JP6050710B2 - Method for producing aqueous dispersion of binder resin composition for toner - Google Patents

Description

  The present invention relates to a method for producing an aqueous dispersion of a binder resin composition for toner, and a method for producing a toner for developing an electrostatic image using the aqueous dispersion.

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

For example, Patent Document 1 includes a graft copolymer obtained by graft copolymerizing a polymerizable vinyl monomer with a polyester resin for the purpose of improving low-temperature fixability, storage stability, and crush resistance. An electrostatic charge image developing toner comprising toner particles containing a wax stabilizer which is a resin, a wax and an iminoacetic acid compound is disclosed.
Patent Document 2 discloses a binder resin for an electrophotographic toner obtained by polymerizing a raw material monomer of a condensation polymerization resin and a raw material monomer of an addition polymerization resin for the purpose of improving filming resistance and low-temperature fixability. A binder resin for an electrophotographic toner is disclosed in which the raw material monomer of the addition polymerization resin contains an alkyl (meth) acrylate (C12-18) ester.

JP 2012-88345 A JP 2008-20848 A

By including the wax in the toner, oilless fixing can be realized, and the fixing property is improved. However, the polyester resin and the wax are particularly difficult to mix because the polarities are greatly different. In particular, in the production of the toner by the emulsion aggregation method in which a shearing force cannot be applied, poor wax dispersion becomes remarkable. As a result, there is a problem of deterioration in storage stability and durability, which is considered to be caused by bleed-out or falling off of wax during preparation of toner and during storage.
An object of the present invention is to provide a method for producing an aqueous dispersion of a binder resin composition for a toner capable of obtaining a toner having excellent heat-resistant storage stability, durability, and low-temperature fixability, and heat-resistant storage stability, durability, and low-temperature fixability. And a method for producing a toner excellent in toner.

  The present inventor considered that the factors affecting the heat-resistant storage stability, durability, and low-temperature fixability are the structure of the resin and the conditions for producing the aqueous dispersion of the binder resin composition. Heat resistant storage stability by mixing a composite resin containing a polyester resin segment and a specific vinyl resin segment in one molecule and a wax, and then adding water at a temperature equal to or higher than the melting point of the wax and phase inversion emulsification. It was found that an aqueous dispersion of a binder resin composition capable of obtaining a toner having excellent durability and low-temperature fixability can be obtained.

That is, the present invention provides the following [1] and [2].
[1] A method for producing an aqueous dispersion of a binder resin composition for toner, comprising the following steps 1 and 2.
Step 1: A step of obtaining a mixture by mixing a composite resin containing a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms and a wax. 2: Step of adding phase-phase emulsification by adding an aqueous medium to the mixture [2] A method for producing a toner for developing an electrostatic image, comprising the following steps A and C.
Step A: Step C of aggregating the aqueous dispersion of the binder resin composition for toner obtained by the production method [1] to obtain aggregated particles Step C: Step of fusing the aggregated particles

  According to the present invention, a method for producing an aqueous dispersion of a binder resin composition for a toner capable of obtaining a toner having excellent heat-resistant storage stability, durability, and low-temperature fixability, and heat-resistant storage stability, durability, and low-temperature fixability. And a method for producing a toner excellent in quality.

The method for producing an aqueous dispersion of the binder resin composition for toner of the present invention includes the following steps 1 and 2.
Step 1: A step of obtaining a mixture by mixing a composite resin containing a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms and a wax. 2: A step of adding a water-based medium to the mixture and emulsifying the phase inversion.

The reason why the toner for developing an electrostatic charge image obtained using the aqueous dispersion of the binder resin composition of the present invention is excellent in heat-resistant storage stability, durability and low-temperature fixability is not clear, but is considered as follows. It is done.
In the method for producing an aqueous dispersion of the binder resin composition of the present invention, a composite resin containing a polyester resin segment and a specific vinyl resin segment in one molecule is mixed with a wax to obtain a mixture. An aqueous medium is added to the mixture and emulsified by phase inversion.
The vinyl resin segment of this composite resin has a constituent component derived from a monomer having a hydrophobic long-chain alkyl group having 10 to 20 carbon atoms, and this portion has high affinity with wax. Therefore, it is considered that the wax is dispersed in the composite resin in the mixture.
Furthermore, when an aqueous medium is added to this mixture and phase inversion emulsification is performed, the vinyl resin segment of the composite resin has a high affinity for wax as described above, and the polyester resin segment of the composite resin has a hydrophilic ester bond. Therefore, it is considered that a resin layer is formed on the surface of the wax so as to surround the wax. As a result, the aqueous dispersion of the binder resin composition obtained by the production method of the present invention is such that the binder resin composition particles in which the wax is encapsulated in the composite resin are well dispersed in the aqueous medium. become. Therefore, the toner obtained using this dispersion can prevent bleed-out and falling off of the wax, and is considered to be excellent in heat-resistant storage stability, durability and low-temperature fixability.
The present invention will be described below.

[Method for Producing Aqueous Dispersion of Binder Resin Composition for Toner]
The method for producing an aqueous dispersion of the binder resin composition for toner according to the present invention includes the following steps 1 and 2.
Step 1: A step of obtaining a mixture by mixing a composite resin containing a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms and a wax. 2: A step of adding an aqueous medium to the mixture and performing phase inversion emulsification Further, in the step 1, the organic solvent is further used, and the step 3 of removing the organic solvent from the dispersion obtained in the step 2 is included. May be.
Furthermore, you may have the process 4 which mixes surfactant with the aqueous dispersion obtained at the process 2 or 3.
Next, each step will be described.

<Step 1>
Step 1 is a step of mixing a composite resin including a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms and a wax to obtain a mixture. It is.
In addition to these composite resins and waxes, one or more of organic solvents, neutralizing agents, and surfactants may be mixed.

(Composite resin)
The composite resin includes a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms.
In addition, this composite resin has three components: a constituent segment derived from the polyester resin segment and a vinyl monomer, and a constituent portion derived from an amphoteric monomer capable of reacting with both the polyester resin segment and the constituent component derived from the vinyl monomer. It preferably consists of parts. It should be noted that components other than these three components may be included as long as the object of the present invention is not impaired, but it is preferable not to include components other than the three components.
As described above, since the vinyl resin segment of the composite resin has a hydrophobic alkyl group, a resin layer can be satisfactorily formed on the surface of the wax. Further, since the polyester resin segment of the composite resin has a hydrophilic ester bond, the binder resin composition particles having the wax and the composite resin can be favorably dispersed in the aqueous medium during phase inversion emulsification.

≪Polyester resin segment≫
The polyester resin constituting the polyester resin segment is not particularly limited as long as it is a polyester resin for toners that has physical properties generally used for toners, but is obtained by condensation polymerization of an alcohol component and a carboxylic acid component. can get. Hereinafter, typical embodiments of the polyester resin for toner used in the present invention will be described.
The polyester resin constituting the polyester resin segment may be an amorphous resin or a crystalline resin (crystalline polyester). Here, the crystallinity of a resin such as polyester is the crystallinity defined by the ratio between the softening point and the maximum endothermic peak temperature by a differential scanning calorimeter (DSC), that is, “softening point / maximum endothermic peak temperature”. Expressed by an 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, “crystalline polyester” refers to a polyester having a crystallinity index of 0.6 to 1.4, preferably 0.8 to 1.2, more preferably 0.9 to 1.1. “Amorphous resin” refers to a resin having a crystallinity index greater than 1.4 or less than 0.6.
The above “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the measurement method conditions described in the examples. If the maximum peak temperature is within 20 ° C. from the softening point, the maximum peak temperature is the melting point of the crystalline resin (crystalline polyester), and the peak with the difference from the softening point exceeding 20 ° C. is glass of amorphous resin. The peak is attributed to the transition.
The crystallinity of the polyester resin constituting the polyester resin segment can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like.

