JP2016133770A - Method for manufacturing electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an electrophotographic toner excellent in low-temperature fixability, heat-resistant storage stability under high humidity, charge rising property and bending resistance of a printed matter.SOLUTION: The method for manufacturing an electrophotographic toner including a crystalline resin (C) and an amorphous resin (A1) comprises: the step 1 of mixing the crystalline resin (C), an organic solvent and a neutralizer to obtain a mixture; the step 2 of mixing the mixture with at least water to obtain the dispersion of the crystalline resin (C); the step 3 of obtaining an aqueous dispersion of resin particles (X) including the crystalline resin (C) by removing the organic solvent from the dispersion; and the step 4 of aggregating and fusing the resin particles (X) including the crystalline resin (C) and resin particles (Y) including an amorphous resin (A1) in an aqueous medium. The crystalline resin (C) is one or more kinds of crystalline resins selected from a crystalline polyester resin (CP) and a crystalline composite resin (CH).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, and the like, and an electrophotographic toner obtained by the production method.

  From the viewpoint of increasing the speed and energy saving of a printing apparatus, a toner having excellent low-temperature fixability is required. However, if the toner softening point or glass transition temperature is designed to be low in order to improve the low-temperature fixability, there is a problem that the storage stability is lowered. Therefore, in order to achieve both low-temperature fixability and storage stability, toners using crystalline polyester have been developed.

For example, Patent Document 1 discloses fusion of agglomerated particles obtained by agglomerating an aqueous dispersion of a binder resin for toner, with low temperature fixability, charging stability under high temperature and high humidity, and heat resistant storage stability as problems. A method for producing an electrophotographic toner comprising the particles, wherein the binder resin contains a crystalline polyester resin, the aqueous dispersion is obtained through the following steps 1 to 4, and all the surfactants are added. 80 to 100% by weight of the amount is mixed in step 2 and step 4, and the weight ratio of the amount of surfactant added in step 2 and step 4 is the weight of surfactant added in step 2 / step No. 4 discloses a method for producing an electrophotographic toner in which the weight of the surfactant added is 10/90 to 40/60.
Step 1: A step of mixing at least a binder resin, an organic solvent and a neutralizing agent to obtain a mixture.
Step 2: A step of 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.

JP2013-221990A

According to the technique of Patent Document 1, by mixing a specific amount of a surfactant in a specific process, it becomes possible to cause the surfactant to effectively act on the surface of the dispersion, thereby forming an aqueous dispersion having a uniform particle size. Can be made. As a result, the dispersion of the aggregation speed between the particles is reduced, and uniform aggregated particles can be obtained. The crystalline polyester resin can be uniformly dispersed in the toner, and the low-temperature fixability is improved. However, further improvements in low-temperature fixability, heat-resistant storage stability under high humidity, charge build-up property, and printed paper folding resistance are desired.
The present invention provides a method for producing an electrophotographic toner excellent in low-temperature fixability, heat-resistant storage stability under high humidity, charge rising property, and printed paper bending resistance, and an electrophotographic toner obtained by the production method. This is the issue.

  The present inventors have prepared a crystalline polyester resin or a crystalline composite resin and an amorphous resin using a long-chain aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms as a binder resin constituting an electrophotographic toner. Is used in a specific production method, and it is found that an electrophotographic toner excellent in low-temperature fixability, heat-resistant storage stability under high humidity, charge rising property, and printed paper folding resistance can be obtained. It came to complete.

That is, the present invention provides the following method for producing an electrophotographic toner and an electrophotographic toner.
[1] A method for producing an electrophotographic toner 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,
The polycondensation resin constituting the crystalline polyester resin (CP) and the polycondensation resin component (CH-1) is an alcohol component containing an aliphatic diol of 80 mol% or more and 100 mol% or less, and a carbon number of 14 or more. A method for producing an electrophotographic toner, which is a resin obtained by polycondensation of a carboxylic acid component containing 20 mol% or less of an aliphatic dicarboxylic acid compound of 80 mol% or less and 100 mol% or less.
Step 1: Step of mixing a crystalline resin (C), an organic solvent, and a neutralizing agent to obtain a mixture Step 2: Mixing the mixture obtained in Step 1 with at least water to form a crystalline resin (C) Step 3: Obtaining an aqueous dispersion of resin particles (X) containing crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2 Step 4: 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] An electrophotographic toner obtained by the production method described in [1] above.

