JP6488516B2 - Toner for electrophotography - Google Patents

Description

  The present invention relates to an electrophotographic toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

From the viewpoint of increasing the speed and energy saving of a printing apparatus, a toner having excellent low-temperature fixability is required.
In addition, as the print-on-demand market has grown in recent years, the demand for higher image quality for electrophotographic technology is increasing. In particular, when color printing is performed by electrophotography, high gloss (high gloss) of an image after low-temperature fixing is desired.

  For example, Patent Document 1 is a toner having toner particles containing at least a binder resin, a colorant and a crystalline polyester, and the toner contains 3 to 50% by mass of tetrahydrofuran-insoluble matter derived from the binder resin. The tetrahydrofuran-insoluble component contains a hybrid resin, the tetrahydrofuran-insoluble component is hydrolyzed, and then the tetrahydrofuran-soluble component of the component that is filtered and filtered is measured by molecular weight distribution measured by GPC. The crystalline polyester has a main peak in the range of 10,000 to 1,000,000, and has a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower in a DSC curve measured by a differential scanning calorimeter (DSC). Toner is disclosed.

  On the other hand, in Patent Document 2, the problem is an electrophotographic toner whose charge amount and image quality are not influenced by the environment. In the electrophotographic toner containing at least a binder resin and a colorant, the binder resin forms a continuous phase. An electrophotographic toner comprising a polycondensation resin and an addition polymerization resin forming a dispersed phase, wherein the dispersed phase having a diameter of 2 μm or less in the resin cross section occupies 90% or more of the entire cross-sectional area of the dispersed phase Is disclosed.

JP 2008-102390 A JP-A-7-98518

However, even with the techniques of Patent Documents 1 and 2, the durability of the toner obtained and the gloss of the printed matter are not sufficient, and further improvements have been desired.
An object of the present invention is to provide an electrophotographic toner that is excellent in durability and gloss of printed matter.

The present inventors use a non-crystalline composite resin (A) obtained from a specific raw material and a release agent as a binder resin that constitutes an electrophotographic toner, so that the toner is excellent in durability and gloss of printed matter. It was found that can be obtained.
That is, the present invention provides the following electrophotographic toner.
An alcohol component containing 60 to 100 mol% of an alkylene oxide adduct of bisphenol A represented by the following general formula (I), 75 to 95 mol% of isophthalic acid compound and 2 to 8 carbon atoms A non-condensation resin component (A1) obtained by polycondensation with a carboxylic acid component containing 5 to 25 mol% of the following aliphatic saturated dicarboxylic acid compound and a styrene resin component (A2) An electrophotographic toner containing a crystalline composite resin (A) and a release agent.

(Wherein R ¹ O and OR ¹ are oxyalkylene groups, x and y represent the average number of added moles of alkylene oxide, each being a positive number, and the sum of x and y is 1 or more and 16 It is the following.)

  ADVANTAGE OF THE INVENTION According to this invention, the toner for electrophotography which is excellent in durability and the gloss of printed matter can be provided.

  The electrophotographic toner of the present invention (hereinafter also simply referred to as “toner”) comprises an alcohol component containing 60 mol% or more and 100 mol% or less of an alkylene oxide adduct of bisphenol A represented by the general formula (I). Polycondensation obtained by polycondensation of a carboxylic acid component containing 75 mol% to 95 mol% of an isophthalic acid compound and 5 mol% to 25 mol% of an aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms An electrophotographic toner containing an amorphous composite resin (A) having a resin-based resin component (A1) and a styrene-based resin component (A2), and a release agent.

The reason why the toner of the present invention is excellent in durability and gloss of printed matter (hereinafter also simply referred to as “gloss”) is not clear, but is considered as follows.
The toner of the present invention contains an amorphous composite resin (A) having a polycondensation resin component (A1) and a styrene resin component (A2) as a binder resin, and the polycondensation resin component (A1). The carboxylic acid component, which is the raw material monomer, contains 75 to 95 mol% of the isophthalic acid compound and 5 to 25 mol% of the aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms.
The amorphous composite resin (A) obtained using an isophthalic acid compound as a raw material has a lower viscosity at the time of melting than the case where a terephthalic acid compound or the like is used as a raw material because of less entanglement of polymer chains. easy. Further, by using an aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms as a raw material, the mobility of the resulting polymer can be increased, and the amorphous composite resin (A) tends to have a low melt viscosity. . Thereby, it is considered that the binder resin containing the amorphous composite resin (A) used in the present invention is liable to decrease the melt viscosity at the time of fixing and to improve the gloss of the printed matter.
In addition to the low melt viscosity, the amorphous composite resin (A) contains 60 mol% or more of an alkylene oxide adduct of bisphenol A as an alcohol component that is a raw material monomer of the polycondensation resin component (A1). These high-hydrophobic sites of the amorphous composite resin (A) improve the dispersibility of the mold release agent while containing 100 mol% or less and having the styrene resin component (A2). Therefore, the obtained toner is considered to be excellent in durability.

[Amorphous composite resin (A)]
The amorphous composite resin (A) is a resin having a polycondensation resin component (A1) and a styrene resin component (A2), and is storable under gloss and high temperature and high humidity (hereinafter simply referred to as “storability”). (B) raw material monomer of polycondensation resin component (A1), (b) raw material monomer of styrene resin component (A2), and (c) polycondensation resin component (A1). More preferably, it is a resin obtained by polymerizing a bi-reactive monomer capable of reacting with both the raw material monomer and the raw material monomer of the styrene resin component (A2).
Moreover, within the range which does not inhibit the objective of this invention, you may include structural parts other than these three structural parts, but it is preferable not to include structural parts other than three structural parts.

In the present invention, the crystallinity of the resin is represented by the crystallinity index defined by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the value of [softening point / maximum endothermic peak temperature]. The
The amorphous composite resin (A) is a resin having a crystallinity index exceeding 1.4 or less than 0.6, preferably exceeding 1.5, or 0.5 or less, more preferably 1 .6 or more or 0.5 or less.
The crystallinity of the resin can be adjusted by the types and ratios of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The maximum endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. In crystalline resins, the maximum endothermic peak temperature is the melting point. The crystallinity index can be measured by the method described in the examples.

  In the amorphous composite resin (A), the total content of the polycondensation resin component (A1), the styrene resin component (A2) and the components derived from both reactive monomers is gloss, storage stability and durability. From this viewpoint, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.

<Polycondensation resin component (A1)>
The polycondensation resin component (A1) is an alcohol component (hereinafter referred to as “alcohol component (A-)” containing an alkylene oxide adduct of bisphenol A in an amount of 60 mol% to 100 mol% from the viewpoint of gloss, storage stability and durability. al) ") and a carboxylic acid component containing 75 mol% to 95 mol% of an isophthalic acid compound and 5 mol% to 25 mol% of an aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms. , Also referred to as “carboxylic acid component (A-ac)”).
As the resin constituting such a polycondensation resin component (A1), a polyester resin is preferable.

(Alcohol component (A-al))
The alcohol component (A-al) contains from 60 mol% to 100 mol% of an alkylene oxide adduct of bisphenol A represented by the following general formula (I) from the viewpoint of gloss, storage stability and durability.

In the formula, R ¹ O and OR ¹ are oxyalkylene groups, x and y represent the average number of added moles of alkylene oxide, each is a positive number, and the sum of x and y is 1 or more and 16 or less. It is.

Examples of the alkylene oxide adduct of bisphenol A represented by the general formula (I) include a propylene oxide adduct of bisphenol A, an ethylene oxide adduct of bisphenol A, and among these, gloss, storage stability and durability. From the viewpoint of properties, a propylene oxide adduct of bisphenol A is preferred.
The average number of added moles of propylene oxide in the propylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, and still more preferably 1.5 or more, from the viewpoint of gloss, storage stability and durability. And preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and still more preferably 4 or less.
These alcohol components (A-al) can be used alone or in combination of two or more.
The content of the alkylene oxide adduct of bisphenol A represented by the general formula (I) in the alcohol component (A-al) is preferably 60 mol% or more from the viewpoint of gloss, storage stability and durability, More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more, Preferably it is 100 mol% or less, More preferably, it is 100 mol%.
In the alkylene oxide adduct of bisphenol A represented by the general formula (I), the content of the propylene oxide adduct of bisphenol A is preferably 60 mol% or more from the viewpoint of gloss, storage stability and durability. Preferably it is 80 mol% or more, More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more, Preferably it is 100 mol% or less, More preferably, it is 100 mol%.

