JP2019091060A - Method for manufacturing electrophotographic toner - Google Patents

Abstract

To provide a method for manufacturing an electrophotographic toner that is excellent in low-temperature fixability, heat-resistant storage property under high humidity, charging start-up property, and folding resistance of a print.SOLUTION: In a method for manufacturing an electrophotographic toner containing a crystalline resin (C) and an amorphous resin (A1), the crystalline resin (C) consists of a crystalline polyester resin (CP) and a polycondensation resin component (CH-1) (a polycondensation resin obtained through polycondensation of an alcohol component containing an aliphatic diol in an amount of 80 mol% or more and 100 mol% or less, and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms in an amount of 80 mol% or more and 100 mol% or less). As manufacturing steps, the method for manufacturing an electrophotographic toner includes: a step 1 of mixing the crystalline resin (C), an organic solvent, and a neutralizer to obtain a mixture; a step 2 of obtaining a dispersing element of the crystalline resin (C); a step 3 of removing the organic solvent from the dispersing element to obtain an aqueous dispersing element; and a step 4 of aggregating and fusing resin particles in an aqueous medium.SELECTED DRAWING: None

Description

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

  From the viewpoint of speeding up the printing apparatus and energy saving, toners excellent in low-temperature fixability are required. However, if the softening point or the glass transition temperature of the toner is designed to be low in order to improve low temperature fixability, the storage stability is adversely affected. Therefore, in order to achieve both low temperature fixing ability and storage stability, development of toner using crystalline polyester has been conducted.

For example, Patent Document 1 is directed to fusing aggregated particles obtained by aggregating an aqueous dispersion of a binder resin for toners, with low-temperature fixability, charge stability under high temperature and high humidity, and heat resistant storage stability as subjects. A binder resin containing a crystalline polyester resin, the aqueous dispersion is obtained through the following steps 1 to 4, and the total addition of surfactant is carried out. 80 to 100% by weight of the amount is mixed in step 2 and step 4 and the weight ratio of the addition amount of surfactant mixed in step 2 and step 4 is weight / step of surfactant added in step 2 A method of producing a toner for electrophotography, which is 10/90 to 40/60 as the weight of surfactant added in 4, is disclosed.
Step 1: A step of mixing at least a binder resin, an organic solvent and a neutralizing agent to obtain a mixture.
Step 2: mixing at least water and a surfactant with the mixture obtained in Step 1 to obtain a resin dispersion.
Step 3: A step of obtaining an aqueous dispersion of a binder resin by removing the organic solvent from the resin dispersion obtained in Step 2.
Step 4: A step of mixing a surfactant with the aqueous dispersion obtained in Step 3.

Unexamined-Japanese-Patent No. 2013-221990

According to the technique of Patent Document 1, it is possible to effectively cause the surfactant to act on the surface of the dispersion by mixing a specific amount of the surfactant in a specific step, and an aqueous dispersion having uniform particle diameter is formed. It can be done. As a result, the variation in aggregation speed between particles is reduced, uniform aggregated particles can be obtained, and the crystalline polyester resin can be uniformly dispersed in the toner, thereby improving the low temperature fixing property and the like. However, further improvements in low-temperature fixability, heat-resistant storage stability under high humidity, charge buildup, and folding resistance of printed matter are desired.
The present invention provides a process for producing a toner for electrophotography which is excellent in low temperature fixability, heat resistant storage stability under high humidity, charge rising property and folding resistance of printed matter, and a toner for electrophotography obtained by the process. To be an issue.

  The present inventors have found that a crystalline polyester resin or a crystalline composite resin using a long chain aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms as a binder resin constituting a toner for electrophotography and an amorphous resin It has been found that the use of the present invention in a specific production method makes it possible to obtain an electrophotographic toner which is excellent in low-temperature fixability, heat-resistant storage stability under high humidity, charge rising property and folding resistance of printed matter. It came to complete.

That is, the present invention provides the following method for producing an electrophotographic toner and the electrophotographic toner.
[1] A method for producing a toner for electrophotography, comprising a crystalline resin (C) and an amorphous resin (A1),
The crystalline resin (C) is selected from a crystalline polyester resin (CP) and a crystalline composite resin (CH) containing a polycondensation resin component (CH-1) and a styrene resin component (CH-2) One or more crystalline resins,
An alcohol component in which the crystalline polyester resin (CP) and the polycondensation resin constituting the polycondensation resin component (CH-1) contain 80 to 100 mol% of aliphatic diol, and having 14 or more carbon atoms A method for producing a toner for electrophotography, which is a resin obtained by polycondensing a carboxylic acid component containing 80 mol% or more and 80 mol% or more and 100 mol% or less of an aliphatic dicarboxylic acid compound of 20 or less.
Step 1: Step of mixing crystalline resin (C), organic solvent, and neutralizing agent to obtain a mixture Step 2: Mix at least water with the mixture obtained in Step 1, crystalline resin (C) Step 3: Step of obtaining an aqueous dispersion of resin particles (X) containing a crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2: Step 2: The resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A) are aggregated and fused in an aqueous medium Step [2] A toner for electrophotography obtained by the production method according to the above [1].

  According to the present invention, a method for producing a toner for electrophotography which is excellent in low temperature fixability, heat resistant storage stability under high humidity, charge rising property and bending resistance of printed matter, and toner for electrophotography obtained by the production method Can be provided.

[Method for producing electrophotographic toner]
The method for producing the electrophotographic toner (hereinafter, also simply referred to as “toner”) of the present invention is a method for producing a toner for electrophotography comprising the crystalline resin (C) and the amorphous resin (A1). The crystalline resin (C) is selected from a crystalline polyester resin (CP) and a crystalline composite resin (CH) containing a polycondensation resin component (CH-1) and a styrene resin component (CH-2) The polycondensation resin that constitutes the crystalline polyester resin (CP) and the polycondensation resin component (CH-1) is at least 80 mol% to 100 mol% of the aliphatic diol. It is a resin obtained by polycondensation of an alcohol component contained below and a carboxylic acid component containing 80 mol% or more and 100 mol% or less of an aliphatic dicarboxylic acid compound having 14 or more and 20 or less carbon atoms. Including, electronic A method for producing a true toner.
Step 1: Step of mixing crystalline resin (C), organic solvent, and neutralizing agent to obtain a mixture Step 2: Mix at least water with the mixture obtained in Step 1, crystalline resin (C) Step 3: Step of obtaining an aqueous dispersion of resin particles (X) containing a crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2: Step 2: The resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A1) are coagulated and fused in an aqueous medium Process

The reason why the toner obtained by the production method of the present invention is excellent in low-temperature fixability, heat-resistant storage stability under high humidity, charge rising property, and folding resistance of printed matter is not clear, but is considered as follows.
The crystalline resin (C) used in the production method of the present invention uses a long chain aliphatic dicarboxylic acid compound having high affinity with an organic solvent as a raw material monomer. Therefore, the resin particles (X) containing the crystalline resin (C) obtained in the step 3 are finely dispersed stably in the organic solvent, and the resin particles (X) and the amorphous resin (the amorphous resin It is considered that the crystalline resin (C) is finely dispersed in the toner by aggregating and fusing the resin particles (Y) containing A1), and the low temperature fixability is excellent.
Furthermore, since the obtained toner contains a structural unit derived from a highly hydrophobic long-chain aliphatic dicarboxylic acid compound, the hygroscopicity can be reduced, whereby the heat-resistant storage stability under high humidity (hereinafter simply referred to as simply It is considered to be excellent also for "preservability" and charge buildup.
Moreover, since the domain which finely dispersed crystalline resin (C) using a long chain aliphatic dicarboxylic acid compound has high flexibility, it is excellent also in the bending resistance of the printed matter which was a problem in the conventional crystalline polyester. it is conceivable that.

[Crystalline resin (C)]
The crystalline resin (C) is selected from a crystalline polyester resin (CP) and a crystalline composite resin (CH) containing a polycondensation resin component (CH-1) and a styrene resin component (CH-2). One or more resins. Among these, from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter, crystallinity including a polycondensation resin component (CH-1) and a styrene resin component (CH-2) Composite resins (CH) are preferred.

In the present invention, the crystallinity of the resin is represented by the ratio of the softening point to the maximum peak temperature of endotherm by differential scanning calorimeter, that is, the crystallinity index defined by the value of [softening point / maximum peak temperature of endotherm]. .
The crystalline resin is a resin having a crystallinity index of 0.6 or more and 1.4 or less, preferably 0.7 or more and 1.2 or less, and more preferably 0.9 or more and 1.2 or less.
The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, and the production conditions (eg, reaction temperature, reaction time, cooling rate) and the like. The endothermic maximum peak temperature refers to the temperature of the highest end of the observed endothermic peaks. In the crystalline resin, the maximum peak temperature of the endotherm is taken as the melting point. The crystallinity index can be measured by the method described in the examples.
The crystalline composite resin (CH) and the crystalline polyester resin (CP) will be described below.

<Crystalline composite resin (CH)>
The crystalline composite resin (CH) contains a polycondensation resin component (CH-1) and a styrene resin component (CH-2), and the polycondensation resin component (CH-1) and a styrene resin It consists of a component (CH-2) and a component derived from an amphireactive monomer that can react with any of the polycondensation resin component (CH-1) and the styrene resin component (CH-2) preferable. In addition, components other than these three components may be included within the scope of the object of the present invention, but it is preferable not to include components other than three components.

Mass ratio of the polycondensation resin component (CH-1) to the styrene resin component (CH-2) in the crystalline composite resin (CH) (Polycondensation resin component (CH-1) / Styrene resin component ( CH-2) is preferably 60/40 or more, more preferably 70/30 or more, still more preferably 80/20 or more, from the viewpoint of low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter Still more preferably, it is 85/15 or more, and preferably 98/2 or less, more preferably 95/5 or less, still more preferably 92/8 or less.
In the above calculation of the mass ratio, the mass of the polycondensation resin component (CH-1) was obtained by removing the dewatering amount at the condensation reaction from the total amount of the raw material monomers of the polycondensation resin component (CH-1). In addition, the mass of the styrene resin component (CH-2) is the total amount of the raw material monomer of the styrene resin component (CH-2) and the polymerization initiator. Moreover, the bi-reactive monomer used as needed is calculated as a mass of a polycondensation type-resin component (CH-1). The same applies to the amorphous composite resin (AH1) and the amorphous composite resin (AH2) described later.

  The total content of the components derived from the polycondensation resin component (CH-1), the styrene resin component (CH-2), and both reactive monomers in the crystalline composite resin (CH) is the low temperature fixability. From the viewpoint of storage stability, charge buildup resistance, and folding resistance of printed matter, preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% The following, more preferably 100 mol%.

(Polycondensation resin component (CH-1))
The polycondensation resin component (CH-1) is an alcohol component containing 80% by mole or more and 100% by mole or less of an aliphatic diol from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter Hereinafter, a carboxylic acid component containing 80 mol% or more and 100 mol% or less of an alcohol component (CH-al) and an aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms (hereinafter referred to as “carboxylic acid component (hereinafter It is a resin component obtained by polycondensing with "CH-ac)".
As a resin which comprises such a polycondensation type-resin component (CH-1), a polyester resin is preferable.

[Alcohol component (CH-al)]
The alcohol component (CH-al) contains an aliphatic diol in an amount of 80% by mole or more and 100% by mole or less from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter.
The carbon number of the aliphatic diol is preferably 2 or more, more preferably 4 or more from the viewpoint of low temperature fixability, charge buildup property and folding resistance of printed matter, and low temperature fixability, storage property, charge buildup It is preferably 12 or less, more preferably 8 or less, still more preferably 6 or less, and still more preferably 4 or less from the viewpoint of the properties and the folding resistance of the printed matter.
As the aliphatic diol having 2 or more and 12 or less carbon atoms, an α, ω-aliphatic diol is preferable from the viewpoint of enhancing crystallinity and improving low-temperature fixability, and, for example, ethylene glycol, 1,3-propanediol, 1 2,4-butanediol, 1,4-butenediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, etc. Be Among these, ethylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable, from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter.
The content of the aliphatic diol, preferably an aliphatic diol having 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, in the alcohol component (CH-al) has low-temperature fixability, storage stability, and charge build-up. It is 80 mol% or more and 100 mol% or less, preferably 90 mol% or more, more preferably 95 mol% or more, and still more preferably 100 mol% from the viewpoint of the properties and the folding resistance of the printed matter.

The alcohol component (CH-al) may contain other alcohols other than aliphatic diols.
As other alcohol components that the alcohol component (CH-al) may contain, aromatic diols, alicyclic diols, polyhydric alcohols having a valence of 3 or more, or alkylene oxides having 2 to 4 carbon atoms (average addition 1 or more and 16 or less) adducts etc. are mentioned.
Specific examples of other alcohols which the alcohol component (CH-al) may contain include aromatic diols such as bisphenol A or the like, alkylene oxide (average addition mole number 1 to 16 or less) adducts thereof, hydrogenated bisphenol A and the like Alicyclic diols or their alkylene oxide (average addition mole number is 2 or more and 12 or less) adducts having 2 or more and 4 or less carbon atoms, and trivalent or more polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane and sorbitol, or those The alkylene oxide (average addition mole number 1-16 or less) adduct etc. of carbon number 2 or more and 4 or less of 5

  These alcohol components (CH-al) can be used alone or in combination of two or more.