  According to the present invention, a method for producing an electrophotographic toner excellent in low-temperature fixability, heat-resistant storage stability under high humidity, charge rising property, and printed paper bending resistance, and an electrophotographic toner obtained by the production method are provided. Can be provided.

[Method for producing toner for electrophotography]
The method for producing an electrophotographic toner (hereinafter also simply referred to as “toner”) of the present invention is a method for producing an electrophotographic toner containing 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). The polycondensation resin constituting the crystalline polyester resin (CP) and the polycondensation resin component (CH-1) is an aliphatic diol of 80 mol% or more and 100 mol%. A resin obtained by polycondensation of an alcohol component contained below and a carboxylic acid component containing an aliphatic dicarboxylic acid compound having from 14 to 20 carbon atoms in an amount of from 80 mol% to 100 mol%. Including, electronic A method for producing a true toner.
Step 1: Step of mixing a crystalline resin (C), an organic solvent, and a neutralizing agent to obtain a mixture Step 2: Mixing the mixture obtained in Step 1 with at least water to form a crystalline resin (C) Step 3: Obtaining an aqueous dispersion of resin particles (X) containing crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2 Step 4: The resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A1) are aggregated 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 printed paper folding resistance is not clear, but is considered as follows.
The crystalline resin (C) used in the production method of the present invention uses, as a raw material monomer, a long-chain aliphatic dicarboxylic acid compound having a high affinity with an organic solvent. Therefore, the resin particles (X) containing the crystalline resin (C) obtained in Step 3 are stably finely dispersed in an organic solvent. Subsequently, in Step 4, the resin particles (X) and the amorphous resin ( By aggregating and fusing the resin particles (Y) containing A1), it is considered that the crystalline resin (C) is finely dispersed in the toner and has excellent low-temperature fixability.
Further, since the toner obtained contains a structural unit derived from a long-chain aliphatic dicarboxylic acid compound having a high hydrophobicity, the hygroscopic property can be reduced. It is also considered to be excellent in “preservability” and charge rising property.
In addition, since the domain in which the crystalline resin (C) using the long-chain aliphatic dicarboxylic acid compound is finely dispersed is highly flexible, it is excellent in the bending resistance of the printed matter, which was a problem with 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 viewpoint of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter, crystallinity containing a polycondensation resin component (CH-1) and a styrene resin component (CH-2). Composite resin (CH) is preferred.

In the present invention, the crystallinity of the resin is represented by the crystallinity index defined by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the value of [softening point / maximum endothermic peak temperature]. .
The 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, more preferably 0.9 or more and 1.2 or less.
The crystallinity of the resin can be adjusted by the types and ratios of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The maximum endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. In crystalline resins, the maximum endothermic peak temperature is the melting point. The crystallinity index can be measured by the method described in the examples.
Hereinafter, the crystalline composite resin (CH) and the crystalline polyester resin (CP) will be described.

<Crystalline composite resin (CH)>
The crystalline composite resin (CH) includes a polycondensation resin component (CH-1) and a styrene resin component (CH-2). The polycondensation resin component (CH-1) and the styrene resin Component (CH-2) and a component derived from a bireactive monomer capable of reacting with both the polycondensation resin component (CH-1) and the styrene resin component (CH-2) preferable. Moreover, within the range which does not inhibit the objective of this invention, you may include structural parts other than these three structural parts, but it is preferable not to include structural parts other than three structural parts.

In the crystalline composite resin (CH), 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 preferably 60/40 or more, more preferably 70/30 or more, and still more preferably 80/20 or more, from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. 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 calculation of the mass ratio, the mass of the polycondensation resin component (CH-1) was obtained by removing the amount of dehydration during the condensation reaction from the total amount of raw material monomers of the polycondensation resin component (CH-1). A value is used, and the mass of a styrene resin component (CH-2) uses the total amount of the raw material monomer and polymerization initiator of a styrene resin component (CH-2). Moreover, the amphoteric monomer used if necessary is calculated as the mass of the polycondensation 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 polycondensation resin component (CH-1), the styrene resin component (CH-2), and the components derived from both reactive monomers in the crystalline composite resin (CH) is low temperature fixability. From the viewpoints of storage stability, charge build-up property and bending resistance of printed matter, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol%. Hereinafter, it is more preferably 100 mol%.