The alcohol component (A-al) may contain other alcohol components other than the alkylene oxide adduct of bisphenol A represented by the general formula (I).
Examples of other alcohol components that can be contained in the alcohol component (A-al) include the same alcohols as those exemplified as the alcohol component (C-al) used as a raw material monomer of the crystalline resin (C) described later.

(Carboxylic acid component (A-ac))
The carboxylic acid component (A-ac) is composed of 75 mol% to 95 mol% of isophthalic acid compound and 5 mol of aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms from the viewpoints of gloss, storage stability and durability. % Or more and 25 mol% or less.

  In the carboxylic acid component (A-ac), the content of the isophthalic acid compound is 75 mol% or more, preferably 80 mol% or more, more preferably 85 mol% or more, and still more preferably 87, from the viewpoint of gloss and durability. From the same viewpoint, it is 95 mol% or less, preferably 92 mol% or less.

In the carboxylic acid component (A-ac), the content of the aliphatic saturated dicarboxylic acid compound having 2 or more and 8 or less carbon atoms is 5 mol% or more, preferably 8 mol% or more from the viewpoint of gloss, and is stored. From the viewpoint of property and durability, it is 25 mol% or less, preferably 20 mol% or less, more preferably 18 mol% or less, and still more preferably 15 mol% or less.
Examples of the aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms include oxalic acid (2 carbon atoms), malonic acid (3 carbon atoms), succinic acid (4 carbon atoms), glutaric acid (5 carbon atoms), Examples include adipic acid (carbon number 6), pimelic acid (carbon number 7), suberic acid (carbon number 8), and among these, succinic acid is preferred from the viewpoint of gloss, storage stability and durability.
The number of carbon atoms of the aliphatic saturated dicarboxylic acid compound is 2 or more from the viewpoint of productivity, preferably 3 or more, more preferably 4 or more, and 8 or less, preferably 6 from the viewpoint of gloss, storage stability and durability. Hereinafter, it is more preferably 4.

The carboxylic acid component (A-ac) may contain a carboxylic acid component other than the isophthalic acid compound and the aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms.
Other carboxylic acid components that can be contained in the carboxylic acid component (A-ac) include dicarboxylic acid compounds other than isophthalic acid compounds and aliphatic saturated dicarboxylic acid compounds having 2 to 8 carbon atoms, and trivalent or higher polyvalent carboxylic acids. Examples thereof include compounds, anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms.
Examples of the dicarboxylic acid compound include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds, and alicyclic dicarboxylic acid compounds other than isophthalic acid compounds and aliphatic saturated dicarboxylic acid compounds having 2 to 8 carbon atoms.
Examples of the aromatic dicarboxylic acid compound include phthalic acid and terephthalic acid.
Examples of the aliphatic dicarboxylic acid compound other than the aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms include maleic acid (4 carbon atoms), fumaric acid (4 carbon atoms), citraconic acid (5 carbon atoms), and itacon. Acid (5 carbon atoms), glutaconic acid (5 carbon atoms), azelaic acid (9 carbon atoms), sebacic acid (10 carbon atoms), undecanedioic acid (11 carbon atoms), dodecanedioic acid (12 carbon atoms), tridecane Diacid (carbon number 13), tetradecanedioic acid (carbon number 14), pentadecanedioic acid (carbon number 15), hexadecanedioic acid (carbon number 16), heptadecanedioic acid (carbon number 17), octadecanedioic acid (carbon number) 18), nonadecanedioic acid (carbon number 19), eicosanedioic acid (carbon number 20), docosanedioic acid (carbon number 22), and the like.
Examples of the trivalent or higher polyvalent carboxylic acid compound include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like.
These carboxylic acid components (A-ac) can be used alone or in combination of two or more.

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (A-ac) to the alcohol component (A-al) is preferably 0.7 or more, more preferably 0, from the viewpoint of gloss, storage stability and durability. 0.8 or more, more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1.1 or less.

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

<Styrene resin component (A2)>
The styrene resin component (A2) is a segment made of a styrene resin.
The content of the styrene resin component (A2) in the amorphous composite resin (A) is the gross amount, the shelf life and the durability in the total amount of the polycondensation resin component (A1) and the styrene resin component (A2). From the viewpoint of safety, preferably 5% by mass or more, from the viewpoint of gloss and durability, more preferably 10% by mass or more, still more preferably 15% by mass or more, and from the viewpoint of gloss, storage stability and durability. The amount is preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.
In the calculation of the content of the styrene resin component (A2), the mass of the polycondensation resin component (A1) is calculated from the total amount of raw material monomers of the polycondensation resin component (A1), and the amount of dehydration during the condensation reaction. In addition, the mass of the styrene resin component (A2) is the total amount of the raw material monomer and the polymerization initiator of the styrene resin component (A2). Moreover, the amphoteric monomer used if necessary is calculated as the mass of the polycondensation resin component (A1).

  Examples of styrenic resins include polystyrene, styrene derivative polymers, styrene-acrylic copolymers, and the like, from the viewpoint of gloss, storage stability and durability, polystyrene, styrene derivative polymers, and styrene-acrylic copolymers. One or more selected from the group consisting of polystyrene and styrene-acrylic copolymer is more preferable, and a styrene-acrylic copolymer is more preferable.

The raw material monomer for the styrene resin component (A2) is preferably at least one selected from styrene and styrene derivatives from the viewpoints of gloss, storage stability and durability, and among these, from the viewpoint of the raw material price of the monomer and storage stability Is more preferably styrene.
The styrene derivative is preferably at least one selected from methyl styrene, α-methyl styrene, β-methyl styrene, t-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid and salts thereof.
In the present specification, one or more selected from styrene and styrene derivatives are referred to as “styrene compound”.

  In the raw material monomer of the styrene-based resin component (A2), the content of the styrene compound is preferably 50% by mass or more, more preferably 60% by mass or more, and still more preferably 70% by mass from the viewpoints of gloss, storage stability and durability. % Or more, more preferably 75% by mass or more, and from the same viewpoint, it is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.

As raw material monomers for the styrene resin component (A2) used in addition to the styrene compound, alkyl (meth) acrylates; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride Vinyl esters such as vinyl acetate and vinyl propionate; ethylenic monocarboxylic acid esters such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N-vinyl Examples include N-vinyl compounds such as pyrrolidone.
“Alkyl (meth) acrylate” means both alkyl acrylate and alkyl methacrylate. The same applies to the following.

Among the raw material monomers of the styrene resin component (A2) used in addition to these styrene compounds, alkyl (meth) acrylates are preferable from the viewpoints of gloss, storage stability and durability.
From the above viewpoint, the carbon number of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, and preferably 22 or less, more preferably 18 or less, More preferably, it is 12 or less. In addition, carbon number of this alkyl ester means carbon number derived from the alcohol component which comprises ester.
Specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and (iso or tertiary) butyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like.
Here, “(iso or tertiary)” and “(iso)” mean that both of these groups are present and not present, and these groups are not present. Indicates normal. In addition, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

  In the raw material monomer of the styrene resin component (A2), the content of the alkyl (meth) acrylate is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably, from the viewpoint of gloss, storage stability and durability. From the same viewpoint, it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and still more preferably 25% by mass or less.

  The mass ratio of alkyl (meth) acrylate to styrene compound (alkyl (meth) acrylate / styrene compound) in the raw material monomer of the styrene-based resin component (A2) is preferably 0 from the viewpoint of gloss, storage stability and durability. / 100 or more, more preferably 10/90 or more, and preferably 80/20 or less, more preferably 50/50 or less, still more preferably 40/60 or less, and even more preferably 30/70 or less.

  These raw material monomers for the styrenic resin component (A2) may be used alone or in combination of two or more.

<Amotropic monomer>
It is preferable that the amorphous composite resin (A) further contains a structural unit derived from the both reactive monomers.
When an amphoteric monomer is used as the raw material monomer of the amorphous composite resin (A), the amphoteric monomer reacts with both the polycondensation resin component (A1) and the styrene resin component (A2). The amorphous composite resin (A) can be produced satisfactorily.
Thereby, the polycondensation resin component (A) is bonded to the polycondensation resin component (A1) and the styrene resin component (A2) via the structural unit derived from the both reactive monomers, and the polycondensation resin component (A1) and the styrene resin component (A2) are uniformly dispersed, and the gloss, storage stability and durability are good.

