more, more preferably 40% by mass or more from the viewpoint of storage stability, and the low temperature fixability of the toner From the viewpoint of improving, it is preferably 100% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass or less.

The glass transition point of the amorphous resin (B) is preferably 45 ° C. or more, more preferably 55 ° C. or more, and preferably 80 ° C. or less from the viewpoint of improving the low temperature fixability and storage stability of the toner. And more preferably 75 ° C. or less.
The number average molecular weight of the amorphous resin (B) is preferably 1,000 or more, more preferably 1,500 or more, and preferably 6,000 or less, more preferably 5,000 or less. The weight average molecular weight of the amorphous resin (B) is preferably 2,000 or more, more preferably 3,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less. .

The acid value of the amorphous resin (B) is preferably 1 mg KOH / g or more, more preferably 2 mg KOH / g or more, still more preferably 3 mg KOH / g or more, from the viewpoint of improving the low temperature fixability and storage stability of the toner. And from the same viewpoint, it is preferably 25 mg KOH / g or less, more preferably 20 mg KOH / g or less, and still more preferably 15 mg KOH / g or less.
The hydroxyl value of the amorphous resin (B) is preferably 1 mg KOH / g or more, more preferably 5 mg KOH / g or more, still more preferably 10 mg KOH / g or more from the viewpoint of improving the low temperature fixability and storage stability of the toner. And preferably 80 mg KOH / g or less, more preferably 70 mg KOH / g or less, still more preferably 65 mg KOH / g or less.
The maximum endothermic peak temperature of the amorphous resin (B) is preferably 50 ° C. or more, more preferably 60 ° C. or more, still more preferably 65 ° C. or more, from the viewpoint of low temperature fixability of the toner and storage stability. And from the same viewpoint, it is preferably 85 ° C. or less, more preferably 80 ° C. or less, and still more preferably 75 ° C. or less.
In addition, the number average molecular weight of amorphous resin (B), a weight average molecular weight, an acid value, a hydroxyl value, a softening point, a glass transition point, and the highest peak temperature of an endotherm are measured by the measuring method as described in an Example.

(Method for producing amorphous resin (B))
There is no restriction | limiting in particular in the manufacturing method of amorphous resin (B), Although it can manufacture by a well-known method, amorphous polyester is obtained by the polycondensation reaction of an alcohol component and a carboxylic acid component. The polycondensation reaction is preferably carried out in the presence of an esterification catalyst, and more preferably carried out in the co-presence of the aforementioned esterification catalyst and an esterification co-catalyst from the viewpoints of reactivity, molecular weight adjustment and physical property adjustment of the resin. .
The amount of the esterification catalyst, the amount of the esterification promoter, and the like are as described above.

The polycondensation reaction between the alcohol component and the carboxylic acid component is, for example, preferably 180 ° C. or more, more preferably 190 ° C. or more in the presence of the above-mentioned esterification catalyst and in an inert gas atmosphere from the viewpoint of reactivity. C., more preferably at least 195.degree. C., and preferably at 250.degree. C. or less, more preferably 240.degree. C. or less, still more preferably 235.degree. C. or less.
For example, in order to increase the strength of the resin, all monomers are charged at one time, and in order to reduce low molecular weight components, a divalent monomer is first reacted, and then a method such as adding and reacting a trivalent or higher monomer is used. May be The reaction may be promoted by reducing the pressure of the reaction system in the latter half of the polymerization.

<Optional Additive>
In the toner for electrophotography of the present invention, colorants, charge control agents, waxes, magnetic powders, fluidity improvers, conductivity modifiers, extender pigments, reinforcing fillers such as fibrous substances, antioxidants, antiaging agents Additives, such as an agent and a cleaning property improvement agent, may be contained suitably.

[Colorant]
There is no restriction | limiting in particular as a coloring agent, According to the objective, it can select suitably. 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 (copper phthalocyanine), phthalocyanine green, and malachite Various pigments such as green oxalate; acridine type, xanthene type, azo type, benzoquinone type, azine type, anthraquino System, indigo, thioindigo, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used singly or in combination of two or more.
When the coloring agent is contained, the amount of the coloring agent is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 100 parts by mass of the total amount of the resin from the viewpoint of image quality improvement. The amount is preferably 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 10 parts by mass or less.

[Charge control agent]
Examples of charge control agents include chromium-based azo dyes, iron-based azo dyes, aluminum azo dyes, and salicylic acid metal complexes. These may be used alone or in combination of two or more.
When a charge control agent is added, the amount of the charge control agent is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, based on 100 parts by mass of the total resin, from the viewpoint of improving image quality. More preferably, it is 0.5 parts by mass or more, and preferably 8 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.

〔wax〕
Waxes include polyolefin waxes, paraffin waxes, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide and stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba oil, etc. Plant waxes; animal waxes such as beeswax; and waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresine, microcrystalline wax, and Fischer-Tropsch wax. These can be used individually by 1 type or in combination of 2 or more types.
The melting point of the wax is preferably 60 ° C. or more, and preferably 160 ° C. or less, more preferably 150 ° C. or less, from the viewpoint of improving the low-temperature fixability of the toner.
When a wax is added, the amount of the wax is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably from the viewpoint of resin dispersibility with respect to 100 parts by mass of the total amount of resins. Is 1 part by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

[External additive]
An external additive may be added to the surface of the toner. As the external additive, silica fine particles whose surface is hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, inorganic fine particles such as carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin, etc. Of fine particles can be used.
The number average particle diameter of the external additive is preferably 4 nm or more, more preferably 8 nm or more, more preferably 12 nm or more, and preferably 200 nm or less, more preferably 50 nm or less, from the viewpoint of toner fluidity. More preferably, it is 30 nm or less. The amount of the external additive is preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the toner before being treated with the external additive.

[Method for producing electrophotographic toner]
The method for producing a toner for electrophotography of the present invention includes the step of dispersing a resin containing a crystalline resin (A) in an aqueous medium. By passing through the process, low molecular weight components contained in the crystalline resin (A), unreacted ethylene glycol monomer and the like are removed, and excellent low temperature fixability, storage stability and printing durability can be obtained. it can.
In the above process, the binder resin may be only the crystalline resin (A), or may be a kneaded product of the crystalline resin (A) and another resin. It is more preferable to disperse only the crystalline resin (A) in water from the viewpoint of storage stability under high temperature and high humidity.