[Carboxylic acid component (CH-ac)]
The carboxylic acid component (CH-ac) is 80 mol% to 100 mol of an aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms from the viewpoint of low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter It contains less than%.
As the aliphatic dicarboxylic acid compound having 14 or more and 20 or less carbon atoms, an α, ω-linear aliphatic dicarboxylic acid compound is preferable from the viewpoint of enhancing crystallinity and improving low-temperature fixability, for example, tetradecanedioic acid (carbon Number 14), pentadecanedioic acid (carbon number 15), hexadecanedioic acid (carbon number 16), heptadecanedioic acid (carbon number 17), octadecanedioic acid (carbon number 18), nonadecanedioic acid (carbon number 19), eicosane Examples thereof include diacids (having 20 carbon atoms) or alkyl esters having 1 to 3 carbon atoms. Among them, tetradecanedioic acid, hexadecanedioic acid and octadecanedioic acid are preferable, and tetradecanedioic acid is more preferable, from the viewpoint of low temperature fixing ability, storage ability, charge buildup ability and folding resistance of printed matter.
The carbon number of the aliphatic dicarboxylic acid compound is preferably 14 or more from the viewpoint of low temperature fixability, storage property, charge buildup property, and fold resistance of printed matter, and low temperature fixability, charge buildup property, and printed matter From the viewpoint of bending resistance, preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less.
The carbon number of the aliphatic dicarboxylic acid compound is obtained by including the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.
The content of the aliphatic dicarboxylic acid compound having a carbon number of 14 or more and 20 or less in the carboxylic acid component (CH-ac) is 80 from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. The molar ratio is not less than 90 mol%, preferably not less than 90 mol%, more preferably not less than 95 mol%, still more preferably 100 mol%.

The carboxylic acid component (CH-ac) may contain another carboxylic acid component other than the aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms.
As another carboxylic acid component which a carboxylic acid component (CH-ac) may contain, dicarboxylic acid compounds other than aliphatic dicarboxylic acid compounds having 14 to 20 carbon atoms, polyvalent carboxylic acid compounds having 3 or more valences, and the like Anhydride and those C1-C3 alkyl ester etc. are mentioned.
Examples of dicarboxylic acid compounds include aromatic dicarboxylic acid compounds, aliphatic dicarboxylic acid compounds other than aliphatic dicarboxylic acid compounds having 14 to 20 carbon atoms, and alicyclic dicarboxylic acid compounds.
Examples of aromatic dicarboxylic acid compounds include phthalic acid, isophthalic acid and terephthalic acid.
Examples of aliphatic dicarboxylic acid compounds other than aliphatic dicarboxylic acid compounds having 14 to 20 carbon atoms include malonic acid (3 carbon atoms), maleic acid (4 carbon atoms), fumaric acid (4 carbon atoms), citraconic acid (C5), itaconic acid (C5), glutaconic acid (C5), succinic acid (C4), adipic acid (C6), azelaic acid (C9), sebacic acid Formula 10), undecanedioic acid (carbon number 11), dodecanedioic acid (carbon number 12), tridecanedioic acid (carbon number 13), docosane diacid (carbon number 22) and the like.
Examples of trivalent or higher polyvalent carboxylic acid compounds include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid and pyromellitic acid.

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

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (CH-ac) to the alcohol component (CH-al) is preferably from the viewpoint of low temperature fixability, storage stability, charge rising property, and folding resistance of printed matter Is 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1.1 or less .

(Styrene resin component (CH-2))
The styrene resin component (CH-2) is a segment made of a styrene resin.
The content of the styrenic resin component (CH-2) in the crystalline composite resin (CH) is preferably 2% by mass or more from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. More preferably, it is 5% by mass or more, further preferably 8% by mass or more, and from the same viewpoint, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less More preferably, it is 15% by mass or less.

  Examples of the styrene-based resin include polystyrene, polymers of styrene derivatives, styrene-acrylic copolymers, etc., from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter, polystyrene, styrene derivatives 1 or more types chosen from the polymer and a styrene- acryl copolymer of 1 are preferable, 1 or more types chosen from a polystyrene and a styrene- acryl copolymer are more preferable, and a styrene- acryl copolymer is still more preferable.

The raw material monomer of the styrene resin component (CH-2) is preferably at least one selected from styrene and a styrene derivative from the viewpoints of low temperature fixability, storage stability, charge rising property, and folding resistance of printed matter, Among these, from the viewpoint of the raw material cost of the monomer and the storage stability, styrene is more preferable, and using styrene and an alkyl (meth) acrylate in combination is even more preferable.
The term "alkyl (meth) acrylate" means both alkyl acrylate and alkyl methacrylate. The same applies to the following.

  When styrene is used, the content of the structural unit derived from styrene in the styrene resin component (CH-2) is preferably 50 from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. % Or more, more preferably 60% by mass or more, still more preferably 65% by mass or more, still more preferably 70% by mass or more, and from the same viewpoint, preferably 100% by mass or less, more preferably 95% by mass % Or less, more preferably 90% by mass or less, still more preferably 85% by mass or less.

  The styrene derivative is preferably one or more selected from methylstyrene, α-methylstyrene, β-methylstyrene, t-butylstyrene, chlorostyrene, chloromethylstyrene, methoxystyrene, styrene sulfonic acid and salts thereof.

As the alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, (iso) amyl (meth) acrylate, Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) dodecyl (meth) acrylate, (iso) palmityl (meth) acrylate, Examples include (iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate and the like.
Among these, 2-ethylhexyl acrylate and / or butyl acrylate are preferable from the viewpoint of improving low-temperature fixability by introducing a vinyl ester into the styrene resin component (CH-2) to increase the Tg to improve the low-temperature fixability. Acrylate is more preferred.
The carbon number of the alkyl group of the alkyl (meth) acrylate is preferably 2 or more, more preferably 4 or more, still more preferably 6 from the viewpoints of low temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter. From the above and from the same viewpoint, it is preferably 12 or less, more preferably 10 or less.

  When an alkyl (meth) acrylate is used, the content of the structural unit derived from the alkyl (meth) acrylate in the styrenic resin component (CH-2) is the low temperature fixability, the preservability, the charge rising property, and the bending resistance of printed matter It is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more from the viewpoint of the properties, and from the same viewpoint preferably 50% by mass or less, more preferably 40% by mass The content is more preferably 30% by mass or less, still more preferably 25% by mass or less.

[Bi-reactive monomer]
The crystalline composite resin (CH) preferably further contains a constitutional unit derived from a bireactive monomer.
When a bireactive monomer is used as a raw material monomer of the crystalline composite resin (CH), the bireactive monomer reacts with both the polycondensation resin component (CH-1) and the styrene resin component (CH-2). By doing this, the crystalline composite resin (CH) can be favorably produced.
That is, the crystalline composite resin (CH) of the present invention polymerizes the raw material monomer of the polycondensation resin component (CH-1), the raw material monomer of the styrenic resin component (CH-2), and the bireactive monomer. What is obtained by carrying out is preferable. As a result, in the crystalline composite resin (CH), the polycondensation resin component (CH-1) and the styrene resin component (CH-2) are bonded via the constitutional unit derived from the bireactive monomer, and the polycondensation is performed. The system resin component (CH-1) and the styrene resin component (CH-2) are uniformly dispersed, and the low temperature fixability, the preservability, the charge rising property, and the bend resistance of the printed matter become excellent. .

As the bireactive monomer, a compound having in the molecule one or more functional groups selected from a carboxy group, a hydroxyl group, an epoxy group, a primary amino group and a secondary amino group, and an ethylenically unsaturated bond And compounds having the formula: Among these, from the viewpoint of reactivity, preferably a compound having a hydroxyl group and / or a carboxy group and an ethylenically unsaturated bond, more preferably a compound having a carboxy group and an ethylenically unsaturated bond.
Specifically, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like can be mentioned as the bireactive monomer. From the viewpoint of the reactivity of the polycondensation reaction and the addition polymerization reaction, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable.

  The amount of the dual reactive monomer used is the alcohol component (CH-), which is a raw material monomer of the polycondensation resin component (CH-1), from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. al) per 100 mol parts, preferably 1 mol part or more, more preferably 3 mol parts or more, and preferably 30 mol parts or less from the viewpoint of low temperature fixability and heat resistant storage stability under high humidity More preferably, it is 25 mol parts or less, more preferably 20 mol parts or less, still more preferably 15 mol parts or less, still more preferably 10 mol parts or less.

(Method for producing crystalline composite resin (CH))
The crystalline composite resin (CH) can be produced, for example, by any of the following methods (1) to (3). In addition, it is preferable that a bireactive monomer is supplied to a reaction system with the raw material monomer of a styrene resin component (CH-2) from a reactive viewpoint. From the same viewpoint, a catalyst such as an esterification catalyst or an esterification co-catalyst may be used, and a polymerization initiator and a polymerization inhibitor may be used.

(1) After step (X) of polycondensation reaction by alcohol component (CH-al) and carboxylic acid component (CH-ac), raw material monomer of styrenic resin component (CH-2) and both reactions as needed Method of carrying out the step (Y) of the addition polymerization reaction with a reactive monomer.
In addition, in step (X), a part of carboxylic acid component (CH-ac) is subjected to a polycondensation reaction, and then step (Y) is carried out, and then the reaction temperature is raised again to obtain carboxylic acid component (CH-ac). It is more preferable to add the remainder of the above to the polymerization system to further advance the reaction of the polycondensation reaction of step (X) and, if necessary, the reaction with the bireactive monomer.

(2) After the step (Y) of the addition polymerization reaction of the styrene-based resin component (CH-2) with the raw material monomer and the bireactive monomer of the polycondensation reaction with the raw material monomer of the polycondensation resin component (CH-1) The method of performing a process (X).
The alcohol component (CH-al) and the carboxylic acid component (CH-ac) are present in the reaction system during the addition polymerization reaction, and an esterification catalyst and, if necessary, an ester at a temperature suitable for the polycondensation reaction. The polycondensation reaction can also be initiated by adding a copromoter, or the alcohol component (CH-al) and the carboxylic acid component (CH-ac) can be introduced into the reaction system at a temperature suitable for the polycondensation reaction. The polycondensation reaction can also be initiated by the addition of In the former case, the molecular weight and molecular weight distribution can be controlled by adding an esterification catalyst and, if necessary, an esterification promoter at a temperature suitable for the polycondensation reaction.

(3) Step (X) of the polycondensation reaction with alcohol component (CH-al) and carboxylic acid component (CH-ac) and addition polymerization with raw material monomer and bireactive monomer of styrenic resin component (CH-2) A method of carrying out the reaction under conditions in which the reaction step (Y) proceeds in parallel.
In this method, step (X) and step (Y) are carried out under reaction temperature conditions suitable for addition polymerization reaction, reaction temperature is raised, and temperature conditions suitable for polycondensation reaction, if necessary, It is preferable to add a trivalent or higher raw material monomer of the polycondensation resin component (CH-1) as a crosslinking agent to the polymerization system, and further carry out the polycondensation reaction of the step (X). At that time, under the temperature condition suitable for the polycondensation reaction, a radical polymerization inhibitor may be added to proceed only with the polycondensation reaction. Both reactive monomers participate in the polycondensation reaction as well as the addition polymerization reaction.

Among the methods (1) to (3), the crystalline composite resin (CH) is preferably produced by the method according to (1), and more preferably produced by the method having the following steps I to III. .
Step I: Step of polycondensing a part of the raw material monomer of the polycondensation resin component (CH-1) Step II: of the styrene resin component (CH-2) in the presence of the polycondensate obtained in step I Step of Addition Polymerization of Raw Material Monomer Step III: Step of Polycondensing Raw Material Monomer of Remaining Polycondensed Resin Component (CH-1) in the Presence of Reactant Obtained in Step II From the viewpoint of low-temperature fixability, it is preferable to use together with the raw material monomer of the styrene resin component (CH-2).
By performing the above steps I to III, the polycondensation resin component (CH-1) and the styrene resin component (CH-2) in the crystalline composite resin (CH) become in an appropriate dispersion state, and a polycondensation type The dispersibility of the resin component (CH-1) is enhanced, and the low temperature fixability, the storage stability, the charge rising property, and the bending resistance of the printed matter can be improved.

[Step I]
Process I is a process of polycondensing a part of the raw material monomers of the polycondensation resin component (CH-1).
In the raw material monomer to be subjected to step I, the amount of the carboxylic acid component (CH-ac) is preferably 10% by mass or more of the total amount of the carboxylic acid component (CH-ac) used for producing the crystalline composite resin (CH) The content is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 70% by mass or less Still more preferably, it is 60% by mass or less.
Further, in the raw material monomer to be subjected to Step I, the amount of the alcohol component (CH-al) is preferably equal to or more than the number of moles of the carboxylic acid component (CH-ac), and is used for producing the crystalline composite resin (CH) The total amount of the alcohol component (CH-al) is more preferable because the unreacted alcohol component (CH-al) serves as a solvent for performing Step II.
The temperature of the polycondensation reaction in step I is preferably 120 ° C. or more, more preferably 130 ° C. or more, and preferably 230 ° C. or less, more preferably 200 ° C. or less, still more preferably 180, from the viewpoint of reactivity. It is less than ° C. The pressure during the polycondensation reaction may be normal pressure.
The termination of the polycondensation reaction in step I is preferably performed at the time when the raw material monomers subjected to step I have reacted at least 95 mol%, more preferably at least 98 mol%.