As the both reactive monomers, one or more functional groups selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group, preferably a hydroxyl group and / or a carboxy group, in the molecule Preferably, it is a compound having a carboxy group and an ethylenically unsaturated bond. By using such a bireactive monomer, gloss, storage stability and durability can be further improved.
The both reactive monomers are preferably at least one selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride from the viewpoints of gloss, storage stability and durability, from acrylic acid, methacrylic acid and fumaric acid. One or more selected are more preferable, and one or more selected from acrylic acid and methacrylic acid are more preferable from the viewpoint of gloss and durability.
However, when used together with a polymerization inhibitor, a carboxylic acid compound having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer for the polycondensation resin component (A1). In this case, fumaric acid or the like is not a bireactive monomer but a raw material monomer for the polycondensation resin component (A1).

  From the viewpoint of gloss, storage stability and durability, the use amount of the both reactive monomers is preferably 1 mol part with respect to 100 mol parts in total of the alcohol component (A-al) of the polycondensation resin component (A1). Or more, more preferably 2 mol parts or more, still more preferably 4 mol parts or more, and from the same viewpoint, preferably 30 mol parts or less, more preferably 20 mol parts or less, still more preferably 15 mol parts or less, More preferably, it is 10 mol part or less, More preferably, it is 8 mol part or less.

<Method for Producing Amorphous Composite Resin (A)>
The amorphous composite resin (A) can be produced, for example, by any of the following methods (1) to (3). In addition, it is preferable that both reactive monomers are supplied to a reaction system with the raw material monomer of a styrene resin component (A2) from a reactive viewpoint. From the same viewpoint, a catalyst such as an esterification catalyst or an esterification cocatalyst may be used, and a polymerization initiator and a polymerization inhibitor may be further used.

(1) After the step (X) of the polycondensation reaction with the alcohol component (A-al) and the carboxylic acid component (A-ac), the raw material monomer of the styrene resin component (A2) and, if necessary, the bireactive monomer A method of performing the step (Y) of the addition polymerization reaction by the method.
In the step (X), a part of the carboxylic acid component (A-ac) is subjected to a polycondensation reaction, and then the step (Y) is performed. Then, the reaction temperature is increased again, and the carboxylic acid component (A-ac) More preferred is a method in which the remainder of) is added to the polymerization system to further proceed with the polycondensation reaction in step (X) and, if necessary, the reaction with both reactive monomers.

(2) Step (X) of the polycondensation reaction with the raw material monomer of the polycondensation resin component (A1) after the step (Y) of the addition polymerization reaction with the raw material monomer of the styrene resin component (A2) and the both reactive monomers How to do.
The alcohol component (A-al) and the carboxylic acid component (A-ac) are present in the reaction system during the addition polymerization reaction, and are esterified at a temperature suitable for the polycondensation reaction and, if necessary, an ester. The polycondensation reaction can be started by adding a co-catalyst, and the alcohol component (A-al) and the carboxylic acid component (A-ac) are later introduced into the reaction system under temperature conditions suitable for the polycondensation reaction. ) Can be added to start the polycondensation reaction. In the former case, the molecular weight and molecular weight distribution can be adjusted by adding an esterification catalyst and, if necessary, an esterification co-catalyst at a temperature suitable for the polycondensation reaction.

(3) Step (X) of the polycondensation reaction with the alcohol component (A-al) and the carboxylic acid component (A-ac) and the addition polymerization reaction with the raw material monomer and the both reactive monomers of the styrene resin component (A2) A method in which the reaction is carried out under conditions in which the step (Y) proceeds in parallel.
In this method, the step (X) and the step (Y) are performed under a reaction temperature condition suitable for the addition polymerization reaction, the reaction temperature is increased, and under a temperature condition suitable for the polycondensation reaction, if necessary, It is preferable to add a trivalent or higher valent raw material monomer of the polycondensation resin component (A1) to the polymerization system as a cross-linking agent, and further perform a polycondensation reaction in the step (X). At that time, under a temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor can be added to advance only the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.

The amorphous composite resin (A) is preferably produced by the method according to (1) among the methods (1) to (3) above, and more preferably produced by the method having the following steps I to III. preferable.
Step I: Step of polycondensing a part of the raw material monomer of the polycondensation resin component (A1) Step II: Add the raw material monomer of the styrene resin component (A2) in the presence of the polycondensate obtained in Step I Step of polymerizing Step III: Step of polycondensing the remaining raw material monomer of the polycondensation resin component (A1) in the presence of the reaction product obtained in Step II. From the viewpoint of durability, it is preferably used together with the raw material monomer of the styrene resin component (A2).
By performing the above steps I to III, the polycondensation resin component (A1) and the styrene resin component (A2) in the amorphous composite resin (A) are appropriately dispersed, and the polycondensation resin component ( The dispersibility of A1) is increased, and gloss, storage stability and durability can be improved.

(Process I)
Step I is a step of polycondensing a part of the raw material monomer of the polycondensation resin component (A1).
In the raw material monomer to be used in Step I, the amount of the carboxylic acid component (A-ac) is preferably 40% by mass or more based on the total amount of the carboxylic acid component (A-ac) used in the production of the amorphous composite resin (A). More preferably, it is 60 mass% or more, More preferably, it is 80 mass% or more, Preferably it is 97 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 93 mass% or less.
Moreover, in the raw material monomer to be used in Step I, the amount of the alcohol component (A-al) is preferably equal to or greater than the number of moles of the carboxylic acid component (A-ac), for the production of the amorphous composite resin (A). The total amount of the alcohol component (A-al) to be used is more preferable because the unreacted alcohol component (A-al) serves as a solvent when performing Step II.
The temperature of the polycondensation reaction in Step I is preferably 160 ° C. or higher, more preferably 200 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower, from the viewpoint of reactivity. The pressure during the polycondensation reaction may be a normal pressure.
The completion of the polycondensation reaction in Step I is preferably performed when the raw material monomer subjected to Step I reacts preferably at 95 mol% or more, more preferably 98 mol% or more.

(Step II)
Step II is a step of subjecting the raw material monomer of the styrene resin component (A2) to addition polymerization in the presence of the polycondensate obtained in Step I.
From the viewpoint of reactivity, the temperature of the addition polymerization reaction in Step II is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and preferably 200 ° C. or lower, more preferably 180 ° C. or lower.
In addition, the raw material monomer of the styrene resin component (A2) to be subjected to the addition polymerization reaction in Step II may be added to the reaction system in Step I in advance, and in that case, a polymerization initiator may be added in Step II.
At the end of the reaction in Step II, the residual raw material monomer of the styrene-based resin component (A2) is preferably 1000 ppm (wt / wt) or less with respect to the resin obtained in Step 2.

(Step III)
Step III is a step of polycondensing the remaining raw material monomers of the polycondensation resin component (A1) in the presence of the reaction product obtained in Step II.
The temperature of the polycondensation reaction in Step III is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C., from the viewpoint of reactivity. It is below ℃. The pressure during the polycondensation reaction in Step III may be a normal pressure.

  After Step III, it is preferable to perform Step IV in which a polycondensation reaction is further performed under reduced pressure from the viewpoint of causing the polycondensation reaction to proceed and reducing the acid value of the amorphous composite resin (A) to a preferred range.

(Process IV)
The temperature of the polycondensation reaction in Step IV is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. or lower.
Here, the reduced pressure is a pressure less than normal pressure (101.3 kPa), preferably 80 kPa or less, more preferably 50 kPa or less, and still more preferably 20 kPa or less.
It is preferable to perform the process IV until the produced | generated amorphous composite resin (A) becomes the said preferable acid value. Step IV is preferably performed in the presence of the esterification catalyst.

  It is preferable to perform process I-III or process I-IV in the same container.

(Esterification catalyst)
Examples of the esterification catalyst suitably used for the polycondensation reaction include a titanium compound and a tin (II) compound having no Sn—C bond, and these may be used alone or in combination of two or more. it can.
As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group, an alkenyloxy group or an acyloxy group having 1 to 28 carbon atoms in total is more preferable.
Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred is a tin (II) compound having a Sn-O bond, and among them, di (2-ethylhexanoic acid) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous composite resin (A). ) Tin (II) is more preferred.
The amount of the esterification catalyst used is the total amount of the alcohol component (A-al) and the carboxylic acid component (A-ac) from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous composite resin (A). Preferably, it is 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, further preferably 0.3 parts by mass or more, and preferably 2.0 parts by mass or less, more preferably 100 parts by mass or more. Preferably it is 1.5 mass parts or less, More preferably, it is 1.0 mass part or less.