  In the step of dispersing the resin according to the present invention in the aqueous medium, the content of the crystalline resin (A) in the resin is preferably 5% by mass or more from the viewpoint of improving the storage stability and low temperature fixability of the toner. More preferably, it is 10% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, further preferably 95% by mass or more, still more preferably substantially 100% by mass, further preferably 100% by mass.

More specifically, the method for producing a toner for electrophotography of the present invention preferably includes the following steps 1 to 3.
Step 1: Dispersing Resin Containing Crystalline Resin (A) in Water Step 2: Aqueous Dispersion Containing Crystalline Resin (A) and Amorphous Resin (B), and, if Needed, Raw Material for Toner Are coagulated to obtain agglomerated particles. Step 3: A step of fusing the agglomerated particles obtained in step 2

  The total amount of the crystalline resin (A) and the amorphous resin (B) used is preferably 5% by mass or more, more preferably from the viewpoint of improving the storage stability of the toner and the low temperature fixability of the toner. 30% by mass or more, more preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, more preferably 90% by mass or more, preferably 100% by mass or less, more preferably 99 It is less than mass%.

In the present specification, the aqueous dispersion may be such that the binder resin is present in a dispersed state in a solvent containing an aqueous medium. The aqueous dispersion is preferably present for 24 hours at 25 ° C. without separation.
In the present specification, particles made of a binder resin contained in an aqueous dispersion of a binder resin may be referred to as "binder resin particles".

<Step 1>
The aqueous dispersion for toners for electrophotography of the present invention (hereinafter, also referred to as “aqueous dispersion”) contains the binder resin of the present invention.
The aqueous dispersion of the present invention preferably comprises the following steps 1A-1a and 1A-1b (hereinafter collectively referred to simply as "step 1A"), or step 1B-1 and step 1B-2 (below The said process can be named generically and it can manufacture only by "the process 1B."

Step 1A-a: A step of adding an aqueous medium to an organic solvent solution of a binder resin containing a crystalline resin (A) to perform phase inversion emulsification to obtain an aqueous dispersion of binder resin Step 1A-b: A step of adding an aqueous medium to an organic solvent solution of a binder resin containing an amorphous resin (B) to perform phase inversion emulsification to obtain an aqueous dispersion of binder resin

Step 1B-1: A step of melt-kneading a binder resin containing a crystalline resin (A) and an amorphous resin (B) Step 1B-2: The kneaded product obtained in the step 1B-1 is treated with an aqueous medium Process to disperse and obtain aqueous dispersion of binder resin

«Process 1A»
Hereinafter, the binder resin containing the crystalline resin (A) in step 1A-a and the binder resin containing the amorphous resin (B) in step 1A-b are collectively referred to simply as "binder resin", and step 1A The description of the portions common to -a and the steps 1A-b will be omitted.
In the aqueous dispersion, an organic solvent other than the aqueous medium may be present, but the content of the aqueous medium in the total amount of the aqueous medium and the organic solvent is preferably 50% by mass or more, more preferably 70% by mass The content is more preferably 80% by mass or more, more preferably 85% by mass or more. Hereinafter, the phase inversion emulsification method will be described.

The phase inversion emulsification can be performed by adding an aqueous medium to the organic solvent solution of the binder resin. By adding an aqueous medium to the organic solvent solution, first, a W / O phase is formed, and then, the phase is inverted to the O / W phase. Whether or not phase inversion is occurring can be confirmed, for example, by visual observation, conductivity, or the like.
In the phase inversion step, the particle diameter and the like of the binder resin particles can be adjusted by the addition speed and the amount of the aqueous medium as described later.
The organic solvent solution of the binder resin can be produced by a method of dissolving or dispersing the binder resin component in an organic solvent after mixing or kneading as necessary.

[Organic solvent]
The organic solvent is preferably 15.0 MPa ^1/2 or more, more preferably 15.0 MPa ^1/2 or more, as represented by a solubility parameter (SP value: POLYMERHANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc), from the viewpoint of solubility of the binder resin. 16.0MPa ^1/2 or more, more preferably 17.0MPa ^1/2 or more, and, preferably 26.0MPa ^1/2 or less, more preferably 24.0MPa ^1/2 or less, more preferably 22. It is 0 MPa ^1/2 or less.
The following organic solvents are mentioned as a specific example. The parenthesis in the right of the name of the next organic solvent is the SP value, and the unit is MPa ^1/2 . That is, as specific examples, alcohol solvents such as ethanol (26.0), isopropanol (23.5), and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl Ketone solvents such as isobutyl ketone (17.2) and diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6), and dioxane (20.5); Acetic acid ester solvents such as ethyl acetate (18.6) and isopropyl acetate (17.4) can be mentioned. Among these, ketone solvents and acetic acid ester solvents are preferable, one or more selected from methyl ethyl ketone, ethyl acetate and isopropyl acetate are more preferable, ketone solvents are more preferable, and methyl ethyl ketone is still more preferable.
The mass ratio of the organic solvent to the binder resin component (organic solvent / binder resin component) is preferably 0.1 or more, more preferably 0.2 or more, more preferably 0.25 or more, and Preferably it is 1 or less, More preferably, it is 0.5 or less, More preferably, it is 0.35 or less.
In the step, from the viewpoint of improving the dispersion stability of the binder resin, it is preferable to add a neutralizing agent to the binder resin.