(Polycondensation resin component (CH-1))
The polycondensation resin component (CH-1) is an alcohol component containing an aliphatic diol of 80 mol% or more and 100 mol% or less from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. Hereinafter, it is also referred to as “alcohol component (CH-al)” and a carboxylic acid component containing 80 to 100 mol% of an aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms (hereinafter referred to as “carboxylic acid component (hereinafter referred to as“ carboxylic acid component ”). CH-ac) ”) is a resin component obtained by polycondensation.
As the resin constituting such a polycondensation resin component (CH-1), a polyester resin is preferable.

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

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

  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 an aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms in an amount of 80 to 100 mol% from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter. % Or less.
The aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms is preferably an α, ω-linear aliphatic dicarboxylic acid compound from the viewpoint of enhancing crystallinity and improving low-temperature fixability. For example, tetradecanedioic acid (carbon 14), pentadecanedioic acid (15 carbon atoms), hexadecanedioic acid (16 carbon atoms), heptadecanedioic acid (17 carbon atoms), octadecanedioic acid (18 carbon atoms), nonadecanedioic acid (19 carbon atoms), eicosane Examples thereof include diacids (20 carbon atoms) or alkyl esters having 1 to 3 carbon atoms. Among these, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and more preferably tetradecanedioic acid are preferred from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter.
The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 14 or more from the viewpoint of low-temperature fixability, storage stability, charge build-up property, and bending resistance of the printed material, and low-temperature fixability, charge build-up property, and printed material. From the viewpoint of the bending resistance, it is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14.
In addition, the carbon number of the aliphatic dicarboxylic acid compound includes the carbon number of the carboxy group in the carbon number of the linear or branched hydrocarbon group, and does not include the carbon number of the alkyl ester.
The content of the aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms in the carboxylic acid component (CH-ac) is 80 from the viewpoint of low-temperature fixability, storage stability, charge build-up property, and printed paper folding resistance. It is at least 100 mol%, preferably at least 90 mol%, more preferably at least 95 mol%, still more preferably at least 100 mol%.

The carboxylic acid component (CH-ac) may contain a carboxylic acid component other than the aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms.
Other carboxylic acid components that can be contained in the carboxylic acid component (CH-ac) include dicarboxylic acid compounds other than aliphatic dicarboxylic acid compounds having 14 to 20 carbon atoms, trivalent or higher polyvalent carboxylic acid compounds, and those Examples thereof include anhydrides and alkyl esters having 1 to 3 carbon atoms.
Examples of the dicarboxylic acid compound 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 the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, and terephthalic acid.
Examples of the aliphatic dicarboxylic acid compound other than the aliphatic dicarboxylic acid compound having 14 to 20 carbon atoms include malonic acid (3 carbon atoms), maleic acid (4 carbon atoms), fumaric acid (4 carbon atoms), and citraconic acid. (Carbon number 5), itaconic acid (carbon number 5), glutaconic acid (carbon number 5), succinic acid (carbon number 4), adipic acid (carbon number 6), azelaic acid (carbon number 9), sebacic acid (carbon Mathematical formula 10), undecanedioic acid (carbon number 11), dodecanedioic acid (carbon number 12), tridecanedioic acid (carbon number 13), docosanedioic acid (carbon number 22), and the like.
Examples of the trivalent or higher polyvalent carboxylic acid compound include trimellitic acid, 2,5,7-naphthalene tricarboxylic acid, pyromellitic acid and the like.

  These carboxylic acid components (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 preferable from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and printed paper folding resistance. 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 bending resistance of printed matter. More preferably 5% by mass or more, still more 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 More preferably, it is 15 mass% or less.

  Examples of the styrenic resin include polystyrene, a polymer of a styrene derivative, a styrene-acrylic copolymer, and the like, from the viewpoint of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter. 1 type or more chosen from a polymer of these, and a styrene-acrylic copolymer is preferred, 1 type or more chosen from polystyrene and a styrene-acrylic copolymer is more preferred, and a styrene-acrylic copolymer is still more preferred.

