JP2014235409A - Production method of toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a toner for electrostatic charge image development, by which a toner for electrostatic charge image development can be obtained, the toner achieving both of low-temperature fixability and heat-resistant storage property and exhibiting excellent bending resistance of a printed matter obtained by using the toner.SOLUTION: The production method of a toner for electrostatic charge image development includes a step I of obtaining an aggregate X described below in an aqueous medium and a step II of fusing the aggregate X. The aggregate X comprises: resin particles comprising a crystalline polyester (A) having a polyester moiety obtained by using a monomer having a molar average carbon number of 8 to 12; and resin particles comprising an amorphous composite resin (B) including a polyester segment and an addition polymerization resin segment, in which the addition polymerization resin segment contains a structural component derived from an amphoteric reactive monomer by 3 mass% or more and 15 mass% or less. A mass ratio (crystalline polyester (A)/amorphous composite resin (B)) of the crystalline polyester (A) to the amorphous composite resin (B) ranges from 1/99 to 40/60.

Description

  The present invention relates to a method for producing an electrostatic image developing toner, and an electrostatic image developing toner obtained by the method.

In the field of electrophotography, with the development of an electrophotographic system, development of toner for electrophotography corresponding to higher image quality and higher speed is required.
Corresponding to high image quality, a method of obtaining a toner having a narrow particle size distribution and a small particle size is obtained by aggregating and fusing fine resin particles in an aqueous medium to obtain a toner. A toner is manufactured by an aggregation method or an aggregation fusion method. As the binder resin, a styrene acrylic resin or a polyester resin excellent in low-temperature fixability is used, and in order to satisfy a plurality of performances simultaneously, a combination of a plurality of resins has been studied.

For example, Patent Document 1 discloses a core particle containing a crystalline polyester resin, an amorphous polyester resin, and a colorant for the purpose of widening the fixing latitude and improving heat storage properties and charging properties. A core-shell structure having a shell on the surface, wherein the core particles include a composite resin in which a styrene resin and a polyester resin are bonded, and the shell further includes a copolymer resin of polystyrene and (meth) acryl. An electrostatic charge image developing toner is disclosed.
Patent Document 2 discloses α, ω-alkanediol having 4 to 12 carbon atoms and aliphatic dicarboxylic acid having 8 to 12 carbon atoms for the purpose of improving low-temperature fixability, chargeability under high temperature and high humidity, and heat-resistant storage stability. A graft comprising a crystalline polyester obtained by condensation polymerization with an acid, a core containing a release agent having a melting point of 60 to 90 ° C., a side chain segment made of a polyester resin, and a main chain segment made of an addition polymerization resin A core-shell type electrophotographic toner containing a polymer shell, wherein the mass ratio of the side chain segment to the main chain segment is 95/5 to 55/45, is disclosed.
Patent Document 3 includes a crystalline polyester resin containing a specific structure and a styrene acrylic resin for the purpose of improving low-temperature fixability and storage stability and forming a uniform image. A polyester resin and a hybrid resin component, the content of the crystalline polyester resin and the content of the hybrid resin component satisfy a specific relationship, and include a colorant, a binder resin, a release agent, and a toner. The image forming toner is characterized in that the toner has a number average particle size of 3.5 to 6.5 μm and a peak top molecular weight of 2500 to 4800.

JP 2007-93809 A JP 2013-15771 A JP 2008-116580 A

As the speed of electrophotographic printing increases, it is necessary to fix with less energy at the time of printing. For this reason, the toner to be used is required to have fixability at a low temperature. However, in order to fix the toner at a low temperature, it is necessary to lower the softening point and glass transition temperature of the resin used for the toner, which causes a problem of a decrease in the storage stability of the toner at a high temperature, so-called heat resistant storage stability. . Furthermore, in order to enhance the low-temperature fixability, for example, in Patent Documents 1 to 3, attempts have been made to use a crystalline resin that is solid at a normal storage temperature and has a low viscosity at a high temperature during fixing. Even so, the compatibility between these is insufficient. Furthermore, if the compatibility is poor by mixing a crystalline resin, the interface between the resins may be peeled off, or a phenomenon may occur when the printed material is bent. Therefore, there is a demand for a toner that achieves both low-temperature fixability and heat-resistant storage stability and is excellent in the bending resistance of the obtained printed matter.
An object of the present invention is to provide a method for producing an electrostatic image developing toner capable of obtaining an electrostatic image developing toner having both low-temperature fixability and heat-resistant storage stability, and having excellent printed sheet obtained and having excellent bending resistance, and An object of the present invention is to provide a toner for developing an electrostatic image obtained by a production method.

  The inventor considered that the factors that affect the heat-resistant storage stability, the low-temperature fixability, and the bending resistance of the obtained printed matter are the dispersion state of the resin in the toner. As a result, the resin particles containing the specific crystalline polyester and the resin particles containing the specific amorphous composite resin including the polyester segment and the addition polymerization resin segment are agglomerated and fused, thereby being heat-resistant. It has been found that a toner for developing an electrostatic charge image that is excellent in the properties, low-temperature fixability and bending resistance of the obtained printed matter can be obtained.

That is, the present invention provides the following [1] and [2].
[1] A resin particle containing a crystalline polyester (A) having a polyester portion obtained using a monomer having a molar average carbon number of 8 to 12, a polyester segment and an addition polymerization resin segment, the addition polymerization In an aqueous medium, an agglomerate X containing an amorphous composite resin (B) containing 3% by mass or more and 15% by mass or less of a component derived from an amphoteric monomer in an aqueous resin segment. Step I for obtaining, and Step II for fusing the aggregate X,
An electrostatic charge image in which the mass ratio of the crystalline polyester (A) to the amorphous composite resin (B) (crystalline polyester (A) / amorphous composite resin (B)) is 1/99 to 40/60. A method for producing a developing toner.
[2] A toner for developing an electrostatic image obtained by the above production method.

  According to the present invention, there is provided a method for producing an electrostatic image developing toner capable of obtaining an electrostatic image developing toner having both low-temperature fixing property and heat-resistant storage stability, and having excellent folding resistance of the obtained printed matter, and An electrostatic charge image developing toner obtained by the method can be provided.

[Method for producing toner for developing electrostatic image]
The method for producing a toner for developing an electrostatic charge image of the present invention comprises a resin particle containing a crystalline polyester (A) having a polyester portion obtained by using a monomer having a molar average carbon number of 8 to 12, a polyester segment, Resin particles containing an amorphous composite resin (B) containing an addition polymerization resin segment, and containing 3% by mass to 15% by mass of a component derived from an amphoteric monomer in the addition polymerization resin segment; A mass ratio of the crystalline polyester (A) and the amorphous composite resin (B), which includes a step I of obtaining an aggregate X containing the aqueous solution in an aqueous medium and a step II of fusing the aggregate X This is a method for producing a toner for developing an electrostatic charge image, wherein (crystalline polyester (A) / amorphous composite resin (B)) is 1/99 to 40/60.
Hereinafter, the “electrostatic image developing toner” may be simply referred to as “toner”.

The reason why the toner for developing an electrostatic charge image obtained by the production method of the present invention is excellent in low-temperature fixability, heat-resistant storage stability, and bending resistance of the obtained printed matter is not clear, but is considered as follows.
In the production method of the present invention, resin particles containing crystalline polyester and resin particles containing amorphous composite resin are aggregated and fused in an aqueous medium to obtain a toner. In the present invention, since the crystalline polyester is less than the amorphous composite resin, the resulting toner has a structure in which the crystalline domain is dispersed in the amorphous composite resin, and is excellent in low-temperature fixability and heat-resistant storage stability. It is considered to be.
The amorphous composite resin of the present invention has a structure in which a polyester segment and an addition polymerization resin segment are bonded to each other with a relatively large amount of both reactive monomers as junction points, and therefore has a lot of branched structures. Conceivable. In addition, since the crystalline polyester has a long-chain hydrocarbon portion and is hydrophobic, it is well suited to the addition polymerization resin segment, and it is considered that the surface between particles is firmly connected during fusion. As a result, the crystalline domain remains when it becomes toner, and there is no separation between the resins, so that both the low-temperature fixability and the heat-resistant storage stability are compatible, and the obtained printed matter has excellent bending resistance. Conceivable.

In the present invention, the mass ratio of the crystalline polyester (A) to the amorphous composite resin (B) (crystalline polyester (A) / amorphous composite resin (B)) is 1/99 to 40/60. is there. When the ratio is less than 1/99, the low-temperature fixability of the toner is deteriorated, and when it exceeds 40/60, the heat resistant storage stability of the toner is deteriorated and the bending resistance of the obtained printed matter is also deteriorated.
From this viewpoint, the mass ratio (crystalline polyester (A) / amorphous composite resin (B)) is preferably 5/95 or more, more preferably 10/90 or more, and further preferably 15/85 or more. Also, it is preferably 60/40 or less, more preferably 50/50 or less, and still more preferably 45/55 or less.

<Process I>
Step I includes resin particles containing a crystalline polyester (A) having a polyester portion obtained by using a monomer having a molar average carbon number of 8 to 12, a polyester segment and an addition polymerization resin segment, and the addition In an aqueous medium, an aggregate X containing an amorphous composite resin (B) containing 3% by mass or more and 15% by mass or less of a component derived from an amphoteric monomer in a polymerization type resin segment It is a process obtained by.

  In the present invention, the “polyester part” means a part made of a polymer of carboxylic acid and alcohol, and “polyester” in “crystalline polyester” and “amorphous polyester” means the polyester. It is a resin that contains a portion and may contain other portions such as an addition polymerization resin segment.

  Step I is a step of aggregating the resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B) in the aqueous medium to obtain the core aggregate x. Ia and resin particles containing amorphous polyester (C) are further mixed in the aqueous medium, the core aggregate x and the resin particles containing amorphous polyester (C) are aggregated, Step Ib for obtaining the aggregate X may be included (first aspect of Step I). Using the aggregate X obtained in this manner, by performing step II described later, the part derived from the core aggregate becomes the core, and the part derived from the resin particles containing the amorphous polyester (C) As a result, a toner having a core-shell structure can be obtained.

Further, the step Ib may be omitted. That is, the step I includes a step of aggregating the resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B) in the aqueous medium to obtain an aggregate X. You may have (2nd aspect of the process I). A toner having a single structure, that is, a non-core-shell structure can be obtained by performing Step II described later using the aggregate X thus obtained.
Hereinafter, although the 1st aspect of the process I is demonstrated, the 2nd aspect of the process I omits the process Ib in the 1st aspect of the process I.

