JP6204756B2 - Toner for electrostatic image development - Google Patents

Description

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

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 and high speed, the binder resin needs to satisfy various performances such as low-temperature fixability at the same time. Therefore, the composition and physical properties of styrene acrylic resins and polyester resins have been studied, and in addition, in order to satisfy a plurality of performances simultaneously, the combination of a plurality of resins has been studied.

For example, in Patent Document 1, a graft or block copolymer of a crystalline polyester and an amorphous vinyl polymer is used as a binder for the purpose of improving low-temperature fixability, blocking resistance, releasability, and image quality stability. Disclosed is an electrostatic image developing toner in which two types of vinyl resin fine particles having different average particle diameters charged to the same polarity as the base particles are fixed to the base particles by mechanical impact force. Yes.

  Patent Document 2 includes a core layer containing an amorphous resin and a colorant and a shell layer covering the core layer for the purpose of improving low-temperature fixability, heat-resistant storage property, and toner crushability. A toner for developing an electrostatic charge image having a core-shell structure in which a layer includes composite resin particles containing a crystalline polyester resin and an amorphous resin is disclosed.

  Patent Document 3 includes a binder resin and a colorant for the purpose of improving low-temperature fixability, blocking resistance, and document offset resistance, and the binder resin includes a styrene monomer and (meth). An electrostatic charge comprising an amorphous resin obtained from a radical polymerizable monomer unit containing an acrylate monomer and a crystalline resin, and a specific endothermic peak and endothermic amount are measured by a differential scanning calorimeter Image developing toners are disclosed.

  Patent Document 4 discloses an alcohol component containing an aliphatic diol having 2 to 10 carbon atoms and an aliphatic dicarboxylic acid compound having 8 to 12 carbon atoms for the purpose of improving the environmental stability of chargeability and weighted storage stability. After subjecting the carboxylic acid component to a condensation polymerization reaction to cooling to a specific temperature, heat treatment at a specific temperature to obtain a crystalline polyester, an aqueous dispersion containing the obtained crystalline polyester A step of obtaining an aqueous dispersion of aggregated particles by mixing the obtained aqueous dispersion with an aqueous dispersion containing an amorphous resin and then subjecting to an aggregation step, and an aqueous dispersion of the obtained aggregated particles A method for producing a binder resin for toner is disclosed, which includes a step of obtaining an aqueous dispersion of coalesced particles by subjecting the solution to a coalescing step.

JP-A-4-188155 JP 2011-149986 A JP 2011-197659 A JP 2011-107341 A

As printing speed increases, it is necessary to fix toner with low energy. For this purpose, it is necessary to fix the toner at a low temperature. However, in order to improve the low-temperature fixability, when a large amount of crystalline resin or wax component having excellent melting property is blended, the strength of the toner is lowered and the durability is lowered. Transparency when printed is reduced. Therefore, there has been a demand for a toner having improved low-temperature fixability while maintaining durability and transparency.
An object of the present invention is to provide a toner for developing an electrostatic image having excellent low-temperature fixability, durability and transparency, and a method for producing the toner.

  The present inventors have considered that the factors affecting the low-temperature fixability, durability, and transparency of the toner are the thermal characteristics of the resin constituting the toner and the dispersibility when a plurality of resins are used. It was. As a result, an electrostatic charge image developing toner comprising an addition polymerization resin containing styrene and a composite resin comprising a crystalline polyester having a specific structure and an addition polymer containing styrene has low temperature fixability, durability and transparency. I found it excellent.

That is, the present invention provides the following [1] to [2].
[1] An electrostatic charge image developing toner comprising a toner binder resin composition, wherein the toner binder resin composition comprises an addition polymerization resin (A) containing a structural unit derived from styrene, and a carbon number A segment (B1) comprising a crystalline polyester obtained by condensation polymerization of an alcohol component containing an aliphatic diol of 6 to 12 and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms; A composite resin having a segment (B2) composed of an addition polymer containing a derived structural unit and having a mass ratio (B1) / (B2) of the segment (B1) to the segment (B2) of 60/40 to 95/5 An electrostatic charge image developing toner comprising (B) and having a mass ratio (A) / (B) of the addition polymerization resin (A) to the composite resin (B) of 60/40 to 95/5.
[2] A method for producing an electrostatic image developing toner, comprising the following steps 1 to 4.
Step 1: Addition polymerization resin (A) containing a structural unit derived from styrene, an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms, and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms (B1) having a segment (B1) made of a crystalline polyester obtained by condensation polymerization and a segment (B2) made of an addition polymer containing a structural unit derived from styrene, and a mass ratio of (B1) / (B2) Step of Obtaining Aqueous Dispersion of Resin Particles I Containing Composite Resin (B) of which 60/40 to 95/5 is Step 2: Addition Polymer Resin Containing Amorphous Polyester Resin (C) and Structural Unit Derived from Styrene (D) or a process for obtaining a resin aqueous dispersion containing a composite resin (E) having a segment made of polyester and a segment made of an addition polymer containing a structural unit derived from styrene Step 3: Resin aqueous dispersion containing the aqueous dispersion of resin particles I obtained in Step 1 and the amorphous polyester resin (C), addition polymerization resin (D) or composite resin (E) obtained in Step 2 Step of mixing and aggregating the solution to obtain an aqueous dispersion of resin particles II Step 4: Step of fusing the resin particles II obtained in Step 3

  According to the present invention, it is possible to provide an electrostatic image developing toner excellent in low-temperature fixability, durability and transparency, and a method for producing the toner.

[Toner for electrostatic image development]
The toner for developing an electrostatic charge image of the present invention is a toner for developing an electrostatic charge image containing a binder resin composition for toner, and the binder resin composition for toner includes an addition polymerization containing a structural unit derived from styrene. Resin (A) and a crystalline polyester obtained by polycondensation of an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms It has a segment (B1) and a segment (B2) made of an addition polymer containing a structural unit derived from styrene, and the mass ratio (B1) / (B2) of the segment (B1) to the segment (B2) is 60/40. The composite resin (B) which is -95/5 is included, and the mass ratio (A) / (B) of the addition polymerization resin (A) and the composite resin (B) is 60 / 40-95 / 5.

The reason why the toner for developing an electrostatic charge image of the present invention is excellent in low-temperature fixability, durability and transparency is not clear, but is considered as follows.
The binder resin composition for toner used in the present invention contains an addition polymerization resin (A) containing a structural unit derived from styrene and a specific composite resin (B) in a specific ratio. Since there are more addition polymerization resin (A) than composite resin (B), it is thought that the composite resin (B) has taken the structure disperse | distributed in addition polymerization resin (A).
As described above, the composite resin (B) in the present invention has a higher ratio of the segment (B1) made of the crystalline polyester than the segment (B2) made of the addition polymer. The polyester portion is dispersed while maintaining crystallinity, and melts quickly at the melting point of the crystal portion. In addition, since the composite resin (B) in the present invention contains a long-chain aliphatic monomer, the hydrophobic addition polymerization resin (A) derived from styrene and having a main chain of polyethylene and an aromatic ring in the side chain; It is considered that the compatibility of is increased. In this way, when the compatibility between the composite resin (B) and the addition polymerization resin (A) is high, no interfacial peeling occurs between these resins, so it can withstand long-term printing, has no printing unevenness, and is durable. It is considered that it has excellent properties. Moreover, since the crystalline polyester part which becomes normally opaque is disperse | distributed in the addition polymerization resin (A) with a high dispersion degree, it is thought that the transparency at the time of printing on a film is also high.

Hereinafter, each component used in the present invention will be described.
<Addition polymerization resin (A)>
The addition polymerization resin (A) used in the present invention contains a structural unit derived from styrene.
The addition polymerization resin (A) may contain a structural unit derived from another raw material monomer in addition to a structural unit derived from styrene. Other raw material monomers include styrenes other than styrene such as α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; vinyl acetate and propion. Vinyl esters such as vinyl acid; alkyl (1 to 18 carbon) esters of (meth) acrylic acid; esters of ethylenic monocarboxylic acid such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone, and the like. Among these, from the viewpoint of low-temperature fixability, durability and transparency of the toner, (meth) acrylic acid Alkyl (C1-C18) esters are preferred and 2-ethylhexyl acrylate is preferred. Over DOO, long chain alkyl-butyl acrylate and acrylic acid (having 12 to 18 carbon atoms) more preferably at least one selected from ester, butyl acrylate are more preferred. In the present specification, “(meth) acrylic acid” includes both acrylic acid and methacrylic acid.

When the addition polymerization resin (A) contains a structural unit derived from styrene and a structural unit derived from an alkyl ester of (meth) acrylic acid, the content of the structural unit derived from styrene is low-temperature fixing of the toner. From the viewpoint of durability, durability, and transparency, in the addition polymerization resin (A), preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and still more preferably 60% by mass or more. Also, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less, and still more preferably 65% by mass or less.
Further, the total content of the structural unit derived from styrene and the structural unit derived from the alkyl ester of (meth) acrylic acid in the addition polymerization resin (A) depends on the low-temperature fixability, durability and transparency of the toner. From the viewpoint, it is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass.

The addition polymerization resin (A) may be an amorphous resin or a crystalline resin. Here, the crystallinity of the resin such as the addition polymerization resin (A) is the ratio between the softening point and the maximum peak temperature of the endotherm measured by the differential scanning calorimeter (DSC), that is, “softening point / maximum endothermic peak temperature”. Expressed by the defined crystallinity index. 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, “crystallinity” means that the crystallinity index is 0.6 to 1.4, preferably 0.8 to 1.2, more preferably 0.9 to 1.1. “Amorphous” means that the crystallinity index is 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 addition polymerization resin (A), and the peak with a difference from the softening point exceeding 20 ° C is due to the glass transition of the amorphous resin. The resulting peak.