(Esterification promoter)
As the esterification cocatalyst, a pyrogallol compound is preferred. This pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with hydroxyl groups, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ′ Benzophenone derivatives such as 3,3,4-tetrahydroxybenzophenone, catechin derivatives such as epigallocatechin and epigallocatechin gallate, and the like, and gallic acid is preferred from the viewpoint of reactivity.
The amount of esterification cocatalyst used is a total amount of alcohol component (A-al) and carboxylic acid component (A-ac) of 100 from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of amorphous composite resin (A). Preferably it is 0.001 mass part or more with respect to a mass part, More preferably, it is 0.01 mass part or more, More preferably, it is 0.03 mass part or more, Preferably it is 0.2 mass part or less, More preferably Is 0.15 parts by mass or less, more preferably 0.1 parts by mass or less.
From the viewpoint of reactivity, the mass ratio of the esterification cocatalyst to the esterification catalyst [esterification cocatalyst / esterification catalyst] is preferably 0.001 or more, more preferably 0.01 or more, and still more preferably 0.00. It is 05 or more, and preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.15 or less.
(Polymerization inhibitor)
Examples of the polymerization inhibitor include 4-t-butylcatechol.

(Softening point)
The softening point of the amorphous composite resin (A) is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of gloss, storage stability and durability, and preferably 140 ° C. or lower, more preferably 130 ° C. or lower, and further preferably 120 ° C. or lower.
(Glass-transition temperature)
The glass transition temperature of the amorphous composite resin (A) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher from the viewpoint of storage stability and durability, and preferably from the viewpoint of gloss and durability. 65 ° C. or lower, more preferably 60 ° C. or lower.
(Acid value)
From the viewpoint of gloss and durability, the acid value of the amorphous composite resin (A) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably 17 mgKOH / g or more. From the viewpoint of durability, it is preferably 60 mgKOH / g or less, more preferably 40 mgKOH / g or less, still more preferably 27 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous composite resin (A) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, the reaction temperature, the reaction time, and the cooling rate. A softening point, a glass transition temperature, and an acid value are calculated | required by the method as described in an Example.

[Crystalline resin (C)]
The toner of the present invention preferably further contains a crystalline resin (C).
By using the crystalline resin (C), since the viscosity at the time of melting at the time of fixing tends to be lower than the melting point, the toner of the present invention is more excellent in gloss of printed matter.
Further, the toner of the present invention can be made more excellent in storage stability under high temperature and high humidity by using the crystalline resin (C). This is because the amorphous composite resin (A) contains 60 mol% or more and 100 mol% or less of an alkylene oxide adduct of bisphenol A as an alcohol component (A-al) in addition to low melt viscosity, Since the styrenic resin component (A2) is included, these highly hydrophobic portions can improve the dispersibility of the crystalline resin (C), and the crystalline resin (C) is applied to the toner surface. It is thought that it is possible to suppress exposure.

The crystalline resin (C) is selected from a crystalline polyester resin (CP) and a crystalline composite resin (CH) containing a polycondensation resin component (CH-1) and a styrene resin component (CH-2). One or more resins. Among these, crystalline polyester resin (CP) is preferable from the viewpoint of gloss, storage stability and durability.
In the present invention, the crystalline resin (C) is a resin having a crystallinity index of 0.6 or more and 1.4 or less, preferably 0.7 or more and 1.2 or less, more preferably 0.9 or more. 1.2 or less.

  The crystalline polyester resin (CP) combines an alcohol component (hereinafter also referred to as “alcohol component (C-al)”) and a carboxylic acid component (hereinafter also referred to as “carboxylic acid component (C-ac)”). Obtained by condensation.

(Alcohol component (C-al))
The alcohol component (C-al) is preferably an aliphatic diol from the viewpoint of gloss, storage stability and durability.
The carbon number of the aliphatic diol is preferably 2 or more, more preferably 4 or more, from the viewpoint of gloss, storage stability and durability, and from the same viewpoint, preferably 12 or less, more preferably 8 or less, More preferably, it is 6 or less, More preferably, it is 4 or less.
As the aliphatic diol having 2 to 12 carbon atoms, α, ω-aliphatic diols are preferable from the viewpoint of improving crystallinity and improving low-temperature fixability. For example, ethylene glycol, 1,3-propanediol, 1 , 4-butanediol, 1,4-butenediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc. It is done. Among these, ethylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable from the viewpoints of gloss, storage stability and durability.
The content of the aliphatic diol in the alcohol component (C-al), preferably an aliphatic diol having 2 to 12 carbon atoms, more preferably 2 to 4 carbon atoms is in terms of gloss, storage stability and durability. Therefore, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less, more preferably 100% by mass.

The alcohol component (C-al) may contain an alcohol component other than the aliphatic diol.
Other alcohol components other than the aliphatic diol that can be contained in the alcohol component (C-al) include aromatic diols, alicyclic diols, trivalent or higher polyhydric alcohols, or alkylene having 2 to 4 carbon atoms thereof. Examples include oxides (average added mole number of 1 to 16) and adducts.
Specific examples of other alcohols that can be contained in the alcohol component (C-al) include aromatic diols such as bisphenol A or their alkylene oxide (average addition mole number 1 to 16) addition products, hydrogenated bisphenol A, etc. Tricyclic or higher polyhydric alcohols such as alicyclic diols or alkylene oxides having 2 to 4 carbon atoms (average added mole number of 2 to 12), glycerin, pentaerythritol, trimethylolpropane, sorbitol, or the like And an adduct of an alkylene oxide having 2 to 4 carbon atoms (average added mole number of 1 to 16).

(Carboxylic acid component (C-ac))
Examples of the carboxylic acid component (C-ac) include dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, and alkyl esters having 1 to 3 carbon atoms. Among these, From the viewpoint of gloss, storage stability and durability, an aliphatic dicarboxylic acid compound is preferred.
The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 14 or more from the viewpoint of gloss, storage stability and durability, and from the same viewpoint, preferably 20 or less, more preferably 18 or less, still more preferably 16 Hereinafter, it is more preferably 14.
In addition, the carbon number of the aliphatic dicarboxylic acid compound includes the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.
The aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms is preferably an α, ω-linear aliphatic dicarboxylic acid compound from the viewpoint of enhancing crystallinity and improving low-temperature fixability. For example, tetradecanedioic acid (carbon 14), pentadecanedioic acid (15 carbon atoms), hexadecanedioic acid (16 carbon atoms), heptadecanedioic acid (17 carbon atoms), octadecanedioic acid (18 carbon atoms), nonadecanedioic acid (19 carbon atoms), eicosane Examples thereof include diacids (20 carbon atoms) or alkyl esters having 1 to 3 carbon atoms. Among these, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and more preferably tetradecanedioic acid are preferred from the viewpoints of gloss, storage stability and durability.
The content of the aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms in the carboxylic acid component (C-ac) is preferably 80 mol% or more, and more preferably 90 mol%, from the viewpoint of gloss, storage stability and durability. It is at least mol%, more preferably at least 95 mol%, and preferably at most 100 mol%, more preferably at least 100 mol%.

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

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (C-ac) to the alcohol component (C-al) is preferably 0.7 or more, more preferably 0, from the viewpoints of gloss, storage stability and durability. 0.8 or more, more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1.1 or less.

  From the viewpoint of adjusting the physical properties, the alcohol component (C-al) may appropriately contain a monovalent alcohol, and the carboxylic acid component (C-ac) appropriately contains a monovalent carboxylic acid compound. It may be.

  From the viewpoint of reactivity, the temperature of the polycondensation reaction is preferably 120 ° C. or higher, more preferably 160 ° C. or higher, still more preferably 180 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower. is there.

Examples of the esterification catalyst include those similar to the esterification catalyst used for the synthesis of the amorphous composite resin (A), and preferred embodiments thereof are also the same.
The amount of the esterification catalyst used is a total amount of alcohol component (C-al) and carboxylic acid component (C-ac) of 100 from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the crystalline polyester resin (CP). The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably 0.1 parts by mass or more. Is 1.0 part by mass or less, more preferably 0.5 part by mass or less.