(Resin particles containing crystalline polyester (A))
The resin particles containing the crystalline polyester (A) contain a crystalline polyester (A) having a polyester portion obtained using a monomer having a molar average carbon number of 8 to 12. Thus, since the resin particles contain crystalline polyester (A), the resulting toner has a structure in which crystalline domains are dispersed in an amorphous composite resin, and has excellent low-temperature fixability and heat-resistant storage stability. It is thought that it becomes. In addition, since the raw material monomer of the polyester portion of the crystalline polyester (A) has a molar average carbon number of 8 to 12, has a long-chain hydrocarbon portion and is hydrophobic, an amorphous composite resin It is considered to be familiar with the addition polymerization type resin segment (B) and firmly connect the surface between the particles at the time of fusion. As a result, the crystalline domain remains when it becomes toner, and there is no separation between the resins, so that both the low-temperature fixability and the heat-resistant storage stability are compatible, and the obtained printed matter has excellent bending resistance. Conceivable.

  The resin particles containing the crystalline polyester (A) may contain components other than the crystalline polyester (A) as long as the effects of the present invention are not impaired, but both low-temperature fixability and heat-resistant storage stability are compatible. And from a viewpoint of obtaining the toner which is excellent in the bending resistance of the obtained printed matter, it is preferable not to contain components other than crystalline polyester (A). The content of the crystalline polyester (A) in the resin particles containing the crystalline polyester (A) is preferably 80% by mass or more, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and more. More preferably, it is 99-100 mass%, More preferably, it is substantially 100 mass%.

In the present invention, the crystallinity of a resin such as crystalline polyester (A) is the ratio between the softening point and the maximum peak temperature of the endotherm measured by a differential scanning calorimeter (DSC), that is, “softening point / maximum endothermic peak temperature” It is represented by the crystallinity index defined by Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, the “crystalline resin” refers to a resin having a crystallinity index of 0.6 to 1.4, preferably 0.8 to 1.2, more preferably 0.9 to 1.1. “Amorphous resin” refers to a resin having a crystallinity index greater than 1.4 or less than 0.6.
The above “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the measurement method conditions described in the examples. If the maximum peak temperature is within 20 ° C. from the softening point, the maximum peak temperature is the melting point of the crystalline resin (crystalline resin), and the peak at which the difference from the softening point exceeds 20 ° C. is glass of amorphous resin. The peak is attributed to the transition.
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 volume median particle size of the resin particles containing the crystalline polyester (A) is preferably from the viewpoint of easy aggregation, low temperature fixability, heat resistant storage stability, and a toner excellent in bending resistance of printed matter. 10 nm or more, more preferably 50 nm or more, still more preferably 70 nm or more, still more preferably 80 nm or more, preferably 200 nm or less, more preferably 150 nm or less, still more preferably 110 nm or less, still more preferably 100 nm or less. is there.
The resin particles containing the crystalline polyester (A) can be suitably produced by adding an aqueous medium to the crystalline polyester (A) and carrying out phase inversion emulsification.

≪Crystalline polyester (A) ≫
The crystalline polyester (A) has a polyester portion obtained using a monomer having a molar average carbon number of 8 to 12. This polyester part can be obtained by condensation polymerization using an alcohol component and a carboxylic acid component as raw material monomers.

The molar average carbon number of the raw material monomer of this polyester part is 8-12. Thus, since the crystalline polyester (A) has a long-chain hydrocarbon portion and is hydrophobic, the crystalline polyester (A) is well suited to the addition polymerization resin segment of the amorphous composite resin (B). It is thought that the surface is firmly connected. As a result, the crystalline domain remains when it becomes toner, and there is no separation between the resins, so that both the low-temperature fixability and the heat-resistant storage stability are compatible, and the obtained printed matter has excellent bending resistance. Conceivable.
From this viewpoint, the molar average carbon number is preferably 8 to 11, more preferably 9 to 11.
“Mole average carbon number of the raw material monomer of the polyester portion” means a molar average value of carbon numbers of the alcohol component and the carboxylic acid component constituting the polyester, and is calculated by the following calculation formula.
[Mole average carbon number] = [(alcohol component carbon number × alcohol component mole number) + (carboxylic acid component carbon number × carboxylic acid component mole number)] / [alcohol component mole number + carboxylic acid component mole number]
Here, in the calculation of the molar average carbon number in the raw material monomer, the carbon number of the carboxylic acid component is the carbon number excluding the carbon number of the carboxy group portion.
The polyester portion of the crystalline polyester (A) can be suitably obtained by polycondensing a carboxylic acid component containing a dicarboxylic acid having 4 to 12 carbon atoms and an alcohol component containing a diol having 8 to 12 carbon atoms.

  This crystalline polyester (A) may consist of only the said polyester part, and may have another part. The crystalline polyester (A) is preferably a crystalline composite resin including a polyester segment and an addition polymerization resin segment. Since the crystalline polyester (A) contains the addition polymerization resin segment in this way, the compatibility with the amorphous composite resin (B) containing the addition polymerization resin segment is improved. It is considered that the adhesive domain has a structure dispersed in the amorphous composite resin, and is excellent in low-temperature fixability, heat-resistant storage stability, and bending resistance of printed matter.

The crystalline polyester (A) is more preferably a crystalline composite resin that includes the polyester segment and the addition polymerization resin segment, and further includes a component derived from both reactive monomers. Here, the “bi-reactive monomer” is a monomer having reactivity with both the polyester and the addition polymerization resin. The polyester segment and the addition polymerization type resin segment are favorably bonded using the both reactive monomers as a bonding point.
Below, the case where crystalline polyester (A) is a crystalline composite resin is demonstrated.

≪Crystalline composite resin≫
The crystalline composite resin is more preferably a crystalline composite resin containing the polyester segment and the addition polymerization resin segment, and further containing a constituent part derived from both reactive monomers.

[Polyester segment]
The molar average carbon number in the raw material monomer of the polyester segment is 8 to 12, preferably 8 to 8 from the viewpoint of obtaining a toner excellent in low-temperature fixability, heat-resistant storage stability and printed matter bending resistance, as in the above-described polyester portion. 11, more preferably 9-11.

From the same viewpoint, the polyester segment of the crystalline polyester (A) is obtained by polycondensing a carboxylic acid component containing a dicarboxylic acid having 4 to 12 carbon atoms and an alcohol component containing a diol having 8 to 12 carbon atoms. It is preferable that
From the same point of view, the total amount of the dicarboxylic acid having 4 to 12 carbon atoms and the diol having 8 to 12 carbon atoms is preferably 80% of the total amount of the carboxylic acid component and the alcohol component among the monomers used as the raw material for the polyester segment. It is more than mol%, More preferably, it is 90-100 mol%, More preferably, it is 95-100 mol%, More preferably, it is 99-100 mol%.

Examples of the carboxylic acid component that is a raw material monomer for the polyester segment of the crystalline polyester (A) include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and trivalent or higher polyvalent carboxylic acids, and aliphatic dicarboxylic acids are preferred. Further, acid anhydrides of these carboxylic acids and alkyl (1 to 3 carbon atoms) esters thereof may be used. These carboxylic acid components can be used alone or in combination of two or more.
Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Can be mentioned. Among these, succinic acid, adipic acid, sebacic acid, and dodecanedioic acid are preferable, and adipic acid, sebacic acid, and dodecanedioic acid are preferable from the viewpoint of obtaining a toner excellent in low-temperature fixability, heat-resistant storage stability, and bending resistance of printed matter. More preferably, adipic acid and sebacic acid are still more preferable, and sebacic acid is still more preferable.

  From the same viewpoint, the content of the aliphatic dicarboxylic acid is preferably 60 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%, and still more preferably 95 to 95 mol% in the carboxylic acid component. It is 100 mol%, more preferably 100 mol%.

Examples of the alcohol component that is a raw material monomer of the polyester segment of the crystalline polyester (A) include aliphatic diols, aromatic diols, and trivalent or higher polyhydric alcohols. These alcohol components can be used alone or in combination of two or more.
The alcohol component which is a raw material monomer for the polyester segment is preferably an aliphatic diol from the viewpoint of enhancing the crystallinity of the polyester. Examples of the aliphatic diol include 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,11-undecanediol and the like from the same viewpoint. 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol are preferred, 1,10-decanediol and 1,12-dodecanediol are more preferred, and 1,12 is more preferred. -Dodecanediol.
From the same viewpoint, the content of the aliphatic diol is preferably 60 mol% or more, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%, and still more preferably 95 to 100 mol in the alcohol component. %, More preferably 100 mol%.

  The ratio of the carboxylic acid component to 100 mol parts of the alcohol component which is the raw material monomer of the polyester segment is preferably 90 mol parts or more, more preferably 95 mol parts or more, and still more preferably 98 mol parts, from the viewpoint of reactivity and physical property adjustment. More preferably, it is 100 mol parts or more, preferably 150 mol parts or less, more preferably 120 mol parts or less, still more preferably 110 mol parts or less.

[Addition polymerization resin segment]
As the addition polymerization resin segment, the dispersibility is improved by improving the compatibility with the amorphous composite resin (B), thereby obtaining a toner having excellent low-temperature fixability, heat-resistant storage stability and bending resistance of printed matter. From the viewpoint, a styrene resin is preferable. Therefore, as a suitable raw material monomer for the addition polymerization resin, styrene derivatives such as styrene, α-methylstyrene, vinyltoluene and the like are preferable, and styrene is more preferable.
In addition, the addition polymerization type resin segment includes constituent components derived from both reactive monomers described later. Further, the raw material monomer of the addition polymerization resin includes both reactive monomers.

  From the same viewpoint, the content of the styrene derivative is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 85% by mass or more, and still more preferably 88% by mass in the raw material monomer of the addition polymerization resin. % Or more, more preferably 90% by weight or more, still more preferably 92% by weight or more, still more preferably 93% by weight or more, and preferably 99% by weight or less, more preferably 97% by weight or less, Preferably it is 96 mass% or less, More preferably, it is 95 mass% or less, More preferably, it is 94.5 mass% or less, More preferably, it is 94 mass% or less.