[Step II]
Step II is a step of addition polymerization of the raw material monomer of the styrenic resin component (CH-2) in the presence of the polycondensate obtained in step I.
The temperature of the addition polymerization reaction in the step II is preferably 120 ° C. or more, more preferably 130 ° C. or more, and preferably 200 ° C. or less, more preferably 180 ° C. or less from the viewpoint of reactivity.
The raw material monomer of the styrenic resin component (CH-2) to be subjected to the addition polymerization reaction in step II may be added in advance to the reaction system in step I. In that case, the polymerization initiator may be added in step II. .
At the end of the reaction of Step II, the residual raw material monomer of the styrenic resin component (CH-2) is preferably 1000 ppm (wt / wt) or less based on the resin obtained in Step 2.

[Step III]
Step III is a step of polycondensation of the raw material monomer of the remaining polycondensation resin component (CH-1) in the presence of the reactant obtained in Step II.
The temperature of the polycondensation reaction in step III is preferably 120 ° C. or more, more preferably 130 ° C. or more, still more preferably 150 ° C. or more, and preferably 230 ° C. or less, more preferably 220, from the viewpoint of reactivity. It is less than ° C. The pressure during the polycondensation reaction in step III may be normal pressure.

  From the viewpoint of reducing the acid value of the crystalline composite resin (CH) to a preferable range by advancing the polycondensation reaction after the step III, it is preferable to carry out the step IV in which the polycondensation reaction is further performed under reduced pressure.

[Step IV]
The temperature of the polycondensation reaction in step IV is preferably 120 ° C. or more, more preferably 130 ° C. or more, still more preferably 150 ° C. or more, and preferably 230 ° C. or less, more preferably 220 ° C. or less.
Here, the reduced pressure is a pressure less than normal pressure (101.3 kPa), preferably 80 kPa or less, more preferably 50 kPa or less, and still more preferably 20 kPa or less.
Step IV is preferably carried out until the produced crystalline composite resin (CH) reaches a preferred acid value described later. Moreover, it is preferable to perform process IV in presence of the said esterification catalyst.

  Preferably, steps I to III or steps I to IV are performed in the same vessel.

[Esterification catalyst]
As an esterification catalyst suitably used for the polycondensation reaction, a titanium compound and a tin (II) compound not having a Sn-C bond may be mentioned, and these may be used alone or in combination of two or more. it can.
As a titanium compound, a titanium compound having a Ti-O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms in total, an alkenyloxy group or an acyloxy group is more preferable.
Examples of tin (II) compounds not having a Sn-C bond include tin (II) compounds having a Sn-O bond, tin (II) compounds having a Sn-X bond (where X represents a halogen atom), etc. Preferably, tin (II) compounds having a Sn-O bond are more preferable. Among them, di (2-ethylhexanoic acid) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of a crystalline composite resin (CH). Tin (II) is more preferred.
The amount of the esterification catalyst used is 100 in total of the alcohol component (CH-al) and the carboxylic acid component (CH-ac) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the crystalline composite resin (CH). The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.2 parts by mass or more, and preferably 1.5 parts by mass or less, more preferably, per mass part. Is 1.0 part by mass or less, more preferably 0.5 part by mass or less.

[Esterification promoter]
As the esterification promoter, pyrogallol compounds are preferred. The pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted by a hydroxyl group, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ' And benzophenone derivatives such as 3,4-tetrahydroxybenzophenone; and catechin derivatives such as epigallocatechin and epigallocatechin gallate. Gallic acid is preferable from the viewpoint of reactivity.
[Polymerization inhibitor]
As a polymerization inhibitor, 4-t-butyl catechol etc. are mentioned.

(Softening point)
The softening point of the crystalline composite resin (CH) is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 80 ° C. or more, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. And, from the viewpoint of low-temperature fixability, it is preferably 120 ° C. or less, more preferably 100 ° C. or less, still more preferably 90 ° C. or less.
(Melting point)
The melting point of the crystalline composite resin (CH) is preferably 50 ° C. or more, more preferably 60 ° C. or more, still more preferably 70 ° C. or more, from the viewpoint of storage stability, charge rising property and folding resistance of printed matter. And, from the viewpoint of low-temperature fixability, it is preferably 110 ° C. or less, more preferably 90 ° C. or less, still more preferably 80 ° C. or less.
(Acid number)
The acid value of the crystalline composite resin (CH) is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 20 mgKOH / g, from the viewpoint of low temperature fixability, charge buildup property, and folding resistance of printed matter. and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, from the viewpoint of low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter.
The softening point, the melting point and the acid value of the crystalline composite resin (CH) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time and the cooling rate. The softening point, the melting point and the acid value are determined by the methods described in the examples.

<Crystalline polyester (CP)>
The crystalline polyester (CP) is an aliphatic component having an aliphatic diol content of 80 to 100 mol% (hereinafter, also referred to as “alcohol component (CP-al)”), and an aliphatic having 14 to 20 carbon atoms. It is a resin obtained by polycondensing a carboxylic acid component (hereinafter, also referred to as “carboxylic acid component (CP-ac)”) containing 80 to 100 mol% of a dicarboxylic acid compound.
Examples of the alcohol component (CP-al) and the carboxylic acid component (CP-ac) include the same as the alcohol component (CH-al) and the carboxylic acid component (CH-ac), and preferred types and equivalents thereof The ratio is also the same.
In the polycondensation reaction of the alcohol component (CP-al) and the carboxylic acid component (CP-ac), the type and amount of use of the esterification catalyst and the esterification co-catalyst are the weight of the crystalline composite resin (CH) It is the same as the type and amount used in the polycondensation reaction of the condensation resin portion (CH-1), and the preferred embodiments are also the same.

  The temperature of the polycondensation reaction is preferably 120 ° C. or more, more preferably 160 ° C. or more, still more preferably 180 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less.

[Softening point]
The softening point of the crystalline polyester (CP) is preferably 60 ° C. or more, more preferably 70 ° C. or more, still more preferably 75 ° C. or more, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. And, from the viewpoint of low temperature fixability, it is preferably 120 ° C. or less, more preferably 100 ° C. or less, and still more preferably 90 ° C. or less.
[Melting point]
The melting point of the crystalline polyester (CP) is preferably 50 ° C. or more, more preferably 60 ° C. or more, still more preferably 70 ° C. or more, from the viewpoint of storage stability, charge rising property and folding resistance of printed matter From the viewpoint of low-temperature fixability, it is preferably 110 ° C. or less, more preferably 90 ° C. or less, and still more preferably 80 ° C. or less.
[Acid number]
The acid value of the crystalline polyester (CP) is preferably 5 mg KOH / g or more, more preferably 10 mg KOH / g or more, still more preferably from the viewpoint of low-temperature fixability, storage stability, charge rise property, and folding resistance of printed matter. It is 20 mg KOH / g or more, and from the same viewpoint, preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less.
The softening point, the melting point and the acid value of the crystalline polyester (CP) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time and the cooling rate.

[Amorphous resin (A1)]
The amorphous resin (A1) is a resin having a crystallinity index of more than 1.4 or less than 0.6, preferably more than 1.5 or less than 0.5, more preferably 1. 6 or more or 0.5 or less.
As the amorphous resin (A1), an amorphous polyester (AP), a polyester resin component (AH1-1) and a styrene resin from the viewpoints of low temperature fixing property, storage property, charge rising property and folding resistance of printed matter One or more selected from an amorphous composite resin (AH1) containing a resin component (AH1-2) and an amorphous styrenic resin (AS) are preferable. Among them, an amorphous composite resin (AH1) and an amorphous styrenic resin (AS) containing a polyester resin component (AH1-1) and a styrenic resin component (AH1-2) from the viewpoint of low temperature fixability. It is more preferable to use one or more selected from the above, and from the viewpoint of charge rising property and folding resistance of printed matter, an amorphous styrenic resin (AS) is more preferable.
Therefore, an amorphous styrenic resin (AS) is preferable from the viewpoint of low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter.

(Softening point)
The softening point of the amorphous resin (A1) is preferably 50 ° C. or more, more preferably 70 ° C. or more, still more preferably 85 ° C. or more, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. And, from the viewpoint of low temperature fixability, it is preferably 150 ° C. or less, more preferably 130 ° C. or less, and still more preferably 125 ° C. or less.
(Glass-transition temperature)
The glass transition temperature of the amorphous resin (A1) is preferably 30 ° C. or more, more preferably 40 ° C. or more, still more preferably 50 ° C. or more, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. And from the viewpoint of low-temperature fixability, it is preferably 90 ° C. or less, more preferably 70 ° C. or less, still more preferably 60 ° C. or less.
(Acid number)
The acid value of the amorphous resin (A1) is preferably 0 mg KOH / g or more, and preferably 40 mg KOH / g or less, from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. More preferably, it is 30 mg KOH / g or less, still more preferably 25 mg KOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous resin (A1) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate.
Next, the amorphous styrenic resin (AS), the amorphous polyester (AP), and the amorphous composite resin (AH1) which are preferably used as the amorphous resin (A1) will be described.

(Amorphous styrenic resin (AS))
Examples of the amorphous styrenic resin (AS) used as the amorphous resin (A1) include polystyrene, a polymer of a styrene derivative, a styrene-acrylic copolymer, etc. From the viewpoint of flexibility and print folding resistance, one or more selected from polystyrene, a polymer of styrene derivative and a styrene-acrylic copolymer is preferable, and one or more selected from polystyrene and a styrene-acrylic copolymer is More preferred is styrene-acrylic copolymer.

As a raw material monomer of amorphous styrene resin (AS), the thing similar to what was mentioned as a raw material monomer of the said styrene resin component (CH-2) is mentioned. Among these, it is preferable to use styrene and an alkyl (meth) acrylate in combination.
When styrene is used, the content of styrene in the raw material monomer of the amorphous styrenic resin (AS) is preferably 50% by mass from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. % Or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, and from the same viewpoint, preferably 95% by mass or less, more preferably 90% by mass The content is more preferably 85% by mass or less. The polymerization initiator is not included in the raw material monomer of the styrene resin.

As an alkyl (meth) acrylate, the thing similar to what was mentioned as a raw material monomer of the said styrene resin component (CH-2) is mentioned, Among these, n-butyl acrylate is preferable.
The carbon number of the alkyl group of the alkyl (meth) acrylate used as a raw material monomer of the amorphous styrenic resin (AS) is from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter It is preferably 2 or more, more preferably 3 or more, and preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, still more preferably 6 or less.
When using an alkyl (meth) acrylate, the content of the alkyl (meth) acrylate in the raw material monomer of the amorphous styrenic resin (AS) is the low temperature fixability, the preservability, the charge rising property, and the folding resistance of printed matter From the viewpoint of the above, it is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less.

The amorphous styrenic resin (AS) can be produced by subjecting the raw material monomers to an addition polymerization reaction.
The temperature of the addition polymerization reaction is preferably 120 ° C. or more, more preferably 130 ° C. or more, still more preferably 150 ° C. or more, and preferably 230 ° C. or less, more preferably 220 ° C. or less is there.
Moreover, it is preferable to accelerate the reaction by reducing the pressure of the reaction system in the latter half of the polymerization.

[Softening point]
The softening point of the amorphous styrenic resin (AS) is preferably 90 ° C. or more, more preferably 105 ° C. or more, still more preferably 115 ° C. or more, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. And from the viewpoint of low-temperature fixability, preferably 150 ° C. or less, more preferably 135 ° C. or less, and still more preferably 125 ° C. or less.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous styrenic resin (AS) is preferably 30 ° C. or more, more preferably 40 ° C. or more, still more preferably 50 ° C., from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. The temperature is preferably 90 ° C. or less, more preferably 70 ° C. or less, and still more preferably 60 ° C. or less from the viewpoint of low-temperature fixability.
[Acid number]
The acid value of the amorphous styrenic resin (AS) is preferably 0 mg KOH / g or more, and preferably 30 mg KOH / g, from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. It is at most g, more preferably at most 25 mg KOH / g, even more preferably at most 10 mg KOH / g.
The softening point, glass transition temperature, and acid value of the amorphous styrenic resin (AS) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate. .

(Amorphous polyester (AP))
The amorphous polyester (AP) used as the amorphous resin (A1) has an alcohol component (hereinafter also referred to as "alcohol component (AP-al)") and a carboxylic acid component (hereinafter referred to as "carboxylic acid component (AP) It is obtained by carrying out a polycondensation reaction with -ac).

[Alcohol component (AP-al)]
As an alcohol component (AP-al), the thing similar to the said alcohol component (CH-al) is mentioned.
Among these, aromatic diols such as bisphenol A or their alkylene oxide (average addition mole number: 1 or more and 16 or less) adducts are preferable from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. Preferably, the propylene oxide adduct of bisphenol A is more preferred.
The content of the propylene oxide adduct of bisphenol A in the alcohol component (AP-al) is preferably 80 mol% or more, more preferably from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. It is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 98 mol% or more, and preferably 100 mol% or less, more preferably 100 mol%.
The average addition mole number of propylene oxide of the propylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. , More preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, still more preferably 4 or less.
These alcohol components (AP-al) can be used alone or in combination of two or more.