The raw material monomer for the styrene resin component (CH-2) is preferably at least one selected from styrene and styrene derivatives from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and printed paper bending resistance. Among these, styrene is more preferable from the viewpoint of the raw material price of the monomer and storage stability, and it is more preferable to use styrene and alkyl (meth) acrylate in combination.
“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-based resin component (CH-2) is preferably 50 from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter. % By mass or more, more preferably 60% by mass or more, further 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, and still more preferably 85% by mass or less.

  The styrene derivative is preferably at least one selected from methyl styrene, α-methyl styrene, β-methyl styrene, t-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid and salts thereof.

Examples of the alkyl (meth) acrylate include 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, (Iso) stearyl (meth) acrylate, (iso) behenyl (meth) acrylate, etc. are mentioned.
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, and 2-ethylhexyl is preferable. Acrylate is more preferred.
The number of carbon atoms in the alkyl group of the alkyl (meth) acrylate is preferably 2 or more, more preferably 4 or more, and still more preferably 6 from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. From the same viewpoint, it is preferably 12 or less, more preferably 10 or less.

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

[Amotropic monomer]
It is preferable that the crystalline composite resin (CH) further contains a structural unit derived from the both reactive monomers.
When an amphoteric monomer is used as a raw material monomer for the crystalline composite resin (CH), the amphoteric monomer reacts with both the polycondensation resin component (CH-1) and the styrene resin component (CH-2). By doing so, the crystalline composite resin (CH) can be produced satisfactorily.
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 styrene resin component (CH-2), and the both reactive monomers. What is obtained by making it be preferable is used. As a result, the polycondensation resin (CH) is bonded to the polycondensation resin component (CH-1) and the styrene resin component (CH-2) via a structural unit derived from both reactive monomers. -Based resin component (CH-1) and styrene-based resin component (CH-2) are uniformly dispersed, and low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter are improved. .

As the both reactive monomers, a compound having 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 in the molecule, an ethylenically unsaturated bond, The compound which has is mentioned. Among these, from the viewpoint of reactivity, a compound having a hydroxyl group and / or a carboxy group and an ethylenically unsaturated bond is preferable, and a compound having a carboxy group and an ethylenically unsaturated bond is more preferable.
Specifically, examples of the both reactive monomers include acrylic acid, methacrylic acid, maleic acid and maleic anhydride. From the viewpoint of the reactivity of the polycondensation reaction and the addition polymerization reaction, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable.

  The amount of both reactive monomers 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 build-up property, and bending resistance of printed matter. al) 100 mol parts, preferably 1 mol parts 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, it is 20 mol parts or less, More preferably, it is 15 mol parts or less, More preferably, it is 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 both reactive monomers are 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 cocatalyst may be used, and a polymerization initiator and a polymerization inhibitor may be further used.

(1) After the step (X) of the polycondensation reaction with the alcohol component (CH-al) and the carboxylic acid component (CH-ac), the raw material monomer of the styrene-based resin component (CH-2) and, if necessary, both reactions A step (Y) of an addition polymerization reaction with a functional monomer.
In the step (X), a part of the carboxylic acid component (CH-ac) is subjected to a polycondensation reaction, and then the step (Y) is performed. Then, the reaction temperature is increased again, and the carboxylic acid component (CH-ac) More preferred is a method in which the remainder of) is added to the polymerization system and the polycondensation reaction in step (X) and, if necessary, the reaction with both reactive monomers are further advanced.

(2) After the step (Y) of the addition polymerization reaction with the raw material monomer of the styrene resin component (CH-2) and the both reactive monomers, the polycondensation reaction with the raw material monomer of the polycondensation resin component (CH-1) A method of performing step (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 are esterified at a temperature suitable for the polycondensation reaction and, if necessary, an ester. The polycondensation reaction can be started by adding a co-catalyst, and the alcohol component (CH-al) and the carboxylic acid component (CH-ac) are later introduced into the reaction system under temperature conditions suitable for the polycondensation reaction. ) Can be added to start the polycondensation reaction. In the former case, the molecular weight and molecular weight distribution can be adjusted by adding an esterification catalyst and, if necessary, an esterification co-catalyst at a temperature suitable for the polycondensation reaction.