  Raw material monomers for addition polymerization resin segments that can be used in addition to styrene derivatives include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; vinyl chloride and the like Halovinyls; vinyl esters such as vinyl acetate and vinyl propionate; esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N -N-vinyl compounds such as vinylpyrrolidone. In the present specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

  Among these, (meth) acrylic acid alkyl esters are preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability, heat-resistant storage stability, and printed paper bending resistance. From the above viewpoint, the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 22, and more preferably 8 to 18. In addition, carbon number of this alkyl ester says carbon number derived from the alcohol component which comprises ester. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, 2-ethylhexyl Examples include (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is preferred. "(Iso or tertiary)", "(iso)" means including both present and absent groups, and when these groups are not present, Indicates normal. Further, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

The content of the (meth) acrylic acid alkyl ester is preferably 50% by mass or less in the raw material monomer of the addition polymerization resin segment from the viewpoint of obtaining a toner having excellent low-temperature fixability, heat-resistant storage stability, and printed paper bending resistance. 30 mass% or less is more preferable, and 20 mass% or less is further more preferable.
A resin obtained by addition polymerization of a raw material monomer containing a styrene derivative and a (meth) acrylic acid alkyl ester is also referred to as a styrene- (meth) acrylic resin.

  In the raw material monomer of the crystalline composite resin, the content of the raw material monomer of the addition polymerization type resin segment is the raw material monomer of the polyester segment from the viewpoint of obtaining a toner having excellent low-temperature fixability, heat-resistant storage stability and bending resistance of printed matter. 100 parts by weight, preferably 10 parts by weight or more, more preferably 20 parts by weight or more, still more preferably 30 parts by weight or more, still more preferably 40 parts by weight or more, still more preferably 45 parts by weight or more, Further, it is preferably 75 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 65 parts by mass or less, still more preferably 60 parts by mass or less, and still more preferably 55 parts by mass or less.

[Components derived from both reactive monomers]
The amphoteric monomer used for the component derived from the amphoteric monomer is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. The compound which has the functional group of these is mentioned. Among these, from the viewpoint of reactivity, a compound having a hydroxyl group and / or a carboxyl group is preferable, and a compound having a carboxyl group and an ethylenically unsaturated bond is more preferable. By using such a bireactive monomer, the dispersibility of the crystalline polyester (A) in the composite resin can be further improved.

Specifically, examples of the both reactive monomers include acrylic acid, methacrylic acid, maleic acid and maleic anhydride. From the viewpoint of the reactivity of the condensation polymerization reaction and the addition polymerization reaction, acrylic acid and methacrylic acid are more preferable.
From the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter by increasing the branched structure, the content of the constituent parts derived from both reactive monomers is In the addition polymerization resin segment of the reactive polyester (A), preferably 3% by mass or more, more preferably 4% by mass or more, still more preferably 5% by mass or more, still more preferably 5.5% by mass or more, and still more preferably. Is 6% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, still more preferably 8% by mass or less, and still more preferably 7% by mass or less. It is.

[Physical properties of crystalline composite resin]
The softening point of the crystalline composite resin used in the present invention is preferably at least 80 ° C., more preferably from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. 82 ° C or higher, more preferably 84 ° C or higher, still more preferably 85 ° C or higher, still more preferably 86 ° C or higher, preferably 120 ° C or lower, more preferably 100 ° C or lower, still more preferably 95 ° C or lower. More preferably, it is 92 degrees C or less, More preferably, it is 90 degrees C or less.
The melting point of the crystalline composite resin used in the present invention is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, still more preferably 80 ° C. or higher, and preferably 95 ° C. or lower, from the same viewpoint. More preferably, it is 90 degrees C or less, More preferably, it is 85 degrees C or less.

From the same viewpoint, the acid value of the crystalline composite resin is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more. Preferably it is 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less, More preferably, it is 20 mgKOH / g or less, More preferably, it is 18 mgKOH / g or less.
The softening point, melting point, and acid value can be easily adjusted by adjusting the raw material monomer composition, molecular weight, catalyst amount, etc., or selecting reaction conditions.
The total content of the polyester segment, the addition polymerization resin segment, and the constituent parts derived from both reactive monomers in the crystalline composite resin is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99. It is at least mol%, more preferably 100 mol%.

≪Method for producing crystalline composite resin≫
The crystalline composite resin is preferably produced by any one 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 another addition polymerization type resin segment from a reactive viewpoint. From the viewpoint of reactivity, 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 (A) of the condensation polymerization reaction with the alcohol component and the carboxylic acid component, the step of the addition polymerization reaction with the raw material monomer of the addition polymerization resin segment other than the both reactive monomers and, if necessary, the both reactive monomers Method to perform (B).
In Step (A), a part of the carboxylic acid component is subjected to a condensation polymerization reaction, and then, after performing Step (B), the reaction temperature is increased again, and the remainder of the carboxylic acid component is added to the polymerization system. A method in which the polycondensation reaction in step (A) and the reaction with both reactive monomers as necessary are further promoted is more preferred.

(2) A method in which the step (A) of the polycondensation reaction with the raw material monomer of the polyester segment is performed after the step (B) of the addition polymerization reaction with the raw material monomer of the addition polymerization resin segment.
The alcohol component and the carboxylic acid component are present in the reaction system during the addition polymerization reaction, and the condensation polymerization is performed by adding an esterification catalyst and, if necessary, an esterification co-catalyst at a temperature suitable for the condensation polymerization reaction. The reaction can be started, or the polycondensation reaction can be started by adding it later to the reaction system under temperature conditions suitable for the polycondensation reaction. In the former case, the molecular weight and molecular weight distribution can be adjusted by adding an esterification catalyst and, if necessary, an esterification co-catalyst at a temperature suitable for the condensation polymerization reaction.

(3) A method in which the step (A) of the condensation polymerization reaction using the alcohol component and the carboxylic acid component and the step (B) of the addition polymerization reaction using the raw material monomer of the addition polymerization resin segment are performed in parallel.
In this method, step (A) and step (B) are performed under reaction temperature conditions suitable for addition polymerization reaction, the reaction temperature is increased, and under temperature conditions suitable for condensation polymerization reaction, if necessary, It is preferable to add a trivalent or higher raw material monomer of the polyester segment to the polymerization system as a crosslinking agent, and further perform the polycondensation reaction in the step (A). At that time, under a temperature condition suitable for the condensation polymerization reaction, a radical polymerization inhibitor can be added to advance only the condensation polymerization reaction. Both reactive monomers are involved in the condensation polymerization reaction as well as the addition polymerization reaction.
Among these, the method (1) is preferable from the viewpoint that the degree of freedom of the reaction temperature of the condensation polymerization reaction is high.
The methods (1) to (3) are preferably performed in the same container.
The temperature of the condensation polymerization reaction is preferably 120 ° C. or higher, more preferably 145 ° C. or higher, further preferably 150 ° C. or higher, preferably 180 ° C. or lower, more preferably 170 ° C. or lower, and further preferably 165 ° C. or lower. It is.

The temperature of the addition polymerization reaction is preferably 120 ° C or higher, more preferably 140 ° C or higher, still more preferably 160 ° C or higher, still more preferably 200 ° C or higher, and preferably 260 ° C or lower. More preferably, it is 250 degrees C or less, More preferably, it is 245 degrees C or less, More preferably, it is 240 degrees C or less.
Moreover, it is preferable to accelerate the polycondensation reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

[Esterification catalyst]
Examples of the esterification catalyst suitably used for the condensation polymerization 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 a titanium compound, the titanium compound which has a Ti-O bond is preferable, and the compound which has a C1-28 total carbon number alkoxy group, an alkenyloxy group, or an acyloxy group 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) tin (II) is more preferable from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. .

  The abundance of the esterification catalyst is preferably 0.1 parts by mass or more, more preferably 100 parts by mass or more, more preferably 100 parts by mass with respect to the total amount of alcohol component and carboxylic acid component, from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. Is 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably. Is 1 part by mass or less.

[Esterification cocatalyst]
The esterification cocatalyst need not be used, but may be used. As the esterification cocatalyst, a pigalol compound is preferred. This pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with a hydroxyl group, 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.

(Resin particles containing amorphous composite resin (B))
The resin particles containing the amorphous composite resin (B) include a polyester segment and an addition polymerization resin segment, and the addition polymerization resin segment has a constitution derived from 3% by mass to 15% by mass of both reactive monomers. An amorphous composite resin (B) containing components is contained. Thus, since the amorphous composite resin (B) has a structure in which the polyester segment and the addition polymerization resin segment are bonded with a relatively large amount of both reactive monomers as the junction, it has many branched structures. It is thought that. As a result, the crystalline domain is well dispersed in the amorphous composite resin when it becomes a toner, and the resulting toner has both low-temperature fixability and heat-resistant storage stability, while being able to bend the printed matter obtained. It is thought that it is excellent in performance.

  The resin particles containing the amorphous composite resin (B) may contain components other than the amorphous composite resin (B) as long as the effects of the present invention are not impaired. From the viewpoint of obtaining a toner having both storability and excellent bending resistance of the obtained printed matter, it is preferable not to contain any components other than the amorphous composite resin (B). The content of the amorphous composite resin (B) in the resin particles containing the amorphous composite resin (B) is preferably 80% by mass or more, more preferably 90 to 100% by mass, and still more preferably 95 to 100%. It is 99 mass%, More preferably, it is 99-100 mass%.

The volume-median particle size of the resin particles containing this amorphous composite resin (B) is from the viewpoint of easy aggregation, low-temperature fixability, heat-resistant storage stability, and a toner excellent in bending resistance of printed matter. Preferably it is 10 nm or more, more preferably 50 nm or more, still more preferably 70 nm or more, still more preferably 80 nm or more, preferably 200 nm or less, more preferably 150 nm or less, still more preferably 110 nm or less, still more preferably 100 nm. It is as follows.
The resin particles containing the amorphous composite resin (B) can be suitably produced by adding an aqueous medium to the amorphous composite resin (B) and performing phase inversion emulsification.

≪Amorphous composite resin (B) ≫
The amorphous composite resin (B) includes a polyester segment and an addition polymerization resin segment, and includes 3% by mass or more and 15% by mass or less of a component derived from an amphoteric monomer in the addition polymerization resin segment.

[Polyester segment]
Examples of the carboxylic acid component that is a raw material monomer for the polyester segment of the amorphous composite resin (B) include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and trivalent or higher polyvalent carboxylic acids. It is preferable that one or both of the group dicarboxylic acids are included, and it is more preferable that both are included. Further, acid anhydrides of these carboxylic acids and alkyl (1 to 3 carbon atoms) esters thereof may be used. These carboxylic acid components can be used alone or in combination of two or more.