[Alcohol component]
Examples of the alcohol component that is a raw material monomer of the polyester resin that constitutes the polyester resin segment 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, which 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 excellent in heat-resistant storage stability, durability, and low-temperature fixability. Is preferred.

(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 above formula (I) is preferably 70 mol% or more and 100 mol% in the alcohol component from the viewpoint of obtaining a toner excellent in heat-resistant storage stability, durability and low-temperature fixability. Hereinafter, it is more preferably 80 mol% or more and 100 mol% or less, and still more preferably 90 mol% or more and 100 mol% or less.

When the polyester resin used in the present invention is a crystalline polyester, the alcohol component that is a raw material monomer of the polyester resin is preferably 2 or more carbon atoms, and more preferably carbon atoms, from the viewpoint of enhancing the crystallinity of the polyester. It is preferable to contain an aliphatic diol having 14 or less, more preferably 6 or less carbon atoms.
When the alcohol component of the polyester resin contains an aliphatic diol, the content of the aliphatic diol is preferably within the alcohol component of the polyester resin, from the viewpoint of enhancing the low-temperature fixability, durability, and heat-preservability of the toner. It is 1 mol% or more, more preferably 1 mol% or more, still more preferably 5 mol% or more, preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol% or less.

In addition, trivalent or higher alcohols may be used from the viewpoint of improving low-temperature fixability, durability, and heat-resistant storage stability of the toner.
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 polyester resin contains a trihydric or higher alcohol, the content of the trihydric or higher alcohol is selected from the viewpoint of enhancing the low-temperature fixability, durability and heat preservability of the toner. Preferably it is 0.1 mol% or more, more preferably 1 mol% or more, still more preferably 5 mol% or more, preferably 30 mol% or less, more preferably 20 mol% or less, still more preferably 10 mol%. It is as follows.

[Carboxylic acid component]
Examples of the carboxylic acid component that is a raw material monomer of the polyester resin constituting the polyester resin segment include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, trivalent or higher polyvalent carboxylic acids, and acid anhydrides 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 fumaric acid is more preferable from the viewpoint of improving heat-resistant storage stability, durability, and low-temperature fixability 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 viewpoint of improving heat-resistant storage stability, durability, and low-temperature fixability of the toner.

The content of the aliphatic dicarboxylic acid is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 40 mol in the carboxylic acid component from the viewpoint of heat-resistant storage stability, durability, and low-temperature fixability of the toner. % Or more, preferably 80 mol% or less, more preferably 70 mol% or less, and still more preferably 60 mol% or less.
In addition, the content of the aromatic dicarboxylic acid is preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably, in the carboxylic acid component from the viewpoint of heat-resistant storage stability, durability, and low-temperature fixability of the toner. It is 40 mol% or more, preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less.
The molar ratio of the aliphatic dicarboxylic acid to the aromatic dicarboxylic acid [aliphatic dicarboxylic acid / aromatic dicarboxylic acid] is preferably 20/80 to 80/20 from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. More preferably, it is 30 / 70-70 / 30, More preferably, it is 40 / 60-60 / 40.
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, from the viewpoint of heat-resistant storage stability, durability and low-temperature fixability of the toner. More preferably, it is 99 mol% or more, More preferably, it 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.
In the case of using a trivalent or higher polyvalent carboxylic acid, the content thereof is preferably 0.1 mol% in the carboxylic acid component of the polyester resin from the viewpoint of improving heat-resistant storage stability, durability and low-temperature fixability of the toner. As mentioned above, 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.

≪Vinyl resin segment≫
The vinyl resin segment contains a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms. That is, the starting vinyl monomer of the vinyl resin segment has a vinyl monomer having an alkyl group having 10 to 20 carbon atoms. Thus, since the vinyl resin segment has a hydrophobic long-chain alkyl group having 10 to 20 carbon atoms, it has a high affinity with the wax. Therefore, the wax is contained in the composite resin containing the vinyl resin segment. Disperse well in
From this viewpoint, the alkyl group of the vinyl monomer having an alkyl group having 10 to 20 carbon atoms preferably has 11 to 19 carbon atoms, and more preferably 12 to 18 carbon atoms. The vinyl monomer having an alkyl group having 10 to 20 carbon atoms is preferably at least one of stearyl (meth) acrylate and lauryl (meth) acrylate, and more preferably stearyl (meth) acrylate.

  As a starting vinyl monomer for the vinyl resin segment, other vinyl monomers can be used together with a vinyl monomer having an alkyl group having 10 to 20 carbon atoms. Examples of the other vinyl monomers include styrene compounds such as styrene and 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; esters of ethylenic monocarboxylic acid such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N- such as N-vinylpyrrolidone; Examples include vinyl compounds. From the viewpoint of reactivity, a styrene compound is preferable, and styrene is more preferable.

  The content of the vinyl monomer having an alkyl group having 10 or more and 20 or less carbon atoms in the raw material vinyl monomer, which is a component derived from the vinyl resin segment, improves the affinity with the wax and improves the wax in the composite resin. From the viewpoint of improving the heat resistant storage stability, durability, and low-temperature fixability of the toner by dispersing, it is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably. It is 15 mass% or more. In addition, the content is preferably 50% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass from the viewpoint of improvement of emulsification property and low temperature fixability during phase inversion emulsification in Step 2. Hereinafter, it is more preferably 25% by mass or less.

  The total content of the vinyl monomer having an alkyl group of 10 to 20 carbon atoms and the styrene compound in the raw vinyl monomer, which is a component derived from the vinyl resin segment, is the heat-resistant storage stability, durability, and low-temperature fixability of the toner. From the viewpoint of improving the ratio, it is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 99% by mass or more, and still more preferably 100% by mass.

  The content of the styrene compound in the raw material vinyl monomer, which is a component derived from the vinyl resin segment, is preferably 50% by mass or more, more preferably from the viewpoint of improving the heat resistant storage stability, durability, and low-temperature fixability of the toner. Is 60% by mass or more, more preferably 70% by mass or more, and still more preferably 75% by mass or more. The content is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass from the viewpoint of improving emulsification and improving low-temperature fixability during phase inversion emulsification in Step 2. Hereinafter, it is still more preferably 85% by mass or less.

  In the raw material monomer of the composite resin, the content of the raw material monomer of the vinyl resin segment improves the affinity with the wax and disperses the wax well in the composite resin, so that the heat resistant storage stability and durability of the toner are improved. From the viewpoint of improving the low-temperature fixability, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, and still more preferably 30% by mass. As mentioned above, More preferably, it is 35 mass% or more. In addition, the content is preferably 60% by mass or less, more preferably 55% by mass or less, and still more preferably 50% by mass from the viewpoint of improving emulsification and low-temperature fixability during phase inversion emulsification in Step 2. Hereinafter, it is more preferably 45% by mass or less, still more preferably 40% by mass or less.

  The content of the vinyl monomer having an alkyl group having 10 or more and 20 or less carbon atoms in the total amount of the raw material monomer of the composite resin improves the affinity with the wax so that the wax is well dispersed in the composite resin. From the viewpoint of improving the heat resistant storage stability, durability, and low-temperature fixability of the toner, it is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, and even more preferably 6% by mass or more. More preferably, it is 7 mass% or more. In addition, the content is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 12% by mass from the viewpoint of improving emulsification and low-temperature fixability during the phase inversion emulsification in Step 2. Hereinafter, it is more preferably 10% by mass or less.