[Carboxylic acid component (AP-ac)]
As a carboxylic acid component (AP-ac), the thing similar to what was mentioned as said carboxylic acid component (CH-ac) is mentioned.
Among them, aliphatic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds are preferable from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter, and aliphatic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds More preferably,
As an aliphatic carboxylic acid compound, fumaric acid is preferable. The carbon number of the aliphatic dicarboxylic acid compound is preferably 2 or more, and preferably 10 or less, more preferably 6 or less, from the viewpoint of low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter. More preferably, it is 4 or less.
Terephthalic acid is preferred as the aromatic dicarboxylic acid compound. The content of the aromatic dicarboxylic acid compound in the carboxylic acid component (AP-ac), preferably terephthalic acid, is preferably 30 moles from the viewpoint of low-temperature fixability, storage stability, charge buildup, and folding resistance of printed matter. % Or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, still more preferably 60 mol% or less.
These alcohol components (AP-ac) can be used alone or in combination of two or more.
From the viewpoint of adjusting physical properties, the alcohol component (AP-al) may appropriately contain a monohydric alcohol, and the carboxylic acid component (AP-ac) appropriately contains a monovalent carboxylic acid compound. It may be

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (AP-ac) to the alcohol component (AP-al) is preferably from the viewpoint of low-temperature fixing ability, storage stability, charge buildup ability, and folding resistance of printed matter Is 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.9 or less .

  Amorphous polyester (AP) is an esterification catalyst, an esterification co-catalyst, a polymerization inhibitor, if necessary, in an inert gas atmosphere of an alcohol component (AP-al) and a carboxylic acid component (AP-ac). It can manufacture by polycondensing using etc.

  The temperature of the polycondensation reaction is preferably 120 ° C. or more, more preferably 160 ° C. or more, still more preferably 200 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less.

As an esterification catalyst, an esterification co-catalyst, and a polymerization inhibitor suitably used for a polycondensation reaction, the thing similar to what is used for manufacture of the said crystalline composite resin (CH) is mentioned.
The amount of the esterification catalyst used is the total of 100 of the alcohol component (AP-al) and the carboxylic acid component (AP-ac) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous polyester (AP). The amount is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, and preferably 2.0 parts by mass or less, more preferably, per mass part. Is 1.5 parts by mass or less, more preferably 1.0 parts by mass or less.
The amount of the esterification co-catalyst used is the total of 100 mass of the alcohol component (AP-al) and the carboxylic acid component (AP-ac) from the viewpoint of reactivity, molecular weight adjustment and physical property adjustment of the amorphous polyester (AP). The amount is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, still more preferably 0.03 parts by mass or more, and preferably 0.2 parts by mass or less, more preferably It is 0.15 parts by mass or less, more preferably 0.1 parts by mass or less.
The mass ratio of the esterification promoter to the esterification catalyst [esterification promoter / esterification catalyst] is preferably 0.001 or more, more preferably 0.01 or more, still more preferably 0. It is not less than 05, and preferably not more than 0.5, more preferably not more than 0.3, still more preferably not more than 0.15.

[Softening point]
The softening point of the amorphous polyester (AP) is preferably 50 ° C. or more, more preferably 70 ° C. or more, still more preferably 85 ° C. or more, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. And, from the viewpoint of low-temperature fixability, it is preferably 130 ° C. or less, more preferably 110 ° C. or less, still more preferably 95 ° C. or less.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous polyester (AP) is preferably 30 ° C. or more, more preferably 40 ° C. or more, still more preferably 50 ° C. or more, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. And from the viewpoint of low-temperature fixability, it is preferably 90 ° C. or less, more preferably 70 ° C. or less, still more preferably 60 ° C. or less.
[Acid number]
The acid value of the amorphous polyester (AP) is preferably 0 mg KOH / g or more, more preferably 10 mg KOH / g or more, still more preferably 15 mg KOH / g, from the viewpoint of storage stability, charge rising property and folding resistance of printed matter. From the viewpoint of low-temperature fixability, it is preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and still more preferably 25 mg KOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous polyester (AP) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate.

(Amorphous composite resin (AH1)
The amorphous composite resin (AH1) used as the amorphous resin (A1) contains a polyester resin component (AH1-1) and a styrene resin component (AH1-2), and the polyester resin component (AH1) -1), a component derived from a bireactive monomer capable of reacting with any of a styrene resin component (AH1-2), a polyester resin component (AH1-1) and a styrene resin component (AH1-2) It is preferable that it consists of. In addition, components other than these three components may be included within the scope of the object of the present invention, but it is preferable not to include components other than three components.
Examples of the dual reactive monomer include those similar to the dual reactive monomer that can be used for the above-mentioned crystalline composite resin (CH), and preferred types and amounts used are also the same.

  Mass ratio of polyester resin component (AH1-1) and styrene resin component (AH1-2) in amorphous composite resin (AH1) (polyester resin component (AH1-1) / styrene resin component (AH1-2) ) Is preferably 50/50 or more, more preferably 60/40 or more, and still more preferably 70/30 or more, from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. And from the same viewpoint, it is preferably 95/5 or less, more preferably 90/10 or less, and still more preferably 85/15 or less.

  The total content of the polyester resin component (AH1-1), the styrenic resin component (AH1-2), and the component derived from the bireactive monomer in the amorphous composite resin (AH1) is low-temperature fixability, It is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less from the viewpoints of storage stability, charge rising property, and folding resistance of printed matter. More preferably, it is 100 mol%.

[Polyester resin component (AH1-1)]
The polyester resin component (AH1-1) is an alcohol component (hereinafter, also referred to as "alcohol component (AH1-al)") from the viewpoint of low temperature fixing property, storage property, charge rising property, and folding resistance of printed matter, It is obtained by polycondensing a carboxylic acid component (hereinafter, also referred to as “carboxylic acid component (AH1-ac)”).
Examples of the alcohol component (AH1-al) and the carboxylic acid component (AH1-ac) include the same as the alcohol component (AP-al) and the carboxylic acid component (AP-ac), and preferred embodiments are also the same. .

The equivalent ratio (COOH group / OH group) of the carboxylic acid component (AH1-ac) to the alcohol component (AH1-al) is preferably from the viewpoint of low temperature fixability, storage stability, charge rising property, and folding resistance of printed matter Is 0.6 or more, more preferably 0.7 or more, still more preferably 0.8 or more, and preferably 1.2 or less, more preferably 1.0 or less, still more preferably 0.9 or less .
From the viewpoint of adjusting physical properties, a monohydric alcohol may be suitably contained in the alcohol component (AH1-al), and a monobasic carboxylic acid compound is suitably contained in the carboxylic acid component (AH1-ac). It may be

[Styrenic resin component (AH1-2)]
The styrene resin component (AH1-2) is a segment made of a styrene resin.
Examples of the styrene-based resin include polystyrene, polymers of styrene derivatives, styrene-acrylic copolymers, etc., from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter, polystyrene, styrene derivatives 1 or more types chosen from the polymer and a styrene- acryl copolymer of 1 are preferable, 1 or more types chosen from a polystyrene and a styrene- acryl copolymer are more preferable, and a styrene- acryl copolymer is still more preferable.
As a raw material monomer of a styrene-type resin component (AH1-2), the thing similar to the raw material monomer of the said styrene-type resin component (CH-2) is mentioned, A preferable kind and usage-amount are also the same.

  The amorphous composite resin (AH1) can be produced by the same method as the method (1) to (3) for producing the crystalline composite resin (CH).

The temperature of the polycondensation reaction is preferably 120 ° C. or more, more preferably 130 ° C. or more, still more preferably 150 ° C. or more, and preferably 250 ° C. or less, more preferably 240 ° C. or less from the viewpoint of reactivity. is there.
The temperature of the addition polymerization reaction is preferably 120 ° C. or more, more preferably 130 ° C. or more, and preferably 200 ° C. or less, more preferably 180 ° C. or less from the viewpoint of reactivity.

[Esterification catalyst, esterification co-catalyst, polymerization inhibitor]
As an esterification catalyst, an esterification co-catalyst, and a polymerization inhibitor suitably used for the polycondensation reaction, an esterification catalyst, an esterification co-catalyst, and a polymerization inhibitor used for the production of the above-mentioned amorphous polyester (AP) And the preferred embodiments are also the same.

[Softening point]
The softening point of the amorphous composite resin (AH1) is preferably 60 ° C. or more, more preferably 80 ° C. or more, and still more preferably from the viewpoint of low temperature fixability, storage stability, charge rising property and folding resistance of printed matter. The temperature is 95 ° C. or higher, and preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and still more preferably 110 ° C. or lower.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous composite resin (AH1) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, further preferably from the viewpoint of low temperature fixability, storage stability, charge buildup resistance, and folding resistance of printed matter. Is 50 ° C. or higher, and preferably 90 ° C. or lower, more preferably 70 ° C. or lower, and still more preferably 60 ° C. or lower.
[Acid number]
The acid value of the amorphous composite resin (AH1) is preferably 0 mgKOH / g or more, more preferably 10 mgKOH / g or more, and further preferably from the viewpoint of low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter. Preferably, it is 15 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, and still more preferably 25 mg KOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous composite resin (AH1) can be appropriately adjusted according to the type and ratio of the raw material monomers, and the production conditions such as the reaction temperature, the reaction time, and the cooling rate.

In the production method of the present invention, besides the crystalline resin (C) and the amorphous resin (A1), known resins used for toner, for example, other than the crystalline resin (C) and the amorphous resin (A1) Of polyester, styrene-acrylic copolymer, epoxy, polycarbonate, polyurethane and the like.
Next, steps 1 to 4 in the production method of the present invention will be described.

The production method of the present invention includes the following steps 1 to 4.
Step 1: Step of mixing crystalline resin (C), organic solvent, and neutralizing agent to obtain a mixture Step 2: Mix at least water with the mixture obtained in Step 1, crystalline resin (C) Step 3: Step of obtaining an aqueous dispersion of resin particles (X) containing a crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2: Step 2: The resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A1) are coagulated and fused in an aqueous medium Process

<Step 1>
Step 1 is a step of mixing the crystalline resin (C), the organic solvent, and the neutralizing agent to obtain a mixture.

<Organic solvent>
As the organic solvent, from the viewpoint of solubility, alcohol solvents such as isopropanol and isobutanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether and dioxane; ethyl acetate Preferred are acetic acid ester solvents such as isopropyl acetate and the like. Among these, ketone solvents are more preferable, and methyl ethyl ketone is more preferable, from the viewpoints of low-temperature fixing ability, storage ability, bending resistance, and charge rising property.
The mass ratio [organic solvent / crystalline resin (C) (total amount of crystalline polyester resin (CP) and crystalline composite resin (CH)) of the organic solvent and the crystalline resin (C) in step 1 is From the viewpoint of low-temperature fixability, storage stability, charge buildup, and folding resistance of printed matter, it is preferably 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and preferably Is 2.0 or less, more preferably 1.5 or less, and still more preferably 1.3 or less.

<Neutralizer>
Examples of the neutralizing agent used in step 1 include metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonia; organics such as trimethylamine, ethylamine, diethylamine, triethylamine, triethanolamine and tributylamine Base is mentioned. Among these, metal hydroxides and ammonia are preferable, metal hydroxides are more preferable, hydroxides of alkali metals are more preferable, and one or more selected from sodium hydroxide and potassium hydroxide are more preferable, and water is more preferable. Sodium oxide is even more preferred.
The degree of neutralization of the crystalline resin (C) by the neutralizing agent is controlled by adjusting the volume median particle diameter (D ₅₀ ) of the resin particles (X) obtained in the step 3, low temperature fixability, storage property, charge rise property And 30 mol% or more, more preferably 50 mol% or more, and still more preferably 60 mol% or more from the viewpoint of improving the folding resistance of the printed matter, and from the same viewpoint, preferably 150 mol%. The following content is more preferably 120 mol% or less, still more preferably 100 mol% or less, and still more preferably 80 mol% or less.
The degree of neutralization (mol%) of the resin can be determined by the following equation.
Degree of neutralization = {[mass of neutralizing agent (g) / equivalent of neutralizing agent] / [acid value of resin (mg KOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

<Surfactant>
In the process 1, it is preferable to use a surfactant from the viewpoint of the low temperature fixability of the toner obtained, the storage stability, the charge rising property, and the folding resistance of the printed matter.
Surfactants include nonionic surfactants, anionic surfactants and cationic surfactants. Among these, from the viewpoint of the emulsion stability of the resin, nonionic surfactants and / or anionic surfactants are preferable, and anionic surfactants are more preferable.
As nonionic surfactants, polyoxyethylene alkyl aryl ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Polyethylene glycol monostearate, polyoxyethylene fatty acid esters such as polyethylene glycol monooleate, oxyethylene / oxypropylene block copolymer, etc. are mentioned, among them, polyoxyethylene alkyl ethers from the viewpoint of the emulsion stability of the resin Is preferred.
Examples of the anionic surfactant include alkyl benzene sulfonates such as sodium alkyl benzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate, etc. From the viewpoint of emulsion stability, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, and alkyl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyl trimethyl ammonium chloride and dialkyl dimethyl ammonium chloride.
Among these, from the viewpoint of the emulsion stability of the binder resin, polyoxyethylene alkyl ethers and alkyl ether sulfates are preferable, and polyoxyethylene alkyl ether sulfates are more preferable. The polyoxyethylene alkyl ether sulfate is preferably a sodium salt from the same viewpoint.