Specific examples of the aromatic dicarboxylic acid include terephthalic acid, phthalic acid, and isophthalic acid. Among these, terephthalic acid is preferable from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter.
From the same viewpoint, the content of the aromatic dicarboxylic acid is preferably 55 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, and preferably 80 mol% in the carboxylic acid component. % Or less, more preferably 75 mol% or less, still more preferably 70 mol% or less.

The aliphatic dicarboxylic acid preferably contains an aliphatic dicarboxylic acid having 2 to 6 carbon atoms.
Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. Can be mentioned. Examples of the aliphatic dicarboxylic acid include succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. . Among these, fumaric acid, dodecenyl succinic acid, and octenyl succinic acid are preferable, and fumaric acid is more preferable from the viewpoint of obtaining a toner excellent in low-temperature fixability, heat-resistant storage stability, and bending resistance of printed matter.

  From the same viewpoint, the content of the aliphatic dicarboxylic acid is preferably 10 mol% or more, more preferably 15 mol% or more, still more preferably 20 mol% or more, still more preferably 25 mol% or more in the carboxylic acid component. Moreover, it is preferably 50 mol% or less, more preferably 45 mol% or less, still more preferably 40 mol% or less, and still more preferably 35 mol% or less.

From the same viewpoint, the molar ratio of aliphatic dicarboxylic acid to aromatic dicarboxylic acid [aliphatic dicarboxylic acid / aromatic dicarboxylic acid] is preferably 20/80 to 50/50, more preferably 25/75 to 45/55. More preferably, it is 30 / 70-40 / 60.
The total amount of aliphatic dicarboxylic acid and aromatic dicarboxylic acid in the carboxylic acid component is preferably 90 mol% or more, more preferably, from the viewpoint of obtaining a toner excellent in low-temperature fixability, heat-resistant storage stability and bending resistance of printed matter. It is 95-100 mol%, More preferably, it is 99-100 mol%, More preferably, it is 100 mol%.

Examples of the alcohol component that is a raw material monomer for the polyester segment of the amorphous composite resin (B) include aliphatic diols, aromatic diols, and trivalent or higher polyhydric alcohols, and aromatic diols are preferred. These alcohol components can be used alone or in combination of two or more.
The alcohol component of the polyester segment of the amorphous composite resin (B) contains an alkylene oxide adduct of bisphenol A represented by the following formula (I) from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. It is preferable to do.

(In the formula, R represents an alkylene group having 2 or 3 carbon atoms. X and y are average added moles of an alkyleneoxy group, represent a positive number, and the sum of x and y is preferably 1 or more. More preferably 1.5 or more, still more preferably 2 or more, and preferably 16 or less, more preferably 5 or less, still more preferably 3 or less.)

As the alkylene oxide adduct of bisphenol A represented by the above formula (I), specifically, a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxyphenyl) propane polyoxyethylene adduct and the like.
The alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 70 to 100 mol%, more preferably 80 in the alcohol component from the viewpoint of heat-resistant storage stability, durability and low-temperature fixability of the toner. To 100 mol%, more preferably 90 to 100 mol%.

  The ratio of the carboxylic acid component to 100 mol parts of the alcohol component which is the raw material monomer of the polyester segment of the amorphous composite resin (B) is preferably 70 mol parts or more, more preferably 80 mol, from the viewpoint of reactivity and physical property adjustment. Part or more, more preferably 85 parts by mole or more, still more preferably 90 parts by mole or more, and preferably 110 parts by mole or less, more preferably 100 parts by mole or less, still more preferably 95 parts by mole or less.

[Addition polymerization resin segment]
As the addition polymerization resin segment, by improving the compatibility with the crystalline polyester (A) and improving the dispersibility of the crystalline polyester in the composite resin, the low temperature fixability, the heat resistant storage stability and the printed matter resistance. From the viewpoint of obtaining a toner excellent in bendability, a styrene resin is preferable. Therefore, as a suitable raw material monomer for the addition polymerization resin, styrene derivatives such as styrene, α-methylstyrene, vinyltoluene and the like are preferable, and styrene is more preferable.
In addition, the addition polymerization type resin segment includes constituent components derived from both reactive monomers described later. Further, the raw material monomer of the addition polymerization resin includes both reactive monomers.

  From the same viewpoint, the content of the styrene derivative is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and even more preferably 75% by mass in the raw material monomer of the addition polymerization resin. % Or more, preferably 97% by mass or less, more preferably 96.8% by mass or less, still more preferably 96.5% by mass or less, still more preferably 96% by mass or less, and still more preferably 85% by mass. It is as follows.

  Raw material monomers for addition polymerization resin segments that can be used in addition to styrene derivatives include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; vinyl chloride and the like Halovinyls; vinyl esters such as vinyl acetate and vinyl propionate; esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N -N-vinyl compounds such as vinylpyrrolidone. In the present specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

  Among these, (meth) acrylic acid alkyl esters are preferable from the viewpoint of obtaining a toner having excellent low-temperature fixability, heat-resistant storage stability, and printed paper bending resistance. From the above viewpoint, the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 22, and more preferably 8 to 18. In addition, carbon number of this alkyl ester says carbon number derived from the alcohol component which comprises ester. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, etc. are mentioned, 2-ethylhexyl (meth) acrylate is preferred, 2-ethylhexyl acrylate Is more preferable. "(Iso or tertiary)", "(iso)" means including both present and absent groups, and when these groups are not present, Indicates normal. Further, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

From the same viewpoint, the content of the (meth) acrylic acid alkyl ester is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, in the raw material monomer of the addition polymerization resin. More preferably, it is 18 mass% or more, Preferably it is 40 mass% or less, More preferably, it is 35 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less.
A resin obtained by addition polymerization of a raw material monomer containing a styrene derivative and a (meth) acrylic acid alkyl ester is also referred to as a styrene- (meth) acrylic resin.

  In the raw material monomer of the amorphous composite resin, the content of the raw material monomer of the addition polymerization resin segment is the polyester segment raw material from the viewpoint of obtaining a toner excellent in low-temperature fixability, heat-resistant storage stability and printed paper folding resistance. The amount is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and still more preferably 45 parts by mass or more, relative to 100 parts by mass of the monomer. Moreover, it is preferably 75 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 65 parts by mass or less, still more preferably 60 parts by mass or less, and still more preferably 55 parts by mass or less.

[Components derived from both reactive monomers]
The amphoteric monomer used for the component derived from the amphoteric monomer is at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. The compound which has the functional group of these is mentioned. Among these, from the viewpoint of reactivity, a compound having a hydroxyl group and / or a carboxyl group is preferable, and a compound having a carboxyl group and an ethylenically unsaturated bond is more preferable. By using such a bireactive monomer, the dispersibility of the crystalline polyester (A) can be further improved.

Specifically, examples of the both reactive monomers include acrylic acid, methacrylic acid, maleic acid and maleic anhydride. From the viewpoint of the reactivity of the condensation polymerization reaction and the addition polymerization reaction, acrylic acid and methacrylic acid are more preferable.
The content of the constituent parts derived from the both reactive monomers is such that the amorphous composite resin (B) can be obtained from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. In the addition polymerization type resin segment, preferably 3% by mass or more, more preferably 3.2% by mass or more, further preferably 3.5% by mass or more, still more preferably 4% by mass or more, and preferably 15% or more. It is at most 10 mass%, more preferably at most 5 mass%, still more preferably at most 4.5 mass%.

[Physical properties of amorphous composite resin (B)]
The softening point of the amorphous composite resin (B) used in the present invention is preferably 90 ° C. or higher from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent printed paper folding resistance. More preferably 95 ° C. or more, still more preferably 100 ° C. or more, still more preferably 105 ° C. or more, still more preferably 110 ° C. or more, and preferably 140 ° C. or less, more preferably 130 ° C. or less, still more preferably Is 125 ° C. or lower, more preferably 120 ° C. or lower, and still more preferably 115 ° C. or lower.
Further, the glass transition temperature of the amorphous composite resin (B) used in the present invention is preferably 50 ° C. or higher, more preferably 52 ° C. or higher, further preferably 55 ° C. or higher, from the same viewpoint. Preferably it is 75 degrees C or less, More preferably, it is 65 degrees C or less, More preferably, it is 62 degrees C or less.

From the same viewpoint, the acid value of the amorphous composite resin (B) is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and still more preferably 15 mgKOH / g or more. Yes, preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and still more preferably 18 mgKOH / g or less.
The softening point, glass transition temperature, and acid value can be easily adjusted by adjusting the raw material monomer composition, molecular weight, catalyst amount, etc., or by selecting reaction conditions.
In the amorphous composite resin (B), the total content of the polyester segment, the addition polymerization resin segment and the constituent parts derived from both reactive monomers is preferably 90 mol% or more, more preferably 95 mol% or more, More preferably, it is 99 mol% or more, More preferably, it is 100 mol%.

≪Method for producing amorphous composite resin (B) ≫
The amorphous composite resin (B) is produced by any one of the methods (1) to (3) as in the case of the crystalline composite resin as one embodiment of the crystalline polyester (A). Is preferred. In addition, it is preferable that both reactive monomers are supplied to a reaction system with the raw material monomer of another addition polymerization type resin segment from a reactive viewpoint. From the viewpoint of reactivity, 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.
Among these, the method (1) is preferable from the viewpoint that the degree of freedom of the reaction temperature of the condensation polymerization reaction is high.
The methods (1) to (3) are preferably performed in the same container.
The temperature of the polycondensation reaction is preferably 220 ° C. or higher, more preferably 225 ° C. or higher, further preferably 230 ° C. or higher, preferably 245 ° C. or lower, more preferably 240 ° C. or lower, still more preferably 238 ° C. or lower. It is.

The temperature of the addition polymerization reaction is preferably 120 ° C. or higher, more preferably 140 ° C. or higher, still more preferably 160 ° C. or higher, still more preferably 200 ° C. or higher, and preferably 235 ° C. or lower. More preferably, it is 230 degrees C or less, More preferably, it is 225 degrees C or less, More preferably, it is 220 degrees C or less.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

[Esterification catalyst]
As the esterification catalyst suitably used for the above polycondensation, those similar to those used in the production of the crystalline composite resin as one embodiment of the crystalline polyester (A) can be suitably used. .

  The abundance of the esterification catalyst is preferably 0.1 parts by mass or more, more preferably 100 parts by mass or more, more preferably 100 parts by mass with respect to the total amount of alcohol component and carboxylic acid component, from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. Is 0.2 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more, and preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably. Is 1 part by mass or less.