≪Amotropic monomer≫
When an amphoteric monomer is used as the raw material monomer for the composite resin, the amphoteric monomer reacts with both the polyester resin segment and the vinyl resin segment, whereby a composite resin can be produced. That is, in the composite resin of the present invention, the vinyl resin segment preferably includes a structural unit derived from an amphoteric monomer, and the structural unit derived from the amphoteric monomer includes the vinyl resin segment and the It is preferable that it becomes a bonding point of a polyester resin segment.
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.
The amount of both reactive monomers used is preferably 2 mol parts or more with respect to 100 mol parts of the alcohol component, from the viewpoint of dispersibility of the vinyl resin component, heat resistant storage stability, durability and low temperature fixability of the toner. More preferably 3 mol parts or more, still more preferably 5 mol parts or more, still more preferably 6 mol parts or more, still more preferably 7 mol parts or more, and preferably 20 mol parts or less, more preferably 18 mol parts. Part or less, more preferably 15 parts by mole or less, still more preferably 12 parts by mole or less, and still more preferably 10 parts by mole or less.

≪Physical properties of composite resin≫
The softening point of the composite resin used in the present invention 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 heat-resistant storage stability, durability and low-temperature fixability of the toner. Preferably it is 100 ° C. or higher, more preferably 105 ° C. or higher, preferably 130 ° C. or lower, more preferably 125 ° C. or lower, still more preferably 120 ° C. or lower, still more preferably 115 ° C. or lower, even more preferably. It is 113 degrees C or less.
The glass transition temperature of the composite resin used in the present invention is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and still more preferably 47 ° C. or higher, from the viewpoints of heat-resistant storage stability, durability, and low-temperature fixability of the toner. More preferably, it is 50 ° C. or higher, preferably 65 ° C. or lower, more preferably 60 ° C. or lower, still more preferably 57 ° C. or lower, and still more preferably 55 ° C. or lower.

The acid value of the composite resin is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, still more preferably 10 mgKOH / g or more, and still more preferably, from the viewpoint of heat-resistant storage stability, durability and low-temperature fixability of the toner. It is 12 mgKOH / g or more, preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 20 mgKOH / g or less, and still more preferably 18 mgKOH / g or less.
The softening point, glass transition temperature, and acid value can be easily adjusted by adjusting the raw material monomer composition, molecular weight, catalyst amount, etc., or by selecting reaction conditions.
The total content of the polyester resin segment, the vinyl resin segment and the both reactive resin segments in the composite resin is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, more More preferably, it is 100 mol%.

(Production method of composite resin)
The composite resin 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 a vinyl-type resin component 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) A method in which after the step (A) of the condensation polymerization reaction with the alcohol component and the carboxylic acid component, the step (B) of the addition polymerization reaction with the raw material monomer of the vinyl resin component and, if necessary, the both reactive monomers is performed.
In Step (A), a part of the carboxylic acid component is subjected to a condensation polymerization reaction, and then, after performing Step (B), the reaction temperature is increased again, and the remainder of the carboxylic acid component is added to the polymerization system. A method in which the polycondensation reaction in step (A) and the reaction with both reactive monomers as necessary are further promoted is more preferred.

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

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

≪Esterification catalyst≫
Examples of the esterification catalyst suitably used for the condensation polymerization include a titanium compound and a tin (II) compound having no Sn-C bond, and these may be used alone or in combination of two or more. it can.

As a titanium compound, the titanium compound which has a Ti-O bond is preferable, and the compound which has a C1-28 total carbon number alkoxy group, an alkenyloxy group, or an acyloxy group is more preferable.
Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred is a tin (II) compound having a Sn-O bond, and among them, di (2-ethylhexanoic acid) tin (II) is more preferable from the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment. .

  The abundance of the esterification catalyst is preferably 0.01 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 1 part by mass or more, preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 6 parts by mass or less.

≪Esterification cocatalyst≫
As the esterification cocatalyst, a pigalol compound is preferred. This pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with hydroxyl groups, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ′ Benzophenone derivatives such as 3,3,4-tetrahydroxybenzophenone, catechin derivatives such as epigallocatechin and epigallocatechin gallate, and the like, and gallic acid is preferred from the viewpoint of reactivity.
The amount of esterification cocatalyst present in the polycondensation reaction is preferably 0.001 part by mass or more with respect to the total amount of 100 parts by mass of the alcohol component and carboxylic acid component subjected to the polycondensation reaction from the viewpoint of reactivity More preferably 0.01 parts by mass or more, still more preferably 0.1 parts by mass or more, and preferably 1 part by mass or less, more preferably 0.8 parts by mass or less, still more preferably 0.6 parts by mass. It is as follows. Here, the abundance of the esterification cocatalyst means the total amount of the esterification cocatalyst subjected to the condensation polymerization reaction.
From the viewpoint of reactivity, the mass ratio of the esterification cocatalyst to the esterification catalyst (esterification cocatalyst / esterification catalyst) is preferably 0.001 or more, more preferably 0.002 or more, and still more preferably 0.00. 003 or more, preferably 0.01 or less, more preferably 0.008 or less, and still more preferably 0.005 or less.

(wax)
As the wax, ester wax, hydrocarbon wax, silicone wax, fatty acid amide and the like can be used. Of these, ester waxes are preferred from the viewpoint of improving the low-temperature fixability of the toner and maintaining good heat-resistant storage stability.
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.
The acid value of the ester wax is 1 mgKOH / g or more, preferably 2 mgKOH / g or more, more preferably 3 mgKOH / g or more from the viewpoint of improving the low-temperature fixability of the toner and maintaining good heat-resistant storage stability. Moreover, it is 10 mgKOH / g or less, Preferably it is 8 mgKOH / g or less, More preferably, it is 7 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. Among these, from the viewpoint of improving the low-temperature fixability of the toner and maintaining good heat-resistant storage stability, a synthetic ester wax is preferable, an ester composed of a long-chain alcohol and a fatty acid is more preferable, and a fatty acid ester of pentaerythritol is more preferable. More preferred is pentaerythritol behenate.
Specific examples of the hydrocarbon wax include low-molecular-weight polyolefins such as polyethylene, polypropylene, and polybutene; and mineral / petroleum waxes such as ozokerite, ceresin, paraffin wax, microcrystalline wax, and Fischer-Tropsch wax.

  The amount of the wax used is preferably 1% by mass or more, more preferably 100% by mass with respect to 100 parts by mass of the composite resin from the viewpoints of improving the releasability of the toner and improving the low-temperature fixability, and heat resistance and durability. Is 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 55% by mass or less, more preferably 50% by mass or less. More preferably, it is 45 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 35 mass% or less.

(blend)
The mixture includes the composite resin described above and the wax described above. This mixture further preferably contains at least one of an organic solvent and a neutralizing agent, more preferably contains a neutralizing agent, and further preferably contains an organic solvent and a neutralizing agent.
In the case where the mixture does not contain an organic solvent, it is preferable to perform phase inversion emulsification in Step 2 described later by adding an aqueous medium to the mixture at a temperature equal to or higher than the melting point of the wax.
<Organic solvent>
From the viewpoint of improving the dispersibility of the composite resin, the organic solvent preferably has a solubility parameter (SP value: POLYMER HANDBOOK THIRD EDITION 1989 by John Wiley & Sons, Inc), preferably 15.0 MPa ^1/2 or more , more preferably 16.0MPa ^1/2, and even more preferably at 17.0MPa ^1/2 or more, and preferably 26.0MPa ^1/2 or less, more preferably 24.0MPa ^1/2 or less, more preferably Is 22.0 MPa ^1/2 or less.

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

  The mass ratio of the organic solvent to the composite resin (organic solvent / composite resin) is preferably 0.03 or more, more preferably 0.05 or more, from the viewpoint of heat-resistant storage stability, durability, and low-temperature fixability of the toner. Preferably it is 0.1 or more, preferably 5 or less, more preferably 1.5 or less, still more preferably 1 or less, still more preferably 0.8 or less, and still more preferably 0.6 or less.