〔Neutralizer〕
Examples of the neutralizing agent include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; and organic bases such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine and tributylamine. Be Among these, sodium hydroxide is preferred.
The temperature at which the neutralization agent is added for neutralization is preferably 30 ° C. or more, more preferably 50 ° C. or more, more preferably 60 ° C. or more, and preferably 90 ° C. or less, more preferably 85 ° C. C. or less, more preferably 80.degree. C. or less.
The degree of neutralization (mol%) of the binder resin by the neutralizing agent is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less More preferably, it is 100 mol% or less, more preferably 60 mol% or less.
The degree of neutralization (mol%) of the binder resin can be determined by the following equation.
Degree of neutralization = {[added mass of neutralizing agent (g) / equivalent of neutralizing agent] / [[acid value of binder resin (mg KOH / g) × mass of resin (g)] / (56 × 1000) ] × 100

[Water based medium]
The aqueous medium is preferably one containing water as a main component.
As components other than water, aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol, isopropanol and butanol; dialkyls (1 to 3 carbon atoms) such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran The organic solvent which melt | dissolves in water is mentioned. Among these, from the viewpoint of preventing mixing in the toner, alcohol-based organic solvents such as methanol, ethanol, isopropanol and butanol, which are organic solvents which do not dissolve polyester-based resins, can be suitably used.
The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 95% by mass or more, from the viewpoint of improving the dispersion stability of the binder resin particles. It is 100% by mass. The water is preferably deionized water or distilled water.

The temperature at which the aqueous medium is added is preferably 15 ° C. or more, more preferably 20 ° C. or more, more preferably 25 ° C. or more, from the viewpoint of improving the dispersion stability of the binder resin particles, and preferably It is 90 ° C. or less, more preferably 80 ° C. or less, more preferably 75 ° C. or less.
From the viewpoint of improving the dispersion stability of the binder resin particles, the addition rate of the aqueous medium is preferably 0.1 parts by mass or more per 100 parts by mass of the binder resin until phase inversion is completed. More preferably, it is 1 part by weight or more, more preferably 3 parts by weight or more, and preferably 50 parts by weight or less, more preferably 20 parts by weight or less, more preferably 10 parts by weight / It is less than a minute. There is no limitation on the addition rate of the aqueous medium after phase inversion.
The amount of the aqueous medium to be added is preferably 100 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the dispersion stability of the binder resin particles and from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. The content is preferably 200 parts by mass or more, more preferably 250 parts by mass or more, and preferably 900 parts by mass or less, more preferably 700 parts by mass or less, more preferably 500 parts by mass or less.

[Surfactant]
Surfactants include nonionic surfactants, anionic surfactants, and cationic surfactants. Among these, from the viewpoint of improving the dispersion stability of the binder resin particles, at least one selected from nonionic surfactants and anionic surfactants is 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. may be mentioned. Among them, from the viewpoint of improving the dispersion stability of the binder resin particles, Polyoxyethylene alkyl ethers are preferred.
Examples of anionic surfactants include alkyl benzene sulfonates such as sodium alkyl benzene sulfonate, alkyl sulfates such as alkyl sodium sulfate, alkyl ether sulfates such as alkyl ether sodium sulfate, and the like, and among these, binder resins From the viewpoint of improving the dispersion stability of the particles, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, alkyl ether sulfate is more preferable, sodium alkyl ether sulfate is more preferable, and sodium polyoxyethylene lauryl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyl trimethyl ammonium chloride and dialkyl dimethyl ammonium chloride.

[Removal of organic solvent]
After phase inversion emulsification, if necessary, it may have a step of removing the organic solvent from the dispersion obtained by phase inversion emulsification.
The method of removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, distillation is preferable. 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 is preferably 1% by mass or less, more preferably 0.5% by mass or less, and more preferably substantially 0% in the aqueous dispersion.
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 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 and distilled off. 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 particles, it is preferable to distill off while keeping the temperature and pressure constant.

[Addition of surfactant]
After the phase inversion emulsification, a step of mixing the surfactant with the aqueous dispersion may be included.
The amount of surfactant added in this step is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the binder resin from the viewpoint of dispersion stability of the binder resin particles. More preferably, it is 2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, more preferably 10 parts by mass or less.
At the time of surfactant addition, it is preferable to stir using a generally used mixing and stirring apparatus such as an anchor wing, an external circulation stirring apparatus, and the like.
When a mixing / stirring apparatus such as an anchor blade is used, the peripheral speed of stirring is preferably 20 m / min or more, more preferably 40 m / min or more, more preferably 60 m / min or more, more preferably from the viewpoint of dispersibility. It is 80 m / min or more, and preferably 200 m / min or less, more preferably 150 m / min or less, 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, 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, more preferably 35 ° C. or less.

«Process 1 B»
In step 1B-1, the binder resin containing the crystalline resin (A) and the amorphous resin (B) is melt-kneaded.
Further, in step 1B-1, it is preferable to further melt and knead the colorant, and it is preferable to melt and knead together other additives such as other waxes and charge control agents.

  The melt-kneading can be performed using a known kneader such as a closed kneader, a single-screw or twin-screw extruder, or an open roll kneader. Using an open-roll type kneader from the viewpoint of being able to efficiently disperse additives such as a colorant, a charge control agent, and a wax in a toner efficiently without using repeated kneading and the use of a dispersing aid. The open-roll type kneader is preferably provided with a supply port and a mixture discharge port along the axial direction of the roll.

  The toner raw materials such as the binder resin, polyester, colorant, charge control agent, and wax are preferably mixed in advance with a mixer such as a Henschel mixer or a ball mill and then supplied to the kneader.

  An open roll type kneader is a machine in which the kneading section is not sealed but released, and the heat of kneading generated at the time of kneading can be easily dissipated. The continuous open-roll type kneader is preferably a kneader equipped with at least two rolls, and the continuous open-roll type kneader used in the present invention is two rolls having different circumferential speeds, That is, it is a kneader equipped with two rolls of a high rotation side roll having a high peripheral speed and a low rotation side roll having a low peripheral speed. In the present invention, from the viewpoint of improving the dispersibility of additives such as colorants, charge control agents, and waxes in toner, from the viewpoint of reducing mechanical force at the time of melt-kneading and suppressing heat generation, and at the time of melt-kneading From the viewpoint of reducing the temperature, the high rotation side roll is preferably a heating roll, and the low rotation side roll is preferably a cooling roll.

The temperature of the roll can be adjusted, for example, by the temperature of the heat medium passed inside the roll.
The heating temperature in the roll is preferably 20 ° C. or more, more preferably 30 ° C. or more, more preferably 40 ° C. or more, and preferably 200 ° C. or less, more preferably 150 ° C. or less.