[Esterification cocatalyst]
As the esterification co-catalyst, those similar to those used in the production of the crystalline composite resin as one embodiment of the crystalline polyester (A) can be suitably used. Acid is preferred.
When using an esterification cocatalyst, the amount of esterification cocatalyst present in the polycondensation reaction is 100 parts by mass with respect to the total amount of alcohol component and carboxylic acid component subjected to the polycondensation reaction, from the viewpoint of reactivity. Preferably it is 0.001 mass part or more, More preferably, it is 0.01 mass part or more, More preferably, it is 0.02 mass part or more, Preferably it is 0.1 mass part or less, More preferably, it is 0.05 mass part Hereinafter, it is more preferably 0.03 parts by mass. Here, the abundance of the esterification cocatalyst means the total amount of the esterification cocatalyst subjected to the condensation polymerization reaction.
From the viewpoint of reactivity, the mass ratio of the esterification cocatalyst to the esterification catalyst (esterification cocatalyst / esterification catalyst) is preferably 0.01 or more, more preferably 0.02 or more, and still more preferably 0.00. 03 or more, preferably 0.1 or less, more preferably 0.08 or less, and still more preferably 0.05 or less.

(Aqueous medium)
As described above, in step 1, resin particles containing crystalline polyester (A) and resin particles containing amorphous composite resin (B) are obtained in an aqueous medium.
As the aqueous medium, those mainly containing water are preferable.
Examples of components other than water include aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol, isopropanol and butanol; dialkyl (carbon atoms 1 to 3) ketones such as acetone and methyl ethyl ketone; and water such as cyclic ethers such as tetrahydrofuran. Examples include organic solvents that dissolve. Among these, from the viewpoint of preventing mixing into the toner, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol that do not dissolve the resin can be more preferably used.
The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and further preferably 100% by mass. The water is preferably deionized water or distilled water.

(Process Ia)
Step Ia is a step of obtaining the core aggregate x by aggregating the resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B) in the aqueous medium. It is.
In Step Ia, an aqueous dispersion (A) obtained by dispersing resin particles containing crystalline polyester (A) in an aqueous medium is used as a supply source of resin particles containing crystalline polyester (A). It is preferable. Similarly, an aqueous dispersion (B) obtained by dispersing resin particles containing an amorphous composite resin (B) in an aqueous medium as a supply source of the resin particles containing the amorphous composite resin (B). Is preferably used.
It is preferable that the aqueous dispersion (A) and the aqueous dispersion (B) are mixed to obtain a mixed dispersion, and the resin particles are aggregated in the mixed dispersion to obtain the core aggregate x.
It is preferable to add a flocculant for efficient aggregation. In addition, aggregation may be performed after adding additives such as a coloring agent, a charge control agent, a release agent, a conductivity adjusting agent, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent. The additive can also be used as an aqueous dispersion.

≪Aqueous dispersion (A) ≫
In this aqueous dispersion (A), the crystalline polyester (A) and an organic solvent are mixed to obtain a mixture (Step 1), an aqueous medium is added to the mixture, phase inversion emulsification is performed to roughen the resin particles. The step of obtaining a dispersion (Step 2), the step of obtaining an aqueous dispersion of resin particles by distilling off the organic solvent from the crude dispersion (Step 3), and the step of adding a surfactant (Step 4) are performed. Thus, it can be suitably manufactured. However, at least one of the steps 1, 3 and 4 may be omitted.

[Step 1]
In Step 1, the mixture is obtained by mixing the crystalline polyester (A), the organic solvent and, if necessary, the neutralizing agent.
From the viewpoint of improving the dispersibility of the crystalline polyester (A), the organic solvent is preferably 15.0 MPa ¹ when expressed by a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc). ^{/ 2} or more, more preferably 16.0MPa ^1/2, and even more preferably at 17.0MPa ^1/2 or more, and preferably 26.0MPa ^1/2 or less, more preferably 24.0MPa ^1/2 or less More preferably, it is 22.0 MPa ^1/2 or less.

Specific examples include the following organic solvents. The parentheses on the right side of the name of the next organic solvent are SP values, and the unit is MPa ^1/2 . That is, specific examples include alcohol solvents such as ethanol (26.0), isopropanol (23.5), and isobutanol (21.5); acetone (20.3), methyl ethyl ketone (19.0), methyl Ketone solvents such as isobutyl ketone (17.2) and diethyl ketone (18.0); ether solvents such as dibutyl ether (16.5), tetrahydrofuran (18.6) and dioxane (20.5); Examples thereof include acetate solvents such as ethyl acetate (18.6) and isopropyl acetate (17.4). Among these, from the viewpoint of improving the dispersibility of the crystalline polyester (A), a ketone solvent and an acetate solvent are preferable, and at least one selected from the group consisting of methyl ethyl ketone, ethyl acetate, and isopropyl acetate is more preferable. Further, from the viewpoint of heat resistant storage stability of the toner, ethyl acetate and / or isopropyl acetate is more preferable, and ethyl acetate is still more preferable.

  The mass ratio of the organic solvent to the crystalline polyester (A) (organic solvent / crystalline polyester (A)) is preferably 0.03 or more, more preferably from the viewpoint of improving the dispersibility of the crystalline polyester (A). Is 0.05 or more, more preferably 0.1 or more, preferably 5 or less, more preferably 1.5 or less, still more preferably 1 or less, still more preferably 0.8 or less, and still more preferably. 0.6 or less.

Examples of the neutralizing agent used in the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. Of the organic base. Among these, from the viewpoint of obtaining a toner excellent in low-temperature fixability, heat-resistant storage stability and bending resistance of printed matter, a neutralizing agent having a pKa of 12 or less is preferable, and a neutralizing agent having a pKa of 10 or less is more preferable. From the same viewpoint, a neutralizer having a pKa of 8 or more is more preferable. Of these, ammonia (pKa = 9.3) and triethylamine (pKa = 9.8) are preferable, and ammonia is more preferable.
From the same viewpoint, the neutralization degree of the crystalline polyester (A) is preferably 60 mol% or more, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, and still more preferably. It is 90-100 mol%, More preferably, it is 95-100 mol%. 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

  In addition, you may add arbitrary components to a mixture in the range which does not affect the effect of this invention. Examples thereof include inorganic salts, organic solvents other than those described above, and surfactants described later.

The said mixture can be obtained by mixing the crystalline polyester (A) mentioned above, an organic solvent, and the neutralizing agent as needed.
In the method for producing the mixture, the order of adding the raw materials is not limited, but it is preferable to mix the neutralizing agent after mixing the crystalline polyester (A) and the organic solvent.
At the time of mixing, it is preferable to stir with a commonly used mixing and stirring device such as an anchor blade or an external circulation stirring device.

  The temperature at the time of mixing is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, from the viewpoints of stabilizing the process temperature, shortening the process time, and reducing the viscosity of the solution. The temperature is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, and still more preferably 75 ° C. or lower. Further, the stirring is preferably performed until there is no significant phase separation or insoluble matter, and the stirring time depends on the stirring speed and temperature conditions, but is preferably 0.5 hours or more, more preferably It is 1 hour or longer, preferably 5 hours or shorter, more preferably 3 hours or shorter.

[Step 2]
Step 2 is a step in which an aqueous medium is added to the above mixture, and phase inversion emulsification is performed to obtain a coarse dispersion of resin particles.
As the aqueous medium, those mainly containing water are preferable.
Examples of components other than water include aliphatic alcohols having 1 to 5 carbon atoms such as methanol, ethanol, isopropanol and butanol; dialkyl (carbon atoms 1 to 3) ketones such as acetone and methyl ethyl ketone; and water such as cyclic ethers such as tetrahydrofuran. Examples include organic solvents that dissolve. Among these, from the viewpoint of preventing mixing into the toner, alcohol-based organic solvents such as methanol, ethanol, isopropanol, and butanol that do not dissolve the resin can be more preferably used.
From the viewpoint of improving the emulsion stability of the resin, the content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and 100% by mass. Further preferred. The water is preferably deionized water or distilled water.

The temperature at which the aqueous medium is added is preferably equal to or higher than the melting point of the crystalline polyester (A) from the viewpoint of improving the emulsion stability of the resin. Specifically, the temperature when adding the aqueous medium is preferably 20 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 60 ° C. or higher, still more preferably 65 ° C. or higher, and preferably 90 ° C. ° C or lower, more preferably 85 ° C or lower, still more preferably 80 ° C or lower, and still more preferably 75 ° C or lower.
The addition rate of the aqueous medium is preferably 0.1 parts by mass / min with respect to 100 parts by mass of the crystalline polyester (A) until the phase inversion is completed from the viewpoint of obtaining resin composition particles having a small particle size. Or more, more preferably 0.5 parts by weight or more, further preferably 1 part by weight or more, still more preferably 3 parts by weight or more, still more preferably 4 parts by weight or more, Preferably it is 50 parts by weight or less, more preferably 30 parts by weight or less, more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, even more preferably 8 parts by weight or less. It is. 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 150 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass of the crystalline polyester (A) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. Preferably it is 200 parts by mass or more, more preferably 300 parts by mass or more, still more preferably 400 parts by mass or more, preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, still more preferably 1000 parts by mass. Hereinafter, it is more preferably 700 parts by mass or less, and still more preferably 500 parts by mass or less.
Also, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step, the aqueous medium is added so that the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is 70/30 to 98/2. It is preferable to do. From this viewpoint, it is more preferably 80/20 or more, further preferably 85/15 or more, more preferably 95/15 or less, still more preferably 90/10 or less.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among these, from the viewpoint of dispersibility of the crystalline polyester (A), a nonionic surfactant and / or an anionic surfactant are preferable, and an anionic surfactant is 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, polyoxyalkylene alkyl ether sulfates such as sodium polyoxyalkylene alkyl ether sulfate, and the like. Among these, from the viewpoint of emulsion stability of the resin, sodium alkylbenzenesulfonate and polyoxyalkylene alkyl ether sulfate are preferable, and polyoxyalkylene alkyl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
Of the surfactants, polyoxyethylene alkyl ethers and polyoxyalkylene alkyl ether sulfates are preferred from the viewpoint of dispersibility of the crystalline polyester (A) and emulsion stability of the resin, and polyoxyalkylene alkyl ether sulfates. Is more preferable.