(Softening point)
The softening point of the crystalline polyester resin (CP) is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, more preferably 75 ° C. or higher, from the viewpoint of gloss, storage stability and durability, and the same viewpoint. Therefore, it is preferably 120 ° C. or lower, more preferably 100 ° C. or lower, and still more preferably 90 ° C. or lower.
(Melting point)
The melting point of the crystalline polyester resin (CP) is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, further preferably 70 ° C. or higher, from the viewpoint of gloss, storage stability and durability, and from the same viewpoint. Preferably, it is 110 degrees C or less, More preferably, it is 90 degrees C or less, More preferably, it is 80 degrees C or less.
(Acid value)
The acid value of the crystalline polyester resin (CP) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g or more, from the viewpoint of gloss, storage stability and durability. From the same viewpoint, it is preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less.
(Hydroxyl value)
The hydroxyl value of the crystalline polyester resin (CP) is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more from the viewpoint of gloss, storage stability and durability, and from the same viewpoint, preferably 30 mgKOH. / G or less, more preferably 20 mgKOH / g or less, still more preferably 10 mgKOH / g or less.
The softening point, melting point, acid value, and hydroxyl value of the crystalline polyester resin (CP) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, reaction temperature, reaction time, and cooling rate. The softening point, melting point, acid value, and hydroxyl value are determined by the methods described in the examples.

In the production method of the present invention, in addition to the amorphous composite resin (A) and the crystalline resin (C), known resins used for the toner, for example, the amorphous composite resin (A) and the crystalline resin (C ), Polyester, styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like.
In the toner of the present invention, the total content of the amorphous composite resin (A) and the crystalline resin (C) is preferably 80% by mass or more, more preferably 90%, from the viewpoint of gloss, storage stability and durability. It is at least mass%, more preferably at least 95 mass%, and preferably at most 100 mass%, more preferably at least 100 mass%.

  In the toner of the present invention, the mass ratio of the amorphous composite resin (A) to the crystalline resin (C) (crystalline resin (C) / amorphous composite resin (A)) is preferable from the viewpoint of gloss. Is 2/98 or more, more preferably 5/95 or more, still more preferably 8/92 or more, and from the viewpoint of storage stability and durability, preferably 40/60 or less, more preferably 30/70 or less, More preferably, it is 20/80 or less.

[Release agent]
As the release agent used in the toner of the present invention, polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla Plant waxes such as wax, tree wax, jojoba oil; animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, Fischer-Tropsch wax, etc. It can use individually or in mixture of 2 or more types. Among these, paraffin wax is preferable from the viewpoint of gloss, storage stability and durability.
The amount of the release agent used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 2 parts by mass with respect to the total amount of the binder resin, from the viewpoint of resin dispersibility. The amount is 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.
Next, a method for producing the toner of the present invention will be described.

[Toner Production Method]
The toner of the present invention is preferably produced by a production method including the following steps 1 to 4.
Step 1: Amorphous composite resin (A), an organic solvent, and a neutralizing agent are mixed to obtain a mixture. Step 2: At least water is mixed into the mixture obtained in Step 1, to obtain an amorphous composite. Step of obtaining dispersion of resin (A) Step 3: An aqueous dispersion of resin particles (X) containing amorphous composite resin (A) by removing the organic solvent from the dispersion obtained in Step 2 Step 4: Step of agglomerating and fusing the resin particles (X) containing the amorphous composite resin (A) obtained in Step 3 in an aqueous medium. However, it is preferable to prepare a release agent dispersion and agglomerate and fuse together with the resin particles (X) in Step 4.

<Step 1>
Step 1 is a step of obtaining a mixture by mixing the amorphous composite resin (A), the organic solvent, and the neutralizing agent.

<Organic solvent>
As an organic solvent, from the viewpoint of solubility, alcohol solvents such as isopropanol and isobutanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether and dioxane; ethyl acetate and isopropyl acetate An acetic acid ester solvent such as Among these, from the viewpoint of gloss, storage stability and durability, a ketone solvent is more preferable, and methyl ethyl ketone is more preferable.
The mass ratio [organic solvent / amorphous composite resin (A)] between the organic solvent and the amorphous composite resin (A) in step 1 is preferably 0.3 from the viewpoint of gloss, storage stability and durability. Above, more preferably 0.5 or more, still more preferably 0.7 or more, and preferably 2.0 or less, more preferably 1.5 or less, still more preferably 1.3 or less.

<Neutralizing agent>
Examples of the neutralizing agent used in Step 1 include metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; organic bases such as trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. Can be mentioned. Among these, metal hydroxide and ammonia are preferable, metal hydroxide is more preferable, alkali metal hydroxide is more preferable, one or more selected from sodium hydroxide and potassium hydroxide is still more preferable, Sodium oxide is even more preferred.
The degree of neutralization of the amorphous composite resin (A) with the neutralizing agent is adjusted by adjusting the volume-median particle size (D ₅₀ ) of the resin particles (X) obtained in the step 3, and the gloss, storage stability and durability are adjusted. From the viewpoint, it is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and from the same viewpoint, preferably 150 mol% or less, more preferably 120 mol% or less, More preferably, it is 100 mol% or less, More preferably, it is 80 mol% or less.
In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = {[mass of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (mgKOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

<Surfactant>
In Step 1, a surfactant is preferably used from the viewpoint of gloss, storage stability and durability of the toner obtained.
Surfactants include nonionic surfactants, anionic surfactants and cationic surfactants. Among these, nonionic surfactants and / or anionic surfactants are preferable from the viewpoint of emulsion stability of the resin, and anionic surfactants are more preferable.
Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Examples include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers. Among these, from the viewpoint of emulsion stability of the resin, polyoxyethylene alkyl ethers Is preferred.
Examples of the anionic surfactant include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, and alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate. From the viewpoint of emulsion stability, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, and alkyl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
Among these, from the viewpoint of emulsion stability of the binder resin, polyoxyethylene alkyl ethers and alkyl ether sulfates are preferable, and polyoxyethylene alkyl ether sulfates are more preferable. The polyoxyethylene alkyl ether sulfate is preferably a sodium salt from the same viewpoint.

The polyoxyethylene alkyl ether sulfate preferably contains polyoxyethylene alkyl ether sulfate (EO2) having an addition mole number of ethylene oxide of 2 mol.
In the anionic surfactant, the content of polyoxyethylene alkyl ether sulfate is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably 90% from the viewpoint of gloss, storage stability and durability. More preferably, it is 95 mass% or more, More preferably, it is 100 mass% or less, More preferably, it is 100 mass%.

The amount of the surfactant used is preferably 1 part by mass or more, more preferably 2 parts by mass as a solid content from the viewpoint of gloss, storage stability and durability with respect to 100 parts by mass of the amorphous composite resin (A). 5 parts by mass or more, more preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, and even more preferably 5.5 parts by mass or less. More preferably, it is 5 parts by mass or less.
The addition amount of the surfactant in the step 1 is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more, in the total addition amount of the surfactants in the steps 1 to 4. And preferably 100% by mass or less, more preferably 100% by mass.

<Optional component>
In this step, optional components such as a colorant, a charge control agent, a surfactant, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent may be added.
These additives may be mixed with the binder resin in advance, and in that case, it is preferable to melt-knead the binder resin and the additive.
For melt kneading, it is preferable to use an open roll type biaxial kneader. An open roll type biaxial kneader is a kneader in which two rolls are arranged close to each other in parallel, and a heating function or a cooling function can be imparted by passing a heat medium through each roll. Therefore, the open roll type biaxial kneader is an open type part to be melt kneaded, and is provided with a heating roll and a cooling roll. The kneading heat can be easily dissipated.

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, thioy Zico type, phthalocyanine type, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
The amount of the colorant used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably from the viewpoint of improving the image density of the toner with respect to 100 parts by mass of the total amount of the binder resin. Is 1.0 part by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 10 parts by mass or less.

(Charge control agent)
Examples of the charge control agent include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. You may use these individually or in combination of 2 or more types.
The amount of the charge control agent used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably from 100 parts by mass of the total amount of the binder resin, from the viewpoint of charging stability of the toner. Is 0.5 parts by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, and still more preferably 1.5 parts by mass or less.

<Process 2>
Step 2 is a step of obtaining a dispersion of the amorphous composite resin (A) by mixing at least water with the mixture obtained in Step 1.
In this step, by adding an aqueous medium to the mixture, first, a W / O phase is formed, and then the phase is inverted to the O / W phase. Whether or not phase inversion has occurred can be confirmed, for example, by visual observation or electrical conductivity.
The phase inversion step can be adjusted by the addition rate and amount of the aqueous medium as described later.