  The roll rotation speed is preferably 50r /, from the viewpoint of improving the dispersibility of the colorant, charge control agent, and additives such as wax in the toner, and reducing the mechanical force during melt-kneading and suppressing heat generation. min or more, more preferably 100 r / min or more, more preferably 150 r / min or more, and preferably 350 r / min or less, more preferably 300 r / min or less, more preferably 250 r / min or less.

  The structure, size, material and the like of the roll are not particularly limited, and the roll surface may be smooth, corrugated, uneven or the like, but the kneading shear is increased to improve the coloring agent, charge control agent, wax, etc. From the viewpoint of improving the dispersibility of the additive in the toner, and from the viewpoint of reducing the mechanical force at the time of melt-kneading and suppressing the heat generation, a plurality of spiral grooves being cut on the surface of each roll preferable.

In Step 1B-2, the kneaded product obtained in Step 1B-1 is dispersed by an aqueous medium to obtain an aqueous dispersion of a binder resin.
It is preferable to produce the kneaded product and, if necessary, the above-mentioned optional components such as surfactants and colorants in an aqueous medium to obtain a dispersion of resin particles.
For example, the kneaded material can be dispersed by stirring in an aqueous medium at a temperature equal to or higher than the melting temperature of the kneaded material. As a stirrer used for the said stirring, a chi-type stirrer etc. are mentioned, for example.
The stirring speed is preferably 50 r / min or more and 200 r / min or less. The stirring temperature is preferably 50 ° C. or more and 100 ° C. or less. After the above stirring, it is preferable to obtain a finely divided resin dispersion through a filter (for example, a wire mesh of 100 to 300 mesh).

  The solid content concentration of the aqueous dispersion obtained in step 1 is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less.

<Step 2>
Step 2 is a step of aggregating the aqueous dispersion of the binder resin to obtain aggregated particles.
An aqueous dispersion of a binder resin can be produced by the method described in the above-mentioned step 1, and, for example, when step 1 is step 1A, the dispersion obtained respectively in step 1A-a and step 1A-b Can be obtained by mixing.
In step 2, it is preferable to add a coagulant in order to carry out aggregation efficiently. In addition, additives such as a colorant, a charge control agent, a wax, a conductive regulator, a reinforcing filler such as a fibrous substance, an antioxidant, and an antioxidant may be added and then aggregated.

[Flocculant]
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. Among these, inorganic coagulants are preferable, and inorganic metal salts are more preferable.
Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and the like, among which calcium chloride is preferable. The valence number of the central metal of the inorganic metal salt is preferably divalent or higher.
The amount of the aggregating agent used is preferably 0.10 parts by mass or more, more preferably 0 based on 100 parts by mass of the binder resin particles, from the viewpoint of controlling aggregation of the binder resin particles to obtain a desired particle diameter. .15 parts by mass or more, more preferably 0.20 parts by mass or more, and preferably 5 parts by mass or less, more preferably 1 part by mass or less, more preferably 0.5 parts 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 step 2, the solid content concentration in the system is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 15% by mass or more from the viewpoint of causing uniform aggregation, and preferably It is 50% by mass or less, more preferably 40% by mass or less, more preferably 30% by mass or less.
The temperature at which the coagulant is dropped is preferably 0 ° C. or more, more preferably 10 ° C. or more, more preferably 15 ° C. or more, and preferably 60 ° C. or less, from the viewpoint of improving the productivity of the toner. More preferably, it is 55 degrees C or less, More preferably, it is 50 degrees C or less.

[Colorant]
As a coloring agent used at the process 2, the thing similar to the coloring agent which the binder resin of this invention can contain is mentioned, A preferable aspect is also the same.
The colorant may be added as a colorant dispersion containing colorant particles.
The volume median particle size (D ₅₀ ) of the colorant particles is preferably 50 nm or more, more preferably 80 nm or more, more preferably 100 nm or more, from the viewpoint of obtaining a toner from which a high quality image can be obtained. Is 500 nm or less, more preferably 300 nm or less, more preferably 150 nm or less.

[Charge control agent]
Examples of the charge control agent used in the step 2 include the same ones as the charge control agent that can be contained in the binder resin of the present invention, and preferred embodiments are also the same.
The charge control agent may be added as a charge control agent dispersion containing charge control agent fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 200 nm or more, more preferably 300 nm or more, and preferably 800 nm or less, more preferably 700 nm or less Preferably it is 600 nm or less.

The volume median particle size (D ₅₀ ) of the agglomerated particles obtained in step 2 is preferably 2 μm or more, more preferably 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 9 μm or less And more preferably 7 μm or less.

<Step 3>
Step 3 is a step of fusing the aggregated particles obtained in step 2 above. In this step, the particles in the aggregated particles, which are mainly in the state of being physically attached to each other, are fused and integrated to form fused particles.

In this step, it is preferable to maintain the temperature at a temperature higher than the glass transition temperature of the polyester resin from the viewpoint of improving the fusion property of the aggregated particles.
The holding temperature in this step is preferably 10 ° C. or more higher than the glass transition temperature of the amorphous resin (B), from the viewpoint of improving the fusion property of aggregated particles and the viewpoint of improving the productivity of toner. The temperature is preferably 13 ° C. or more, more preferably 15 ° C. or more, and preferably 50 ° C. or less, more preferably 40 ° C. or more, more preferably 50 ° C. or more, higher than the glass transition temperature of the polyester resin. The temperature is 30 ° C. or higher.
Specifically, the holding temperature 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, 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. As an anionic surfactant, 1 or more types chosen from an alkyl ether sulfate, an alkyl sulfate, and a linear alkyl benzene sulfonate are preferable, and an alkyl ether sulfate is more preferable.

«Post-processing process»
The toner used in the present invention can be suitably obtained by appropriately subjecting the fused particles obtained in the above steps to a solid-liquid separation step such as filtration, a washing step, and a drying step.
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.
Furthermore, an external additive may be added for the purpose of improving the fluidity and the like.
When an external additive is added, the amount thereof is preferably 0 with respect to 100 parts by mass of toner particles before the treatment with the external additive, from the viewpoint of improving the fluidity of the toner and the environmental stability of the degree of charge. 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass or less, more preferably 3 parts by mass or less It is.