The polyoxyethylene alkyl ether sulfate preferably contains polyoxyethylene alkyl ether sulfate (EO2) in which the number of moles of ethylene oxide added is 2 moles.
The content of the polyoxyethylene alkyl ether sulfate in the anionic surfactant is preferably 80% by mass or more, more preferably from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. Is at least 85 mass%, more preferably at least 90 mass%, still more preferably at least 95 mass%, and preferably at most 100 mass%.

The amount of the surfactant used is preferably 1 mass as solid content with respect to 100 parts by mass of the crystalline resin (C) from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. Part or more, more preferably 2.5 parts by mass or more, further preferably 3 parts by mass or more, and preferably 10 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 6 parts by mass or less, still more The amount is preferably 5.5 parts by mass or less, more preferably 5 parts by mass or less.
The addition amount of the surfactant in step 1 is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more in the total of the addition amounts of the surfactant in steps 1 to 4. And preferably 100% by mass or less, more preferably 100% by mass.

<Optional component>
Also, in this step, optional components such as a coloring agent, a charge control agent, a mold release agent, a surfactant, a conductive regulator, a reinforcing filler such as a fibrous substance, an antioxidant, and an antiaging agent are added. May be
The additives such as the colorant and the charge control agent may be mixed with the binder resin in advance, and in that case, it is preferable to melt-knead the binder resin and the additive.
It is preferable to use an open roll type twin-screw kneader for melt kneading. The open-roll type twin-screw kneader is a kneader in which two rolls are disposed in parallel and in close proximity, and a heating function or a cooling function can be provided by passing a heat medium through each roll. Therefore, the open-roll type twin-screw kneader has a part to be melt-kneaded as an open type, and is provided with a heating roll and a cooling roll, so unlike an ordinary twin-screw kneader, it occurs during melt kneading. The heat of kneading can be dissipated easily.

(Colorant)
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned and it can select suitably according to the objective. Specifically, carbon black, inorganic complex oxide, chromium yellow, Hansa yellow, benzidine yellow, Sureren yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, Vulcan orange, watch young red, permanent red, permanent anchor 3B, Brylly anchor Min 6B, Dupont oil red, pyrazolone red, lisole red, rhodamine B lake, lake red C, bengal, aniline blue, ultramarine blue, chalco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate etc Pigments of acridine type, xanthene type, azo type, benzoquinone type, azine type, anthraquinone type, indigo type, 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 amount of the colorant used is preferably 0.1 parts by mass or more, more preferably 100 parts by mass in total of the crystalline resin (C) and the amorphous resin (A1) from the viewpoint of improving the image density of the toner. The amount is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and preferably 40 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 10 parts by mass 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. You may use these individually or in combination of 2 or more types.
The amount of the charge control agent used is preferably 0.01 parts by mass or more, more preferably 100 parts by mass in total of the crystalline resin (C) and the amorphous resin (A1), from the viewpoint of charging stability of the toner. The amount is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and preferably 3.0 parts by mass or less, more preferably 2.0 parts by mass or less, still more preferably 1.5 parts by mass It is below.

(Release agent)
As a mold release agent, polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide, etc .; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant-based waxes such as oil; Animal-based waxes such as beeswax; Waxes such as mineral and petroleum-based waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, Fischer-Tropsch wax, etc. These may be used alone or in combination of two or more Can be mixed and used.
The amount of the release agent used is preferably 0.1 parts by mass or more, more preferably 0.1 parts by mass or more, based on the total of the crystalline resin (C) and the amorphous resin (A1), from the viewpoint of resin dispersibility. It is 5 parts by mass or more, more preferably 2 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less.

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

The aqueous medium is preferably one containing water as a main component. The water content is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, from the viewpoint of improving the emulsion stability of the resin in the aqueous medium. It is 100 mass% or less, more preferably 100 mass%. The water is preferably deionized water or distilled water.
As components other than water, an organic solvent which is dissolved in water such as methanol, ethanol, acetone, cyclic ether such as tetrahydrofuran, etc. may be mentioned.

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

  The addition rate of the aqueous medium is preferably 0.1 parts by mass / min or more with respect to 100 parts by mass of the crystalline resin (C) until phase inversion is completed, from the viewpoint of obtaining resin particles with a small particle diameter. More preferably, it is 1 part by mass or more, more preferably 3 parts by mass or more, still more preferably 4 parts by mass or more, and preferably 50 parts by mass or less, more preferably 30 parts by mass / Min or less, more preferably 20 parts by mass / min or less, still more preferably 10 parts by mass / min or less. There is no limitation on the addition rate of the aqueous medium after phase inversion.

  The amount of the aqueous medium used is preferably 100 parts by mass or more, more preferably 200 parts by mass or more, further preferably 100 parts by mass of the crystalline resin (C) from the viewpoint of obtaining uniform aggregated particles in the subsequent aggregation step. The amount is preferably 400 parts by mass or more, more preferably 600 parts by mass or more, and preferably 2000 parts by mass or less, more preferably 1500 parts by mass or less, still more preferably 1000 parts by mass or less, still more preferably 800 parts by mass It is below.

<Step 3>
Step 3 is a step of obtaining an aqueous dispersion of resin particles (X) containing a crystalline resin (C) by removing the organic solvent from the dispersion obtained in step 2.
The method of removing the organic solvent is not particularly limited, and any method can be used. However, since it is dissolved in water, distillation is preferable. Also, the organic solvent may not be completely removed but may remain in the aqueous dispersion. In this case, the residual amount of the organic solvent in the aqueous dispersion is preferably 1% by mass or less, more preferably 0.5% by mass or less, and substantially more preferably 0%.
When removing the organic solvent by distillation, it is preferable to raise the temperature to a temperature above the boiling point of the organic solvent to be used and to distill it off while stirring. Further, from the viewpoint of maintaining the dispersion stability of the resin particles (X), it is more preferable that the temperature is raised to a temperature equal to or higher than the boiling point of the organic solvent to be used under reduced pressure. Note that the temperature may be raised after depressurization, or may be reduced after raising the temperature. From the viewpoint of maintaining the dispersion stability of the resin particles (X), it is preferable to distill off at a constant temperature and pressure.
Furthermore, after step 3, step 3-1 of mixing a surfactant with the obtained aqueous dispersion may be performed.

  The solid content concentration of the aqueous dispersion of the present invention is preferably 3% by mass or more, more preferably 5% by mass or more, and more preferably by adding water as appropriate from the viewpoint of the stability and easy handling of the aqueous dispersion. The content is preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

The volume median particle diameter (D ₅₀ ) of the resin particles (X) obtained in this step is preferably 30 nm or more, more preferably from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. Is preferably 50 nm or more, more preferably 70 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, still more preferably 150 nm or less, still more preferably 130 nm or less.
In the present specification, the volume median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by volume fraction is 50% as calculated from the smaller particle size.

<Step 4>
Step 4 aggregates resin particles (X) containing the crystalline resin (C) obtained in step 3 and resin particles (Y) containing the amorphous resin (A1) in an aqueous medium, It is a process of fusing.
The mass ratio (resin particles (X) / resin particles (Y)) of the resin particles (X) containing the crystalline resin (C) to the resin particles (Y) containing the amorphous resin (A1) is low temperature From the viewpoints of fixability, storage stability, bending resistance, and charge rising property, it is preferably 3/97 or more, more preferably 5/95 or more, still more preferably 7/93 or more, still more preferably 10/90 or more, Still more preferably, it is 13/87 or more, and from the same viewpoint, preferably 40/60 or less, more preferably 30/70 or less, still more preferably 20/80 or less, still more preferably 17/83 or less.
Step 4 preferably includes the following steps 4-1 to 4-3 from the viewpoint of the low temperature fixing property of the obtained toner, the storage stability, the charge rising property, and the folding resistance of the printed matter.

Step 4-1: Aggregate resin particles (X) containing the crystalline resin (C) obtained in step 3 and resin particles (Y) containing the amorphous resin (A1) in an aqueous medium Step 4-2: Step of Obtaining Aggregated Particles (1) Step 4-2: Aggregate the resin particles (Z) containing the amorphous resin (A2) in the aggregated particles (1) obtained in Step 4-1, Step of obtaining agglomerated particles (2) Step 4-3: Step of fusing cored particles obtained in step 4-2 to obtain core-shell particles Hereinafter, steps 4-1 to 4-3 will be described. .

(Step 4-1)
Step 4-1 aggregates the resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A1) in an aqueous medium It is a process of obtaining agglomerated particles (1).

The resin particles (Y) are preferably obtained as an aqueous dispersion of resin particles (Y), and by using an amorphous resin (A1) as a binder resin, the same as the aqueous dispersion of the resin particles (X). It can be manufactured by the method of
The volume median particle diameter (D ₅₀ ) of the resin particles (Y) is preferably 70 nm or more, more preferably 90 nm or more, still more preferably 100 nm or more, and preferably 200 nm or less from the viewpoint of toner productivity. More preferably, it is 150 nm or less, still more preferably 130 nm or less.
The solid content concentration of the aqueous dispersion of resin particles (Y) is preferably 3% by mass or more, more preferably 5% by mass or more, by appropriately adding water from the viewpoint of the stability of the dispersion and ease of handling, etc. It is more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

  In step 4-1, an aqueous dispersion of resin particles (X) and an aqueous dispersion of resin particles (Y) are mixed, and resin particles (X) and resin particles (Y) are mixed, and aggregation is performed. It is preferable to In addition, in the process 4-1, in order to perform aggregation efficiently, it is preferable to add a coagulant | flocculant.

As the coagulant, a cationic surfactant of a quaternary salt, an organic coagulant such as polyethylene imine, and an inorganic coagulant such as an inorganic metal salt and an inorganic ammonium salt are used. From the viewpoint of the particle size distribution of the toner and the heat resistant storage stability, inorganic coagulants are preferable, and inorganic metal salts are more preferable.
Examples of inorganic metal salts include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride and the like. The valence number of the central metal of the inorganic metal salt is preferably divalent or higher in view of the particle diameter distribution of the toner and the heat resistant storage stability.
When a coagulant is added, its addition amount is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, based on 100 parts by mass in total of resin particles (X) and resin particles (Y). More preferably, it is 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less.
The coagulant is preferably dissolved in an aqueous medium and added, and it is preferable to sufficiently stir the addition of the coagulant and after completion of the addition.

In the aggregation step, the solid concentration in the system is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably, in order to cause uniform aggregation. It is 40% by mass or less, more preferably 30% by mass or less.
In the aggregation step, the temperature at the time of addition of the coagulant is preferably 10 ° C. or more, more preferably 15 ° C. or more, still more preferably 18 ° C. or more, from the viewpoint of uniformly dispersing the coagulant and causing uniform aggregation. And preferably 40 ° C. or less, more preferably 35 ° C. or less, still more preferably 30 ° C. or less.
The holding temperature after addition of the coagulant is preferably 40 ° C. or more, more preferably 45 ° C. or more, still more preferably 47 ° C. or more, and preferably 65 ° C. or less, more preferably 60 ° C. or less, more preferably Is 55 ° C. or less.

In addition, in step 4-1, the aforementioned additives such as a colorant, a charge control agent, a mold release agent, a conductivity regulator, a reinforcing filler such as a fibrous substance, an antioxidant, and an antiaging agent are added. It may be coagulated from
Additives such as colorants, charge control agents, and mold release agents may be mixed in advance with the binder resin, or a dispersion obtained by dispersing each additive separately in a dispersion medium such as water, that is, colorant fine particles The colorant dispersion to be contained, the charge control agent dispersion to contain charge control agent fine particles, and the release agent dispersion to contain release agent fine particles may be prepared and subjected to the aggregation step.
The volume median particle size (D ₅₀ ) of the colorant fine particle is preferably 50 nm or more, more preferably 100 nm or more, and preferably 200 nm or less, more preferably 150 nm or less.
The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 800 nm or less, more preferably 500 nm or less.
The volume median particle size (D ₅₀ ) of the release agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 1000 nm or less, more preferably 700 nm or less.

(Step 4-2)
Step 4-2 is a step of aggregating resin particles (Z) containing the amorphous resin (A2) in the agglomerated particles (1) obtained in the step 4-1 to obtain agglomerated particles (2) is there.

(Amorphous resin (A2))
The amorphous resin (A2) is a resin having a crystallinity index of more than 1.4 or less than 0.6, preferably more than 1.5 or less than 0.5, more preferably 1. 6 or more or 0.5 or less.
As the amorphous resin (A2), an amorphous composite resin (AH2) containing an amorphous polyester, an amorphous styrenic resin, a polyester resin component (AH2-1) and a styrenic resin component (AH2-2) Amorphous composite resin (AH2) is preferable from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter.