(Neutralizer)
Examples of the neutralizing agent used in the present invention include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia, trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine, and tributylamine. Of the organic base. Among these, from the viewpoint of heat-resistant storage stability, durability, and low-temperature fixability of the toner, a neutralizer having a pKa of 12 or less is preferable, a neutralizer having a pKa of 10 or less is more preferable, and the same viewpoint To a neutralizer having a pKa of 8 or more. Of these, ammonia (pKa = 9.3) and triethylamine (pKa = 9.8) are preferable, and ammonia is more preferable.
The degree of neutralization of the composite resin with the neutralizing agent is preferably 20 mol% or more, more preferably 25 mol% or more, and even more preferably 30 mol% or more, from the viewpoint of heat-resistant storage stability, durability, and low-temperature fixability of the toner. More preferably, it is 40 mol% or more, more preferably 50 mol% or more, preferably 100 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, and still more preferably. It is 80 mol% or less, More preferably, it is 75 mol% or less. In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = {[mass of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (mgKOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

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

(Production method of the mixture)
The said mixture can be obtained by mixing at least 1 sort (s) of an organic solvent and a neutralizing agent as needed further, the composite resin mentioned above, wax.
In the method for producing the mixture, the order of adding the raw materials is not limited, but it is preferable to mix the neutralizing agent after mixing the composite resin, the organic solvent and the wax.
At the time of mixing, it is preferable to stir with a commonly used mixing and stirring device such as an anchor blade or an external circulation stirring device.

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

<Step 2>
Step 2 is a step in which an aqueous medium is added to the mixture and phase inversion emulsification is performed. Moreover, you may add surfactant as needed. By this phase inversion emulsification, an aqueous dispersion of the binder resin composition for toner, in which the particles of the binder resin composition for toner containing the composite resin and the wax are dispersed in the aqueous medium, can be obtained.

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

From the viewpoint of improving the emulsion stability of the resin, the temperature at which the aqueous medium is added is not lower than the melting temperature of the wax in the organic solvent when an organic solvent is used in Step 1 and the mixture contains the organic solvent. Preferably, when the mixture does not contain an organic solvent, it is preferably at least the melting point of the wax.
Further, from the viewpoint of improving the emulsion stability of the resin, the glass transition temperature or higher of the composite resin is preferable. Specifically, the temperature at which the aqueous medium is added is preferably 20 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 40 ° C. or higher, and still more preferably, from the viewpoint of improving the emulsion stability of the resin. The temperature is 42 ° C or higher, preferably 75 ° C or lower, more preferably 70 ° C or lower, still more preferably 65 ° C or lower, and still more preferably 60 ° C or lower.
From the viewpoint of obtaining resin composition particles having a small particle size, the addition rate of the aqueous medium is preferably 0.1 parts by mass / min or more, more preferably 100 parts by mass with respect to 100 parts by mass of the composite resin until phase inversion is completed. Is 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 50 parts by mass. Parts / min or less, more preferably 30 parts by mass / min or less, still more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less, and even more preferably 8 parts by mass / min or less. There is no restriction | limiting in the addition rate of the aqueous medium after phase inversion.

The amount of the aqueous medium used is preferably 100 parts by mass or more, more preferably 150 parts by mass or more, further preferably 200 parts by mass with respect to 100 parts by mass of the composite resin from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation process. Part or more, more preferably 300 parts by weight or more, still more preferably 400 parts by weight or more, preferably 2000 parts by weight or less, more preferably 1500 parts by weight or less, still more preferably 1000 parts by weight or less, and still more. Preferably it is 700 mass parts or less, More preferably, it is 500 mass parts or less.
In addition, when the mixture obtained in step (1) contains an organic solvent, from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step, the mass ratio of the aqueous medium to the organic solvent (aqueous medium / The aqueous medium is preferably added so that the organic solvent is 70/30 to 98/2. From this viewpoint, it is more preferably 80/20 or more, further preferably 85/15 or more, more preferably 95/15 or less, still more preferably 90/10 or less.

(Surfactant)
Examples of the surfactant include nonionic surfactants, anionic surfactants, and cationic surfactants. Among these, from the viewpoint of dispersibility of the composite resin, nonionic surfactants and / or anionic surfactants are preferable, and anionic surfactants are more preferable.

Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Examples include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers. Among these, from the viewpoint of emulsion stability of the resin, polyoxyethylene alkyl ethers Is preferred.
Examples of anionic surfactants include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, alkyl ether sulfates such as sodium alkyl ether sulfate, and the like. From the viewpoint of properties, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, and alkyl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
From the viewpoint of the dispersibility of the composite resin and the emulsion stability of the resin, among the surfactants, polyoxyethylene alkyl ethers and alkyl ether sulfates are preferable, and alkyl ether sulfates are more preferable.

(Particulate resin composition particles for toner)
The volume median particle diameter (D ₅₀ ) of the particles of the binder resin composition for toner in the aqueous dispersion of the obtained binder resin composition for toner is preferably 50 nm or more from the viewpoint of toner productivity. More preferably 100 nm or more, still more preferably 120 nm or more, still more preferably 140 nm or more, still more preferably 150 nm or more, and preferably 400 nm or less, more preferably 350 nm or less, still more preferably 300 nm or less, even more Preferably it is 250 nm or less, More preferably, it is 200 nm or less.

<Step 3>
Step 3 may include a step of removing the organic solvent from the dispersion obtained in Step 2 after Step 2.
The method for removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, it is preferably distilled. Further, the organic solvent may not be completely removed and may remain in the aqueous dispersion. In this case, the residual amount of the organic solvent is preferably 1% by mass or less, more preferably 0.5% by mass or less, and still more preferably 0% in the aqueous dispersion.

  When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used while stirring. Further, from the viewpoint of maintaining the dispersion stability of the composite resin, it is more preferable to raise the temperature to a temperature equal to or higher than the boiling point of the organic solvent to be used at the reduced pressure and distill it off. Note that the temperature may be increased after the pressure is reduced, or the pressure may be decreased after the temperature is increased. From the viewpoint of maintaining the dispersion stability of the composite resin, it is preferable to distill off at a constant temperature and pressure.

<Step 4>
As step 4, after step 2 or step 3, a step of mixing a surfactant with the aqueous dispersion obtained in step 2 or step 3 may be included.
The amount of the surfactant added in Step 4 is preferably 50% by mass or more of the total amount of the surfactant added in Steps 1 to 4 from the viewpoint of heat-resistant storage stability, durability and low-temperature fixability of the toner. 100% by mass or less, more preferably 60% by mass or more and 100% by mass or less, still more preferably 70% by mass or more and 100% by mass or less, still more preferably 80% by mass or more and 100% by mass or less, and still more preferably 90% by mass or more. 100% by mass or less.
Further, the amount of the surfactant added in Step 4 is preferably 0.5 parts by mass or more, more preferably 100 parts by mass or more with respect to 100 parts by mass of the composite resin, from the viewpoints of heat-resistant storage stability, durability and low-temperature fixability of the toner. Is 1 part by mass or more, more preferably 1.5 parts by mass or more, preferably 6 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 4.5 parts by mass or less.

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

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

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

From the viewpoint of toner particle size distribution, heat-resistant storage stability, durability, and low-temperature fixability, the pH of the aqueous dispersion is 3 or less, preferably 1 to 3, after step 3 or 4, preferably after step 4. It is preferable to adjust to 1.5 to 2.5.
As a method of adjusting the pH of the aqueous dispersion to 3 or less, a method of adding an acid is preferable. As the acid, from the viewpoint of efficiently lowering the pH, an inorganic acid is preferable, and hydrochloric acid is more preferable.
Moreover, it is preferable to adjust pH of an aqueous dispersion to 4 or more after that, Preferably it is 4-6, More preferably, it is 4.5-5.5.
As a method of adjusting the pH of the aqueous dispersion to 4 or more, a method of adding a base is preferable. The base is preferably an alkali metal hydroxide, more preferably sodium hydroxide, from the viewpoint of efficiently increasing the pH.