As the aqueous medium, those mainly containing water are preferable. The water content is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably from the viewpoint of improving the emulsion stability of the resin in the aqueous medium. It is 100 mass% or less, More preferably, it is 100 mass%. The water is preferably deionized water or distilled water.
Examples of components other than water include organic solvents that dissolve in water, such as methanol, ethanol, acetone; and cyclic ethers such as tetrahydrofuran.

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

  The addition rate of the aqueous medium is preferably 0.1 parts by weight / min with respect to 100 parts by weight of the amorphous composite resin (A) from the viewpoint of obtaining resin particles having a small particle size until the phase inversion is completed. More preferably, it is 1 part by mass / min or more, more preferably 3 parts by mass / min or more, still more preferably 4 parts by mass / min or more, and preferably 50 parts by mass / min or less, more preferably 30 parts by mass. It is not more than part by mass / min, more preferably not more than 20 parts by mass / min, still more preferably not more than 10 parts by mass / min. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

  The amount of the aqueous medium used is preferably 100 parts by mass or more, more preferably 200 parts by mass or more with respect to 100 parts by mass of the amorphous composite resin (A) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. More preferably, it is 400 parts by mass or more, more preferably 600 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, still more preferably 1000 parts by mass or less, and still more preferably 800 parts by mass. It is below mass parts.

<Step 3>
Step 3 is a step of obtaining an aqueous dispersion of resin particles (X) containing the amorphous composite resin (A) by removing the organic solvent from the dispersion obtained in Step 2.
The method for removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, it is preferably distilled. Further, the organic solvent may not be completely removed and 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 still more preferably 0% in the aqueous dispersion.
When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (X), it is more preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used under reduced pressure and to distill it off. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased. From the viewpoint of maintaining the dispersion stability of the resin particles (X), it is preferable to distill off at a constant temperature and pressure.
Further, after step 3, a step of mixing a surfactant with the obtained aqueous dispersion may be performed.

  The solid content concentration of the aqueous dispersion obtained in this step is preferably 3% by mass or more, more preferably 10% by mass or more, by appropriately adding water from the viewpoints of the stability and ease of handling of the aqueous dispersion. More preferably, it is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The volume median particle size (D ₅₀ ) of the resin particles (X) obtained in this step is preferably 30 nm or more, more preferably 50 nm or more, still more preferably 70 nm or more, from the viewpoints of gloss, storage stability and durability. Yes, and preferably 250 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, and still more preferably 130 nm or less.
In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.

<Step 4>
Step 4 is a step of aggregating and fusing the resin particles (X) containing the amorphous composite resin (A) obtained in Step 3 in an aqueous medium.
In Step 4, from the viewpoint of gloss, storage stability and durability, resin particles (X) containing the amorphous composite resin (A) obtained in Step 3 and resin particles containing a crystalline resin (C) (Y) is preferably aggregated and fused in an aqueous medium.

The resin particles (Y) are preferably obtained as an aqueous dispersion of resin particles (Y). By using a crystalline resin (C) as a binder resin, the resin particles (Y) are the same as the aqueous dispersion of the resin particles (X). It can be manufactured by a method.
The volume median particle size (D ₅₀ ) of the resin particles (Y) is preferably 70 nm or more, more preferably 80 nm or more, still more preferably 90 nm or more, and preferably 200 nm or less from the viewpoint of toner productivity. More preferably, it is 140 nm or less, More preferably, it is 110 nm or less.
The solid content concentration of the aqueous dispersion of the resin particles (Y) is preferably 3% by mass or more, more preferably 5% by mass or more, by appropriately adding water from the viewpoint of stability of the dispersion and ease of handling. More preferably, it is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

  In step 4, it is preferable to mix the aqueous dispersion of resin particles (X) and the aqueous dispersion of resin particles (Y) to aggregate the resin particles (X) and the resin particles (Y). In Step 4, it is preferable to add a flocculant in order to efficiently perform the aggregation.

As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoints of toner particle size distribution and storage stability, inorganic flocculants are preferable, and inorganic metal salts are particularly preferable.
Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride. The valence of the central metal of the inorganic metal salt is preferably divalent or higher from the viewpoint of the particle size distribution and storage stability of the toner.
When adding a flocculant, the addition amount is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the resin particles (X) and the resin particles (Y). More preferably, it is 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.

In the aggregation step, the solid content concentration in the system is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably, in order to cause uniform aggregation. It is 40 mass% or less, More preferably, it is 30 mass% or less.
In the coagulation step, from the viewpoint of uniformly dispersing the coagulant and causing uniform coagulation, the temperature during addition of the coagulant is preferably 10 ° C or higher, more preferably 15 ° C or higher, and further preferably 18 ° C or higher. Yes, and preferably 40 ° C. or lower, more preferably 35 ° C. or lower, still more preferably 30 ° C. or lower.
The holding temperature after adding the flocculant is preferably 40 ° C or higher, more preferably 45 ° C or higher, still more preferably 47 ° C or higher, and preferably 65 ° C or lower, more preferably 60 ° C or lower, still more preferably. Is 55 ° C. or lower.

In this step, the additives may be aggregated after adding the colorant, charge control agent, conductivity adjusting agent, reinforcing filler such as fibrous substance, antioxidant, anti-aging agent and the like.
Additives such as a colorant and a charge control agent may be premixed in the binder resin, or a dispersion in which each additive is separately dispersed in a dispersion medium such as water, that is, a colorant containing colorant fine particles. A dispersion liquid and a charge control agent dispersion liquid containing charge control agent fine particles may be prepared and used for the aggregation step.
The volume median particle size (D ₅₀ ) of the colorant fine particles is preferably 50 nm or more, more preferably 100 nm or more, and preferably 200 nm or less, more preferably 150 nm or less.
The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 800 nm or less, more preferably 500 nm or less.
The volume median particle size (D ₅₀ ) of the release agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 1000 nm or less, more preferably 700 nm or less.

Next, the aggregated particles obtained above are fused to obtain fused particles.
The temperature in the system in the fusing process is determined from the viewpoint of the target toner particle size, particle size distribution, shape control and particle fusing property, and from the viewpoint of gloss, storage stability and durability. A) softening point of −55 ° C. or higher is preferable, softening point of −50 ° C. or higher is more preferable, softening point of −45 ° C. or higher is more preferable, softening point + 10 ° C. or lower is preferable, softening point or lower is more preferable, softening A point of −10 ° C. or lower is further preferable, a softening point of −20 ° C. or lower is still more preferable, and a softening point of −30 ° C. or lower is still more preferable.
Specifically, it is preferably 70 ° C or higher, more preferably 75 ° C or higher, and preferably 100 ° C or lower, more preferably 90 ° C or lower.

The electrophotographic toner of the present invention can be suitably obtained by subjecting the fused particles obtained in this step to a solid-liquid separation step such as filtration, a washing step, and a drying step as appropriate.
In the washing step, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. 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.

<Post-processing process>
An external additive may be used in the toner of the present invention in order to improve transferability. As the external additive, inorganic fine particles are preferably used. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide, and zinc oxide. Among these, silica is preferable. As the silica, hydrophobic silica that has been subjected to a hydrophobic treatment is preferable from the viewpoint of transferability of the toner.
Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Among these, hexamethyldisilazane is preferable.

The average particle diameter of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoints of chargeability, fluidity and transferability of the toner. Preferably it is 100 nm or less, More preferably, it is 50 nm or less.
The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.3 parts by mass with respect to 100 parts by mass of the toner before processing with the external additive. And preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3.0 μm or more, more preferably 3.5 μm or more, further preferably 4.0 μm or more, from the viewpoint of gloss, storage stability and durability. Still more preferably, it is 4.5 μm or more, and preferably 9.0 μm or less, more preferably 8.5 μm or less, still more preferably 8.0 μm or less, and still more preferably 7.5 μm or less.

  The electrophotographic toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

  Each property such as resin, resin particles, and toner was measured and evaluated by the following method.