The softening point of the addition polymerization resin (A) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 10 ° C. or higher, and still more preferably, from the viewpoint of low-temperature fixability, durability and transparency of the toner. 110 ° C. or higher, more preferably 115 ° C. or higher, preferably 140 ° C. or lower, more preferably 135 ° C. or lower, still more preferably 130 ° C. or lower, still more preferably 125 ° C. or lower, even more preferably 123 ° C. It is as follows.
When the addition polymerization resin (A) is an amorphous resin, the glass transition temperature of the addition polymerization resin (A) is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and still more preferably from the same viewpoint. It is 47 ° C. or higher, more preferably 50 ° C. or higher, preferably 65 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 58 ° C. or lower, and still more preferably 57 ° C. or lower.

From the same viewpoint, the acid value of the addition polymerization resin (A) is preferably 20 mgKOH / g or less, more preferably 15 mgKOH / g or less, still more preferably 10 mgKOH / g or less, and still more preferably 5 mgKOH / g or less.
The crystallinity index, 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 selecting reaction conditions.

  In addition, you may use a polymerization initiator, a crosslinking agent, etc. for the addition polymerization of the raw material monomer of addition polymerization resin (A) as needed. The addition polymerization conditions for the addition polymerization resin (A) can be appropriately determined based on conventionally known addition polymerization reaction conditions depending on the raw material monomers, the type of the target resin, and the like.

<Composite resin (B)>
The composite resin (B) used in the present invention is obtained by condensation polymerization of an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms. A segment (B1) made of crystalline polyester and a segment (B2) made of an addition polymer containing a structural unit derived from styrene, and the mass ratio (B1) / (segment (B1) to segment (B2) B2) is 60/40 to 95/5.

When the mass ratio (B1) / (B2) is less than 60/40, the crystal portion is reduced and the low-temperature fixability is poor. When the mass ratio (B1) / (B2) is more than 95/5, the compatibility between the composite resin (B) and the addition polymerization resin (A) is lowered, and interfacial peeling occurs between these resins, resulting in durability. Inferior. From this viewpoint, the mass ratio (B1) / (B2) is preferably 70/30 or more, more preferably 80/20 or more, still more preferably 85/15 or more, and preferably 94/6 or less. Preferably it is 93/7 or less. Preferably it is 70 / 30-95 / 5, More preferably, it is 80 / 20-94 / 6, More preferably, it is 85 / 15-93 / 7. Moreover, from a transparency viewpoint, Preferably it is 60 / 40-94 / 6, More preferably, it is 60 / 40-90 / 10, More preferably, it is 60 / 40-85 / 15.
The total content of the segments (B1) and (B2) in the composite resin (B) is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and even more preferably 99. It is at least mol%, more preferably 100 mol%.

(Segment made of crystalline polyester (B1))
The crystalline polyester constituting the segment (B1) made of crystalline polyester comprises an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms. It is obtained by condensation polymerization.

[Alcohol component]
The alcohol component which is a raw material monomer for the segment (B1) contains an aliphatic diol having 6 to 12 carbon atoms. When the aliphatic diol has less than 6 carbon atoms, the composite resin (B) is hardly compatible with the addition polymerization resin (A), so that the low-temperature fixability, durability and transparency of the toner are inferior. When the aliphatic diol has more than 12 carbon atoms, the composite resin (B) becomes difficult to be compatible with the addition polymerization resin (A) and has a high melting point, so that the toner has a low temperature fixability, durability and transparency. It becomes inferior to. From this viewpoint, the aliphatic diol contained in the alcohol component preferably has 8 to 12, more preferably 10 to 12, and still more preferably 12.
Specifically, as the alcohol component, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable, and 1,8-octanediol, 10-decanediol and 1,12-dodecanediol are more preferable, 1,10-decanediol and 1,12-dodecanediol are more preferable, and 1,12-dodecanediol is still more preferable.
From the same viewpoint, the content of the aliphatic diol having 6 to 12 carbon atoms in the alcohol component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more. Preferably it is 95 mol% or more, More preferably, it is 99 mol% or more, More preferably, it is 100 mol%.

[Carboxylic acid component]
The carboxylic acid component which is a raw material monomer of the crystalline polyester constituting the segment (B1) contains an aliphatic dicarboxylic acid having 8 to 12 carbon atoms. When the aliphatic dicarboxylic acid has less than 8 carbon atoms, the composite resin (B) is hardly compatible with the addition polymerization resin (A), so that the low-temperature fixability, durability and transparency of the toner are inferior. When the aliphatic dicarboxylic acid having more than 12 carbon atoms is used, the composite resin (B) is hardly compatible with the addition polymerization resin (A) and has a high melting point. It becomes inferior. From this viewpoint, the carboxylic acid component preferably contains an aliphatic dicarboxylic acid having 10 to 12 carbon atoms, and more preferably contains an aliphatic dicarboxylic acid having 10 carbon atoms.
Specifically, as the carboxylic acid component, 1,8-octane diacid, 1,10-decanedioic acid, and 1,12-dodecanedioic acid are preferable, and 1,10-decanedioic acid, 1,12- Dodecanedioic acid is more preferred, and 1,10-decanedioic acid is even more preferred.
From the same viewpoint, the content of the aliphatic dicarboxylic acid having 8 to 12 carbon atoms in the carboxylic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, Still more preferably, it is 95 mol% or more, More preferably, it is 99 mol% or more, More preferably, it is 100 mol%.

[Molar ratio of carboxylic acid component to alcohol component]
In the crystalline polyester constituting the segment (B1), the molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) is preferably 0.4 or more, more preferably from the viewpoint of reactivity and physical property adjustment. Is 0.5 or more, more preferably 0.7 or more, still more preferably 0.85 or more, preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.15 or less. is there.

(Segment made of addition polymer (B2))
A composite resin (B) contains the segment (B2) which consists of an addition polymer containing the structural unit derived from styrene. For this reason, the compatibility with the addition polymerization resin (A) containing a structural unit derived from styrene is increased, so that the toner has excellent low-temperature fixability, durability, and transparency.

The segment (B2) may contain a structural unit derived from another raw material monomer in addition to the structural unit derived from styrene. Moreover, you may include the site | part originating in a radical polymerization initiator. As the radical polymerization initiator, a peroxide radical polymerization initiator is preferable, and dibutyl peroxide, benzoyl peroxide, t-butyl peroxybenzoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, t-butyl. Hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, 2,2-bis- (4,4-t-butylperoxycyclohexyl) propane, At least one of tris- (t-butylperoxy) triazine is more preferable, and dibutyl peroxide is still more preferable. The segment (B2) preferably contains a constituent part derived from an amphoteric monomer capable of reacting with both the styrene of the segment (B2) and the segment (B1). The structural unit derived from the both reactive monomers can be a bonding point between the segments (B1) and (B2).
Examples of the both reactive monomers include compounds having at least one functional group 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. 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 resin that becomes the dispersed phase 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, and acrylic acid is more preferable.
Moreover, as raw material monomers other than styrene and both reactive monomers, the same thing as addition polymerization resin (A) is preferable from a viewpoint of improving compatibility with addition polymerization resin (A).

The content of the structural unit derived from styrene in the segment (B2) is preferably 80% by mass or more, more preferably 85% by mass or more, and still more preferably, from the viewpoint of low-temperature fixability, durability and transparency of the toner. Is 90% by mass or more, preferably 100% by mass or less, more preferably 99% by mass or less, and still more preferably 95% by mass or less.
In the segment (B2), the content of the structural unit derived from both reactive monomers is preferably 1% by mass or more, more preferably 3% by mass or more, from the viewpoint of low-temperature fixability, durability and transparency of the toner. More preferably, it is 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.

(Physical properties of composite resin (B))
The composite resin (B) may be an amorphous resin or a crystalline resin, but is preferably crystalline.
The softening point of the composite resin (B) is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, still more preferably 70 ° C. or higher, and still more preferably 75, from the viewpoint of low-temperature fixability, durability, and transparency of the toner. Or higher, more preferably 80 ° C. or higher, and preferably 110 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 95 ° C. or lower, still more preferably 93 ° C. or lower, even more preferably 90 ° C. or lower. It is. The melting point of the composite resin (B) used in the present invention is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and still more preferably 70 ° C. or higher, from the viewpoints of low-temperature fixability, durability and transparency of the toner. , More preferably 75 ° C. or higher, still more preferably 80 ° C. or higher, preferably 100 ° C. or lower, more preferably 95 ° C. or lower, still more preferably 90 ° C. or lower, still more preferably 85 ° C. or lower, more More preferably, it is 83 degrees C or less.

  The acid value of the 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 from the viewpoint of low-temperature fixability, durability, and transparency of the toner. Preferably, it is 15 mgKOH / g or more, preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 30 mgKOH / g or less, and still more preferably 25 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.

(Production method of composite resin (B))
The composite resin (B) is preferably produced by any of the following methods (1) to (3). In addition, it is preferable that both reactive monomers are supplied to a reaction system with the raw material monomer of the segment (B2) which consists of an addition polymer 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 polycondensation reaction with the alcohol component and carboxylic acid component, which are raw material monomers of the segment (B1) made of crystalline polyester, addition polymerization with the raw material monomer of the segment (B2) made of an addition polymer A method of performing the reaction step (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. The polycondensation reaction in step (A) and the reaction with both reactive monomers may be further advanced as necessary.