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

Of the above 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: In the presence of the polycondensate obtained in Step I, the styrene resin component (CH-2) Step of addition polymerization of raw material monomer Step III: Step of polycondensing the raw material monomer of the remaining polycondensation resin component (CH-1) in the presence of the reaction product obtained in Step II. From the viewpoint of low-temperature fixability, it is preferably used together with a raw material monomer for 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) are appropriately dispersed, and the polycondensation system 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]
Step I is a step of polycondensing a part of the raw material monomer of the polycondensation resin component (CH-1).
In the raw material monomer used in 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 the production of the crystalline composite resin (CH). Preferably it is 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. More preferably, it is 60 mass% or less.
Moreover, in the raw material monomer to be used in Step I, the amount of the alcohol component (CH-al) is preferably not less than the number of moles of the carboxylic acid component (CH-ac), and is used for the production of 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 when performing Step II.
The temperature of the polycondensation reaction in Step I is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, and preferably 230 ° C. or lower, more preferably 200 ° C. or lower, and still more preferably 180 ° C. from the viewpoint of reactivity. It is below ℃. The pressure during the polycondensation reaction may be a normal pressure.
The completion of the polycondensation reaction in Step I is preferably performed when the raw material monomer subjected to Step I reacts preferably at 95 mol% or more, more preferably 98 mol% or more.

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

[Step III]
Step III is a step of polycondensing the remaining raw material monomers of the polycondensation resin component (CH-1) in the presence of the reaction product obtained in Step II.
The temperature of the polycondensation reaction in Step III is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. It is below ℃. The pressure during the polycondensation reaction in Step III may be a normal pressure.

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

[Step IV]
The temperature of the polycondensation reaction in Step IV is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, further preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. or lower.
Here, the reduced pressure is a pressure less than normal pressure (101.3 kPa), preferably 80 kPa or less, more preferably 50 kPa or less, and still more preferably 20 kPa or less.
Step IV is preferably performed until the produced crystalline composite resin (CH) has a preferable acid value described below. Step IV is preferably performed in the presence of the esterification catalyst.

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

[Esterification catalyst]
Examples of the esterification catalyst suitably used for the polycondensation reaction include a titanium compound and a tin (II) compound having no Sn—C bond, and these may be used alone or in combination of two or more. it can.
As the titanium compound, a titanium compound having a Ti—O bond is preferable, and a compound having an alkoxy group, an alkenyloxy group or an acyloxy group having 1 to 28 carbon atoms in total is more preferable.
Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferred is a tin (II) compound having a Sn-O bond, and in particular, di (2-ethylhexanoic acid) from the viewpoint of reactivity, molecular weight adjustment, and physical property adjustment of the crystalline composite resin (CH). Tin (II) is more preferred.
The amount of the esterification catalyst used is a total amount of alcohol component (CH-al) and carboxylic acid component (CH-ac) of 100 from the viewpoints 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 0.1 parts by mass or more. Is 1.0 part by mass or less, more preferably 0.5 part by mass or less.

[Esterification cocatalyst]
As the esterification cocatalyst, a pyrogallol compound is preferred. This pyrogallol compound has a benzene ring in which three hydrogen atoms adjacent to each other are substituted with hydroxyl groups, and pyrogallol, gallic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, 2,2 ′ Benzophenone derivatives such as 3,3,4-tetrahydroxybenzophenone, catechin derivatives such as epigallocatechin and epigallocatechin gallate, and the like, and gallic acid is preferred from the viewpoint of reactivity.
(Polymerization inhibitor)
Examples of the polymerization inhibitor include 4-t-butylcatechol.

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

<Crystalline polyester (CP)>
The crystalline polyester (CP) includes an alcohol component (hereinafter also referred to as “alcohol component (CP-al)”) containing an aliphatic diol of 80 mol% or more and 100 mol% or less, and an aliphatic group 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 a dicarboxylic acid compound in an amount of 80 mol% to 100 mol%.
Examples of the alcohol component (CP-al) and the carboxylic acid component (CP-ac) include those similar to the alcohol component (CH-al) and the carboxylic acid component (CH-ac), and preferred types and equivalents thereof. The ratio is similar.
In addition, in the polycondensation reaction of the alcohol component (CP-al) and the carboxylic acid component (CP-ac), the types and amounts of the esterification catalyst and esterification co-catalyst are the same as those of the crystalline composite resin (CH). It is the same as the kind in polycondensation reaction of a condensation system resin part (CH-1), and its usage-amount, and its preferable aspect is also the same.