The volume median particle size (D ₅₀ ) of the toner for electrophotography of the present invention is preferably 2 μm or more, more preferably 3 μm or more, more preferably 4 μm or more, and preferably 20 μm or less, more preferably 15 μm or less And more preferably 10 μm or less.

  Each physical property value of resin etc. was measured and evaluated by the following method.

[Endothermic peak temperature, melting point, crystallinity index]
Using a differential scanning calorimeter “Q-100” (manufactured by TEA Instruments Japan Co., Ltd.), let the sample cooled from room temperature to 0 ° C. at a temperature decrease rate of 10 ° C./min stand still for 1 minute and then heat up rate It measured to 150 degreeC at 10 degrees C / min. Among the observed endothermic peaks, the temperature of the peak located on the highest temperature side is taken as the highest peak temperature of the endotherm, and if the highest peak temperature is a difference between the softening point and 20 ° C., it is regarded as a crystalline resin and taken as its melting point. In addition, the crystallinity index was calculated by dividing the softening point by the maximum peak temperature of the endotherm.

[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, diameter 1 mm, length 1 mm Was pushed out of the nozzle. The temperature was compared with the temperature by which the amount of Blanker drop of the flow tester was plotted, and the temperature at which half of the sample flowed out was taken as the softening point.

[Glass transition point of amorphous resin]
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), measure 0.01 to 0.02 g of the sample in an aluminum pan, raise the temperature to 200 ° C., and measure the temperature The sample cooled to 0 ° C at a cooling rate of 10 ° C / min is heated at a heating rate of 10 ° C / min, and the extension of the baseline below the highest peak temperature of the endotherm and the maximum from the rising portion to the peak of the peak The temperature at the point of intersection with the inclined tangent line was taken as the glass transition point.

[Number average molecular weight and weight average molecular weight of resin]
The molecular weight distribution was measured by gel permeation chromatography according to the following method, and the number average molecular weight and the weight average molecular weight were calculated.
(1) Preparation of sample solution The sample was dissolved in chloroform so that the concentration was 0.5 g / 100 ml. Next, this solution was filtered using a fluororesin filter “FP-200” (manufactured by Sumitomo Electric Industries, Ltd.) with a pore size of 2 μm to remove insoluble components, and used as a sample solution.
(2) Molecular weight distribution measurement As a solution, chloroform was flowed at a flow rate of 1 ml / min, and the column was stabilized in a 40 ° C. thermostat. The measurement was carried out by injecting 200 μl of the sample solution therein. The molecular weight of the sample was calculated based on a calibration curve prepared in advance. The calibration curve at this time includes several types of monodispersed polystyrene (monodispersed polystyrene manufactured by Tosoh Corporation; molecular weights 1.11 × 10 ⁶ , 3.97 × 10 ⁵ , 1.89 × 10 ⁵ , 9.89 × 10 ^{5 4} , 1.71 × 10 ⁴ , 9.49 × 10 ³ , 5.87 × 10 ³ , 1.01 × 10 ³ , 5.00 × 10 ² ) were prepared as standard samples.
Measuring device: HPLC LC-9130NEXT (trade name, manufactured by Japan Analysis Industry Co., Ltd.)
Analysis column: JAIGEL-2.5-HA + JAIGEL-MH-A (all trade names, manufactured by Japan Analysis Industry Co., Ltd.)

[Acid value and hydroxyl value of resin]
It measured according to JIS K 0070. However, the solvent for measuring the acid value was a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

Low temperature fixability
An unfixed image was obtained by mounting the toner on an apparatus obtained by modifying the fixing machine of the copying machine “AR-505” (manufactured by Sharp Corporation) so as to enable fixing outside the apparatus (printing area: 2 cm × 12 cm, Adhesion amount: 0.5 mg / cm ² ).
Thereafter, with a fixing device (fixing speed: 390 mm / sec) having a fixing roller adjusted so that the total fixing pressure is 40 kgf, the temperature of the unfixed image is increased at each temperature while sequentially increasing from 100.degree. C. to 240.degree. The fixation test was done. A cellophane adhesive tape "UNICEF cellophane" (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z-1522) was attached to the fixed image, and after passing through a fixing roller set at 30 ° C., 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 Macbeth), and the ratio (both after peeling / before sticking) of the both initially exceeds 90%. The temperature of the roller was taken as the minimum fixing temperature, and the low temperature fixability was evaluated. In addition, the paper used for the fixing test is "CopyBond SF-70NA" (made by Sharp Corporation, 75 g / m < ² >).

[Preservability under high humidity]
4 g of the toner was left for 72 hours under the environment of a temperature of 55 ° C. and a humidity of 85%. After standing, the degree of toner aggregation was visually observed, and the storage stability was evaluated according to the following evaluation criteria. The results are shown in Tables 3-1 and 3-2.
〔Evaluation criteria〕
A: No aggregation was observed after 48 hours and 72 hours.
B: No aggregation was observed after 48 hours but aggregation was clearly observed after 72 hours.
C: Aggregation is already observed within 48 hours.

[Evaluation of printing durability]
A toner is mounted on a laser printer "Page pressed N-4" (made by Casio Computer Co., Ltd., fixing: contact fixing method, development: nonmagnetic one-component development method, developing roll diameter: 2.3 cm), temperature 32 ° C., relative Printing was performed in a diagonal stripe pattern with a blackening rate of 5.5% under conditions of humidity 85%. 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 evaluated as the number of sheets until the streaks were observed because the toner was fused or fixed to the developing roll. As the number of sheets until the streaks are observed is larger, the printing durability of the toner is more excellent.