[Amorphous Composite Resin (AH2)]
The amorphous composite resin (AH2) contains a polyester resin component (AH2-1) and a styrene resin component (AH2-2), and includes a polyester resin component (AH2-1) and a styrene resin component ( It is preferable to be composed of AH2-2) and a component derived from a bireactive monomer capable of reacting with any of the polyester resin component (AH2-1) and the styrene resin component (AH2-2). In addition, components other than these three components may be included within the scope of the object of the present invention, but it is preferable not to include components other than three components.
Examples of the dual reactive monomer include those similar to the dual reactive monomer that can be used for the above-mentioned crystalline composite resin (CH), and preferred types and amounts used are also the same.

  Mass ratio of polyester resin component (AH2-1) and styrene resin component (AH2-2) in amorphous composite resin (AH2) (polyester resin component (AH2-1) / styrene resin component (AH2-2) ) Is preferably 50/50 or more, more preferably 60/40 or more, and still more preferably 70/30 or more, from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. And Preferably it is 95/5 or less, More preferably, it is 90/10 or less, More preferably, it is 85/15 or less.

  The total content of the polyester resin component (AH2-1), the styrene resin component (AH2-2), and the component derived from both reactive monomers in the amorphous composite resin (AH2) is the low temperature fixability, It is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less from the viewpoints of storage stability, charge rising property, and folding resistance of printed matter. More preferably, it is 100 mol%.

[Polyester resin component (AH2-1)]
The polyester resin component (AH2-1) is an alcohol component (hereinafter, also referred to as "alcohol component (AH2-al)") from the viewpoint of low temperature fixing property, storage property, charge rising property, and folding resistance of printed matter, It is obtained by polycondensing a carboxylic acid component (hereinafter, also referred to as “carboxylic acid component (AH2-ac)”).
As an alcohol component (AH2-al), the thing similar to the said alcohol component (AP-al) is mentioned, and the kind and content of preferable resin are also the same.
As a carboxylic acid component (AH2-ac), the thing similar to a carboxylic acid component (AP-ac) is mentioned, The kind of preferable resin is also the same.
The content of the aromatic dicarboxylic acid compound, preferably terephthalic acid, in the carboxylic acid component (AH2-ac) is preferably 40 moles from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. % Or more, more preferably 55 mol% or more, further preferably 65 mol% or more, and preferably 90 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less.
From the viewpoint of adjusting physical properties, the alcohol component (AH2-al) may appropriately contain a monohydric alcohol, and the carboxylic acid component (AH2-ac) appropriately contains a monovalent carboxylic acid compound. It may be

  The equivalent ratio (COOH group / OH group) of the carboxylic acid component (AH2-ac) to the alcohol component (AH2-al) is preferably from the viewpoint of low temperature fixability, storage stability, charge rising property, and folding resistance of printed matter Is 0.7 or more, more preferably 0.8 or more, still more preferably 0.9 or more, and preferably 1.3 or less, more preferably 1.2 or less, still more preferably 1.1 or less .

[Styrene resin component (AH2-2)]
The styrene resin component (AH2-2) is a segment made of a styrene resin.
The styrenic resin constituting the styrenic resin component (AH2-2) and the raw material monomer thereof are the same as the styrenic resin component (CH-2) constituting the crystalline composite resin (CH) and the raw material monomer thereof The types and contents of preferred monomers are also the same.

  The amorphous composite resin (AH2) can be produced by the same method as the above-mentioned amorphous composite resin (AH1), and the conditions of polycondensation reaction and addition polymerization reaction, and esterification catalyst, esterification co-catalyst, The types and amounts of polymerization inhibitors and their preferred embodiments are also the same.

[Softening point]
The softening point of the amorphous resin (A2), preferably the amorphous composite resin (AH2), is preferably 80 ° C. or more, more preferably 100, from the viewpoints of storage stability, charge rising property and folding resistance of printed matter. C. or higher, more preferably 110 ° C. or higher, and preferably 150 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 120 ° C. or lower from the viewpoint of low-temperature fixability.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous resin (A2), preferably the amorphous composite resin (AH2), is preferably 30 ° C. or more, more preferably from the viewpoint of storage stability, charge rising property and folding resistance of printed matter. It is 45 ° C. or more, more preferably 55 ° C. or more, and preferably 90 ° C. or less, more preferably 75 ° C. or less, still more preferably 65 ° C. or less from the viewpoint of low-temperature fixability.
[Acid number]
The acid value of the amorphous resin (A2), preferably the amorphous composite resin (AH2), is preferably 0 mg KOH / g or more from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. More preferably, it is 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, and preferably 40 mg KOH / g or less, more preferably 30 mg KOH / g or less, still more preferably 25 mg KOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous resin (A2), preferably the amorphous composite resin (AH2), are the kind and ratio of the raw material monomers, and the reaction temperature, reaction time, cooling rate, etc. It can be appropriately adjusted according to the manufacturing conditions.

The resin particles (Z) are preferably obtained as an aqueous dispersion of the resin particles (Z), and by using an amorphous resin (A2) as the binder resin, the same as the aqueous dispersion of the resin particles (X). It can be manufactured by the method of
The volume median particle size (D ₅₀ ) of the resin particles (Z) is preferably 70 nm or more, more preferably 90 nm or more, still more preferably 100 nm or more, and preferably 200 nm or less from the viewpoint of toner productivity. More preferably, it is 150 nm or less, still more preferably 130 nm or less.
The solid content concentration of the aqueous dispersion of the resin particles (Z) is preferably 3% by mass or more, more preferably 5% by mass or more, by appropriately adding water, from the viewpoint of the stability of the dispersion and easy handling. It is more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

In step 4-2, the aqueous dispersion of resin particles (Z) is added to the dispersion of aggregated particles (1) described above to further attach resin particles (Z) to the aggregated particles (1), and aggregation is performed. It is preferred to obtain a dispersion of particles (2).
Before adding the aqueous dispersion of resin particles (Z) to the dispersion of aggregated particles (1), an aqueous medium may be added to the dispersion of aggregated particles (1) for dilution. In addition, when an aqueous dispersion of resin particles (Z) is added to the dispersion of aggregated particles (1), the above coagulant is added to efficiently adhere the resin particles (Z) to the aggregated particles (1). You may use in a process.

  The temperature at which the aqueous dispersion of resin particles (Z) is added is preferably 40 ° C. or more, more preferably from the viewpoint of the low-temperature fixability of the obtained toner, the storage stability, the charge rising property, and the folding resistance of printed matter Is 45 ° C. or more, more preferably 50 ° C. or more, and preferably 80 ° C. or less, more preferably 70 ° C. or less, still more preferably 65 ° C. or less.

The amount of the resin particles (Z) added is the resin particles (Z), the resin particles (X), and the resin particles (from the viewpoint of the low temperature fixability of the toner obtained, the storage stability, the charge rising property, and the folding resistance of printed matter). The mass ratio to the Y) [shell (resin particle (Z)) / core (resin particle (X) and resin particle (Y))] is preferably 0.05 or more, more preferably 0.1 or more, still more preferably Is an amount of 0.15 or more, preferably 1 or less, more preferably 0.5 or less, still more preferably 0.3 or less, still more preferably 0.25 or less.
Further, a resin particle (X) containing a crystalline resin (C), a resin particle (Y) containing an amorphous resin (A1), and a resin particle (Z) containing an amorphous resin (A2) The total mass ratio of [(resin particles (X)) / (resin particles (Y) and resin particles (Z))] is from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter, The ratio is preferably 3/97 or more, more preferably 5/95 or more, still more preferably 7/93 or more, still more preferably 10/90 or more, and from the same viewpoint, preferably 40/60 or less, more preferably 30. / 70 or less, more preferably 20/80 or less, still more preferably 17/83 or less, still more preferably 15/85 or less.

The volume median particle size (D ₅₀ ) of the obtained agglomerated particles (2) is the viewpoint of obtaining a toner from which a high quality image can be obtained, and the low temperature fixability, preservability, charge rising property and printed matter of the obtained toner. From the viewpoint of bending resistance, it is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and preferably 10 μm or less, more preferably 9 μm or less, still more preferably 8 μm or less.

The total amount of the resin particles (Z) may be added, and the aggregation may be stopped when the toner particles have grown to an appropriate particle size.
As a method of stopping aggregation, a method of cooling a dispersion, a method of adding an aggregation stopper, a method of diluting a dispersion, and the like can be mentioned. From the viewpoint of reliably preventing unnecessary aggregation, it is preferable to add an aggregation stopper to stop aggregation.
It is preferable to use a surfactant as an aggregation stopper, and it is more preferable to use an anionic surfactant. Among the anionic surfactants, it is more preferable to use one or more selected from alkyl ether sulfates, alkyl sulfates, and linear alkyl benzene sulfonates, and it is further preferable to use alkyl ether sulfates.

<Step 4-3>
Step 4-3 is a step of fusing the aggregated particles (2) obtained in step 4-2 to obtain core-shell particles.
The temperature in the system in step 4-3 is the viewpoint of the target toner particle size, particle size distribution, shape control and particle fusion property, low temperature fixing property, storage property, charge rising property, and bending resistance of printed matter From the viewpoint of toughness, the softening point of the amorphous resin (A1) is preferably -55 ° C or more, more preferably -50 ° C or more, still more preferably -45 ° C or more, and softening point + 10 ° C or less Preferably, the softening point or less is more preferable, the softening point -10 ° C or less is more preferable, the softening point -20 ° C or less is still more preferable, and the softening point -30 ° C or less is still more preferable.
Specifically, it is preferably 70 ° C. or more, more preferably 75 ° C. or more, and preferably 100 ° C. or less, more preferably 90 ° C. or less.

The toner for electrophotography of the present invention can be suitably obtained by appropriately subjecting the core-shell particles obtained in Step 4-3 to a solid-liquid separation step such as filtration, a washing step and a drying step.
In the washing step, the added nonionic surfactant is also preferably completely removed by washing, and washing with an aqueous solution at a cloud point or less of the nonionic surfactant is preferred. It is preferable to carry out washing several times.
In the drying step, any method such as vibration type fluid drying method, spray drying method, freeze drying method, flash jet method, etc. can be adopted. The water content after drying of the toner is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less, from the viewpoint of chargeability.

[Toner for electrophotography]
The electrophotographic toner of the present invention is an electrophotographic toner obtained by the production method of the present invention.
In the toner of the present invention, an external additive may be used to improve transferability. As the external additive, inorganic fine particles are preferably used. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide and zinc oxide. Among these, silica is preferable. As the silica, from the viewpoint of the transferability of the toner, hydrophobicized hydrophobic silica is preferable.
Examples of hydrophobizing agents for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), methyltriethoxysilane, etc. Among these, hexamethyldisilazane is preferred.

The average particle size of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoint of chargeability, fluidity, and transferability of the toner. Preferably it is 100 nm or less, more preferably 50 nm or less.
The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass with respect to 100 parts by mass of the toner before being treated with the external additive. The amount is preferably at least 5 parts by mass, more preferably at most 4 parts by mass, and still more preferably at most 3 parts by mass.
In the toner for electrophotography of the present invention, the mass ratio of the crystalline resin (C) to the amorphous resin (A1) (crystalline resin (C) / amorphous resin (A1)) is low temperature fixability, storage It is preferably 3/97 or more, more preferably 5/95 or more, still more preferably 7/93 or more, still more preferably 10/90 or more, still more preferably from the viewpoints of flexibility, bending resistance and charge rising property. It is 13/87 or more, preferably 40/60 or less, more preferably 30/70 or less, still more preferably 20/80 or less, still more preferably 17/83 or less from the same viewpoint.

The toner for electrophotography of the present invention preferably has a core-shell structure, contains a crystalline resin (C) and an amorphous resin (A1) in the core, and contains an amorphous resin (A2) in the shell It is more preferable to do.
The toner for electrophotography of the present invention contains core-shell particles having a core part containing a crystalline resin (C) and an amorphous resin (A1) and a shell part containing an amorphous resin (A2). (C) / [Amorphous Resin (A1) + Amorphous Resin] [Mass Ratio of Crystalline Resin (C) to Amorphous Resin (A1) and Amorphous Resin (A2)] (A2)] is preferably 3/97 or more, more preferably 5/95 or more, still more preferably 7/93 or more, from the viewpoint of low temperature fixing property, storage property, charge buildup property, and folding resistance of printed matter , Still more preferably 10/90 or more, and from the same viewpoint, preferably 40/60 or less, more preferably 30/70 or less, still more preferably 20/80 or less, still more preferably 17/83 or less, more preferably More preferably, it is 15/85 or less
The toner for electrophotography of the present invention contains core-shell particles having a core part containing a crystalline resin (C) and an amorphous resin (A1) and a shell part containing an amorphous resin (A2). In this case, the mass ratio of the crystalline resin (C) and the amorphous resin (A1) contained in the core portion to the amorphous resin (A2) contained in the shell portion [shell portion (amorphous resin (A2) ) / Core portion [crystalline resin C + amorphous resin (A1)]] is preferably 5/100 or more, more preferably from the viewpoint of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter Is preferably 10/100 or more, more preferably 15/100 or more, and from the same viewpoint, preferably 100/100 or less, more preferably 50/100 or less, still more preferably 30/100 or less, still more preferably 25 / Less than 100

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3.0 μm or more, more preferably 3.5 μm, from the viewpoint of low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter. Or more, more preferably 4.0 μm or more, still more preferably 4.5 μm or more, and preferably 9.0 μm or less, more preferably 8.5 μm or less, still more preferably 8.0 μm or less, still more preferably It is 7.5 μm or less.