(2) Step of condensation polymerization reaction with the raw material monomer of the segment (B1) made of crystalline polyester after the step (B) of the addition polymerization reaction with the raw material monomer of the segment (B2) made of the addition polymer and the both reactive monomers A method of performing (A).
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 segment (B2) made of the addition polymer are performed in parallel.
In this method, the step (A) and the step (B) are carried out under the reaction temperature conditions suitable for the addition polymerization reaction, the reaction temperature is increased, and the step (A) is further performed under the temperature conditions suitable for the condensation polymerization reaction. It is preferable to perform the condensation polymerization reaction. 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. When the bireactive monomer is included as the raw material monomer for the segment (B2), the bireactive monomer is 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 130 ° C. or higher, more preferably 140 ° C. or higher, further preferably 150 ° C. or higher, preferably 180 ° C. or lower, more preferably 170 ° C. or lower, more preferably 165 ° C. or lower. It is.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization. The temperature of the addition polymerization reaction is preferably 150 ° C. or higher, more preferably 160 ° C. or higher, further preferably 180 ° C. or higher, preferably 250 ° C. or lower, more preferably 230 ° C. or lower, still more preferably 210 ° C. or lower. It is.

≪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 0.01 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 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 2 parts by mass or less.

<Contents of addition polymerization resin (A) and composite resin (B)>
As above-mentioned, mass ratio (A) / (B) of addition polymerization resin (A) and composite resin (B) is 60 / 40-95 / 5. When the ratio is less than 60/40, the ratio of the addition polymerization resin (A) is low, so that the durability is poor. When it exceeds 95/5, since the ratio of the addition polymerization resin (A) is low, the low-temperature fixability is inferior. That is, from the viewpoint of durability, the mass ratio (A) / (B) is preferably 70/30 to 95/5, more preferably 80/20 to 95/5, still more preferably 85/15 to 93/7. It is. Further, from the viewpoint of low-temperature fixability, it is preferably 60/40 to 93/7, more preferably 80/20 to 93/7, and still more preferably 87/13 to 92/8. Moreover, from a viewpoint of transparency, Preferably it is 70 / 30-95 / 5, More preferably, it is 80 / 20-95 / 5, More preferably, it is 91 / 9-95 / 5.

  Further, from the viewpoint of low-temperature fixability, durability, and transparency, the segment (B1) is preferably 5% by mass or more, more preferably 6% by mass with respect to the total amount of the resin (A) and the resin (B). More preferably, it is 7% by mass or more, preferably 38% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and still more preferably 15% by mass or less.

  The toner for developing an electrostatic charge image of the present invention may contain other resins in addition to the aforementioned addition polymerization resin (A) and composite resin (B). However, the total amount of the addition polymerization resin (A) and the composite resin (B) in the resin component of the electrostatic charge image developing toner is preferably 80% by mass or more from the viewpoint of low-temperature fixability, durability, and transparency. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, More preferably, it is 99 mass% or more, More preferably, it is 100 mass%.

The electrostatic charge image developing toner of the present invention contains other components such as a release agent, a charge control agent, and a colorant in addition to the resin component such as the addition polymerization resin (A) and the composite resin (B). May be included. Below, another component is demonstrated.
<Release agent>
As the mold release agent, ester wax, hydrocarbon wax, silicone wax, fatty acid amide and the like can be used. Among these, hydrocarbon wax is preferable from the viewpoint of improving the low-temperature fixability, durability, and transparency of the toner.
Specific examples of the hydrocarbon wax include low-molecular-weight polyolefins such as polyethylene, polypropylene, and polybutene; minerals such as ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax; Petroleum-based wax, more preferably paraffin wax. The ester wax refers to a wax having an ester bond and an acid value of 1 mgKOH / g or more and 10 mgKOH / g or less.
Examples of the ester wax include synthetic ester wax and natural ester wax. Examples of the synthetic ester wax include esters composed of a long-chain alcohol and a fatty acid, and preferably at least one fatty acid ester of behenyl behenate, stearyl stearate, and pentaerythritol. The natural ester wax is preferably at least one of carnauba wax and rice wax.

  The content of the release agent is 100 masses of the total amount of the addition polymerization resin (A) and the composite resin (B) from the viewpoint of improving the low-temperature fixability by improving the releasability of the toner, and from the viewpoint of durability and transparency. Part by weight, preferably 1 part by weight or more, more preferably 3 parts by weight or more, still more preferably 4 parts by weight or more, still more preferably 5 parts by weight or more, still more preferably 6 parts by weight or more, Preferably it is 25 parts by mass or less, more preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, still more preferably 9 parts by mass or less, and even more preferably 8 parts by mass or less. is there.

<Charge control agent>
Examples of the charge control agent include chromium azo dyes, iron azo dyes, aluminum azo dyes, and salicylic acid compounds such as 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 preferably 0.1 parts by mass or more with respect to 100 parts by mass of the total amount of the addition polymerization resin (A) and the composite resin (B) from the viewpoint of improving the image quality. 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 8 parts by mass or less, more preferably 7 parts by mass or less. More preferably, it is 5 parts by mass or less, and still more preferably 2 parts by mass or less.

<Colorant>
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 (Copper Phthalocyanine), Phthalocyanine Green, and Malachite Various pigments such as green oxalate; acridine, xanthene, azo, benzoquinone, azine, anthraquino System, indigo, thioindigo, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more. From the viewpoint of improving the image quality, the addition amount of the colorant is preferably 0.1 parts by mass or more, more preferably 0. 5 parts by mass or more, more preferably 1.0 part by mass or more, still more preferably 2.0 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 8 parts by mass. Part or less, more preferably 5.0 parts by weight or less.

<Structure of toner for developing electrostatic image>
The electrostatic image developing toner of the present invention may be an electrostatic image developing toner having a core and a shell, or may be a single-structure electrostatic image developing toner having no core and shell.
The toner for developing an electrostatic charge image having a single structure contains the resin (A) and the resin (B) as described above. Moreover, you may contain other components, such as the above-mentioned mold release agent, a charge control agent, and a coloring agent other than the resin component as needed. The type and content of each component are as described above.
Next, a toner for developing an electrostatic image having a core and a shell will be described.

<Toner for developing electrostatic image having core and shell>
The toner for developing an electrostatic charge image having a core and a shell according to the present invention has a structure in which the core includes the resin (A) and the resin (B), and the shell is derived from the amorphous polyester resin (C) and styrene. It contains at least one selected from an addition polymerization resin (D) containing units and a composite resin (E) having a segment consisting of polyester and a segment consisting of an addition polymer containing a structural unit derived from styrene.
According to the toner for developing an electrostatic charge image having a core and a shell, the low-temperature fixability, durability and transparency can be further improved by devising the composition and quantity ratio of the core and shell.
In addition, the mass ratio [core / shell] of the resin constituting the core and the resin constituting the shell is preferably 70/30 to 98/2, more preferably 80/20 to 95/5, and still more preferably from this viewpoint. Is 85/15 to 93/7.

(core)
As described above, the core includes the resin (A) and the resin (B). If necessary, in addition to the resin component, other components such as a release agent, a charge control agent, and a colorant may be included. The types and contents of these components are as described above.

(shell)
The shell has an amorphous polyester resin (C), an addition polymerization resin (D) containing a structural unit derived from styrene, and a composite having a segment made of polyester and a segment made of an addition polymer containing a structural unit derived from styrene 1 type or more chosen from resin (E) is included.
From the viewpoint of improving the low-temperature fixability, durability and transparency of the toner, the shell preferably contains at least the amorphous polyester resin (C), and more preferably comprises only the amorphous polyester resin (C). .

[Amorphous polyester resin (C)]
The amorphous polyester resin (C) is obtained by condensation polymerization of an alcohol component and a carboxylic acid component. Next, the alcohol component and the carboxylic acid component will be described.

≪Alcohol ingredient≫
Examples of the alcohol component that is a raw material monomer of the amorphous polyester resin (C) include aliphatic diols, aromatic diols, and trihydric or higher polyhydric alcohols. These alcohol components can be used alone or in combination of two or more.
The alcohol component that is a raw material monomer of the polyester resin contains an alkylene oxide adduct of bisphenol A represented by the following formula (I) from the viewpoint of obtaining a toner having excellent low-temperature fixability, durability, and transparency of the toner. It is preferable.

  (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 mol% or more and 100 mol% or less in the alcohol component from the viewpoint of obtaining a toner excellent in low-temperature fixability, durability and transparency. More preferably, it is 80 mol% or more and 100 mol% or less, and still more preferably 90 mol% or more and 100 mol% or less.

Further, from the viewpoint of enhancing the low-temperature fixability, durability and transparency of the toner, a trivalent or higher alcohol may be used.
Specific examples of the trivalent or higher alcohol include glycerin, pentaerythritol, trimethylolpropane, and the like, and glycerin is preferable from the viewpoint of reactivity and molecular weight adjustment.
When the alcohol component of the amorphous polyester resin (C) contains a trihydric or higher alcohol, the content of the trihydric or higher alcohol is preferably 0.1 mol% in the alcohol component of the polyester resin from this viewpoint. More preferably, it is 1 mol% or more, more preferably 5 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.

≪Carboxylic acid ingredient≫
Examples of the carboxylic acid component that is a raw material monomer of the amorphous polyester resin (C) include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, acid anhydrides thereof, and alkyls thereof (carbons). (Equation 1 or more and 3 or less) esters. 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, 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 dodecenyl succinic acid is more preferable from the viewpoint of low-temperature fixability, durability, and transparency of the toner.
Specific examples of the aromatic dicarboxylic acid include terephthalic acid, phthalic acid, and isophthalic acid. Among these, terephthalic acid is preferable from the same viewpoint.

The content of the aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more in the carboxylic acid component from the viewpoint of low-temperature fixability, durability and transparency. In addition, it is preferably 20 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less. Further, from the same viewpoint, the content of the aromatic dicarboxylic acid is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more in the carboxylic acid component, and preferably It is 99 mol% or less, More preferably, it is 98 mol% or less, More preferably, it is 97 mol% or less.
From the same viewpoint, the total amount of aliphatic dicarboxylic acid and aromatic dicarboxylic acid in the carboxylic acid component is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and even more preferably. Is 100 mol%.