The volume median particle diameter (D ₅₀ ) of the obtained resin particles containing the crystalline polyester (A) is preferably 50 nm or more, more preferably 60 nm or more, still more preferably 70 nm or more, from the viewpoint of toner productivity. More preferably 80 nm or more, still more preferably 185 nm or more, and preferably 200 nm or less, more preferably 150 nm or less, still more preferably 110 nm or less, still more preferably 100 nm or less, still more preferably 95 nm or less. is there.

[Step 3]
Step 3 is a step of obtaining an aqueous dispersion of resin particles by distilling off the organic solvent from the coarse dispersion.
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% by mass 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 crystalline polyester (A), it is more preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent used under the reduced pressure and distill 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 crystalline polyester (A), it is preferable to distill off at a constant temperature and pressure.

[Step 4]
Step 4 is a step of adding a surfactant to the aqueous dispersion of resin particles.
The amount of the surfactant added in Step 4 is preferably the total amount of surfactant added in Steps 1 to 4 from the viewpoint of obtaining a toner having excellent low-temperature fixability, heat-resistant storage stability, and printed paper folding resistance. Is 50% by mass or more, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, and still more preferably 99 to 100% by mass.
Further, the amount of the surfactant to be added in the step 4 is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and more preferably 1 part by mass or more with respect to 100 parts by mass of the crystalline polyester (A) from the same viewpoint. Preferably it is 5 parts by mass or more, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and still more preferably 15 parts by mass or less.

When the surfactant is added, it is preferable to stir with a commonly used mixing and stirring device such as an anchor blade or an external circulation stirring device.
When a mixing stirring device such as an anchor blade is used, the peripheral speed of stirring is preferably 20 m / min or more, more preferably 40 m / min or more, still more preferably 60 m / min or more, and still more preferably, from the viewpoint of dispersibility. Is 80 m / min or more, preferably 200 m / min or less, more preferably 150 m / min or less, and still more preferably 100 m / min or less.

  The temperature at the time of addition of the surfactant in step 4 is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, further preferably 20 ° C. or higher, from the viewpoint of dispersibility of the surfactant in water, etc. Preferably it is 50 degrees C or less, Preferably it is 40 degrees C or less, Preferably it is 35 degrees C or less.

  The solid content concentration of the aqueous dispersion obtained through the production process of the aqueous dispersion including Step 1 to Step 4 is preferably 3 by appropriately adding water from the viewpoint of the stability of the dispersion and ease of handling. It is at least 5 mass%, more preferably at least 5 mass%, even more preferably at least 15 mass%, preferably at most 40 mass%, more preferably at most 30 mass%, still more preferably at most 25 mass%.

≪Aqueous dispersion (B) ≫
This aqueous dispersion (B) is similar to the above aqueous dispersion (A) except that the amorphous composite resin (B) is used instead of the crystalline polyester (A). By passing, it can manufacture suitably.

(Flocculant)
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 viewpoint of the particle size distribution of the toner, heat resistant storage stability and gloss of printed matter, an inorganic flocculant is preferable, and an inorganic metal salt is 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 of the toner, heat resistant storage stability, and gloss of the printed matter.
When the flocculant is added, the amount added is a resin particle containing the crystalline polyester (A) from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. And 100 parts by mass of the total amount of the resin particles containing the amorphous composite resin (B), preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and further 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 10 parts by mass or less, more preferably 7 parts by mass or less, still more preferably 1 part by mass or less. More preferably, it is 0.8 mass part or less, More preferably, it is 0.5 mass part 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 further preferably 15% by mass or more, in order to cause uniform aggregation. It is 50 mass% or less, More preferably, 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. In addition, it is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, and further 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, preferably 65 ° C. or lower, more preferably 60 ° C. or lower, still more preferably. Is 55 ° C. or lower.

(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, Indigo dyes, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
From the viewpoint of improving the image quality, the addition amount of the colorant is preferably based on 100 parts by mass of the total amount of resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B). Is 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, still more preferably 2.0 parts by mass or more, and preferably 20 parts by mass or less. More preferably, it is 10 mass parts or less, More preferably, it is 8 mass parts or less, More preferably, it is 5 mass parts or less.
This colorant may be added as a colorant dispersion containing colorant fine particles. 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.

(Charge control agent)
Examples of charge control agents include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid metal complexes. Various charge control agents may be used alone or in combination of two or more.
When the charge control agent is added, the addition amount is 100 mass of the total amount of the resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B) from the viewpoint of improving the image quality. Is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, still more preferably 0.5 parts by mass or more, still more preferably 0.6 parts by mass or more, and preferably Is 8 parts by mass or less, more preferably 7 parts by mass or less, still more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less.
The charge control agent may be added as a charge control agent dispersion containing charge control agent fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 800 nm or less, more preferably 500 nm or less.

(Process Ib)
In the step Ib, resin particles containing the amorphous polyester (C) are further mixed in the aqueous medium, and the resin particles containing the core aggregate x and the amorphous polyester (C) are aggregated. In this step, the aggregate X is obtained.
That is, the core aggregate x including the resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B) is present in the aqueous medium by Step Ia. In step Ib, resin particles containing amorphous polyester (C) are further mixed in the aqueous medium containing the core aggregate x, and the core aggregate x and amorphous polyester (C) are mixed. The resin particles containing are agglomerated. Thereby, crystalline polyester (3) adheres to the outermost surface of the aggregate x for cores, and the aggregate X which consists of the aggregate x for cores and the crystalline polyester (3) which covers the surface is obtained.
After aggregation, an aggregation terminator may be added as necessary. In addition, when using an aggregation terminator, it is preferable to use a surfactant as the aggregation terminator, and it is more preferable to use an anionic surfactant. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates, and it is more preferable to use alkyl ether sulfates. .

The volume-median particle size of the resin particles containing the amorphous polyester (C) is preferably from the viewpoint of easy aggregation, low temperature fixability, heat resistant storage stability, and a toner excellent in bending resistance of printed matter. Is 10 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more, still more preferably 110 nm or more, preferably 200 nm or less, more preferably 150 nm or less, still more preferably 140 nm or less, and still more preferably 130 nm or less. It is.
The resin particles containing the amorphous polyester (C) can be suitably produced by adding an aqueous medium to the amorphous polyester (C) and performing phase inversion emulsification.
As a supply source of the resin particles containing the amorphous polyester (C), an aqueous dispersion (C) obtained by dispersing the resin particles containing the amorphous polyester (C) in an aqueous medium is used. Is preferred.

≪Amorphous polyester (C) ≫
The amorphous polyester (C) can be obtained by polycondensing a carboxylic acid component and an alcohol component.
Examples of the carboxylic acid component of the amorphous polyester (C) include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and trivalent or higher polyvalent carboxylic acids. One or both of aliphatic dicarboxylic acids and aromatic dicarboxylic acids can be used. It is preferable to include, and it is more preferable to include both. Further, acid anhydrides of these carboxylic acids and alkyl (1 to 3 carbon atoms) esters thereof may be used. These carboxylic acid components can be used alone or in combination of two or more.

Specific examples of the aromatic dicarboxylic acid include terephthalic acid, phthalic acid, and isophthalic acid. Among these, terephthalic acid is preferable from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter.
The content of the aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 20 mol% or more in the carboxylic acid component, from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. Is 30 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol%, and preferably 95 mol% or less.
The aliphatic dicarboxylic acid preferably contains an aliphatic dicarboxylic acid having 2 to 6 carbon atoms.
Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,10- Examples include decanedicarboxylic acid and dodecanedioic acid. Examples of the aliphatic dicarboxylic acid include succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms such as dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. . Among these, fumaric acid, dodecenyl succinic acid, and octenyl succinic acid are preferable, and fumaric acid and dodecenyl succinic acid are more preferable from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. .

  From the same viewpoint, the content of the aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, still more preferably 5 mol% or more in the carboxylic acid component. Moreover, it is preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 20 mol% or less, and still more preferably 10 mol% or less.

Examples of the alcohol component that is a raw material monomer of the amorphous polyester (C) include aliphatic diols, aromatic diols, trihydric or higher polyhydric alcohols, and aromatic diols are preferable. These alcohol components can be used alone or in combination of two or more.
The alcohol component of the amorphous polyester (C) is a bisphenol represented by the above formula (I) from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. It is preferable to contain an alkylene oxide adduct of A.

As the alkylene oxide adduct of bisphenol A represented by the above formula (I), specifically, a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxyphenyl) propane polyoxyethylene adduct and the like.
The alkylene oxide adduct of bisphenol A represented by the formula (I) is preferable in the alcohol component from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. Is 70 to 100 mol%, more preferably 80 to 100 mol%, and still more preferably 90 to 100 mol%.

  The ratio of the carboxylic acid component to 100 mol parts of the alcohol component which is the raw material monomer of the amorphous polyester (C) is preferably 70 mol parts or more, more preferably 80 mol parts or more, from the viewpoint of reactivity and physical property adjustment. Preferably it is 85 mol part or more, More preferably, it is 90 mol part or more, Preferably it is 110 mol part or less, More preferably, it is 100 mol part or less, More preferably, it is 95 mol part or less.

Amorphous polyester (C) from the standpoint of obtaining a toner having higher heat resistance of the shell portion of the toner than that of the core portion, achieving both low-temperature fixability and heat-resistant storage stability, and excellent printed paper bending resistance. The softening point of is preferably higher than the softening point of the crystalline polyester (A). From this viewpoint, the temperature difference between the softening points of the amorphous polyester (C) and the crystalline polyester (A) is preferably 2 ° C. or higher, more preferably 4 ° C. or higher, still more preferably 5 ° C. or higher, and still more preferably. Is 8 ° C. or higher, more preferably 10 ° C. or higher, preferably 35 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 25 ° C. or lower, still more preferably 20 ° C. or lower, still more preferably 15 It is below ℃.
The softening point of the amorphous polyester (C) is preferably 85 ° C or higher, more preferably 90 ° C or higher, still more preferably 95 ° C or higher, still more preferably 100 ° C or higher, and still more preferably 105 ° C or higher. Also, it is preferably 140 ° C. or lower, more preferably 135 ° C. or lower, still more preferably 130 ° C. or lower, still more preferably 120 ° C. or lower, and still more preferably 115 ° C. or lower.
Further, from the same viewpoint, the glass transition temperature of the amorphous polyester (C) is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, still more preferably 55 ° C. or higher, and still more preferably 60 ° C. or higher. Moreover, it is preferably 85 ° C. or lower, more preferably 80 ° C. or lower, further preferably 75 ° C. or lower, and still more preferably 70 ° C. or lower.