[Production of crystalline resin (A)]
Synthesis Examples A1 to A7, A9 to A11 (Resins A1 to A7, A9 to A11)
The alcohol components shown in the table were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 120 ° C. At 120 ° C., the carboxylic acid components shown in the table were added, and the mixture was further heated to 160 ° C. and reacted for 6 hours. Then, the raw material monomer of the addition polymerization type resin part shown to a table | surface, a bi-reactive monomer, and a polymerization initiator were dripped over 1 hour by the dropping funnel. After the addition polymerization reaction was aged for 1 hour while being maintained at 160 ° C., the temperature was raised to 200 ° C. over 8 hours, and the reaction was allowed to proceed at 8.3 kPa for 30 minutes. Further, di (2-ethylhexanoic acid) tin (II) is added, reacted at 200 ° C. for 1 hour, and reacted at 8.3 kPa for 1 hour to obtain crystalline hybrid resin (Resin A1 to A7, A9 to A11) were obtained. Physical properties of the obtained resin were measured and shown in Tables 1-1 and 1-2.

Synthesis Example A8 (Resin A8)
The alcohol components shown in the table were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 120 ° C. At 120 ° C., the carboxylic acid components shown in the table were added and the temperature was raised to 200 ° C. over 14 hours. Furthermore, di (2-ethylhexanoic acid) tin (II) was added, reacted at 200 ° C. for 1 hour, and reacted at 8.3 kPa for 1 hour to obtain a crystalline resin (Resin A 8) . Physical properties of the obtained resin were measured and shown in Table 1-2.

Synthesis Example A12 (Resin A12)
The alcohol components shown in the table were placed in a 10 L four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 120 ° C. The carboxylic acid component shown in the table is added at 120 ° C., and the mixture is further heated to 160 ° C., and the raw material monomer of the addition polymerization resin portion shown in the table, the bireactive monomer, and the polymerization initiator are added by a dropping funnel for 1 hour. Dripped. After aging the addition polymerization reaction while maintaining at 160 ° C. for 1 hour, tin (II) ethyl (2-ethylhexanoate) and gallic acid were added, and the temperature was raised to 200 ° C. over 4 hours. The mixture was reacted at 200 ° C. for 6 hours and then at 8.3 kPa for 1 hour to obtain a crystalline hybrid resin (Resin A12). Physical properties of the obtained resin were measured and shown in Table 1-2.

[Production of Amorphous Resin (B)]
Synthesis Example B1 (Resin B1)
Raw material monomers other than trimellitic anhydride shown in the table, tin (II) di (2-ethylhexanoate), 10 l volume four equipped with thermometer, stainless steel stir bar, flow down condenser and nitrogen inlet tube Polycondensation was carried out for 6 hours at 235 ° C. in a mantle heater under a nitrogen atmosphere in a neck flask. Then, after adding trimellitic anhydride at 200 ° C., the temperature is raised to 210 ° C. to carry out a polycondensation reaction, and the reaction is carried out until the softening point reaches the softening point shown in the table, amorphous resin (Resin B1 Got). Physical properties of the obtained resin were measured and shown in Table 2.

Synthesis Example B2 (Resin B2)
Raw material monomers other than trimellitic anhydride shown in the table and tin (II) di (2-ethylhexanoate), equipped with a thermometer, a stainless steel stirring rod, a downflow condenser, and a nitrogen inlet tube, and a 5 L volume four port The flask was placed in a flask and heated to 180 ° C. in a mantle heater in a nitrogen atmosphere, heated to 220 ° C. over 5 hours, and polycondensed at 220 ° C. for 5 hours. Then, after adding trimellitic anhydride, a polycondensation reaction is carried out at 220 ° C. for 1 hour, and the reaction is carried out until the softening point reaches the softening point shown in the table at 8.3 kPa, and an amorphous resin (Resin B2) Got). Physical properties of the obtained resin were measured and shown in Table 2.

[Production of resin aqueous dispersion]
Production Examples A1 to A12 (Production of Aqueous Dispersions a-1 to a-12 of Crystalline Resin (A))
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 100 g of ethyl acetate and 100 g of resins A1 to A12 shown in the table were charged, and dissolved at 70 ° C. for 2 hours I did. A 5% by mass aqueous solution of sodium hydroxide was added to the obtained solution so that the degree of neutralization was 80 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes. Anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Corporation, sodium dodecylbenzene sulfonate) was added to 270 g of ion-exchanged water while stirring at 280 r / min (peripheral velocity 88 m / min). An aqueous solution mixed with 0.9 g as a solid content was added over 70 minutes. Then, while keeping the temperature at 65 to 75 ° C., ethyl acetate was distilled off under reduced pressure. After cooling to 30 ° C., the solid content concentration of the dispersion was measured, and adjusted to 20 mass% with ion exchange water to obtain an aqueous dispersion. Thereafter, while stirring at a rate of 280 r / min (peripheral velocity 88 m / min), 2.1 g of an anionic surfactant "Neoperex G-15" (manufactured by Kao Corporation) is mixed with the aqueous dispersion as a solid content. The mixture was stirred for 30 minutes to obtain aqueous dispersions a-1 to a-12 containing resin particles.

Production Examples B1 to B2 (Production of Aqueous Dispersions b-1 to b-2 of Amorphous Resin (B))
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 100 g of ethyl acetate and 100 g of the resins B1 to B2 shown in the table were charged and dissolved at 40 ° C. for 2 hours I did. A 5% by mass aqueous solution of sodium hydroxide was added to the obtained solution so that the degree of neutralization was 80 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes. Anionic surfactant "Neoperex (registered trademark) G-15" (manufactured by Kao Corporation, sodium dodecylbenzene sulfonate) was added to 270 g of ion-exchanged water while stirring at 280 r / min (peripheral velocity 88 m / min). An aqueous solution mixed with 0.9 g as a solid content was added over 70 minutes. Then, while keeping the temperature at 65 to 75 ° C., ethyl acetate was distilled off under reduced pressure. After cooling to 30 ° C., the solid content concentration of the dispersion was measured, and adjusted to 20 mass% with ion exchange water to obtain an aqueous dispersion. Thereafter, while stirring at a rate of 280 r / min (peripheral velocity 88 m / min), 2.1 g of an anionic surfactant "Neoperex G-15" (manufactured by Kao Corporation) is mixed with the aqueous dispersion as a solid content. The mixture was stirred for 30 minutes to obtain aqueous dispersions b-1 to b-2 containing resin particles.