[Method for producing toner for developing electrostatic image]
The method for producing an electrostatic charge image developing toner according to the present invention includes the following steps A and C.
Step A: Step of aggregating the aqueous dispersion of the binder resin composition for toner obtained by the above-described production method to obtain aggregated particles Step C: Step of fusing the aggregated particles The electrostatic charge according to the present invention The method for producing an image developing toner includes the following step B, and in step C, the aggregated particles obtained in step B may be fused. That is, the method for producing an electrostatic charge image developing toner according to the present invention may include the following steps A, B and C.
Step A: Aggregating the aqueous dispersion of the binder resin composition for toner obtained by the above-described manufacturing method to obtain aggregated particles Step B: Aqueous dispersion of polyester resin into the dispersion obtained in Step A And at least one kind of aqueous dispersion of styrene acrylic resin is mixed and agglomerated to obtain agglomerated particles Step C: Step of fusing the agglomerated particles obtained in Step B Hereinafter, steps A to C will be described. .

<Process A>
Step A is a step of obtaining aggregated particles by aggregating the aqueous dispersion of the binder resin composition for toner obtained by the above-described production method.
By this step A, a dispersion in which aggregated particles are dispersed in a medium is obtained.
In Step A, it is preferable to add a flocculant in order to efficiently perform the aggregation. In Step A, the colorant, the charge control agent, the release agent, the conductivity adjusting agent, the reinforcing filler such as a fibrous substance, the antioxidant, and the anti-aging agent are added and then agglomerated. May be. The additive can also be used as an aqueous dispersion.

(Flocculant)
As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoint of the particle size distribution of the toner, heat resistant storage stability and gloss of printed matter, an inorganic flocculant is preferable, and an inorganic metal salt is particularly preferable.
Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride. The valence of the central metal of the inorganic metal salt is preferably divalent or higher from the viewpoint of the particle size distribution of the toner, heat resistant storage stability, and gloss of the printed matter.
When the flocculant is added, the addition amount is preferably 0.001 part by mass or more, more preferably 0, with respect to 100 parts by mass of the composite resin, from the viewpoint of heat-resistant storage stability, durability and low-temperature fixability of the toner. 0.005 parts by mass or more, more preferably 0.01 parts by mass or more, still more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 10 parts by mass or less. The amount is preferably 7 parts by mass or less, more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and still more preferably 0.5 parts by mass or less.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after completion of the addition.
In the aggregation step, the solid content concentration in the system is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more, in order to cause uniform aggregation. It is 50 mass% or less, More preferably, it is 40 mass% or less, More preferably, it is 30 mass% or less.
In the coagulation step, from the viewpoint of uniformly dispersing the coagulant and causing uniform coagulation, the temperature during addition of the coagulant is preferably 10 ° C or higher, more preferably 15 ° C or higher, and further preferably 18 ° C or higher. In addition, it is preferably 40 ° C. or lower, more preferably 35 ° C. or lower, and further preferably 30 ° C. or lower. The holding temperature after adding the flocculant is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 47 ° C. or higher, preferably 65 ° C. or lower, more preferably 60 ° C. or lower, still more preferably. Is 55 ° C. or lower.

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, Indigo dyes, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
The addition amount of the colorant is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and further preferably 1.0 parts by mass with respect to 100 parts by mass of the composite resin from the viewpoint of improving the image quality. Part or more, more preferably 2.0 parts by weight or more, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 8 parts by weight or less, and even more preferably 5 parts by weight or less. is there.
This colorant may be added as a colorant dispersion containing colorant fine particles. The volume median particle size (D ₅₀ ) of the colorant fine particles is preferably 50 nm or more, more preferably 100 nm or more, and preferably 200 nm or less, more preferably 150 nm or less.

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

In addition, additives such as a colorant and a charge control agent may be premixed in the composite resin when preparing the resin particles, and a dispersion in which each additive is separately dispersed in a dispersion medium such as water is prepared. Then, it may be mixed with an aqueous dispersion of a composite resin and subjected to an aggregation process.
When the additive is added to the composite resin in advance when preparing the resin particles, it is preferable to melt-knead the composite resin and the additive in advance.
For melt kneading, it is preferable to use an open roll type biaxial kneader. An open roll type biaxial kneader is a kneader in which two rolls are arranged close to each other in parallel, and a heating function or a cooling function can be imparted by passing a heat medium through each roll. Therefore, the open roll type biaxial kneader is an open type part to be melt kneaded, and is provided with a heating roll and a cooling roll, so that it occurs during melt kneading unlike a normal biaxial kneader. The kneading heat can be easily dissipated.
In addition, an aqueous dispersion of each additive can be obtained by mixing each additive, a surfactant, and water and dispersing the mixture with a disperser.

<Process B>
Step B is a step in which the dispersion obtained in Step A is mixed with at least one of an aqueous dispersion of a polyester resin and an aqueous dispersion of a styrene acrylic resin and aggregated to obtain aggregated particles.
Thereby, a core-shell type toner can be obtained through the process C described later. That is, the aggregate part obtained in the process A mainly constitutes the core part, and the part aggregated in the process B mainly constitutes the shell part.
From the viewpoint of heat resistant storage stability, durability, and low-temperature fixability, it is preferable to mix at least a polyester resin aqueous dispersion of the polyester resin aqueous dispersion and styrene acrylic resin aqueous dispersion. It is more preferable to mix only the aqueous dispersion.
The “dispersion obtained in step A” is a dispersion obtained by aggregating the aqueous dispersion of the binder resin composition for toner described above, in which the aggregated particles are dispersed in a medium. Means that.

(Aqueous dispersion of polyester resin)
The polyester resin constituting the aqueous dispersion of the polyester resin is not particularly limited as long as it is a polyester resin for toners having physical properties generally used for toners, but the alcohol component and the carboxylic acid component are condensed. Obtained by polymerization.
The kind and content of the alcohol component that is a raw material of the polyester resin, the molar ratio of the alcohol component and the carboxylic acid component, and the physical properties of the polyester resin are the same as those of the polyester resin constituting the polyester resin segment of the composite resin described above.

From the viewpoint of improving the heat resistance storage stability, durability and low-temperature fixability of the toner by making the heat resistance of the toner shell higher than that of the core, the softening point of the polyester resin should be higher than the softening point of the composite resin. Is preferred. From this viewpoint, the temperature difference between the softening points of the polyester resin and the composite resin is preferably 2 ° C. or higher, more preferably 4 ° C. or higher, still more preferably 5 ° C. or higher, still more preferably 8 ° C. or higher, and still more preferably. The temperature is 10 ° C or higher, preferably 35 ° C or lower, more preferably 30 ° C or lower, still more preferably 25 ° C or lower, still more preferably 20 ° C or lower, still more preferably 15 ° C or lower.
The softening point of the polyester resin constituting the aqueous dispersion of the polyester resin is preferably 95 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 105 ° C. or higher, still more preferably 110 ° C. or higher, and even more preferably 115. It is 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, and still more preferably 123 ° C. or lower.
Further, the glass transition temperature of the polyester resin constituting the aqueous dispersion of the polyester resin is preferably 45 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. Preferably it is 55 degreeC or more, More preferably, it is 60 degreeC or more, Preferably it is 85 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 75 degrees C or less, More preferably, it is 70 degrees C or less.

The acid value of the polyester resin constituting the aqueous dispersion of the polyester resin is preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, and still more preferably, from the viewpoints of heat resistant storage stability, durability and low-temperature fixability of the toner. Is 10 mgKOH / g or more, more preferably 12 mgKOH / g or more, preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less, still more preferably 20 mgKOH / g or less, still more preferably 18 mgKOH / g or less. It is.
The softening point, glass transition temperature, number average molecular weight, weight average molecular weight, acid value and hydroxyl value can be easily adjusted by adjusting the raw material monomer composition, molecular weight, catalyst amount, etc., or by selecting reaction conditions.