Specific examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4,5-benzenetetracarboxylic acid. An acid (pyromellitic acid) is mentioned.
When a trivalent or higher polyvalent carboxylic acid is used, the content thereof is preferably 0.1 mol% or more in the carboxylic acid component of the polyester resin from the viewpoint of improving the low temperature fixability, durability and transparency of the toner. More preferably, it is 1 mol% or more, More preferably, it is 5 mol% or more, Preferably it is 30 mol% or less.

  From the viewpoint of adjusting physical properties, the alcohol component may contain a monovalent alcohol as appropriate, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

≪Molar ratio of carboxylic acid component to alcohol component≫
The molar ratio (carboxylic acid component / alcohol component) of the carboxylic acid component to the alcohol component that is the raw material monomer for the polycondensation reaction is preferably 0.4 or more, more preferably 0.5 or more, from the viewpoint of reactivity and physical property adjustment. More preferably, it is 0.7 or more, still more preferably 0.85 or more, preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.15 or less.

≪Physical properties of amorphous polyester resin (C) ≫
The softening point of the amorphous polyester resin (C) is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, still more preferably 95 ° C. or higher, and still more preferably, from the viewpoint of low-temperature fixability, durability and transparency. 100 ° C or higher, more preferably 105 ° C or higher, preferably 140 ° C or lower, more preferably 130 ° C or lower, still more preferably 125 ° C or lower, still more preferably 120 ° C or lower, still more preferably 115 ° C. It is as follows.
Further, from the same viewpoint, the glass transition temperature of the amorphous polyester resin (C) is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, still more preferably 60 ° C. or higher, and still more preferably 62 ° C. or higher. Moreover, it is preferably 80 ° C. or lower, more preferably 75 ° C. or lower, still more preferably 70 ° C. or lower, and still more preferably 68 ° C. or lower.

From the same viewpoint, the acid value of the amorphous polyester resin (C) is preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and preferably 1 mgKOH / g. As mentioned above, More preferably, it is 5 mgKOH / g or more, More preferably, it is 10 mgKOH / g or more.
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 addition, you may use a polymerization initiator, a crosslinking agent, etc. for the addition polymerization of the raw material monomer of an amorphous polyester resin (C) as needed. The addition polymerization conditions for the amorphous polyester resin (C) can be appropriately determined based on conventionally known addition polymerization reaction conditions depending on the raw material monomer, the type of the target resin, and the like.

[Addition polymerization resin (D)]
The addition polymerization resin (D) used in the present invention contains a structural unit derived from styrene.
The addition polymerization resin (D) is preferably an addition polymerization resin described as a preferred example of the above addition polymerization resin (A). The addition polymerization resin (D) may be the same as or different from the above addition polymerization resin (A).

[Composite resin (E)]
The composite resin (E) used in the present invention has a segment made of polyester and a segment made of an addition polymer containing a structural unit derived from styrene.
This composite resin (E) is preferably a composite resin in which the polyester in the segment made of polyester is a crystalline polyester, and more preferably a composite resin described as a preferred example of the above-described composite resin (B). . The composite resin (E) may be the same as or different from the composite resin (B) described above.

[Method for producing toner for developing electrostatic image]
A preferred method for producing the toner for developing an electrostatic charge image of the present invention comprises the following steps 1 to 4. Thereby, an electrostatic image developing toner having a core and a shell can be suitably obtained.
Alternatively, Steps 2 and 3 may be omitted, and in Step 4, the aqueous dispersion of resin particles I obtained in Step 1 may be fused to obtain the electrostatic image developing toner of the present invention. Thereby, an electrostatic image developing toner having no shell portion can be obtained.
Step 1: Addition polymerization resin (A) containing a structural unit derived from styrene, an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms, and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms (B1) having a segment (B1) made of a crystalline polyester obtained by condensation polymerization and a segment (B2) made of an addition polymer containing a structural unit derived from styrene, and a mass ratio of (B1) / (B2) Step of Obtaining Aqueous Dispersion of Resin Particles I Containing Composite Resin (B) of which 60/40 to 95/5 is Step 2: Addition Polymer Resin Containing Amorphous Polyester Resin (C) and Structural Unit Derived from Styrene (D) or a process for obtaining a resin aqueous dispersion containing a composite resin (E) having a segment made of polyester and a segment made of an addition polymer containing a structural unit derived from styrene Step 3: Resin aqueous dispersion containing the aqueous dispersion of resin particles I obtained in Step 1 and the amorphous polyester resin (C), addition polymerization resin (D) or composite resin (E) obtained in Step 2 Step of mixing and aggregating the solution to obtain an aqueous dispersion of resin particles II Step 4: Step of fusing the resin particles II obtained in Step 3 Hereinafter, an electrostatic charge image developing toner having a core and a shell A manufacturing method will be described.

<Step 1>
In step 1, an aqueous dispersion of resin particles I containing the aforementioned addition polymerization resin (A) and composite resin (B) is obtained.
In this step 1, from the viewpoint of obtaining a toner having excellent low-temperature fixability, durability and transparency, a resin aqueous dispersion containing an addition polymerization resin (A) and a resin aqueous dispersion containing a composite resin (B) are mixed, The step of agglomerating the addition polymerization resin (A) and the composite resin (B) to obtain an aqueous dispersion of the resin particles I is preferable. Therefore, the process will be described next.
In the present specification, the “aqueous dispersion” means that the medium in which the resin is dispersed may contain a solvent such as an organic solvent, but water is preferably 50% by mass or more, more preferably 70% by mass. % Or more, more preferably 90% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass.

(Preparation of resin aqueous dispersion containing addition polymerization resin (A))
The resin aqueous dispersion containing the addition polymerization resin (A) is prepared by mixing the addition polymerization resin (A), an organic solvent and water, and further, if necessary, a neutralizing agent and a surfactant, stirring, and then organically by distillation or the like. It can be suitably obtained by removing the solvent. Preferably, the addition polymerization resin (A) and, if necessary, the surfactant are dissolved in an organic solvent, and then water and, if necessary, a neutralizing agent are mixed. In addition, when stirring a mixture, arbitrary mixing stirring apparatuses, such as an anchor wing | blade, can be used.

Examples of the organic solvent include alcohol solvents such as ethanol, isopropanol and isobutanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether, tetrahydrofuran and dioxane; and ethyl acetate. . Among these, from the viewpoint of dispersibility of the addition polymerization resin (A), methyl ethyl ketone and ethyl acetate are preferable, and ethyl acetate is more preferable.
Examples of the neutralizing agent include alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; organic bases such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine and tributylamine. From the viewpoint of workability, sodium hydroxide is preferable.
Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap (such as alkyl ether carboxylate); amine salt type and quaternary ammonium salt Type cationic surfactants; polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, and polyoxyethylene alkenyl ethers Polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, polyethylene glycol monostearate Polyoxyethylene fatty acid esters such as over preparative and polyethylene glycol monooleate, non-ionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers, and the like. When using a surfactant, the amount used is preferably 0.1 parts by mass or more, more preferably 100 parts by mass with respect to 100 parts by mass of the addition polymerization resin (A), from the viewpoint of dispersibility of the addition polymerization resin (A). Is 0.5 parts by mass or more, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

The amount of the organic solvent mixed with the resin containing the addition polymerization resin (A) is based on 100 parts by mass of the addition polymerization resin (A) from the viewpoint of the solubility of the addition polymerization resin (A) and the removal of the organic solvent in a subsequent step. Preferably, it is 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 preferably 70 parts by mass or less, more preferably 65 parts by mass. Part or less, more preferably 60 parts by weight or less, and still more preferably 55 parts by weight or less.
The temperature at which the addition polymerization resin (A) and the organic solvent are mixed is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and preferably 90 ° C. from the viewpoint of the solubility of the addition polymerization resin (A). C. or lower, more preferably 80 C or lower.
From the viewpoint of the dispersibility of the addition polymerization resin (A), the solid content concentration of the resulting addition polymerization resin (A) is preferably 5% by mass or more, more preferably 10% by adding water as appropriate. % Or more, more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

  The volume median particle size of the resin particles containing the addition polymerization resin (A) in the aqueous dispersion is preferably 50 nm or more, more preferably 100 nm or more from the viewpoint of uniform aggregation in the subsequent aggregation step. Also, it is preferably 1,000 nm or less, more preferably 500 nm or less, still more preferably 400 nm or less, and still more preferably 350 nm or less. The volume median particle size can be measured by the method described in the examples.

(Preparation of aqueous resin dispersion containing composite resin (B))
The resin aqueous dispersion containing the composite resin (B) is mixed with the composite resin (B), the organic solvent and water, and further mixed with a neutralizing agent and a surfactant as necessary. It is suitably obtained by removing.
More preferably, the resin aqueous dispersion containing the composite resin (B) can be prepared through at least the steps B1 to B3 among the following steps B1 to B4.
Step B1: Step of obtaining a mixture by mixing at least the composite resin (B), an organic solvent and a neutralizing agent Step B2: Step of obtaining a resin dispersion by mixing at least water with the mixture obtained in Step B1 B3: Step of obtaining a resin aqueous dispersion containing the composite resin (B) by removing the organic solvent from the resin dispersion obtained in Step B2. Step B4: Surface active on the resin aqueous dispersion obtained in Step B3 Mixing agent

In addition, it is preferable to mix 70-100 mass% of the total addition amount of surfactant by process B2 and / or process B4. Thereby, the composite resin (B) can be uniformly dispersed in the resin aqueous dispersion containing the composite resin (B). That is, when it is obtained through steps B1 to B3, and when 70 to 100% by mass of the total addition amount of the surfactant is mixed in step B2, it is obtained through steps B1 to B4, and the surfactant. In the case of mixing 70 to 100% by mass of the total added amount in Step B2 and Step B4, it is obtained through Steps B1 to B4, and 70 to 100% by mass of the total added amount of the surfactant is only in Step B4. When mixing with, it is mentioned.
The amount of the surfactant used is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more with respect to 100 parts by mass of the composite resin (B) from the viewpoint of dispersibility of the composite resin (B). Moreover, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

Examples of the organic solvent include alcohol solvents such as ethanol, isopropanol and isobutanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether, tetrahydrofuran and dioxane; and ethyl acetate. . Among these, from the viewpoint of dispersibility of the composite resin (B), methyl ethyl ketone and ethyl acetate are preferable, and ethyl acetate is more preferable.
Examples of the neutralizing agent include alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; organic bases such as ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine and tributylamine. From the viewpoint of workability, sodium hydroxide is preferable.
Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap (such as alkyl ether carboxylate); amine salt type and quaternary ammonium salt Type cationic surfactants; polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether and polyoxyethylene lauryl ether, and polyoxyethylene alkenyl ethers Polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, polyethylene glycol monostearate Polyoxyethylene fatty acid esters such as over preparative and polyethylene glycol monooleate, non-ionic surfactants such as polyoxyethylene / polyoxypropylene block copolymers, and the like.