  From the same viewpoint, the glass transition temperature of the amorphous polyester (C) is preferably 5 ° C. or higher, more preferably 6 ° C. or higher, than the glass transition temperature of the amorphous composite resin (B). Moreover, it is preferably 15 ° C. or lower, more preferably 10 ° C. or lower.

  From the same viewpoint, the acid value of the amorphous polyester (C) is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, still more preferably 12 mgKOH / g or more. Yes, preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and still more preferably 18 mgKOH / g or less.

≪Aqueous dispersion (C) ≫
This aqueous dispersion (C) undergoes steps 1 to 4 in the same manner as the aqueous dispersion (A) except that the amorphous polyester (C) is used instead of the crystalline polyester (A). Thus, it can be suitably manufactured.

<Process II>
Step II is a step of fusing the aggregate X.
The temperature in the system in Step II is the desired toner particle size, particle size distribution, shape control and particle fusing point, low-temperature fixability and heat-resistant storage stability, and bend resistance of the printed matter obtained. From the viewpoint of obtaining a toner excellent in heat resistance, 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 stirring speed is preferably a speed at which the aggregated particles do not settle.

<Post process>
By appropriately subjecting the fused particles obtained in step II to a solid-liquid separation step such as filtration, a washing step, and a drying step, the electrostatic image developing toner of the present invention can be suitably obtained.
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.
Further, an external additive may be added for the purpose of improving fluidity. Examples of the external additive include silica fine particles whose surface is hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and inorganic fine particles such as carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin, and the like. Fine particles can be used.

The number average particle diameter of the external additive is preferably 4 to 200 nm, more preferably 8 to 30 nm, from the viewpoint of the fluidity of the toner.
When the external additive is added, the addition amount is preferably 0 with respect to 100 parts by mass of the toner before the processing with the external additive, from the viewpoint of the fluidity of the toner, the environmental stability of the charging degree, and the storage stability. .1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass. It is not more than part by mass, more preferably not more than 3 parts by mass, and still more preferably not more than 2 parts by mass.

The volume median particle diameter (D ₅₀ ) of the toner is preferably 3.0 μm or more, more preferably 3.5 μm or more, and still more preferably 4.0 μm or more, from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. More preferably, it is 4.5 μm or more, preferably 8.5 μm or less, more preferably 8.0 μm or less, still more preferably 7.5 μm or less, still more preferably 7.0 μm or less, and still more preferably. 5.0 μm or less.

Further, from the same viewpoint, the coefficient of variation (CV value) (%) of the particle size distribution of the toner is preferably 40% or less, more preferably 35% or less, and further preferably 30% or less. (A) From the viewpoint of improving the productivity of the dispersion, it is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more. The CV value is a value represented by the following formula, and is obtained by the method described in the examples.
CV value (%) = [standard deviation of particle size distribution (μm) / volume median particle size (μm)] × 100

[Toner for electrostatic image development]
The electrostatic image developing toner of the present invention can be produced by the production method described above.
By adopting the first aspect of step I described above (steps Ia and Ib are carried out), a core-shell type electrostatic image developing toner containing amorphous polyester in the shell portion can be obtained. Further, by adopting the second aspect of the above-mentioned step I (implementing step Ia), a non-core-shell (single structure) electrostatic charge image developing toner can be obtained.

  Mass ratio of total amount of crystalline polyester (A) and amorphous composite resin (B) to amorphous polyester (C) [total amount of crystalline polyester (A) and amorphous composite resin (B) / amorphous The quality polyester (C)] is preferably 60/40 or more, more preferably 70/30 or more, from the viewpoint of obtaining a toner having both low-temperature fixability and heat-resistant storage stability and excellent bending resistance of the obtained printed matter. More preferably, it is 80/20 or more, more preferably 85/15 or more, preferably 100/0 or less, more preferably 99/1 or less, still more preferably 95/5 or less, and still more preferably 90 /. 10 or less.

  In relation to the above-described embodiment, the present invention discloses the following method for producing an electrostatic image developing toner and electrostatic image developing toner.

<1> Resin particles containing a crystalline polyester (A) having a polyester portion obtained using a monomer having a molar average carbon number of 8 to 12, a polyester segment and an addition polymerization resin segment, the addition polymerization In an aqueous medium, an agglomerate X containing an amorphous composite resin (B) containing 3% by mass or more and 15% by mass or less of a component derived from an amphoteric monomer in an aqueous resin segment. Step I for obtaining, and Step II for fusing the aggregate X,
An electrostatic charge image in which the mass ratio of the crystalline polyester (A) to the amorphous composite resin (B) (crystalline polyester (A) / amorphous composite resin (B)) is 1/99 to 40/60. A method for producing a developing toner.

<2> In step I, the resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B) are aggregated in the aqueous medium to obtain an aggregate x for cores. And the resin particles containing the amorphous polyester (C) are further mixed in the aqueous medium to agglomerate the resin particles containing the core aggregate x and the amorphous polyester (C). The process for producing an electrostatic charge image developing toner according to <1>, further comprising the step Ib of obtaining the aggregate X.
<3> The method for producing a toner for developing an electrostatic charge image according to <2>, wherein the amorphous polyester (C) has a volume-median particle size of 10 nm to 200 nm.
<4> In the step I, the volume-median particle size of the resin particles containing the crystalline polyester (A) is 30 nm or more and 300 nm or less, and the volume of the resin particles containing the amorphous composite resin (B) The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <3>, wherein the unit particle diameter is 30 nm to 300 nm.
<5> Any of <1> to <4>, wherein the polyester segment of the amorphous composite resin (B) is obtained by condensation polymerization of a carboxylic acid component containing an aromatic dicarboxylic acid and an alcohol component. A method for producing a toner for developing an electrostatic image as described above.
<6> The polyester segment of the amorphous composite resin (B) is obtained by condensation polymerization of a carboxylic acid component containing an aliphatic dicarboxylic acid having 2 to 6 carbon atoms and an alcohol component. <1> A method for producing a toner for developing an electrostatic charge image according to any one of to <5>.
<7> The method for producing a toner for developing an electrostatic charge image according to <6>, wherein the aliphatic dicarboxylic acid having 2 to 6 carbon atoms is fumaric acid.
<8> A polyester part of the crystalline polyester (A) obtained by polycondensing a carboxylic acid component containing a dicarboxylic acid having 4 to 12 carbon atoms and an alcohol component containing a diol having 8 to 12 carbon atoms. The method for producing an electrostatic charge image developing toner according to any one of <1> to <7>.
<9> Among monomers serving as raw materials for the polyester portion of the crystalline polyester (A), the total amount of the dicarboxylic acid having 4 to 12 carbon atoms and the diol having 8 to 12 carbon atoms is the total amount of the carboxylic acid component and the alcohol component. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <8>, wherein the toner is 80 mol% or more.
<10> The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <9>, wherein the crystalline polyester (A) is a crystalline composite resin including a polyester segment and an addition polymerization resin segment. .
<11> A crystal in which the crystalline polyester (A) includes a polyester segment and an addition polymerization resin segment, and includes 3% by mass to 15% by mass of a component derived from an amphoteric monomer in the addition polymerization resin segment. The method for producing a toner for developing an electrostatic charge image according to any one of <1> to <10>, wherein the toner is an adhesive composite resin.
<12> Any one of <1> to <11>, wherein the resin particles containing the crystalline polyester (A) are obtained by adding an aqueous medium to the crystalline polyester (A) and performing phase inversion emulsification. A method for producing a toner for developing an electrostatic image as described above.

<13> An electrostatic charge image developing toner obtained by the production method according to any one of <1> to <12>.
<14> The structure according to <13>, having a core-shell structure including a core portion containing the crystalline polyester (A) and the amorphous composite resin (B) and a shell portion containing the amorphous polyester (C). Toner for developing electrostatic images.
<15> The toner for developing an electrostatic charge image according to <15>, wherein the amorphous polyester (C) of the shell part has a glass transition temperature of 50 ° C. or higher and 80 ° C. or lower.
<16> The glass transition temperature of the amorphous polyester (C) of the shell portion is higher than the glass transition temperature of the amorphous composite resin (B) by 5 ° C. or more, <14> or <15> Toner for developing electrostatic images.
<17> Mass ratio of total amount of crystalline polyester (A) and amorphous composite resin (B) to amorphous polyester (C) [total amount of crystalline polyester (A) and amorphous composite resin (B) / Amorphous polyester (C)] is an electrostatic image developing toner according to any one of <14> to <16>, wherein the toner is 60/40 or more and 99/1 or less.

  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, glass transition temperature, etc.]
(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 diameter 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 temperature of endothermic peak Using a differential scanning calorimeter “Q-100” (manufactured by T.A. Instruments Japan Co., Ltd.), the temperature is reduced from room temperature (20 ° C.) to 10 ° C./min. The sample cooled to 0 ° C. was allowed to stand for 1 minute as it was, and then measured while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the highest endothermic peak temperature.
(3) Melting point Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample was weighed into an aluminum pan and up to 200 ° C. The temperature was raised, and the temperature was cooled to 0 ° C. at a temperature lowering 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. Of the endothermic peaks observed, the temperature of the peak with the largest peak area was taken as the melting point.
(4) 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 The temperature was raised to 0 ° C., and the temperature was cooled to 0 ° C. at a rate of temperature drop 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 temperature of the endothermic peak and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.

[Volume-median particle size of the 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. From this, the volume median particle size (D ₅₀ ) was determined.

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particles, Binder Resin Composition Particles, Colorant Particles, and Charge Control Agent Particles]
(1) Measuring apparatus: Laser diffraction 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.

The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume median particle size (D ₅₀ )) × 100

[Solid content concentration of aqueous dispersion, binder resin composition particles, colorant dispersion, charge control agent dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory), a sample 5 g was dried at a temperature of 150 ° C. and in a measurement mode 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 (mass%) of sample = [(W−W0) / W] × 100
W: Sample mass before measurement (initial sample mass)
W0: Sample weight after measurement (absolute dry weight)

[Low-temperature fixability of toner]
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so that fixing outside the apparatus was possible, and a printed matter was obtained in an unfixed state (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). After that, using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure becomes 40 kgf, the fixing roll temperature is gradually increased from 80 ° C. to 240 ° C. by 5 ° C., and unfixed at each temperature. A fixing test of the printed matter in the state was performed. A cellophane adhesive tape “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) is pasted on the image portion of the printed matter, passed through a fixing roller set at 30 ° C., and then the tape is peeled off. It was. The optical reflection density before and after the tape was peeled was measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth Co.), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The temperature of the fixing roller that exceeded the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixing property. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

[Heat resistant storage stability of toner]
A 25 mL container (diameter: about 3 cm) was charged with 5 g of toner and allowed to stand for 96 hours in an environment of a temperature of 55 ° C. and a humidity of 75%. 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 84 hours.
B: Aggregation is not observed after 60 hours, but aggregation is observed after 84 hours.
C: Aggregation is not observed after 48 hours, but aggregation is observed after 60 hours.
D: Aggregation is not observed after 36 hours, but aggregation is observed after 48 hours.
E: Aggregation is not observed after 24 hours, but aggregation is observed after 36 hours.
F: Aggregation is observed after 24 hours.