Preferred types of the carboxylic acid component that is a raw material of the polyester resin constituting the aqueous dispersion of the polyester resin are the same as the carboxylic acid component of the polyester resin constituting the polyester portion of the composite resin, and aliphatic dicarboxylic acid and aromatic It is preferable to include a group dicarboxylic acid, and it is more preferable to include terephthalic acid and fumaric acid.
The content of the aliphatic dicarboxylic acid in the carboxylic acid component is described above from the viewpoint of improving the heat resistance storage stability, durability, and low-temperature fixability of the toner by making the heat resistance of the shell portion of the toner higher than that of the core portion. The content of the aliphatic dicarboxylic acid in the raw material carboxylic acid component of the polyester resin segment of the composite resin is preferably less. From the viewpoint, the content is preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol% or more, and preferably 25 mol% or less, more preferably in the carboxylic acid component. Is 20 mol% or less, more preferably 15 mol% or less.
Further, the content of the aromatic dicarboxylic acid in the carboxylic acid component is such that the heat resistance of the toner shell portion is made higher than that of the core portion to improve the heat resistant storage stability, durability, and low-temperature fixability of the toner. The content of the aromatic dicarboxylic acid in the raw material carboxylic acid component of the polyester resin segment of the composite resin is preferably larger. From the viewpoint, the content is preferably 75 mol% or more, more preferably 80 mol% or more, still more preferably 85 mol% or more, and preferably 98 mol% or less, more preferably in the carboxylic acid component. Is 95 mol% or less, more preferably 90 mol% or less.

From the viewpoint of toner productivity, the volume median particle diameter (D ₅₀ ) of the polyester resin particles in this aqueous dispersion is preferably 50 nm or more, more preferably 100 nm or more, still more preferably 120 nm or more, and still more. Preferably it is 140 nm or more, More preferably, it is 150 nm or more, Preferably it is 400 nm or less, More preferably, it is 350 nm or less, More preferably, it is 300 nm or less, More preferably, it is 250 nm or less, More preferably, it is 200 nm or less.

(Aggregated particles)
The volume median particle diameter (D ₅₀ ) of the obtained aggregated particles is preferably 3.0 μm or more, more preferably 3.5 μm or more, still more preferably 4.0 μm or more, and still more from the viewpoint of low-temperature fixability of the toner. Preferably, it is 4.5 μm or more, preferably 8.5 μm or less, more preferably 8.0 μm or less, still more preferably 7.5 μm or less, still more preferably 7.0 μm or less, and even more preferably 6.5 μm. It is as follows.
<Process C>
In Step C, after adding an aggregation terminator as necessary to the aqueous dispersion of aggregated particles obtained in Step A or Step B, the fused particles are obtained by heating as necessary.

The temperature in the system in the fusing process is a composite from the viewpoint of target toner particle size, particle size distribution, shape control and particle fusing property, and heat resistant storage stability, durability and low-temperature fixability of the toner. The softening point of the resin is preferably −40 ° C. or higher, more preferably softening point −35 ° C. or higher, further preferably softening point −25 ° C. or higher, softening point + 10 ° C. or lower, more preferably softening point or lower, softening point −10 ° C. or lower is preferable, softening point −15 ° C. or lower is preferable, and softening point −20 ° C. or lower is preferable.
Specifically, it is preferably 70 ° C. or higher, more preferably 75 ° C. or higher, and preferably 100 ° C. or lower, more preferably 90 ° C. or lower. The stirring speed is preferably a speed at which the aggregated particles do not settle.

  In addition, when using an aggregation terminator, it is preferable to use a surfactant as the aggregation terminator, and it is more preferable to use an anionic surfactant. Of the anionic surfactants, it is more preferable to use at least one selected from the group consisting of alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates, and it is more preferable to use alkyl ether sulfates. .

〔Post-process〕
By appropriately subjecting the fused particles obtained in Step C to a solid-liquid separation step such as filtration, a washing step, and a drying step, the electrostatic image developing toner of the present invention can be suitably obtained.
In the washing step, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of chargeability.
Further, an external additive may be added for the purpose of improving fluidity. Examples of the external additive include silica fine particles whose surface is hydrophobized, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and inorganic fine particles such as carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin, and the like. Fine particles can be used.

The number average particle diameter of the external additive is preferably 4 to 200 nm, more preferably 8 to 30 nm, from the viewpoint of the fluidity of the toner.
When the external additive is added, the addition amount is preferably 0 with respect to 100 parts by mass of the toner before the processing with the external additive, from the viewpoint of the fluidity of the toner, the environmental stability of the charging degree, and the storage stability. .1 part by mass or more, more preferably 0.2 part by mass or more, further preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 5 parts by mass or less, more preferably 4 parts by mass. It is not more than part by mass, more preferably not more than 3 parts by mass, and still more preferably not more than 2 parts by mass.
The volume median particle diameter (D ₅₀ ) of the toner is preferably 3.0 μm or more, more preferably 3.5 μm or more, and still more preferably 4.0 μm or more, from the viewpoint of heat resistant storage stability, durability and low-temperature fixability of the toner. More preferably, it is 4.5 μm or more, preferably 8.5 μm or less, more preferably 8.0 μm or less, still more preferably 7.5 μm or less, still more preferably 7.0 μm or less, and still more preferably. 6.5 μm or less.

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

<1> A method for producing an aqueous dispersion of a binder resin composition for toner, comprising the following steps 1 and 2.
Step 1: A step of obtaining a mixture by mixing a composite resin containing a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms and a wax. 2: A step of adding a water-based medium to the mixture and emulsifying the phase inversion.

<2> The method for producing an aqueous dispersion of the binder resin composition for toner according to <1>, wherein a neutralizing agent is further mixed in Step 1.
<3> The method for producing an aqueous dispersion of the binder resin composition for toner according to <1> or <2>, wherein a surfactant is further mixed in Step 2.
<4> The binder resin for toner according to any one of <1> to <3>, wherein the content of the wax is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the composite resin. A method for producing an aqueous dispersion of a composition.
<5> The binder resin composition for toner according to any one of <1> to <4>, wherein the content of the vinyl resin segment in the composite resin is 25% by mass or more and 60% by mass or less. A method for producing an aqueous dispersion.

<6> The above <1> to <5>, wherein the monomer component that is a raw material of the vinyl resin segment contains a vinyl monomer component having an alkyl group having 10 to 20 carbon atoms in an amount of 5% by mass to 50% by mass. A method for producing an aqueous dispersion of a binder resin for toner according to any one of the above.
<7> The method for producing an aqueous dispersion of a binder resin composition for toner according to any one of the above <1> to <6>, wherein the vinyl resin segment includes a structural unit derived from a bireactive monomer. .
<8> For toner according to any one of the above <1> to <7>, further comprising an organic solvent in step 1 and a step 3 of removing the organic solvent from the dispersion obtained in step 2. A method for producing an aqueous dispersion of a binder resin composition.
<9> The method for producing an aqueous dispersion of the binder resin composition for toner according to <8>, wherein the temperature at which the aqueous medium is added in the step 2 is equal to or higher than the dissolution temperature of the wax in the organic solvent. .
<10> Manufacture of aqueous dispersion of binder resin composition for toner according to <8> or <9>, further comprising step 4 of mixing a surfactant with the aqueous dispersion obtained in step 2 or 3. Method.