[Process B1]
Step B1 is a step in which at least the composite resin (B), the organic solvent, and the neutralizing agent are mixed to obtain a mixture.
When stirring, an arbitrary mixing and stirring device such as an anchor blade can be used.

The amount of the organic solvent mixed with the resin containing the composite resin (B) is preferably based on 100 parts by mass of the composite resin (B) from the viewpoint of the solubility of the composite resin (B) and the removal of the organic solvent in the subsequent step. Is 10 parts by mass or more, more preferably 20 parts by mass or more, more preferably 30 parts by mass or more, still more preferably 40 parts by mass or more, and preferably 70 parts by mass or less, more preferably 65 parts by mass or less, More preferably, it is 60 mass parts or less, More preferably, it is 55 mass parts or less.
The temperature at which the composite resin (B) and the organic solvent are mixed is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and preferably 90 ° C. or lower, from the viewpoint of solubility of the composite resin (B). More preferably, it is 80 degrees C or less.

Step B2 is a step of obtaining a resin dispersion by mixing at least water with the mixture obtained in Step B1.
From the viewpoint of improving dispersibility, the amount of water used is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, and still more preferably 200 parts by mass or more, relative to 100 parts by mass of the composite resin (B). More preferably, it is 250 mass parts or more, Preferably it is 500 mass parts or less, More preferably, it is 400 mass parts or less, More preferably, it is 350 mass parts or less, More preferably, it is 300 mass parts or less.
The temperature at which the step B2 is performed is preferably the same as that in the step B1 from the viewpoint of the solubility of the composite resin (B).

Step B3 is a step of obtaining a resin aqueous dispersion containing the composite resin (B) by removing the organic solvent from the resin dispersion obtained in Step B2.
It is preferable to remove the solvent by reducing the pressure of the mixture or resin dispersion.
The temperature at which Step B3 is carried out is preferably the same as Step B1 from the viewpoint of the solubility of the composite resin (B).

  Step B4 is a step of mixing a surfactant with the resin aqueous dispersion obtained in Step B3. However, B4 may be omitted. In addition, when B4 is abbreviate | omitted, 70-100 mass% of the total addition amount of surfactant is mixed by process B2.

  From the viewpoint of dispersibility of the composite resin (B), the solid content concentration of the composite resin (B) obtained through the above steps is preferably 5% by mass or more, more preferably by adding water appropriately. It is adjusted to 10% by mass or more, more preferably 15% by mass or more, preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

  The volume median particle size of the resin particles containing the composite resin (B) in the aqueous dispersion is preferably 50 nm or more, more preferably 60 nm or more, from the viewpoint of uniform aggregation in the subsequent aggregation step. Further, it is preferably 500 nm or less, more preferably 300 nm or less, still more preferably 200 nm or less, and still more preferably 150 nm or less. The volume median particle size can be measured by the method described in the examples.

(Preparation of aqueous dispersion of resin particles I (aggregation step))
Next, the resin aqueous dispersion containing the addition polymerization resin (A) and the resin aqueous dispersion containing the composite resin (B) are mixed, and the addition polymerization resin (A) and the composite resin (B) are aggregated to obtain resin particles. An aqueous dispersion of I is obtained.
In addition, for example, a coloring agent, a release agent, a charge control agent, a conductivity adjusting agent, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent are added to the aqueous dispersion of the resin particles I. It may be agglomerated after adding an additive such as. The types and amounts used of the colorant, release agent, and charge control agent are as described above.
The additive can also be used as an aqueous dispersion. An aqueous dispersion of each additive is obtained by mixing each additive, a surfactant and water and dispersing the mixture with a disperser.
Further, in the aggregating step, an aggregating agent can be added to effectively agglomerate.

[Aqueous dispersion of colorant]
The volume median particle size (D ₅₀ ) of the aqueous dispersion of the colorant is preferably 50 nm or more, more preferably 80 nm or more, still more preferably 100 nm or more, and preferably 500 nm or less, more preferably 300 nm or less, More preferably, it is 200 nm or less.
The solid content concentration of the aqueous dispersion of the colorant is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably. Is 30% by mass or less, more preferably 25% by mass or less. In addition, the kind of coloring agent is as above-mentioned.

[Aqueous dispersion of release agent]
The volume median particle size (D ₅₀ ) of the aqueous dispersion of the release agent is preferably 100 nm or more, more preferably 300 nm or more, still more preferably 500 nm or more, and preferably 1000 nm or less, more preferably 800 nm or less. More preferably, it is 600 nm or less.
The solid content concentration of the aqueous dispersion of the release agent is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 40% by mass or less. Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less. In addition, the kind of mold release agent is as above-mentioned.

[Aqueous dispersion of charge control agent]
The volume median particle size (D ₅₀ ) of the aqueous dispersion of the charge control agent is preferably 100 nm or more, more preferably 200 nm or more, still more preferably 300 nm or more, and preferably 1000 nm or less, more preferably 800 nm or less. More preferably, it is 500 nm or less.
The solid content concentration of the aqueous dispersion of the charge control agent is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and preferably 40% by mass or less. Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less. In addition, the kind of charge control agent is as above-mentioned.

[Flocculant]
As the aggregating agent, a quaternary ammonium salt cationic surfactant, polyethyleneimine, or the like is used in the organic system, and an inorganic metal salt, an inorganic ammonium salt, a divalent or higher metal complex, or the like is used in the inorganic system. .
Examples of the inorganic metal salt include metal salts such as sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate; polyaluminum chloride, polyaluminum hydroxide, and Examples thereof include inorganic metal salt polymers such as calcium polysulfide. Examples of the inorganic ammonium salt include ammonium sulfate, ammonium chloride, and ammonium nitrate.
When the flocculant is added, the amount added is preferably 0.1 parts by weight or more, more preferably 100 parts by weight with respect to 100 parts by weight of the resin used in this step, from the viewpoint of environmental resistance of the toner and uniform aggregation. It is 0.15 parts by mass or more, more preferably 0.2 parts by mass or more, preferably 5 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.5 parts by mass or less.
In order to cause uniform agglomeration, the flocculant is preferably added after being dissolved in an aqueous medium, and is preferably sufficiently stirred at the time of addition of the flocculant and after completion of the addition.

≪Conditions for this process≫
From the same viewpoint, the temperature in the system in the aggregation step is equal to or higher than the “softening point of the resin constituting the core—75 ° C.” (temperature lower by 75 ° C. than the softening point, the same applies hereinafter) in order to cause uniform aggregation. And it is preferable that it is below the softening point of resin which comprises a core.
In the present invention, the softening point when two or more kinds of resins are used is a temperature obtained by weighted averaging the softening points of all the resins by the mass ratio. Moreover, when using a masterbatch, let the temperature averaged including the resin used for it be a softening point.

[Volume Median Particle Size of Resin Particle I]
The volume median particle size of the resin particles I obtained in the step 1 is preferably 1 μm or more, more preferably 2 μm or more, and further preferably 3 μm or more from the viewpoint of producing toner particles uniformly by uniting in the subsequent step. In addition, it is preferably 10 μm or less, more preferably 8 μm or less, and further preferably 7 μm or less.

<Process 2>
Step 2 is a step of obtaining a resin aqueous dispersion containing the amorphous polyester resin (C), the addition polymerization resin (D), or the composite resin (E).
The composition and amount of the amorphous polyester resin (C), the addition polymerization resin (D), and the composite resin (E) are as described above. The method for obtaining the resin aqueous dispersion and the preferred physical properties are the same as in Step 1 above.
The volume median particle size of the resin aqueous dispersion is preferably 10 nm or more, more preferably 20 nm or more, still more preferably 30 nm or more, and preferably 100 nm or less, more preferably, from the viewpoint of producing uniform core-shell particles. Is 80 nm or less, more preferably 70 nm or less.

<Step 3>
Step 3 is a resin aqueous dispersion containing the aqueous dispersion of resin particles I obtained in Step 1 and the amorphous polyester resin (C), addition polymerization resin (D) or composite resin (E) obtained in Step 2. This is a step of mixing and aggregating the liquid to obtain an aqueous dispersion of resin particles II.
Aggregation conditions are the same as in Step 1 described above.

[Step 4]
Step 4 is a step of fusing the resin particles II obtained in step 3 (fusion step). That is, after adding a coagulation terminator to the aqueous dispersion of aggregated particles II obtained in Step 3 as necessary and then subjecting it to a fusion step, the aggregated particles II in the aqueous dispersion are fused. This is a step of obtaining an aqueous dispersion of fused particles.
In step 4, the aggregated particles obtained in step 3 can be fused by heating.
Here, the fusion particles are obtained by fusing to form a resin in which a plurality of resin particles I existing on the inner side of the agglomerated particles II are fused to form a core, and the agglomerated particles I are agglomerated and coated ( C), (D), or (E) are fused to form a shell, and the core and the shell are appropriately bonded to form a core-shell structure.