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

  The properties of the resin, binder resin particles, toner, etc. were measured and evaluated by the following methods.

[Acid number 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 to a mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)) from a mixed solvent of ethanol and ether defined in JIS K 0070.

[Softening point, melting point, crystallinity index, and glass transition temperature of resin]
(1) Softening point Using a flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C./min, a load of 1.96 MPa is applied by a plunger to obtain a diameter It extruded from the nozzle of 1 mm and length 1 mm. The plunger drop of the flow tester was plotted against temperature, and the temperature at which half of the sample flowed out was taken as the softening point.

(2) Maximum peak temperature of endotherm, melting point, crystallinity index A temperature decrease rate of 10 from room temperature (20 ° C.) using a differential scanning calorimeter “Q-100” (manufactured by TA Instruments Japan Co., Ltd.) The sample cooled to 0 ° C. at 0 ° C./min was allowed to stand still for 1 minute, and then measured while raising the temperature to 180 ° C. at a heating rate of 10 ° C./min. Of the observed endothermic peaks, the temperature of the peak located on the highest temperature side was taken as the maximum endothermic peak temperature. Moreover, in crystalline resin, the maximum peak temperature of this heat of fusion was made into melting | fusing point.
The crystallinity index was determined from the ratio [softening point / endothermic maximum peak temperature] between the softening point and the maximum endothermic peak obtained above.

(3) Glass transition temperature Measure 0.01 to 0.02 g of a sample on an aluminum pan using a differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), 200 ° C. The temperature was raised up, and the temperature was cooled to 0 ° C. at a temperature decrease rate of 10 ° C./min. Next, it measured, heating up to 150 degreeC by the temperature increase rate of 10 degrees C / min. The temperature at the intersection point of the extension of the baseline below the maximum endothermic peak temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak was taken as the glass transition temperature.

[Volume median particle size of aggregated particles (D ₅₀ )]
The volume median particle size of the agglomerated particles was measured as follows.
・ Measurement machine: "Coulter Multisizer III" (made by Beckman Coulter Inc.)
・ Aperture diameter: 50μm
Analysis software: "Multisizer III version 3.51" (manufactured by Beckman Coulter Inc.)
-Electrolyte: "Isoton II" (manufactured by Beckman Coulter)
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 conditions: 10 mg of a sample (in terms of solid content) is added to 5 mL of the dispersion, dispersed for 1 minute with an ultrasonic disperser, then 25 mL of an electrolyte is added, and 1 minute with an ultrasonic disperser. The sample was dispersed to prepare a sample dispersion.
Measurement conditions: The particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolyte, and then 30,000 particles are measured, and the particle size distribution thereof The volume median particle size (D ₅₀ ) was determined from

[Volume median particle diameter (D ₅₀ ) of binder resin particles, colorant particles, charge control agent particles, release agent particles]
(1) Measuring device: Laser diffraction particle size measuring device "LA-920" (manufactured by HORIBA, Ltd.)
(2) Measurement conditions: Distilled water was added to the cell for measurement, and the volume median particle size (D ₅₀ ) was measured at a concentration at which the absorbance falls within the appropriate range.

[Solid Content Concentration of Colorant Dispersion, Charge Control Agent Dispersion, Releasing Agent Dispersion, and Aqueous Dispersion of Binder Resin Particles]
Using an infrared moisture meter “FD-230” (manufactured by Ketto Science Research Institute Co., Ltd.), under the conditions of a drying temperature of 150 ° C. and a measurement mode 96 (monitoring time 2.5 minutes / a fluctuation range 0.05%), using a 5 g sample The sample was dried and the water content (mass%) of the sample was measured. The solid content was calculated according to the following formula.
Solid content concentration (mass%) = 100-M
M: Moisture of sample (mass%)

[Minimum fixing temperature of toner]
The toner was mounted on an apparatus in which the fixing device of the copying machine “AR-505” (manufactured by Sharp Corporation) was improved so as to enable fixing outside the apparatus, and a printed matter was obtained in an unfixed state (printing area: 2 cm) X 12 cm, adhesion amount: 0.5 mg / cm ² ). Thereafter, using a fixing device (fixing speed 300 mm / sec) adjusted so that the total fixing pressure is 40 kgf, the temperature of the fixing roll is gradually raised from 80 ° C. to 240 ° C. by 5 ° C. while unfixed at each temperature The fixing test of the printed matter of the state was done. A cellophane adhesive tape "UNICEF Cellophane" (Mitsubishi Pencil Co., Ltd., width: 18 mm, JIS Z1522) was attached to the image portion of the obtained printed matter, passed through a fixing roller set at 30 ° C, and then the tape was peeled . The optical reflection density before and after sticking the tape is measured using a reflection densitometer “RD-915” (manufactured by Gretag Macbeth), and the ratio of both (after peeling / before sticking × 100) is 90% first. The temperature of the fixing roller which exceeded the above was taken as the minimum fixing temperature. The lower the minimum fixing temperature, the better the low-temperature fixability. In addition, "CopyBond SF-70NA" (made by Sharp Corporation, 75 g / m < ² >) was used for fixing paper.

[Heat-resistant storage stability under high humidity of toner]
5 g of the toner was put in a 25 mL container (about 3 cm in diameter), and was left for 72 hours under the environment of temperature 55 ° C. and humidity 90%. The degree of toner aggregation was visually observed every 12 hours, and the heat resistant storage stability under high humidity was evaluated according to the following evaluation criteria. The longer the time when no aggregation is observed, the better the heat-resistant storage stability under high humidity.
(Evaluation criteria)
A: No aggregation was observed even after 72 hours.
B: No aggregation was observed after 60 hours, but aggregation was observed after 72 hours.
C: No aggregation was observed after 36 hours, but aggregation was observed after 48 hours.
D: No aggregation was observed after 24 hours, but aggregation was observed after 36 hours.
E: Cohesion is observed after 24 hours.

[Bending resistance of printed matter]
The toner was mounted on an apparatus obtained by improving the fixing device of a copying machine “AR-505” (manufactured by Sharp Corporation) so as to enable fixing outside the apparatus, and a printed matter was obtained in an unfixed state (printing area: 20 cm) × 20 cm, adhesion amount: 0.5 mg / cm ² ). Thereafter, using a fixing device (fixing speed: 300 mm / sec) adjusted so that the total fixing pressure is 40 kgf, the temperature of the fixing roll was fixed at 160 ° C. This image was folded inward at 50 g / cm ² for 30 seconds, reopened, and the damaged image was wiped with a soft cloth, and the maximum value of the width of the image loss was used as an indicator of the folding resistance of the printed matter. The smaller the maximum value of the width of the image defect, the better the bending resistance of the printed matter. In addition, "CopyBond SF-70NA" (made by Sharp Corporation, 75 g / m < ² >) was used for fixing paper.

[Toner charge rise property]
2.1 g of toner and 27.9 g of silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle diameter: 40 μm) at 50 ° C. and 50% RH in a 50 ml cylindrical polypropylene bottle (manufactured by Nikko Co., Ltd.) The mixture was shaken, and shaken ten times in all directions, and then mixed using a tumbler mixer. The charge amount at a mixing time of 1 minute and 10 minutes was measured using a q / m meter (manufactured by EPPING) to obtain each charge amount. From the 1 min value of the charge amount (charge amount in 1 minute of mixing time) and the 10 min value of the charge amount (charge amount in 10 minutes of mixing time), the rising property of the charge was measured. As (1 min value of the charge amount) / (10 min value of the charge amount) is closer to 1, charging is performed in a shorter mixing time, which indicates that the rising property of the charge is better.
The measuring equipment and settings are as follows.
・ Measurement equipment: "q / m-meter" (manufactured by EPPING)
・ Setting: mesh size: 635 mesh (opening: 24μm, stainless steel)
・ Soft blow: blow pressure (600 V)
Suction time: 90 seconds Charge amount (μC / g) = Total electric amount after 90 seconds (μC) / Suctioned toner amount (g)

[Production of crystalline resin]
Synthesis Examples 1 to 8 and 10 to 13
(Production of Crystalline Composite Resins C-1 to C-8, C-10 to C-13)
Among the raw material components of the polycondensation resin component shown in Table 1, the total amount of alcohol component and half of the carboxylic acid component, the esterification catalyst, equipped with a thermometer, a stainless steel stirring rod, a downflow condenser and a nitrogen introducing pipe 10 The reaction was carried out at 160 ° C., after raising the temperature from 135 ° C. to 160 ° C. over 6 hours in a mantle heater under a nitrogen atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more, and a mixed solution of raw material monomers of a styrenic resin component shown in Table 1, a bireactive monomer and a radical polymerization initiator was dropped over 1 hour. Thereafter, the temperature is maintained at 160 ° C. for 30 minutes, the remaining carboxylic acid component is charged, the temperature is raised from 135 ° C. to 200 ° C. over 8 hours, and reaction is further performed under a reduced pressure of 8 kPa for 2 hours. -1 to C-8 and C-10 to C-13. Physical properties of the resin are shown in Table 1. Incidentally, the reaction rate in the present invention means a value of generation reaction water amount (mol) / theoretical generation water amount (mol) × 100.

Synthesis example 9
(Production of crystalline polyester C-9)
Among the raw material components of the polyester resin component shown in Table 1, the total amount of alcohol component and the total amount of carboxylic acid component, the esterification catalyst, 10 liters of equipped with a thermometer, stainless steel stirring rod, downflow condenser and nitrogen introducing pipe In a four-necked flask, the temperature was raised from 135 ° C. to 200 ° C. over 8 hours in a mantle heater in a nitrogen atmosphere, then reacted at 200 ° C. for 2 hours, and the reaction rate reached 95% or more. It was confirmed. The mixture was further reacted under a reduced pressure of 8 kPa for 2 hours to obtain crystalline polyester C-9. Physical properties of the resin are shown in Table 1.

[Production of amorphous resin]
Synthesis example 14
(Amorphous styrenic resin A-1)
Place 2 liters of xylene into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a downflow condenser, a dropping funnel and a nitrogen inlet tube, and use as a raw material monomer and radical polymerization of styrenic resin shown in Table 2. The initiator was placed in a dropping funnel equipped with a four-necked flask. Thereafter, xylene in a four-necked flask was heated to 135 ° C. under a nitrogen atmosphere, and a mixture of a raw material monomer and a polymerization initiator was dropped into the xylene over one hour from a dropping funnel. The temperature was further raised to 200 ° C. and held at 200 ° C. for 2 hours. Thereafter, xylene was removed by further maintaining the pressure under a reduced pressure of 8 kPa for 1 hour to obtain an amorphous styrenic resin A-1. Physical properties are shown in Table 2.

Synthesis example 15
(Production of Amorphous Polyester A-2)
Put BPA-PO, terephthalic acid, esterification catalyst and esterification cocatalyst shown in Table 3 into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a downflow condenser and a nitrogen inlet tube, The temperature was raised to 235 ° C. for 2 hours in a mantle heater under an atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Then, it cooled to 190 degreeC, the radical polymerization inhibitor and the remaining carboxylic acid component were added, and it heated up to 210 degreeC over 2 hours. Then, after reacting for 1 hour at 210 ° C., the reaction was carried out at 40 kPa until the softening point described in Table 3 was reached, to obtain an amorphous polyester A-2. Physical properties are shown in Table 3.

Synthesis Examples 16 and 17
(Production of Amorphous Composite Resins A-3 and A-4)
Put BPA-PO, terephthalic acid, esterification catalyst and esterification cocatalyst shown in Table 3 into a 10 liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a downflow condenser and a nitrogen inlet tube, The temperature was raised to 235 ° C. for 2 hours in a mantle heater under an atmosphere. After that, it confirmed that the reaction rate reached 95% or more at 235 ° C, cooled to 160 ° C, mixed solution of raw material monomer of styrenic resin component shown in Table 3, bireactive monomer and radical polymerization initiator It dripped over 1 hour. Thereafter, the temperature is maintained at 160 ° C. for 30 minutes, the temperature is raised to 200 ° C., and reaction is further performed under a reduced pressure of 8 kPa for 1 hour, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor and the remaining carboxylic acid component were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting for 1 hour at 210 ° C., the reaction was carried out at 40 kPa until the softening point described in Table 3 was reached, to obtain amorphous composite resins A-3 and A-4. Physical properties are shown in Table 3.

[Production of Colorant Dispersion]
Preparation Example 1
Mix 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, The mixture was dispersed for 10 minutes using a homogenizer to obtain a colorant dispersion containing colorant fine 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]
Preparation Example 2
Mix 50 g of a salicylic acid compound "Bontron E-84" (manufactured by Orient Chemical Industries, Ltd.) as a charge control agent, 5 g of "Emulgen 150" (manufactured by Kao Corporation) as a nonionic surfactant, and 200 g of ion-exchanged water, The glass beads were used and dispersed for 10 minutes using a sand grinder to obtain a charge control agent dispersion containing charge control agent microparticles. The volume median particle size (D ₅₀ ) of the charge control agent fine particles was 400 nm, and the solid content concentration was 22% by mass.