<11> The method for producing an aqueous dispersion of the binder resin composition for toner according to <10>, wherein 50% by mass or more and 100% by mass or less of the total amount of the surfactant is mixed in Step 4.
<12> The toner according to any one of <8> to <11>, wherein in step 1, a mass ratio of the organic solvent to the composite resin (organic solvent / composite resin) is 0.03 or more and 5 or less. For producing an aqueous dispersion of a binder resin composition for use.
<13> In step 2, the aqueous medium is added so that the mass ratio of the aqueous medium to the organic solvent (aqueous medium / organic solvent) is 70/30 to 98/2. 12> The manufacturing method of the aqueous dispersion of the binder resin composition for toners in any one of 12>.
<14> The method for producing an aqueous dispersion of the binder resin composition for toner according to any one of <8> to <13>, wherein the organic solvent is an acetate ester.
<15> The method for producing an aqueous dispersion of a binder resin composition for toner according to any one of <1> to <14>, wherein a neutralizer having a pKa of 12 or less is further mixed in Step 1.

<16> A method for producing an electrostatic image developing toner, comprising the following steps A and C.
Step A: Step C: Aggregating the aqueous dispersion of the binder resin composition for toner obtained by any one of the above production methods <1> to <15> to obtain aggregated particles Step C: Fusing the aggregated particles Step <17> The method for producing a toner for developing an electrostatic charge image according to <16>, which comprises the following step B, and in step C, the aggregated particles obtained in step B are fused.
Step B: A step of mixing the dispersion obtained in Step A with at least one of an aqueous dispersion of a polyester resin and an aqueous dispersion of a styrene acrylic resin and aggregating them to obtain aggregated particles.

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

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

[Softening point and glass transition temperature 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) Maximum peak temperature of endotherm Using a differential scanning calorimeter “Q-100” (manufactured by TI Instruments Japan Co., Ltd.), the temperature is reduced from room temperature (20 ° C.) to 10 ° C./min. The sample cooled to 0 ° C. was allowed to stand for 1 minute as it was, and then measured while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. Of the endothermic peaks observed, the peak temperature on the highest temperature side was defined as the maximum endothermic 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.

[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. The volume-median particle size (D ₅₀ ) and the number percent of the particle size of 2 μm or less were determined.

[Volume Median Particle Size (D ₅₀ ) of Resin Particles, Binder Resin Composition Particles, Colorant Fine Particles, 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.

[Coloring agent dispersion, charge control agent dispersion, aqueous dispersion for shell, solid content concentration of aqueous dispersion of binder resin composition]
Using an infrared moisture meter “FD-230” (manufactured by Kett Science Laboratory), a sample 5 g was dried at a temperature of 150 ° C. and in a measurement mode 96 (monitoring time 2.5 minutes / variation width 0.05%). The sample was dried and the moisture content (% by mass) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (% by mass) = 100-M
M: moisture (mass%) of sample = [(W−W0) / W] × 100
W: Sample mass before measurement (initial sample mass)
W0: Sample weight after measurement (absolute dry weight)

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

[Heat resistant storage stability of toner]
A 25 mL container (diameter: about 3 cm) was charged with 5 g of toner and allowed to stand for 96 hours in an environment of a temperature of 55 ° C. and a humidity of 75%. The degree of occurrence of toner aggregation was visually observed every 12 hours, and heat resistant storage stability was evaluated according to the following evaluation criteria. The longer the time during which no aggregation is observed, the better the heat resistant storage stability.
(Evaluation criteria)
A: Aggregation is not observed even after 84 hours.
B: Aggregation is not observed after 72 hours, but aggregation is observed after 84 hours.
C: Aggregation is not observed after 60 hours, but aggregation is observed after 72 hours.
D: Aggregation is not observed after 36 hours, but aggregation is observed after 48 hours.
E: Aggregation is not observed after 24 hours, but aggregation is observed after 36 hours.
F: Aggregation is observed after 24 hours.

[Toner durability]
Toner is mounted on a non-magnetic one-component developing system printer “OKI Microline 18” (Oki Data Co., Ltd.), and under the conditions of a temperature of 30 ° C. and a humidity of 80%, an oblique stripe with a blackening rate of 5.5% The pattern was printed. In the middle, a black solid image was printed every 500 sheets, and streaks 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. The larger the printing durability, the better the durability.

[Manufacture of composite resin]
Production Examples 1-6 and 10, 11
(Production of composite resins A to F and J and K)
The raw material monomer of the polyester resin other than fumaric acid shown in Table 1, the esterification catalyst and the esterification co-catalyst were placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube. And heated up to 235 ° C. in a mantle heater over 2 hours in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C., cooled to 160 ° C., and a mixed solution of vinyl resin raw material monomer, both reactive monomers and radical polymerization initiator shown in Table 1 was 1 It was added dropwise over time. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., further reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor (4-t-butylcatechol) and fumaric acid were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was carried out at 40 kPa until the softening point shown in Table 1 was reached, and composite resins A to F, J, and K were obtained. In addition, the reaction rate in this invention means the value of production | generation reaction water amount (mol) / theoretical production | generation water amount (mol) x100.

Production Example 7
(Manufacture of polyester resin G)
The raw material monomer of the polyester resin other than fumaric acid shown in Table 1, the esterification catalyst and the esterification co-catalyst were placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube. And heated up to 235 ° C. in a mantle heater over 2 hours in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Thereafter, the mixture was cooled to 180 ° C., 4-t-butylcatechol and fumaric acid were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 1 was reached, to obtain a polyester resin G.
Production Example 8
(Manufacture of polyester resin H)
A polyester resin H was obtained in the same manner as in Production Example 7 except that 4-t-butylcatechol was not used.

Production Example 9
(Production of wax-containing composite resin I)
The raw material monomer of the polyester resin other than fumaric acid shown in Table 1, the esterification catalyst and the esterification co-catalyst were placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube. And heated up to 235 ° C. in a mantle heater over 2 hours in a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C., cooled to 160 ° C., and 480 g of paraffin wax “HNP9” (manufactured by Nippon Seiwa Co., Ltd., melting point: 85 ° C.) (100 mass of resin) 30 parts by mass). Thereafter, in a state where the temperature was kept at 160 ° C., a mixed solution of the vinyl-based resin raw material monomer, the bireactive monomer and the polymerization initiator shown in Table 1 was dropped over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., further reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Thereafter, 4-t-butylcatechol and fumaric acid were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 1 was reached, to obtain a wax-containing composite resin I.

Production Example 12
(Manufacture of composite resin L)
BPA-PO, esterification catalyst and esterification co-catalyst shown in Table 1 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring bar, a flow-down condenser and a nitrogen inlet tube, and in a nitrogen atmosphere. The temperature was raised to 160 ° C. in a mantle heater. A mixed solution of a raw material monomer, a bireactive monomer and a radical polymerization initiator shown in Table 1 was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., further reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor (4-t-butylcatechol) and fumaric acid were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 1 was reached, and composite resin L was obtained.

[Production of colorant dispersion]
Production Example 13
Mixing 50 g of copper phthalocyanine “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd.), 5 g of nonionic surfactant “Emulgen 150” (polyoxyethylene lauryl ether, manufactured by Kao Corporation) and 200 g of ion-exchanged water Then, it was dispersed for 10 minutes using a homogenizer to obtain a colorant dispersion containing fine colorant particles. The volume median particle size (D ₅₀ ) of the colorant fine particles was 120 nm, and the solid content concentration was 22% by mass.

[Production of charge control agent dispersion]
Production Example 14
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 aqueous dispersion for shell]
Production Example 15
(Production of aqueous dispersion of polyester resin)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 150 g of polyester resin H and 75 g of ethyl acetate were charged and dissolved at 30 ° C. over 2 hours. The resulting solution was neutralized by adding a 20% aqueous ammonia solution so as to have a neutralization degree of 100 mol% with respect to the acid value of the resin, and stirred for 30 minutes. Thereafter, 675 g of ion-exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min) while maintaining the temperature at 30 ° C. Subsequently, after heating up to 50 degreeC over 30 minutes, ethyl acetate was distilled off under pressure reduction. Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 250 r / min (peripheral speed 88 m / min), and then an anionic surfactant “Emar E27C” (sodium polyoxyethylene lauryl ether sulfate, Kao Corporation). 16.7 g) was mixed and completely dissolved. Thereafter, the solid content concentration of the dispersion was measured, and ion-exchanged water was added so as to be 20% by mass to obtain an aqueous dispersion for shell. The volume median particle size of the resin particles of the obtained aqueous dispersion for shell was 152 nm.