The temperature in the system in the step 4 is not less than “softening point of all resins—55 ° C.” or more and “the softening point + 10 ° C.” from the viewpoints of target particle size, particle size distribution, shape control and particle fusing property. Or less, more preferably “the softening point−50 ° C.” or more and “the softening point + 10 ° C.” or less, more preferably “the softening point−45 ° C.” or more and “the softening point + 10 ° C.” or less. Specifically, from the same viewpoint, it is preferably maintained at 40 to 90 ° C, more preferably 50 to 80 ° C. The stirring speed is preferably a speed at which the aggregated particles do not settle. Here, the softening point of the total resin is the softening point of the amorphous polyester (a) when the resin contained in the toner consists only of the amorphous polyester (a) and the amorphous polyester (b). The temperature obtained by weighted averaging the softening points of the amorphous polyester (b) is defined as “softening point of all resins”, and when a resin other than the amorphous polyester (a) and the amorphous polyester (b) is used, The temperature obtained by weighted averaging the softening points of all the resins is defined as “softening point of all resins”.
When an aggregation stopper is used, a surfactant is preferably used as the aggregation stopper, and an anionic surfactant is more preferably used from the viewpoints of availability and operability. 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.

〔Post-process〕
By subjecting the fused particles obtained in the step 4 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 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 size of the external additive is preferably 5 nm or more, more preferably 10 nm or more, further preferably 15 nm or more, and preferably 100 nm or less, more preferably 80 nm or less, from the viewpoint of toner fluidity. More preferably, it is 50 nm or less.

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 0.5 part by mass or more, further preferably 1 part by mass or more, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less. It is.
The electrostatic image developing toner of the present invention can be used as a one-component developer or as a two-component developer mixed with a carrier.

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

<1> Addition polymerization resin (A) containing a structural unit derived from styrene, an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms, and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms A segment (B1) made of a crystalline polyester obtained by condensation polymerization and a segment (B2) made of an addition polymer containing a structural unit derived from styrene, and the segments (B1) and (B2) Including a composite resin (B) having a mass ratio (B1) / (B2) of 60/40 to 95/5, the mass ratio (A) / (B) of the addition polymerization resin (A) and the composite resin (B) is 60/40 to 95/5, an electrostatic charge image developing toner.
<2> The toner for developing an electrostatic charge image according to <1>, wherein the segment (B1) is 5 to 38% by mass with respect to the total amount of the resin (A) and the resin (B).
<3> The toner for developing an electrostatic charge image according to <1> or <2>, wherein the release agent is contained in an amount of 5 to 20 parts by mass with respect to a total of 100 parts by mass of the resin (A) and the resin (B). .
<4> The electrostatic image developing toner according to any one of <1> to <3>, wherein the content of the structural unit derived from styrene in the addition polymerization resin (A) is 40% by mass or more. .
<5> The addition polymerization resin (A) is any one of the above items <1> to <4>, including a structural unit derived from styrene and a structural unit derived from an alkyl ester of (meth) acrylic acid. Toner for developing electrostatic images.
<6> The total content of the structural unit derived from styrene and the structural unit derived from the alkyl ester of (meth) acrylic acid in the addition polymerization resin (A) is 80% by mass or more, <5> The toner for developing an electrostatic charge image according to 1.
<7> The electrostatic charge image developing toner according to any one of <1> to <6>, wherein the addition polymerization resin (A) has a softening point of 80 ° C. or higher.
<8> The addition charge resin (A) is an amorphous resin, and the addition charge resin (A) has a glass transition temperature of 40 ° C. or higher, according to any one of the above items <1> to <7>. Toner for image development.
<9> The electrostatic image developing toner according to any one of <1> to <8>, wherein the acid value of the addition polymerization resin (A) is 20 mgKOH / g or less.
<10> The electrostatic charge image development according to any one of <1> to <9>, wherein the total content of the segments (B1) and (B2) in the composite resin (B) is 80 mol% or more. Toner.
<11> The electrostatic charge according to any one of <1> to <10>, wherein the content of the aliphatic diol having 6 to 12 carbon atoms in the alcohol component of the segment (B1) is 70 mol% or more. Toner for image development.
The static content according to any one of <1> to <11> above, wherein the content of the aliphatic dicarboxylic acid having 8 to 12 carbon atoms in the alcohol component of the <12> segment (B1) is 70 mol% or more. Toner for charge image development.
In the crystalline polyester constituting the <13> segment (B1), the molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) is 0.4 or more and 1.5 or less, <1> -The toner for developing an electrostatic charge image according to any one of <12>.
The <14> segment (B2) is the electrostatic image developing toner according to any one of <1> to <13>, which includes a structural unit derived from styrene and a site derived from a radical polymerization initiator.
<15> The toner for developing an electrostatic charge image according to any one of <1> to <14>, wherein the segment (B2) includes a component derived from both reactive monomers.
<16> The toner for developing an electrostatic charge image according to any one of <1> to <15>, wherein the content of the structural unit derived from styrene in the segment (B2) is 80% by mass or more.
The content of the structural unit derived from the both reactive monomers in the <17> segment (B2) is 1% by mass or more and 20% by mass or less, according to any one of the above items <1> to <16>. Toner for developing electrostatic images.
<18> The toner for developing an electrostatic charge image according to any one of <1> to <17>, wherein the softening point of the composite resin (B) is 60 ° C. or higher and 110 ° C. or lower.
<19> The composite resin (B) is a crystalline resin, and the composite resin (B) has a melting point of 60 ° C. or higher and 100 ° C. or lower, according to any one of the above <1> to <18>. Toner for image development.
<20> The toner for developing an electrostatic charge image according to any one of <1> to <19>, wherein the acid value of the composite resin (B) is 1 mgKOH / g or more and 40 mgKOH / g or less.
<21> Any one of the above items <1> to <20>, wherein the total amount of the addition polymerization resin (A) and the composite resin (B) in the resin component of the electrostatic image developing toner is 80% by mass or more. The toner for developing an electrostatic charge image according to 1.
<22> Any one of the above items <1> to <21>, wherein the total amount of the addition polymerization resin (A) and the composite resin (B) in the resin component of the toner for developing an electrostatic image is 80% by mass or more. The toner for developing an electrostatic charge image according to 1.
<23> The above <1> to <22>, containing the charge control agent in an amount of 0.1 parts by mass or more and 8 parts by mass or less with respect to 100 parts by mass of the total amount of the addition polymerization resin (A) and the composite resin (B). The toner for developing an electrostatic image according to any one of the above.
<24> The above-mentioned <1> to <23>, wherein the colorant is contained in an amount of 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the total amount of the addition polymerization resin (A) and the composite resin (B) The toner for developing an electrostatic image according to any one of the above.
<25> A toner for developing an electrostatic charge image having a core and a shell, wherein the core includes a resin (A) and a resin (B), and the mass ratio (A) / (resin (A) to resin (B). B) is 60/40 to 95/5, and the shell is derived from an amorphous polyester resin (C), an addition polymerization resin (D) containing a structural unit derived from styrene, and a segment composed of polyester and styrene. The electrostatic image developing toner according to any one of the above <1> to <24>, comprising at least one selected from the composite resin (E) having a segment composed of an addition polymer containing a structural unit.
<26> The toner for developing an electrostatic charge image according to <25>, wherein a mass ratio [core / shell] of the resin constituting the core and the resin constituting the shell is 70/30 to 98/2.
<27> The alcohol component that is a raw material monomer of the amorphous polyester resin (C) is at least one of an aliphatic diol, an aromatic diol, and a trihydric or higher polyhydric alcohol, <25> or <26 > The toner for developing an electrostatic charge image.
<28> The alcohol component that is a raw material monomer of the amorphous polyester resin (C) is at least one of an aliphatic diol, an aromatic diol, and a trihydric or higher polyhydric alcohol, <25> to <27 above > The toner for developing an electrostatic charge image according to any one of the above.
<29> The carboxylic acid component that is a raw material monomer of the amorphous polyester resin (C) includes aliphatic dicarboxylic acid, aromatic dicarboxylic acid, trivalent or higher polyvalent carboxylic acid, and acid anhydrides and alkyls thereof. The electrostatic image developing toner according to any one of <25> to <28>, wherein the toner is at least one ester (having 1 to 3 carbon atoms).
<30> The electrostatic image developing toner according to any one of <25> to <29>, wherein the softening point of the amorphous polyester resin (C) is 80 ° C. or higher and 140 ° C. or lower.
<31> The toner for developing an electrostatic charge image according to any one of <25> to <30>, wherein the amorphous polyester resin (C) has a glass transition temperature of 50 ° C. or higher and 80 ° C. or lower.
<32> The toner for developing an electrostatic charge image according to any one of <25> to <31>, wherein the acid value of the amorphous polyester resin (C) is 30 mg KOH / g or less and 1 mg KOH / g or more.
<33> A method for producing a toner for developing an electrostatic charge image, comprising the following steps 1 to 4.
Step 1: Addition polymerization resin (A) containing a structural unit derived from styrene, an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms, and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms (B1) having a segment (B1) made of a crystalline polyester obtained by condensation polymerization and a segment (B2) made of an addition polymer containing a structural unit derived from styrene, and a mass ratio of (B1) / (B2) Step 2: Obtaining an aqueous dispersion of resin particles I containing composite resin (B) having a ratio of 60/40 to 95/5 Step 2: Addition polymerization resin containing amorphous polyester resin (C) and structural unit derived from styrene (D) or a process for obtaining a resin aqueous dispersion containing a composite resin (E) having a segment made of polyester and a segment made of an addition polymer containing a structural unit derived from styrene Step 3: Resin aqueous dispersion containing the aqueous dispersion of resin particles I obtained in Step 1 and the amorphous polyester resin (C), addition polymerization resin (D), or composite resin (E) obtained in Step 2 Step 4 for obtaining an aqueous dispersion of resin particles II by mixing and aggregating the solution Step 4: Step <34> for fusing the resin particles II obtained in Step 3 Step 1 comprises adding the addition polymerization resin (A). This is a step of mixing an aqueous resin dispersion containing resin and an aqueous resin dispersion containing composite resin (B), and aggregating the addition polymerization resin (A) and composite resin (B) to obtain an aqueous dispersion of resin particles I. The method for producing a toner for developing an electrostatic charge image according to <33>.
<35> A resin aqueous dispersion containing an addition polymerization resin (A) is prepared by mixing an addition polymerization resin (A), an organic solvent and water, and further, if necessary, mixing a neutralizing agent and a surfactant, followed by distillation. The method for producing a toner for developing an electrostatic charge image according to the above <33> or <34>, which is obtained by removing the organic solvent.
<36> The static fluid according to <34> or <35>, wherein the volume-median particle size of the particles made of the composite resin (B) in the resin aqueous dispersion containing the composite resin (B) is 50 to 200 nm. A method for producing a toner for developing a charge image.
<37> A resin aqueous dispersion containing the composite resin (B) is obtained through at least steps B1 to B3 among the following steps B1 to B4, and 70 to 100% by mass of the total amount of the surfactant is added to step B2. And / or the method for producing a toner for developing an electrostatic charge image according to any one of <34> to <36>, wherein the toner is mixed in Step B4.
Step B1: Step of obtaining a mixture by mixing at least the composite resin (B), an organic solvent and a neutralizer to obtain a mixture Step B2: Step of obtaining a resin dispersion by mixing at least water with the mixture obtained in Step B1 B3: Step of obtaining the resin aqueous dispersion containing the composite resin (B) by removing the organic solvent from the resin dispersion obtained in the step B2. Step B4: Surface active on the resin aqueous dispersion obtained in the step B3 The step <38> of mixing the agent <38> The resin aqueous dispersion containing the composite resin (B) is obtained through steps B1 to B3, and 70 to 100% by mass of the total addition amount of the surfactant is mixed in step B2. The method for producing a toner for developing an electrostatic charge image according to <37>.
<39> The resin aqueous dispersion containing the composite resin (B) is obtained through steps B1 to B4, and 70 to 100% by mass of the total addition amount of the surfactant is mixed in steps B2 and B4. 37>. The method for producing a toner for developing an electrostatic charge image according to 37>.
<40> The resin aqueous dispersion containing the composite resin (B) is obtained through steps B1 to B4, and 70 to 100% by mass of the total addition amount of the surfactant is mixed only in step B4. <37> A method for producing a toner for developing an electrostatic image as described in 1.
<41> The above <37, wherein the surfactant is 0.1 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the composite resin (B) in the resin aqueous dispersion containing the composite resin (B). The method for producing a toner for developing an electrostatic image according to any one of <40> to <40>.
<42> In the above <37> to <41>, the volume median particle size of the resin particles containing the composite resin (B) in the resin aqueous dispersion containing the composite resin (B) is 50 nm or more and 500 nm or less. A method for producing the toner for developing an electrostatic image according to claim 1.