[Production of Release Agent Dispersion]
Preparation Example 3
50 g of paraffin wax "HNP9" (manufactured by Nippon Seiwa Co., Ltd.), 5 g of cationic surfactant "Sanisol (registered trademark) B50" (manufactured by Kao Corp., alkyl benzyl dimethyl ammonium chloride) and 200 g of ion exchanged water at 95 ° C. The mixture is heated and dispersed for 30 minutes at an output of 350 W using an ultrasonic homogenizer (trade name: "UP-400S" manufactured by Doctor Hielscher Co., Ltd.) to disperse the release agent containing release agent particles. I got a liquid. The volume median particle size (D ₅₀ ) of paraffin wax (release agent particles) was 550 nm, and the solid content concentration was 22% by mass.

[Production of Aqueous Dispersion of Binder Resin Particles]
Production Example 1
(Production of Aqueous Dispersion c-1 of Binder Resin Particles)
100 g of crystalline composite resin C-1, 100 g of methyl ethyl ketone, anionic surfactant "Emar E 27 C" (Kaoh Corp.) in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen introduction pipe 16.7 g (4.5% by mass with respect to 100 g of resin) was added, and dissolved at 73 ° C. for 2 hours. A 5% by mass aqueous solution of sodium hydroxide was added to the obtained solution so as to have a degree of neutralization of 70 mol% with respect to the acid value of the resin, and stirred for 30 minutes (Step 1).
While maintaining the temperature at 73 ° C., 675 g of ion exchanged water was added over 77 minutes while stirring at 280 r / min (peripheral velocity 88 m / min) to perform phase inversion emulsification (Step 2). The methyl ethyl ketone was distilled off under reduced pressure while keeping the temperature continuously at 73 ° C. (step 3). Thereafter, the aqueous dispersion was cooled to 30 ° C. while stirring at 280 r / min (peripheral velocity 88 m / min). Thereafter, the solid content concentration of the dispersion was measured, and ion-exchanged water was added to 20% by mass to obtain an aqueous dispersion of binder resin particles in which binder resin particles are dispersed in an aqueous medium. . The volume median particle diameter of the binder resin particles in the obtained aqueous dispersion is shown in Table 4.

Production Examples 2 to 28
(Production of Aqueous Dispersions c-2 to c-28 of Binder Resin Particles)
An aqueous dispersion of binder resin particles c-2 to c is carried out in the same manner as in Production Example 1 except that the kind of resin and the production conditions of the aqueous dispersion are changed as shown in Tables 4 and 5 in Production Example 1. -28 was obtained. The volume median particle diameter of the binder resin particles in the obtained aqueous dispersion is shown in Tables 4 and 5.

Production Example 29
(Production of Aqueous Dispersion c-29 of Binder Resin Particles)
In Production Example 1, the anionic surfactant “Emar E27C” (manufactured by Kao Corporation) was not added in Step 1, and after Step 3, the ion exchange was carried out so that the solid content concentration of the aqueous dispersion would be 20 mass% The same procedure as in Production Example 1 was repeated, except that 16.7 g (4.5% by mass relative to 100 g of resin) of an anionic surfactant "Emar E27C" (manufactured by Kao Corporation) was added after water was added Thus, an aqueous dispersion c-29 of binder resin particles was obtained. The volume median particle diameter of the binder resin particles in the obtained aqueous dispersion is shown in Table 5.

Production Example 30
(Production of Aqueous Dispersion a-1 of Binder Resin Particles)
100 g of amorphous styrenic resin A-1, 100 g of methyl ethyl ketone, 16.7 g (4.5% by mass relative to 100 g of resin) of anionic surfactant "Emar E27C" (manufactured by Kao Corporation) at 25 ° C The mixture was mixed and dissolved at 73.degree. C. for 2 hours. The obtained solution was mixed with 600 g of ion-exchanged water at 73 ° C., and dispersed for 30 minutes at an output of 350 W using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Doctor Hielscher Co., Ltd.). Thereafter, ethyl acetate was distilled off under reduced pressure at 70 ° C. to obtain an aqueous dispersion a-1 of binder resin particles. The volume median particle diameter of the binder resin particles in the obtained aqueous dispersion is shown in Table 5.

Production Examples 31 to 33
(Production of Aqueous Dispersions a-2 to a-4 of Binder Resin Particles)
An aqueous dispersion of binder resin particles a-2 to a-4 was carried out in the same manner as in Production Example 1 except that the type of resin and the production conditions of the aqueous dispersion were changed as shown in Table 5 in Production Example 1. I got

[Production of electrophotographic toner]
Example 1
(Production of Toner A)
45 g of the aqueous dispersion c-1 of the crystalline composite resin C-1, 255 g of the aqueous dispersion a-1 of the amorphous styrenic resin A-1, 8 g of the colorant dispersion, 20 g of the release agent dispersion 2 g of the control agent dispersion and 52 g of deionized water are placed in a 2 L container, and 150 g of a 0.1 mass% aqueous solution of calcium chloride at 20 ° C. while stirring with an anchor type stirrer at 100 r / min (peripheral speed 31 m / min) Was dripped over 30 minutes. Then, it heated up to 50 degreeC, stirring. It was kept at 50 ° C. until the volume median particle size (D ₅₀ ) was 5 μm. After confirming that the volume median particle size (D ₅₀ ) reached 5 μm, 60 g of the aqueous dispersion a-4 of the amorphous composite resin A-4 was immediately added and stirred to be dispersed. Thereafter, a dilution liquid obtained by diluting 4.2 g of an anionic surfactant "Emar E27C" (manufactured by Kao Corporation, solid content 27% by mass) as an aggregation terminator with 37 g of deionized water was added. Then, the temperature was raised to 80 ° C., and after holding at 80 ° C. for 1 hour, the heating was ended. After forming fused particles by this, the mixture was gradually cooled to 20 ° C., filtered with a 150 mesh (150 μm mesh) wire mesh, suction filtered, washed and dried to obtain toner particles.

(External addition process)
1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter 40 nm) relative to 100 parts by mass of the toner particles, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd. 10 L Henschel mixer equipped with ST, A0 stirring blade (number average particle diameter 16 nm) 0.6 parts by mass, titanium oxide “JMT-150 IB” (manufactured by Tayca Co., Ltd., number average particle diameter 15 nm) 0.5 parts by mass The resultant was charged in Japan Coke Industrial Co., Ltd., and stirred at 3000 rpm for 2 minutes to obtain toner A. The evaluation results of the toner are shown in Table 6.

Examples 2 to 28 and Comparative Examples 1 to 3
(Production of Toner B to Z, AA to AE)
Example 6 is the same as Example 1 except that the type of the aqueous dispersion and the mass ratio of the crystalline resin to the amorphous resin in the core are changed to the type and mass ratio shown in Tables 6 and 7. Toners B to Z and AA to AE were obtained. The total amount of the aqueous dispersion used for the core was the same as in Example 1 (300 g). Tables 6 and 7 show the evaluation results of the obtained toner.

From Tables 6 and 7, it is found that the toners of Examples 1 to 28 of the present invention are excellent in the balance of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter compared with the toners of Comparative Examples 1 to 3. Know that
Comparing Examples 1, 4 and 5 and Comparative Examples 1 and 2, the toner of Example 1 using tetradecanedioic acid as a raw material monomer of the polycondensation resin component of the crystalline composite resin exhibits low temperature fixability and storage It is understood that the properties, the charge rising property, and the bending resistance of the printed matter are excellent.
Comparing Examples 1 to 3, the toner of Example 1 using 1,4-butanediol as a raw material monomer of the alcohol component of the polycondensation resin component of the crystalline composite resin has a low-temperature fixability, storage stability, It turns out that it is excellent in charge rising property and the bending resistance of printed matter.
When Examples 1, 6, and 7 are compared, the toner of Example 1 in which the acid value of the crystalline composite resin is 25 mg KOH / g is excellent in low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter I understand that.
Comparing Examples 1, 9 and 10, the mass ratio of the polycondensation resin component to the styrene resin component in the crystalline composite resin [polycondensate resin component / styrene resin component] is 80/20. It is understood that the toner of Example 1 is excellent in low-temperature fixability, storage stability, charge buildup property, and folding resistance of printed matter.
When Example 1 and Example 8 are compared, it can be seen that the toner of Example 1 using the crystalline composite resin is excellent in low-temperature fixability, preservability, charge buildup property, and bend resistance of printed matter.
Comparing Examples 1 and 12 to 15 shows that the toner of Example 1 having a volume average particle size (D ₅₀ ) of 102 nm of the aqueous dispersion of the crystalline composite resin has low-temperature fixability, storage stability, charge rising property, And it turns out that it is excellent in the bending resistance of printed matter.
Comparing Examples 1, 16, and 17, the toner of Example 1 using methyl ethyl ketone as an organic solvent used at the time of producing an aqueous dispersion of a crystalline composite resin has low-temperature fixability, storage stability, charge rising property, and It turns out that it is excellent in the bending resistance of printed matter.
Comparing Examples 1, 18, and 19, the toner of Example 1 using polyoxyethylene alkyl ether sulfate as a surfactant used at the time of production of the aqueous dispersion of the crystalline composite resin exhibits low temperature fixability and storage It is understood that the properties, the charge rising property, and the bending resistance of the printed matter are excellent.
When Examples 1, 20 and 21 are compared, the amount of surfactant used at the time of production of the aqueous dispersion of the crystalline composite resin is 4.5 parts by mass with respect to 100 parts by mass of the crystalline composite resin. It can be seen that the toner of Example 1 is excellent in low-temperature fixability, storage stability, charge build-up property, and folding resistance of printed matter.
Comparing Examples 1, 23, and 24, the toner of Example 1 having a mass ratio of the organic solvent to the crystalline composite resin [organic solvent / crystalline composite resin] of 1.0 is low-temperature fixability and storage stability It is found that the charge buildup resistance and the bending resistance of the printed matter are excellent.
Comparing Examples 1 and 25, in the step 1, the neutralizing agent used to neutralize the crystalline composite resin is from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter. And alukali metal hydroxides are preferred.
Comparing Examples 1, 27, and 28, it is understood that the amorphous resin of the core is preferably a styrene-based resin from the viewpoints of low-temperature fixability, storage stability, charge rising property, and folding resistance of printed matter.

Claims (8)

A method of producing a toner for electrophotography, which comprises a crystalline resin (C) and an amorphous resin (A1),
The crystalline resin (C) contains a crystalline composite resin (CH),
The crystalline composite resin (CH) contains a polycondensation resin component (CH-1) and a styrene resin component (CH-2),
Polycondensation-type resin which comprises polycondensation-type resin component (CH-1) The alcohol component which contains 80 mol% or more and 100 mol% or less of aliphatic diols, and an aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms It is a resin obtained by polycondensation of a carboxylic acid component containing 80 mol% or more and 100 mol% or less,
The aliphatic dicarboxylic acid compound having 14 or more and 20 or less carbon atoms is an α, ω-linear aliphatic dicarboxylic acid compound,
The manufacturing method of the toner for electrophotography including the following processes 1-4.
Step 1: Step of mixing crystalline resin (C), organic solvent, and neutralizing agent to obtain a mixture Step 2: Mix at least water with the mixture obtained in Step 1, crystalline resin (C) Step 3: Step of obtaining an aqueous dispersion of resin particles (X) containing a crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2: Step 2: The resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A1) are coagulated and fused in an aqueous medium Process   The method for producing a toner for electrophotography according to claim 1, wherein the carbon number of the aliphatic diol which is a raw material monomer of the polycondensation resin constituting the polycondensation resin component (CH-1) is 2 or more and 6 or less. .   The mass ratio of the polycondensation resin component (CH-1) to the styrene resin component (CH-2) (polycondensation resin component (CH-1) / styrene resin component (CH-2)) is 60 / The method for producing a toner for electrophotography according to claim 1 or 2, which is 40 or more and 98/2 or less.   The method for producing a toner for electrophotography according to any one of claims 1 to 3, wherein the acid value of the crystalline composite resin (CH) is 5 mgKOH / g or more and 40 mgKOH / g or less.   Amorphous resin (A1) is selected from amorphous composite resin (AH1) having amorphous styrenic resin (AS) and polyester resin component (AH1-1) and styrenic resin component (AH1-2) The method for producing a toner for electrophotography according to any one of claims 1 to 4, wherein the method comprises one or more resins.   The method for producing a toner for electrophotography according to any one of claims 1 to 5, wherein the volume median particle diameter of the resin particle (X) containing the crystalline resin (C) is 30 nm or more and 250 nm or less. The method for producing a toner for electrophotography according to any one of claims 1 to 6, wherein the step 4 has the following steps 4-1 to 4-3.
Step 4-1: Aggregate resin particles (X) containing the crystalline resin (C) obtained in step 3 and resin particles (Y) containing the amorphous resin (A1) in an aqueous medium Step 4-2: Step of Obtaining Aggregated Particles (1) Step 4-2: Aggregate the resin particles (Z) containing the amorphous resin (A2) in the aggregated particles (1) obtained in Step 4-1, Step of obtaining agglomerated particles (2) Step 4-3: Step of fusing the agglomerated particles (2) obtained in step 4-2 to obtain core-shell particles   The electrophotographic subject according to claim 7, wherein the amorphous resin (A2) comprises an amorphous composite resin (AH2) having a polyester resin component (AH2-1) and a styrene resin component (AH2-2). Method of manufacturing toner.