[Production of aqueous dispersion of binder resin composition for toner]
Example 1
(Production of aqueous dispersion 1 of binder resin composition for toner)
In a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 150 g of composite resin A, 75 g of ethyl acetate, ester wax “WEP8” (manufactured by Nippon Seiwa Co., Ltd., penta) 45 g of erythritol behenate (melting point: 78 ° C.) (30 parts by mass with respect to 100 parts by mass of the resin) was charged and dissolved at 70 ° C. over 2 hours. A 20% by mass aqueous ammonia solution (pKa: 9.3) was added to the resulting solution so that the degree of neutralization was 70 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes (step 1).
While maintaining the temperature at 70 ° C., 675 g of ion-exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral speed 88 m / min) (phase 2 emulsification). While maintaining the temperature at 70 ° C., ethyl acetate was distilled off under reduced pressure (Step 3). Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then 16.7 g of an anionic surfactant “Emar E27C” (manufactured by Kao Corporation) was mixed. And completely dissolved (step 4). Thereafter, the solid content concentration of the dispersion is measured, and ion-exchanged water is added so as to be 20% by mass, whereby the binder resin composition for toners in which the binder resin composition particles are dispersed in the aqueous medium. A dispersion was obtained. The volume median particle size of the binder resin composition particles of the obtained aqueous dispersion was 162 nm.

Examples 2 to 6, 8 to 14 and Reference Example 7, and Comparative Examples 1 to 3 and 5
(Production of aqueous dispersions 2 to 17 and 19 of binder resin composition for toner)
In Example 1, the binder resin for toner was used in the same manner as in Example 1 except that the type of resin used in Step 1, the amount of wax, and the temperature during phase inversion emulsification in Step 2 were changed as shown in Table 2. An aqueous dispersion of the composition was obtained. However, since Comparative Example 2 could not be emulsified, the aqueous dispersion 16 was not obtained. Table 2 shows the volume-median particle size of the obtained binder resin composition particles of the aqueous dispersion.

Comparative Example 4
(Production of aqueous dispersion 18 of binder resin composition for toner)
150 g of composite resin A, 75 g of ethyl acetate, 45 g of ester wax “WEP8” (manufactured by Nippon Seiwa Co., Ltd., melting point: 78 ° C.), anionic surfactant (manufactured by Kao Corporation, trade name: “Emar E27C”) 16.7 g was dissolved at 25 ° C. and dissolved at 70 ° C. over 2 hours. A 20% by mass aqueous ammonia solution (pKa: 9.3) was added to the resulting solution so that the neutralization degree was 70 mol% with respect to the acid value of the resin, and then 600 g of ion-exchanged water was mixed. Then, 30 dispersion treatment was performed 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 of the binder resin composition. Table 2 shows the volume-median particle size of the obtained binder resin composition particles of the aqueous dispersion.

[Manufacture of toner for developing electrostatic image]
Example 15
300 g of the aqueous dispersion 1 of the binder resin composition for toner obtained in Example 1, 8 g of the colorant dispersion, 2 g of the charge control agent dispersion, and 52 g of deionized water were placed in a 2 L container, and the anchor type Under stirring at 100 r / min (peripheral speed 31 m / min) with a stirrer, 150 g of a 0.1 mass% calcium chloride aqueous solution was added dropwise at 20 ° C. over 30 minutes. Then, it heated up to 50 degreeC, stirring. 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 an aqueous dispersion for shell shown in Table 2 as a toner shell 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 2 shows the evaluation results of the toner.

Examples 16-20, 22-28 and Reference Example 21, and Comparative Examples 6-9
(Manufacture of toner for developing electrostatic image)
A toner was obtained in the same manner as in Example 15 except that the aqueous dispersion of the binder resin composition for toner in Example 15 was changed as shown in Table 2. Table 2 shows the evaluation results of the toner.

  From Table 2, it can be seen that the electrostatic charge image developing toners of the examples are all excellent in low-temperature fixability, heat-resistant storage stability and durability as compared with the electrostatic charge image developing toners of the comparative examples.

  The toner for developing an electrostatic charge image using the aqueous dispersion of the binder resin composition for toner obtained by the production method of the present invention is excellent in low-temperature fixability, heat-resistant storage stability and durability, and is therefore used in electrophotography. It can be suitably used as a toner. According to the method of the present invention, a toner having such characteristics can be produced efficiently.

Claims (12)

A method for producing an aqueous dispersion of a binder resin composition for toner, comprising the following steps 1 to 3 .
Step 1: Mixing a composite resin containing a polyester resin segment and a vinyl resin segment containing a structural unit derived from a vinyl monomer having an alkyl group having 10 to 20 carbon atoms, a wax , and an organic solvent to mix the mixture Step 2 of obtaining: Step of adding an aqueous medium to the mixture at a temperature equal to or higher than the melting temperature of the wax in the organic solvent and emulsifying the phase inversion.
Step 3: Step of removing the organic solvent from the dispersion obtained in Step 2   The method for producing an aqueous dispersion of a binder resin composition for toner according to claim 1, wherein a neutralizing agent is further mixed in Step 1. 3. The aqueous dispersion of the binder resin composition for toner according to claim 1, wherein in step 1, a mass ratio of the organic solvent to the composite resin (organic solvent / composite resin) is 0.03 or more and 5 or less. Body manufacturing method.   The aqueous dispersion of the binder resin composition for toner according to claim 1, wherein the content of the wax is 5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the composite resin. Manufacturing method.   The method for producing an aqueous dispersion of a binder resin composition for toner according to any one of claims 1 to 4, wherein the content of the vinyl resin segment in the composite resin is 25% by mass or more and 60% by mass or less. .   The monomer component used as the raw material of the said vinyl-type resin segment contains the vinyl monomer component which has a C10-C20 alkyl group 5 mass% or more and 50 mass% or less in any one of Claims 1-5. A method for producing an aqueous dispersion of a binder resin for toner.   The manufacturing method of the aqueous dispersion of the binder resin composition for toners in any one of Claims 1-6 in which the said vinyl-type resin segment contains the structural unit derived from both reactive monomers. A step 4 of mixing the surfactant in the aqueous dispersion obtained in Engineering about 3, a method of manufacturing an aqueous dispersion of toner binder resin composition according to any one of claims 1 to 7. The manufacturing method of the aqueous dispersion of the binder resin composition for toners in any one of Claims 1-8 whose said organic solvent is acetate . In step 2, the mass ratio of the aqueous medium and the organic solvent (aqueous medium / organic solvent) is added to the aqueous medium such that the 70 / 30-98 / 2, in any one of claims 1 to 9 A method for producing an aqueous dispersion of the binder resin composition for toner described above. A method for producing an electrostatic charge image developing toner, comprising the following steps A and C.
Step A: Step C of aggregating the aqueous dispersion of the binder resin composition for toner obtained by the production method according to claim 1 to obtain aggregated particles Step C: Step of fusing the aggregated particles The method for producing a toner for developing an electrostatic charge image according to claim 11, comprising the following step B, and in step C, the aggregated particles obtained in step B are fused.
Step B: A step of mixing the dispersion obtained in Step A with at least one of an aqueous dispersion of a polyester resin and an aqueous dispersion of a styrene acrylic resin and aggregating them to obtain aggregated particles.