  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 JISK0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JISK0070 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Softening point, glass transition temperature, melting point and crystallinity index of resin]
(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) Melting point (maximum endothermic peak temperature)
Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), a sample cooled from room temperature (20 ° C.) to 0 ° C. at a temperature decreasing rate of 10 ° C./min is directly 1 The measurement was performed while the temperature was raised to 180 ° C. at a temperature rising rate of 10 ° C./min. Of the endothermic peaks observed, the temperature at the highest temperature side was defined as the endothermic melting point (maximum peak temperature).

(3) Glass transition temperature Using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.), 0.01 to 0.02 g of a sample is weighed into an aluminum pan, and 200 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 peak temperature of endotherm and the tangent indicating the maximum slope from the peak rising portion to the peak apex.
(4) Crystallinity index The crystallinity index was calculated by dividing the softening point by the maximum endothermic peak temperature.
(Resin acid value)

[Volume Median Particle Size (D ₅₀ ) of Aggregated Particles]
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 Particle Size Distribution (CV Value) of Toner and Toner Particles]
The volume median particle size of the toner and toner particles was measured as follows.
The measuring instrument, aperture diameter, analysis software, and electrolyte solution were the same as the volume median particle diameter of the aggregated particles.
-Dispersion: Polyoxyethylene lauryl ether (manufactured by Kao Corporation, trade name: Emulgen 109P, 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 a toner measurement sample is added to 5 mL of the dispersion, and dispersed for 1 minute with an ultrasonic disperser, and then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. A sample dispersion was prepared.
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.
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

[Volume Median Particle Size (D ₅₀ ) of Resin Particles, Colorant Fine Particles, Release Agent Fine Particles, and Charge Control Agent Fine 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.

[Solid concentration of 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 drying (initial sample mass)
W0: Sample weight after drying (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, JISZ1522) was applied to the image portion of the obtained printed matter, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. . The optical reflection density before and after 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.

[Toner durability]
A toner is mounted on a non-magnetic one-component developing type printer “OKI Microline 18” (manufactured by Oki Data Co., Ltd.), and the blackening rate is 5.5% on A4 size paper at a temperature of 30 ° C. and a humidity of 80%. A pattern of diagonal stripes was printed continuously. A black solid image was printed every 500 sheets, and streaks (white lines) on the image were confirmed. The number of printed sheets up to the time when the streak was visually observed on the image was defined as the number of printed sheets. It shows that it is excellent in durability, so that the number of printing durability is large.

[Toner transparency]
A toner is mounted on a non-magnetic one-component developing system printer “OKI Microline 18” (Oki Data Co., Ltd.), a solid image is printed on an OHP sheet, and a spectral color difference meter “SE-2000” ) And the transmittance was determined. Higher transmittance is preferable.

[Manufacture of composite resin]
Production Examples 1 and 3-6, 9-13
(Production of composite resins A, C to F, and I to M)
The polyester 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. , After raising the temperature from 135 ° C. to 160 ° C. over 6 hours, the reaction was carried out at 160 ° C., and it was confirmed that the reaction rate reached 95% or more. A mixed solution of the polymerizable monomer and the 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 composite resin A, C-F, and IM were obtained. The physical properties of the resin are shown in Table 1-1.
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 of crystalline polyester resin]
Production Example 2
(Crystalline polyester resin B)
The polyester 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. The temperature was raised to 135 ° C. and then raised to 200 ° C. over 10 hours. Furthermore, it was made to react under reduced pressure of 8 kPa for 2 hours, and crystalline polyester resin B was obtained. The physical properties of the resin are shown in Table 1-1.

[Production of addition polymerization resin]
Production Example 7
(Addition polymerization resin G)
2 liters of xylene are placed in a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a falling condenser, a dropping funnel and a nitrogen introducing tube, and the raw material monomer of the addition polymerization resin and the radical polymerization initiator are added. It was placed in a dropping funnel equipped with a three-necked flask. Thereafter, xylene in the four-necked flask was heated to 135 ° C. in a nitrogen atmosphere, and a mixture of the raw material monomer and the polymerization initiator was dropped into xylene from the dropping funnel over 1 hour. Furthermore, the temperature was raised to 200 ° C. and held at 200 ° C. for 2 hours. Thereafter, the pressure was reduced to 8 kPa for 1 hour, xylene was removed, and an addition polymerization resin G was obtained. The physical properties of the resin are shown in Table 1-2.

[Manufacture of amorphous polyester resin]
Production Example 8
(Amorphous polyester resin H)
A polyester monomer other than dodecenyl succinic anhydride shown in Table 1 and an esterification catalyst 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 a nitrogen atmosphere In a mantle heater at 235 ° C. for 10 hours, confirming that the reaction rate reached 95% or more, and further reacted for 1 hour under a reduced pressure of 8 kPa, then added dodecenyl succinic anhydride, The temperature was raised to 235 ° C., and then the reaction was performed until the softening point reached 110 ° C. to obtain an amorphous resin H. The physical properties of the resin are shown in Table 1-3. In the table, BPA-PO means a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane (average added mole number of propyleneoxy group: 2.2), and BPA- EO means a polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane (average added mole number of ethyleneoxy group: 2.2).

[Production of aqueous resin dispersion]
Production Examples 14-24
(Production of aqueous dispersions a, cf, im of composite resin and aqueous dispersion b of crystalline polyester resin)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 50 g of ethyl acetate, composite resin A, C to F, I to M shown in Table 2 or 100 g of crystalline polyester resin B Was dissolved at 70 ° C. for 2 hours. A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the neutralization degree was 100 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes (step B1). While stirring at 280 r / min (peripheral speed 88 m / min), 270 g of ion-exchanged water with an anionic surfactant “Neopelex G-15” (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate) as a solid content 0.9 g of the mixed aqueous solution was added over 70 minutes (step B2). Next, while maintaining the temperature at 65 to 75 ° C., ethyl acetate was distilled off under reduced pressure (step B3). After cooling to 30 ° C., the solid content concentration of the dispersion was measured and adjusted with ion-exchanged water so as to be 20% by mass to obtain an aqueous dispersion. Then, while stirring at 280 r / min (peripheral speed 88 m / min), 2.1 g of an anionic surfactant “Neopelex G-15” (manufactured by Kao Corporation) was mixed with the aqueous dispersion as a solid content. Then, stirring was performed for 30 minutes (step B4), and aqueous dispersions a, cf, im of the composite resin and an aqueous dispersion b of the crystalline polyester resin were obtained, respectively.