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

[Resin softening point, endothermic maximum peak temperature, melting point and glass transition temperature]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a heating rate of 6 ° C./min, and a load of 1.96 MPa was applied by a plunger. The nozzle was extruded from a nozzle having a length of 1 mm and a length of 1 mm. The amount of plunger drop of the flow tester was plotted against the temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

(2) Maximum endothermic peak temperature and melting point Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), the temperature drop rate is 10 ° C./min from room temperature (20 ° C.). The sample cooled to 0 ° C. was allowed to stand still for 1 minute, and then measured while raising the temperature to 180 ° C. at a temperature rising rate of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the maximum endothermic peak temperature. The maximum peak temperature of the heat of fusion is the melting point.

(3) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed into an aluminum pan, and 200 ° C. The temperature was raised to 0 ° C. from the temperature at a temperature drop rate of 10 ° C./min. Next, the measurement was performed while increasing the temperature to 150 ° C. at a temperature increase rate of 10 ° C./min. The glass transition temperature was defined as the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent indicating the maximum slope from the peak rising portion to the peak apex.

[Volume Median Particle Size of Aggregated Particles (D ₅₀ )]
The volume median particle size of the aggregated particles was measured as follows.
・ Measuring machine: "Coulter Multisizer III" (Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
・ Analysis software: “Multisizer III version 3.51” (manufactured by Beckman Coulter)
・ Electrolyte: “Isoton II” (Beckman Coulter, Inc.)
Dispersion: Polyoxyethylene lauryl ether “Emulgen 109P” (manufactured by Kao Corporation, HLB: 13.6) was dissolved in the electrolytic solution to obtain a dispersion having a concentration of 5% by mass.
Dispersion condition: 10 mg of sample (converted to solid content) is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of electrolyte is added, and further for 1 minute with an ultrasonic disperser. A sample dispersion was prepared by dispersing.
Measurement conditions: The sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured and the particle size distribution thereof. The volume-median particle diameter (D ₅₀ ) and the number% of the particle diameter of 2 μm or less were determined.

[Volume Median Particle Size (D ₅₀ ) of Resin Particles, Colorant Fine Particles, Charge Control Agent Fine Particles, Release Agent Particles]
(1) Measuring apparatus: Laser diffraction type particle size measuring instrument “LA-920” (manufactured by Horiba, Ltd.)
(2) Measurement conditions: Distilled water was added to the measurement cell, and the volume-median particle size (D ₅₀ ) was measured at a concentration at which the absorbance was in an appropriate range.

[Solid content concentration of colorant dispersion, charge control agent dispersion, release agent particle dispersion, aqueous dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory Co., Ltd.), 5 g of the sample was subjected to a drying temperature of 150 ° C. and a measurement mode of 96 (monitoring time 2.5 minutes / variation width 0.05%). The sample was dried and the moisture content (% by mass) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture of the sample (% by mass)

[Gloss of printed matter]
A toner was mounted on a copying machine “AR-505” (trade name, manufactured by Sharp Corporation), and an image was printed without fixing (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). An unfixed image was fixed on the print medium at 170 ° C. and 500 mm / sec using the fixing machine of the copying machine. Note that J paper (trade name, manufactured by Fuji Xerox Co., Ltd.) was used as the print medium. A cardboard was laid under the image, and the glossiness of the printed matter was measured using a gloss meter (trade name: “IG-330”, manufactured by Horiba, Ltd.) under light irradiation conditions at an incident angle of 60 °. The higher the value obtained, the better the gloss.

[Heat resistant storage stability of toner (storage stability under high temperature and high humidity)]
A 25 mL container (diameter: about 3 cm) was charged with 5 g of toner and allowed to stand for 72 hours in an environment at a temperature of 55 ° C. and a humidity of 90%. The degree of occurrence of toner aggregation was visually observed every 12 hours, and heat resistant storage stability was evaluated according to the following evaluation criteria. The longer the time during which no aggregation is observed, the better the heat resistant storage stability.
(Evaluation criteria)
A: Aggregation is not observed even after 72 hours.
B: Aggregation is not observed after 60 hours, but aggregation is observed after 72 hours.
C: Aggregation is not observed after 36 hours, but aggregation is observed after 60 hours.

[Toner durability]
A toner is mounted on a non-magnetic one-component development type printer “OKI Microline 18” (manufactured by Oki Data Co., Ltd.) and obliquely blackened to A4 size paper at a temperature of 30 ° C. and a humidity of 80% with 5.5% A stripe pattern was printed continuously. The photoreceptor was visually observed every 500 sheets printed, and white spots resulting from filming of toner on the photoreceptor were visually observed. In the test, the point in time when the generation of white spots was confirmed was regarded as the number of printing durability. The greater the number of printing durability, the better the toner durability.

[Production of amorphous composite resin]
Synthesis Examples 1 to 4 and 6 to 15
(Production of amorphous composite resins A-1 to A-4, A-6 to A-15)
10 liters equipped with BPA-PO, BPA-EO, isophthalic acid, terephthalic acid, esterification catalyst and esterification co-catalyst shown in Tables 1 and 2 equipped with thermometer, stainless steel stirring bar, flow-down condenser and nitrogen inlet tube The sample was heated to 235 ° C. over 2 hours in a mantle heater in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 235 ° C., cooled to 160 ° C., and a mixed solution of the vinyl-based resin raw material monomer, both reactive monomers and the radical polymerization initiator shown in Tables 1 and 2. Was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., further reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor (4-t-butylcatechol) and the remaining carboxylic acid component were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was carried out at 40 kPa until the softening points shown in Tables 1 and 2 were reached. The physical properties of the resin are shown in Tables 1 and 2. In addition, the reaction rate in this invention means the value of production | generation reaction water amount (mol) / theoretical production | generation water amount (mol) x100.

Synthesis example 5
(Production of amorphous polyester resin A-5)
BPA-PO, isophthalic acid, esterification catalyst and esterification co-catalyst shown in Table 1 were placed in a 10 liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and nitrogen was added. The temperature was raised to 235 ° C. over 2 hours in a mantle heater in the atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Then, it cooled to 190 degreeC, the remaining carboxylic acid component was added, and it heated up to 210 degreeC over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 1 was reached. Table 1 shows the physical properties of the resin.

[Production of crystalline polyester resin]
Synthesis Example 16
(Production of crystalline polyester resin B-1)
Of the raw material components shown in Table 3, the total amount of alcohol components, the total amount of carboxylic acid components, esterification catalyst, a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube In a mantle heater in a nitrogen atmosphere, the temperature was raised from 135 ° C. to 200 ° C. over 8 hours, followed by reaction at 200 ° C. for 2 hours, and it was confirmed that the reaction rate reached 95% or more. Furthermore, it was made to react under reduced pressure of 8 kPa for 2 hours, and crystalline polyester resin B-1 was obtained. The physical properties of the resin are shown in Table 3.

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

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

[Production of release agent particle dispersion]
Preparation Example 3
Paraffin wax “HNP9” (produced by Nippon Seiwa Co., Ltd.) 50 g, cationic surfactant “Sanisol (registered trademark) B50” (produced by Kao Corporation, alkylbenzyldimethylammonium chloride) and ion-exchanged water 200 g at 95 ° C. Disperse the release agent containing release agent particles by heating and dispersing using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher Co., Ltd.) at an output of 350 W for 30 minutes. A liquid was obtained. The volume median particle size (D ₅₀ ) of the paraffin wax (release agent particles) was 550 nm, and the solid content concentration was 22% by mass.

[Production of aqueous dispersion of resin particles]
Production Example 1
(Production of aqueous dispersion a-1)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 100 g of amorphous composite resin A-1, 60 g of methyl ethyl ketone, anionic surfactant “Emar E27C (polyoxyethylene) 16.7 g (4.5% by mass relative to 100 g of resin) ”(made by Kao Corporation)” was added and dissolved at 73 ° C. over 2 hours. To the obtained solution, a 5% by mass aqueous sodium hydroxide solution was added so that the neutralization degree was 70 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
While maintaining at 73 ° C., 675 g of ion-exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. Methyl ethyl ketone was distilled off under reduced pressure while maintaining at 73 ° C. Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min). Thereafter, the solid content concentration of the dispersion was measured, and ion-exchanged water was added so as to be 20% by mass to obtain an aqueous dispersion a-1 in which resin particles were dispersed in an aqueous medium. Table 4 shows the volume median particle size of the resin particles in the obtained aqueous dispersion.

Production Examples 2 to 16
(Production of aqueous dispersions a-2 to a-15 and b-1)
In Production Example 1, aqueous dispersions a-2 to a-15 and b-1 were obtained in the same manner as in Production Example 1, except that the type of resin was changed to the resin shown in Table 4. Table 4 shows the volume median particle size of the resin particles in the obtained aqueous dispersion.