[Bending resistance of printed matter]
The toner was mounted on an apparatus in which the fixing machine of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so that fixing outside the apparatus was possible, and a printed matter was obtained in an unfixed state (printing area: 20 cm × 20 cm, adhesion amount: 0.5 mg / cm ² ). Thereafter, fixing was performed at a fixing roll temperature of 160 ° C. using a fixing machine (fixing speed 300 mm / sec) adjusted so that the total fixing pressure was 40 kgf. This image was bent inward at 50 g / cm ² for 30 seconds, reopened, and the damaged image was wiped off with a soft cloth. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

[Production of polyester]
Production Examples 1-4
(Production of crystalline polyesters A-1 to A-4)
The polyester segment raw material monomer and esterification catalyst shown in Table 1 were placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere. Then, after raising the temperature from 135 ° C. to 160 ° C. over 6 hours, the reaction was performed at 160 ° C., and it was confirmed that the reaction rate reached 95% or more, and the raw material monomers for the vinyl-based resin segment shown in Table 1, A mixed solution of both reactive monomers and a radical polymerization initiator was added dropwise over 1 hour. Then, after hold | maintaining at 160 degreeC for 30 minutes, it heated up over 200 hours to 200 degreeC, and also was made to react under reduced pressure of 8 kPa for 2 hours, and crystalline polyester A-1 to A-4 was obtained. The physical properties of the resin are shown in Table 1. 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.

Production Examples 5, 6, 8
(Production of amorphous composite resins B-1, B-2, B-4)
The raw material monomer of the polyester segment other than fumaric acid shown in Table 2, the esterification catalyst and the esterification cocatalyst were added to a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube. And heated up to 235 ° C. in a mantle heater over 2 hours 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 raw material monomer of the vinyl resin segment, the both reactive monomers and the radical polymerization initiator shown in Table 2 The solution 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 fumaric acid 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 performed at 40 kPa until the softening point shown in Table 2 was reached, and amorphous composite resins B-1, B-2, and B-4 were obtained. 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.

Production Examples 7, 9, 10
(Production of amorphous polyester B-3, C-1, C-2)
As shown in Tables 2 and 3, the raw material monomers of polyester other than fumaric acid and dodecenyl succinic anhydride, esterification catalyst and esterification co-catalyst were equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube. The mixture was placed in a liter four-necked flask and heated to 235 ° C. over 2 hours in a mantle heater in a nitrogen atmosphere. Then, after reacting at 235 ° C. for 10 hours, the mixture was reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Then, as shown in Tables 2 and 3, fumaric acid, dodecenyl succinic anhydride, and a radical polymerization inhibitor (4-t-butylcatechol) were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 degreeC for 1 hour, it reacted until it reached the softening point of Table 2 and 3 at 40 kPa, and amorphous polyester B-3, C-1, and C-2 were obtained.

[Production of colorant dispersion]
Production Example 11
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. The mixture was dispersed for 10 minutes using a homogenizer to obtain a colorant dispersion containing colorant particles. The volume median particle size (D ₅₀ ) of the colorant particles was 120 nm, and the solid content concentration was 22% by mass.

[Production of charge control agent dispersion]
Production Example 12
50 g of salicylic acid compound “Bontron E-84” (made by Orient Chemical Co., Ltd.) as a charge control agent, 5 g of “Emulgen 150” (made by Kao Corporation) and 200 g of ion-exchanged water are mixed as a nonionic surfactant. Then, glass beads were used and dispersed for 10 minutes using a sand grinder to obtain a charge control agent dispersion containing charge control agent particles. The volume median particle size (D ₅₀ ) of the charge control agent particles was 400 nm, and the solid content concentration was 22% by mass.

[Production of aqueous dispersion]
Production Example 13
(Production of aqueous dispersion A-1)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 150 g of crystalline polyester A-1 and 75 g of ethyl acetate were charged and dissolved at 70 ° C. over 2 hours. . A 20% by mass aqueous ammonia solution (pKa: 9.3) was added to the obtained solution so that the degree of neutralization was 100 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes (step 1).
While maintaining the temperature at 70 ° C., 675 g of ion-exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min) (phase 2 emulsification). While maintaining the temperature at 70 ° C., ethyl acetate was distilled off under reduced pressure (Step 3). Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then an anionic surfactant “Emar E27C” (sodium polyoxyethylene lauryl ether sulfate, Kao Corporation). 16.7 g of the product (solid content, 28% by mass) were mixed and completely dissolved (step 4). 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. The volume median particle size of the resin particles in the obtained aqueous dispersion was 87 nm.

Production Examples 14 to 23
(Production of aqueous dispersions A-2 to A-4, B-1 to B-4, AB, C-1 and C-2)
In Production Example 13, an aqueous dispersion was obtained in the same manner as in Production Example 13, except that the resin used in Step 1 was changed to the resins shown in Tables 4 to 6. Tables 4 to 6 show the volume-median particle diameters of the resin particles in the obtained aqueous dispersion.

[Manufacture of toner for developing electrostatic image]
Example 1
60 g of the aqueous dispersion A-1 obtained in Production Example 12, 240 g of the aqueous dispersion B-1, 8 g of the colorant dispersion, 2 g of the charge control agent dispersion, and 52 g of deionized water were placed in a 3 L container. Under stirring at 100 r / min (peripheral speed 31 m / min) with an anchor-type stirrer, 150 g of a 0.1 mass% calcium chloride aqueous solution was added dropwise at 20 ° C. over 30 minutes. Then, it heated up to 50 degreeC, stirring. After 3 hours, the volume median particle size reached 4 μm. Thereafter, 33 g of the aqueous dispersion C-1 was added as a toner shell and stirred to form a shell. Thereafter, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 28% by mass) with 37 g of deionized water was added as an aggregation terminator. 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” (Nippon Aerosil Co., Ltd.) with respect to 100 parts by mass of the toner particles. Manufactured, number average particle size 16 nm) 0.6 parts by mass, titanium oxide “JMT-150IB” (manufactured by Teica Co., Ltd., number average particle size 15 nm) 0.5 parts by mass, ST, A0 equipped with a stirring blade 10 L A Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) was added and stirred at 3000 rpm for 2 minutes to obtain a toner. Table 7 shows the evaluation results of the obtained toner.

Examples 2-7 and Comparative Examples 1-5
A toner was obtained in the same manner as in Example 1 except that the aqueous dispersion used was changed to the type and amount of the aqueous dispersion shown in Table 7. The evaluation results of the obtained toner are shown in Tables 7-8.

  From Tables 7 to 8, the electrostatic charge image developing toners of the examples all have low-temperature fixability, heat-resistant storage properties, and bending resistance of the obtained printed matter as compared with the electrostatic charge image developing toners of the comparative examples. It turns out that it is excellent.

  The toner for developing an electrostatic charge image obtained by the production method of the present invention is excellent in low-temperature fixing property, heat-resistant storage property and bending resistance of the obtained printed matter, and therefore can be suitably used as a toner used in electrophotography. According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (10)

Resin particles containing a crystalline polyester (A) having a polyester portion obtained using a monomer having a molar average carbon number of 8 to 12, a polyester segment and an addition polymerization resin segment, the addition polymerization resin segment Step I for obtaining an aggregate X containing, in an aqueous medium, resin particles containing an amorphous composite resin (B) containing a constituent component derived from an amphoteric monomer in an amount of 3% by mass to 15% by mass And Step II of fusing the aggregate X
An electrostatic charge image in which the mass ratio of the crystalline polyester (A) to the amorphous composite resin (B) (crystalline polyester (A) / amorphous composite resin (B)) is 1/99 to 40/60. A method for producing a developing toner.   Step I is a step of aggregating the resin particles containing the crystalline polyester (A) and the resin particles containing the amorphous composite resin (B) in the aqueous medium to obtain the core aggregate x. Ia and resin particles containing amorphous polyester (C) are further mixed in the aqueous medium, the core aggregate x and the resin particles containing amorphous polyester (C) are aggregated, The method for producing a toner for developing an electrostatic charge image according to claim 1, further comprising a step Ib for obtaining the aggregate X.   The volume median particle size of the resin particles containing the crystalline polyester (A) in Step I is 30 nm or more and 300 nm or less, and the volume median particle size of the resin particles containing the amorphous composite resin (B). The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein is 30 nm or more and 300 nm or less.   The polyester segment of the amorphous composite resin (B) is obtained by condensation polymerization of a carboxylic acid component containing an aliphatic dicarboxylic acid having 2 to 6 carbon atoms and an alcohol component. A method for producing a toner for developing an electrostatic image according to any one of the above.   The polyester part of the crystalline polyester (A) is obtained by polycondensing a carboxylic acid component containing a dicarboxylic acid having 4 to 12 carbon atoms and an alcohol component containing a diol having 8 to 12 carbon atoms, The method for producing a toner for developing an electrostatic image according to claim 1.   The method for producing a toner for developing an electrostatic charge image according to claim 1, wherein the crystalline polyester (A) is a crystalline composite resin containing a polyester segment and an addition polymerization type resin segment.   The static resin according to any one of claims 1 to 6, wherein the resin particles containing the crystalline polyester (A) are obtained by phase-inversion emulsification by adding an aqueous medium to the crystalline polyester (A). A method for producing a toner for developing a charge image.   An electrostatic charge image developing toner obtained by the production method according to claim 1.   The electrostatic charge of Claim 8 which has a core-shell structure containing the core part containing the said crystalline polyester (A) and an amorphous composite resin (B), and the shell part containing the said amorphous polyester (C). Toner for image development.   The toner for developing an electrostatic charge image according to claim 9, wherein the glass transition temperature of the amorphous polyester (C) in the shell part is higher by 5 ° C or more than the glass transition temperature of the amorphous composite resin (B). .