Production Example 25
(Manufacture of aqueous dispersion n of composite resin)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction tube, 50 g of ethyl acetate and 100 g of the composite resin A shown in Table 2 were charged and dissolved at 70 ° C. over 2 hours. . A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the neutralization degree was 100 mol% with respect to the acid value of the resin, and an anionic surfactant “Neopelex G-15” (Kao Corporation ), Sodium dodecylbenzenesulfonate) was mixed in an amount of 1.05 g and stirred for 30 minutes (step B1). While stirring at 280 r / min (peripheral speed of 88 m / min), 270 g of ion-exchanged water was added over 70 minutes (step B2). Next, while maintaining the temperature at 65 to 75 ° C., ethyl acetate was distilled off under reduced pressure (step B3). After cooling to 30 ° C., the solid content concentration of the dispersion was measured and adjusted with ion-exchanged water so as to be 20% by mass to obtain an aqueous dispersion. Thereafter, 1.95 g of an anionic surfactant “Neopelex G-15” (manufactured by Kao Corporation) as a solid content was mixed with the aqueous dispersion while stirring at 280 r / min (peripheral speed 88 m / min). Then, stirring was performed for 30 minutes (step B4) to obtain an aqueous dispersion n of the composite resin.

Production Example 26
(Manufacture of aqueous dispersion o of composite resin)
In Step B1, an anionic surfactant “Neopelex G-15” (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate) was mixed as a solid content of 0.75 g. In Step 4, an anionic surfactant was mixed. An aqueous dispersion o of a composite resin was obtained in the same manner as in Production Example 25 except that 2.25 g of “Neopelex G-15” (manufactured by Kao Corporation) was mixed as a solid content.

Production Example 27
(Production of aqueous dispersion g of addition polymerization resin)
Styrene acrylic resin G100 g, ethyl acetate 55 g, and anionic surfactant “Neopelex G-15” (manufactured by Kao Corporation) were dissolved at 25 ° C. and dissolved at 70 ° C. over 2 hours. The obtained solution was mixed with 600 g of ion-exchanged water at 70 ° C. and subjected to 30 dispersion treatment at an output of 350 W using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher Co., Ltd.). . Thereafter, ethyl acetate was distilled off under reduced pressure at 70 ° C. to obtain an aqueous dispersion g of an addition polymerization resin resin.

Production Example 28
(Production of aqueous dispersion h of amorphous polyester resin for shell)
An aqueous dispersion h of an amorphous polyester resin was obtained in the same manner as in Production Example 14 except that the composite resin A was changed to an amorphous polyester resin H.

[Production of colorant dispersion]
Production Example 29
50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (manufactured by Kao Corporation, polyoxyethylene lauryl ether) and 200 g of ion-exchanged water are mixed. Then, using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher Co., Ltd.), the dispersion treatment is performed at an output of 350 W for 30 minutes to obtain a colorant dispersion containing fine colorant particles. It was. The volume median particle size (D ₅₀ ) of the colorant fine particles was 120 nm, and the solid content concentration was 22% by mass.

[Production of release agent particle dispersion]
Production Example 30
[Preparation of release agent dispersion]
50 g of paraffin wax “HNP9” (produced by Nippon Seiwa Co., Ltd.), 5 g of cationic surfactant “Sanisol B50” (produced by Kao Corp., alkylbenzyldimethylammonium chloride) and 200 g of ion-exchanged water were heated to 95 ° C. Then, using a ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher Co., Ltd.), the dispersion treatment was performed at an output of 350 W for 30 minutes, and a release agent dispersion liquid containing release agent fine particles. Got. The volume median particle size (D ₅₀ ) of the paraffin wax (release agent fine particles) was 550 nm, and the solid content concentration was 22% by mass.

[Production of charge control agent dispersion]
Production Example 31
[Production of charge control agent dispersion]
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 fine particles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles was 400 nm, and the solid content concentration was 22% by mass.

[Manufacture of toner for developing electrostatic image]
Example 1
(Manufacture of toner 1)
Example 1
30 g of the aqueous dispersion a of the composite resin obtained in Production Example 14, 270 g of the aqueous dispersion g of the addition polymerization resin obtained in Production Example 27, 8 g of the colorant dispersion, 20 g of the release agent dispersion, and charge control 2 g of the agent dispersion and 52 g of deionized water are placed in a 2 L container, and 150 g of a 0.1 mass% calcium chloride aqueous solution is added at 20 ° C. with stirring of 100 r / min (peripheral speed 31 m / min) with an anchor type stirrer. It was added dropwise over 30 minutes. Then, it heated up to 50 degreeC, stirring. It was held at 50 ° C. until the volume median particle size was 5 μm. After 3 hours, the volume median particle size reached 5 μm. Thereafter, 75 g of the shell aqueous dispersion h was added and dispersed by stirring. 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 size 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 5 shows the evaluation results of the toner.

Examples 2-18, Comparative Examples 1-4
(Manufacture of toners 2 to 22)
A toner was obtained in the same manner as in Example 1, except that the type and amount of the resin aqueous dispersion and the type and amount of the release agent dispersant were changed as shown in Table 5.

  From Tables 5 to 7, it can be seen that the electrostatic image developing toners of the examples are all excellent in low-temperature fixability, durability and transparency as compared with the electrostatic image developing toners of the comparative examples.

  The electrostatic charge image developing toner of the present invention is excellent in low-temperature fixability, durability and transparency, 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 (9)

The total content of the constituent unit derived from styrene, a structural unit derived from a (meth) alkyl ester of viewing contains a structural unit derived from an alkyl ester of acrylic acid, a structural unit derived from a styrene (meth) acrylic acid An addition polymerization resin (A) whose amount is 99% by mass or more , and an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms are condensed. It has a segment (B1) composed of crystalline polyester obtained by polymerization and a segment (B2) composed of an addition polymer containing a structural unit derived from styrene, and the mass ratio of segment (B1) to segment (B2) ( A composite resin (B) in which B1) / (B2) is 60/40 to 95/5,
A toner for developing an electrostatic charge image, wherein the mass ratio (A) / (B) of the addition polymerization resin (A) and the composite resin (B) is 60/40 to 95/5.   The electrostatic image developing toner according to claim 1, wherein the segment (B1) is 5 to 38 mass% with respect to the total amount of the resin (A) and the resin (B).   The electrostatic image developing toner according to claim 1, wherein the release agent is contained in an amount of 5 to 20 parts by mass with respect to a total of 100 parts by mass of the resin (A) and the resin (B). An electrostatic charge image developing toner having a core and a shell,
The core includes the resin (A) and the resin (B), the mass ratio (A) / (B) of the resin (A) to the resin (B) is 60/40 to 95/5, and the shell is amorphous. Polyester resin (C), addition polymerization resin (D) containing a structural unit derived from styrene, and composite resin (E) having a segment made of polyester and a segment made of an addition polymer containing a structural unit derived from styrene The electrostatic image developing toner according to claim 1, comprising at least one selected from the above.   The electrostatic charge image developing toner according to claim 4, wherein a mass ratio of the resin constituting the core and the resin constituting the shell (core / shell) is 70/30 to 98/2. A method for producing a toner for developing an electrostatic charge image, comprising the following steps 1 to 4.
Step 1: a structural unit derived from styrene, a structural unit derived from a (meth) alkyl ester of viewing contains a structural unit derived from an alkyl ester of acrylic acid, a structural unit derived from a styrene (meth) acrylic acid Addition polymerization resin (A) having a total content of 99% by mass or more , and an alcohol component containing an aliphatic diol having 6 to 12 carbon atoms and a carboxylic acid component containing an aliphatic dicarboxylic acid having 8 to 12 carbon atoms (B1) having a segment (B1) made of a crystalline polyester obtained by condensation polymerization and a segment (B2) made of an addition polymer containing a structural unit derived from styrene, and a mass ratio of (B1) / (B2) Step of Obtaining Aqueous Dispersion of Resin Particles I Containing Composite Resin (B) whose A is 60/40 to 95/5 Step 2: Structure Derived from Amorphous Polyester Resin (C) and Styrene Step of obtaining an aqueous resin dispersion containing a composite resin (E) having an addition polymerization resin (D) containing a polymer or a segment consisting of a polyester and a segment consisting of an addition polymer containing a structural unit derived from styrene Step 3: Step 1. Mix the aqueous dispersion of the resin particles I obtained in 1 with the aqueous resin dispersion containing the amorphous polyester resin (C), addition polymerization resin (D), or composite resin (E) obtained in Step 2. And agglomerating to obtain an aqueous dispersion of resin particles II Step 4: Step of fusing the resin particles II obtained in Step 3   In step 1, the resin aqueous dispersion containing the addition polymerization resin (A) and the resin aqueous dispersion containing the composite resin (B) are mixed, and the addition polymerization resin (A) and the composite resin (B) are aggregated to form a resin. The method for producing a toner for developing an electrostatic charge image according to claim 6, which is a step of obtaining an aqueous dispersion of particles I.   The method for producing a toner for developing an electrostatic charge image according to claim 7, wherein the volume-median particle size of the particles made of the composite resin (B) in the resin aqueous dispersion containing the composite resin (B) is 50 to 200 nm. . A resin aqueous dispersion containing the composite resin (B) is obtained through at least steps B1 to B3 among the following steps B1 to B4, and 70 to 100% by mass of the total addition amount of the surfactant is changed to step B2 and / or The method for producing a toner for developing an electrostatic charge image according to any one of claims 6 to 8, which is mixed in Step B4.
Step B1: Step of obtaining a mixture by mixing at least the composite resin (B), an organic solvent and a neutralizing agent Step B2: Step of obtaining a resin dispersion by mixing at least water with the mixture obtained in Step B1 B3: Step of obtaining a resin aqueous dispersion containing the composite resin (B) by removing the organic solvent from the resin dispersion obtained in Step B2. Step B4: Surface active on the resin aqueous dispersion obtained in Step B3 Mixing agent