[Manufacture of toner for developing electrostatic image]
Example 1
(Manufacture of toner A)
270 g of aqueous dispersion a-1 of amorphous composite resin A-1, 30 g of aqueous dispersion b-1 of crystalline polyester resin B-1, 8 g of colorant dispersion, 20 g of release agent particle dispersion, charged 2 g of the control agent dispersion and 52 g of deionized water are placed in a 2 L container, and 150 g of a 0.1 mass% calcium chloride aqueous solution at 20 ° C. with stirring of 100 r / min (peripheral speed 31 m / min) with an anchor type stirrer. Was added dropwise over 30 minutes. Then, it heated up to 50 degreeC, stirring and hold | maintained at 50 degreeC. After confirming that the volume median particle size (D ₅₀ ) reached 7 μm, 4.2 g of an anionic surfactant “Emar E27C” (manufactured by Kao Corporation) was diluted with 37 g of deionized water as an aggregation terminator. Diluent was added. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, and washed and dried to obtain toner particles. .

(External addition process)
Hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter 40 nm) 1.0 part by mass, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd.) A 10 L Henschel mixer equipped with ST and A0 stirring blades (number average particle diameter 16 nm) 0.6 parts by mass, titanium oxide “JMT-150IB” (manufactured by Teika Co., Ltd., number average particle diameter 15 nm) Toner A was obtained by stirring at 3000 rpm for 2 minutes. Table 5 shows the evaluation results of the toner.

Examples 2 to 13, 15 and Comparative Examples 1 to 4
(Manufacture of toners B to R)
Toners B to R were obtained in the same manner as in Example 1 except that the aqueous dispersion was changed to the type and ratio of the aqueous dispersion shown in Table 5. The total amount of the aqueous dispersion used for the core was the same as that in Example 1 (300 g). Table 5 shows the evaluation results of the obtained toner.

Example 14
(Manufacture of toner S)
A total of 200 parts by mass of the binder resin in the mass ratio shown in Table 5, 2 parts by mass of negatively chargeable charge control agent “Bontron E-81” (manufactured by Orient Chemical Co., Ltd.), and colorant “Regal 330R” (manufactured by Cabot Corporation) , Carbon black) and 10 parts by weight of release agent “Mitsui High Wax NP055” (manufactured by Mitsui Chemicals, Inc., polypropylene wax, melting point: 125 ° C.) are added and mixed in a Henschel mixer. Using a rotary twin screw extruder, melt kneading was performed at a roll rotation speed of 200 r / min and a heating temperature of 80 ° C. in the roll. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain toner base particles having a volume-median particle size (D ₅₀ ) shown in Table 5. Thereafter, toner S was obtained through the same external addition process as described above. Table 5 shows the evaluation results of the obtained toner.

When Example 1 and Comparative Example 1 are compared, Example 1 in which the content of the isophthalic acid compound is 89 mol% in the carboxylic acid component (A-ac) that is the raw material monomer of the amorphous composite resin (A). However, it turns out that it is excellent in durability and gloss.
When Example 1 and Comparative Example 2 are compared, an aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms is used as the carboxylic acid component (A-ac) which is a raw material monomer of the amorphous composite resin (A). It can be seen that Example 1 was excellent in gloss.
When Example 1 is compared with Example 15, the carboxylic acid component (A-ac), which is a raw material monomer of the amorphous composite resin (A), contains an aliphatic saturated dicarboxylic acid compound having 2 to 8 carbon atoms. It turns out that Example 1 whose quantity is 10.5 mol% is excellent in storage stability and durability.
When Example 1 and Comparative Example 3 are compared, Example 1 using an amorphous composite resin (A) having a polycondensation resin component (A1) and a styrene resin component (A2) is preservable. It turns out that it is excellent in durability and gloss.
Comparing Example 1 and Example 2, the addition of propylene oxide of bisphenol A in the alkylene oxide adduct of bisphenol A used as the alcohol component (A-al) which is the raw material monomer of the amorphous composite resin (A) It turns out that Example 1 whose content of a thing is 100 mol% is excellent in storage stability, durability, and gloss.
Comparing Example 1 and Example 3, an example using an aliphatic saturated dicarboxylic acid compound having 4 carbon atoms in the carboxylic acid component (A-ac) which is a raw material monomer of the amorphous composite resin (A). 1 is excellent in storage stability, durability and gloss.
When Examples 1, 4 and 5 are compared, Example 1 in which the content of the styrene-based resin component (A2) in the amorphous composite resin (A) is 20% by mass is excellent in storage stability, durability, and gloss. You can see that the balance is excellent.
When Example 1 is compared with Example 6, Example 1 in which the raw material monomer of the styrene-based resin component (A2) contains 80% by mass of styrene and 20% by mass of 2-ethylhexyl acrylate is storable and durable. And it is understood that it is excellent in gloss.
When Example 1 is compared with Example 7, it can be seen that Example 1 in which the amorphous composite resin (A) uses acrylic acid as the both reactive monomer is excellent in durability and gloss.
Comparing Examples 1, 8 and 9, 6 mole parts of both reactive monomers were used with respect to a total of 100 mole parts of the alcohol component (A-al) which is a raw material monomer of the polycondensation resin component (A1). It turns out that Example 1 is excellent in storage stability, durability, and gloss.
When Example 1 is compared with Example 10, it can be seen that Example 1 in which the glass transition temperature of the amorphous composite resin (A) is 58 ° C. is excellent in storage stability and durability.
When Example 1 is compared with Example 11, it can be seen that Example 1 in which the acid value of the amorphous composite resin (A) is 22 mgKOH / g is excellent in durability and gloss.
When Examples 1, 12, and 13 are compared, the mass ratio of the crystalline resin (C) to the amorphous composite resin (A) (crystalline resin (C) / amorphous composite resin (A)) is 10 It turns out that Example 1 which is / 90 is excellent in durability and the balance of gloss.

Claims (6)

An alcohol component containing 60 mol% or more and 100 mol% or less of an alkylene oxide adduct of bisphenol A represented by the following general formula (I), an isophthalic acid compound of 80 mol% or more and 95 mol% or less, and a carbon number of 2 or more and 8 A non-condensation resin component (A1) obtained by polycondensation of a carboxylic acid component containing 5 to 20 mol% of the following aliphatic saturated dicarboxylic acid compound and a styrene resin component (A2) An electrophotographic toner containing a crystalline composite resin (A) , a crystalline resin (C) , and a release agent ,
The mass ratio of the amorphous composite resin (A) to the crystalline resin (C) (crystalline resin (C) / amorphous composite resin (A)) is 2/98 or more and 20/80 or less,
An electrophotographic toner in which the acid value of the amorphous composite resin (A) is 27 mgKOH / g or less .

(Wherein R ¹ O and OR ¹ are oxyalkylene groups, x and y represent the average number of added moles of alkylene oxide, each being a positive number, and the sum of x and y is 1 or more and 16 It is the following.)   2. The electrophotography according to claim 1, wherein the content of the propylene oxide adduct of bisphenol A in the alkylene oxide adduct of bisphenol A represented by the general formula (I) is 60 mol% or more and 100 mol% or less. Toner.   In the amorphous composite resin (A), the content of the styrene resin component (A2) is 5% by mass or more and 40% by mass in the total amount of the polycondensation resin component (A1) and the styrene resin component (A2). The toner for electrophotography according to claim 1, wherein the toner is at most%.   The raw material monomer of the styrene resin component (A2) contains a styrene compound and an alkyl (meth) acrylate, and the content of the alkyl (meth) acrylate in the raw material monomer of the styrene resin component (A2) is 5% by mass or more. The toner for electrophotography according to claim 1, wherein the toner is 50% by mass or less.   The amorphous composite resin (A) comprises (a) a raw material monomer of the polycondensation resin component (A1), (b) a raw material monomer of the styrene resin component (A2), and (c) a polycondensation resin component (A1). The toner for electrophotography according to any one of claims 1 to 4, which is a resin obtained by polymerizing a bi-reactive monomer capable of reacting with both the raw material monomer and the raw material monomer of the styrene resin component (A2). .   The toner for electrophotography according to claim 5, wherein the amount of the both reactive monomers used is 1 mol part or more and 30 mol parts or less with respect to 100 mol parts in total of the alcohol components of the polycondensation resin component (A1). .