[Production of Colorant Dispersion]
Production Example C1 (Production of Colorant Dispersion c-1)
Mix 50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (manufactured by Kao Corporation, polyoxyethylene lauryl ether), and 200 g of ion-exchanged water, Dispersion treatment was carried out for 30 minutes at an output of 350 W using an ultrasonic homogenizer "UP-400S" (manufactured by Hielscher) to obtain a colorant dispersion liquid c-1 containing colorant particles. The volume median particle size (D ₅₀ ) of the colorant particles was 120 nm, and the solid concentration was 22% by mass.

[Production of wax particle dispersion]
Production Example W1 (Production of Wax Dispersion w-1)
50 g of paraffin wax "HNP9" (manufactured by Nippon Seiwa Co., Ltd.), 5 g of cationic surfactant "Sanisol (registered trademark) B50" (manufactured by Kao Corp., alkyl benzyl dimethyl ammonium chloride) and 200 g of ion exchanged water at 95 ° C. The mixture was heated and dispersed for 30 minutes at an output of 350 W using an ultrasonic homogenizer "UP-400S" (manufactured by Haisher Co., Ltd.) to obtain a wax dispersion w-1 containing wax particles. The volume median particle size (D ₅₀ ) of paraffin wax (wax particles) was 550 nm, and the solid concentration was 22% by mass.

[Production of Charge Control Agent Dispersion]
Production Example CH1 (Charge Control Agent Dispersion ch-1)
50 g of a salicylic acid compound "Bontron (registered trademark) E-84" (manufactured by Orient Chemical Industries, Ltd.), 5 g of a non-ionic surfactant "Emulgen 150" (manufactured by Kao Corporation) and 200 g of ion exchange water as a charge control agent Mixing, using glass beads, and dispersing for 10 minutes using a sand grinder, charge control agent dispersion liquid ch-1 containing charge control agent particles was obtained. The volume median particle size (D ₅₀ ) of the charge control agent particles was 400 nm, and the solid concentration was 22% by mass.

[Production of electrophotographic toner]
Examples 1 to 10, Comparative Examples 1 to 5 (Production of Toners 1 to 10, 51 to 55)
(Toner particle production process)
An aqueous dispersion of a crystalline resin (A) and an aqueous dispersion of an amorphous resin (B) were mixed respectively with the mass shown in the table, and 8 g of a colorant dispersion (c-1) and a wax dispersion (w-) 1) 20 g of charge control agent dispersion liquid (ch-1) and 52 g of deionized water are placed in a 2 L container and stirred at 100 r / min (circumferential speed 31 m / min) at 20 ° C. In the above, 150 g of a 0.1% by mass aqueous solution of calcium chloride was added dropwise over 30 minutes. Then, it heated up to 50 degreeC, stirring. It was kept at 50 ° C. until the volume median particle size (D ₅₀ ) was 6 μm. After confirming that the volume median particle size (D ₅₀ ) has reached 6 μm, 4.2 g of an anionic surfactant “Emar E 27 C” (manufactured by Kao Corporation, solid content 28% by mass) is removed as an aggregation terminator. The diluted solution diluted with 37 g of ionic water was added. Then, the temperature was raised to 80 ° C., and after holding at 80 ° C. for 1 hour, the heating was ended. After forming fused particles by this, it is gradually cooled to 20 ° C. and filtered through a 150 mesh (104 μm mesh) wire mesh, suction filtration is carried out, and the toner particles are obtained through washing and drying steps. The
(External addition process)
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 Mitsui Mining Co., Ltd.) and stirred at 3000 rpm for 2 minutes to obtain toners 1 to 10 and 51 to 55.
The evaluation test of the obtained toner was carried out and the results are shown in Tables 3-1 and 3-2.

Example 11 (Production of Toner 11)
(Kneaded product manufacturing process)
150 g of resin A1 and 1350 g of resin B1, 75 g of pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3), charge control agent Bontron (registered trademark) E-84 (Orient After thoroughly stirring 15 g of a chemical compound, salicylic acid compound, and 30 g of paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point: 80 ° C.) with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) Then, melt kneading was performed using a co-rotating twin-screw extruder having a total length of 1560 mm of a kneading portion, a screw diameter of 42 mm and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the heating temperature in the roll was 120 ° C., the feed rate of the mixture was 10 kg / hr, and the average residence time was about 18 seconds.
(Toner particle production process)
In a 5L stainless steel pot, 1100g of toner kneaded material a, 10.5g of nonionic surfactant "Emulgen 430" (Kao Co., Ltd., polyoxyethylene oleyl ether, HLB: 16.2), anionic surfactant 70.0 g of "Neoperex G-15" (manufactured by Kao Corporation, 15% by mass aqueous solution of sodium dodecylbenzene sulfonate) and 420 g of 5% by mass aqueous solution of potassium hydroxide as a neutralizing agent, and using a chi type stirrer It disperse | distributed at 95 degreeC under stirring of 150 r / min. The contents are stirred for 2 hours after reaching 95 ° C, then 2200 g of deionized water is added dropwise at a rate of 6 g / min under a stirring of 150 r / min with a chi type stirrer, 200 mesh (opening: 80 μm) The finely divided resin dispersion was obtained through the wire mesh of The volume median particle diameter (D ₅₀ ) of the resin particles in the obtained resin dispersion was 0.166 μm, the solid concentration was 30.1% by mass, and no resin component remained on the wire mesh.

450 g of the obtained resin dispersion liquid was mixed at room temperature in a 2 L container. Next, under agitation of 100 r / min with a chi type stirrer, 10.95 g of ammonium sulfate (molecular weight: 132.14) as a flocculant and cation modified polyvinyl alcohol "K-210" as a hydrophilic polymer in this mixture An aqueous solution prepared by dissolving 8.3 g of a 5% by mass aqueous solution of Synthetic Chemical Industry Co., Ltd. in 502.68 g of deionized water to form an aqueous solution was added dropwise over 15 minutes at room temperature. Thereafter, the mixed dispersion was heated at 1 ° C./5 min to form aggregated particles, and when it reached 80 ° C., the temperature was raised to 90 ° C. at 90 ° C. at 0.25 ° C./min. Thereafter, the temperature was fixed at 90 ° C. and stirring was performed for 4 hours, and then heating was stopped. During this time, the toner shape changed from aggregated particles to united particles.
The mixture was gradually cooled to room temperature and subjected to a suction filtration step, a washing step and a drying step to obtain a colored resin fine particle powder. The volume median particle size (D ₅₀ ) of the colored resin fine particle powder was 6.0 μm, and the water content was 0.3% by mass.
(External addition process)
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 resultant was introduced into Mitsui Mining Co., Ltd., and stirred at 3000 rpm for 2 minutes to obtain a toner 11.
The evaluation test of the obtained toner was conducted and the results are shown in Table 4.

Example 12 (Production of Toner 12)
(Kneaded product manufacturing process)
Resin consisting of 150 g of crystalline resin A1 and 1350 g of amorphous polyester B1; 75 g of pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3), charge control agent 15 g of Bontron (registered trademark) E-84 (Orient Chemical Industry Co., Ltd., salicylic acid compound), 30 g of paraffin wax “HNP-9” (manufactured by Nippon Seiwa Co., Ltd., melting point: 80 ° C.), Henschel mixer (Mitsui mine) The mixture was thoroughly stirred and then melt-kneaded using a co-rotating twin-screw extruder having a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the heating temperature in the roll was 120 ° C., the feed rate of the mixture was 10 kg / hr, and the average residence time was about 18 seconds. The obtained kneaded product was rolled and cooled by a cooling roller, and then ground by a jet mill to obtain toner particles having a volume median particle diameter (D ₅₀ ) of 6.5 μm.
(Toner particle production process)
In a 5L stainless steel pot, 1000g of toner particles, 10g of nonionic surfactant "Emulgen 430" (manufactured by Kao Corporation, polyoxyethylene oleyl ether, HLB: 16.2), anionic surfactant "Neoperex G" -15 "(Kao Co., Ltd., 15% by mass aqueous solution of sodium dodecylbenzene sulfonate) and 2500 g of deionized water and dispersed at 30 ° C. with stirring at 150 r / min with a chi type stirrer I got a liquid. Toner particles are obtained through a suction filtration step, a washing step and a drying step. The volume median particle size (D ₅₀ ) of the colored resin fine particle powder was 6.5 μm, and the water content was 0.3% by mass.
(External addition process)
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 resultant was introduced into Mitsui Mining Co., Ltd., and stirred at 3000 rpm for 2 minutes to obtain a toner 12.
The evaluation test of the obtained toner was conducted and the results are shown in Table 4.

Comparative Example 6 (Production of Toner 56)
(Kneaded product manufacturing process)
Resin obtained by mixing 150 g of resin A1 and 1350 g of resin B1, 75 g of pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., CI Pigment Blue 15: 3), charge control agent Bontron (registered trademark) E-84 (Orient Chemical Industry Co., Ltd., salicylic acid compound) 15 g, 30 g of paraffin wax “HNP-9” (Nippon Seiwa Co., Ltd., melting point: 80 ° C.) in a Henschel mixer (Mitsui Mining Co., Ltd.) After thoroughly stirring, the mixture was melt-kneaded using a co-rotating twin screw extruder having a total length of 1560 mm, a screw diameter of 42 mm and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the heating temperature in the roll was 120 ° C., the feed rate of the mixture was 10 kg / hr, and the average residence time was about 18 seconds. The obtained kneaded product was rolled and cooled by a cooling roller, and then ground by a jet mill to obtain toner particles having a volume median particle diameter (D ₅₀ ) of 6.5 μm.
(External addition process)
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 resultant was introduced into Mitsui Mining Co., Ltd., and stirred at 3000 rpm for 2 minutes to obtain a toner 56.
The evaluation test of the obtained toner was conducted and the results are shown in Table 4.

  From the above Examples and Comparative Examples, the toner for electrophotography obtained through the step of dispersing the resin containing the crystalline resin (A) in an aqueous medium has low-temperature fixability, storage stability under high humidity, and printing durability It can be understood that the results are excellent.

Claims (7)

Binder resin containing crystalline resin (A) and amorphous resin (B),
Polyester-based resin segment (A1) and styrene-based resin obtained by polycondensation of an alcohol component containing ethylene glycol and an acid component containing an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms by the crystalline resin (A) has a segment (A2), the weight ratio for the segment (A2) of the segment (A1) [(A1) / (A2)] is Ri der 60/40 or 96/4 or less, the non-crystalline resin (a) The mass ratio [(A) / (B)] to the crystalline resin (B) is 4/96 to 20/80, and the amorphous resin (B) causes the alcohol component and the carboxylic acid component to be polycondensed. A method of producing a toner for electrophotography , which is an amorphous polyester obtained , comprising:
A method for producing a toner for electrophotography , comprising the step of dispersing a resin containing a crystalline resin (A) in an aqueous medium. The method for producing a toner for electrophotography according to claim 1, wherein a content of water contained in the aqueous medium is 80% by mass or more. The method for producing a toner for electrophotography according to claim 1 or 2, wherein a content of ethylene glycol in an alcohol component of the crystalline resin (A) is 70 mol% or more and 100 mol% or less. The content of an aliphatic dicarboxylic acid compound having 10 to 14 carbon atoms in the acid component of the crystalline resin (A) is 80 mol% to 100 mol% according to any one of claims 1 to 3. a method of manufacturing an electronic toner for. The method for producing a toner for electrophotography according to any one of claims 1 to 4, wherein the crystalline resin (A) further has a structural unit derived from a bireactive monomer (Z). The content of the structural unit derived from the bireactive monomer (Z) of the crystalline resin (A) is 1 to 15 parts by mole with respect to 100 parts by mole of the total alcohol components of the segment (A1) comprising the polyester resin The method for producing a toner for electrophotography according to claim 5, which is the following. The method for producing a toner for electrophotography according to claim 6 , wherein the amorphous resin (B) contains 30% by mass to 100% by mass of an amorphous resin having a softening point of 120 ° C to 150 ° C.