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

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

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

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

(Amorphous styrene 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, and the like. And at least one selected from polystyrene, a polymer of a styrene derivative, and a styrene-acrylic copolymer, and at least one selected from a polystyrene and a styrene-acrylic copolymer from the viewpoint of the printing property and the bending resistance of the printed material. More preferred is a styrene-acrylic copolymer.

Examples of the raw material monomer for the amorphous styrenic resin (AS) include the same materials as those cited as the raw material monomer for the styrene resin component (CH-2). Among these, it is preferable to use styrene and alkyl (meth) acrylate together.
When styrene is used, the content of styrene in the raw material monomer of the amorphous styrenic resin (AS) is preferably 50 masses from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. % Or more, more preferably 60% by weight or more, still more preferably 70% by weight or more, still more preferably 75% by weight or more, and from the same viewpoint, preferably 95% by weight or less, more preferably 90% by weight. Hereinafter, it is more preferably 85% by mass or less. A polymerization initiator is not included in the raw material monomer of the styrenic resin.

Examples of the alkyl (meth) acrylate include the same as those exemplified as the raw material monomer of the styrene resin component (CH-2). Among these, n-butyl acrylate is preferable.
As the carbon number of the alkyl group of the alkyl (meth) acrylate used as a raw material monomer of the amorphous styrenic resin (AS), from the viewpoint of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter, The number 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, and still more preferably 6 or less.
When alkyl (meth) acrylate is used, the content of alkyl (meth) acrylate in the raw material monomer of amorphous styrenic resin (AS) is low-temperature fixability, storage stability, charge rise, and bending resistance of printed matter. From this viewpoint, 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 monomer to an addition polymerization reaction.
From the viewpoint of reactivity, the temperature of the addition polymerization reaction is preferably 120 ° C. or higher, more preferably 130 ° C. or higher, still more preferably 150 ° C. or higher, and preferably 230 ° C. or lower, more preferably 220 ° C. or lower. 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 higher, more preferably 105 ° C. or higher, and still more preferably 115 ° C. or higher, from the viewpoints of storage stability, charge rising property, and bending resistance of printed matter. From the viewpoint of low-temperature fixability, it is preferably 150 ° C. or lower, more preferably 135 ° C. or lower, and still more preferably 125 ° C. or lower.
〔Glass-transition temperature〕
The glass transition temperature of the amorphous styrenic resin (AS) is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and still more preferably 50 ° C. from the viewpoints of storage stability, charge build-up property, and bending resistance of printed matter. From the viewpoint of low temperature fixability, it is preferably 90 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 60 ° C. or lower.
[Acid value]
The acid value of the amorphous styrenic resin (AS) is preferably 0 mgKOH / g or more, and preferably 30 mgKOH / g, from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter. g or less, more preferably 25 mgKOH / g or less, still more preferably 10 mgKOH / g or less.
The softening point, glass transition temperature, and acid value of the amorphous styrenic resin (AS) can be appropriately adjusted according to the production conditions such as the type and ratio of the raw material monomers, reaction temperature, reaction time, and cooling rate. .

(Amorphous polyester (AP))
The amorphous polyester (AP) used as the amorphous resin (A1) includes 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)”. -Ac) ")) and a polycondensation reaction.

[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 oxides (average added mole number of 1 to 16) are adducts from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. A propylene oxide adduct of bisphenol A is more preferable.
In the alcohol component (AP-al), the content of the propylene oxide adduct of bisphenol A is preferably 80 mol% or more from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and print bending resistance. Preferably it is 90 mol% or more, More preferably, it is 95 mol% or more, More preferably, it is 98 mol% or more, Preferably it is 100 mol% or less, More preferably, it is 100 mol%.
The average number of moles of propylene oxide added to the propylene oxide adduct of bisphenol A is preferably 1 or more, more preferably 1.2 or more, from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. Further, it is preferably 1.5 or more, and preferably 16 or less, more preferably 12 or less, still more preferably 8 or less, and still more preferably 4 or less.
These alcohol components (AP-al) can be used alone or in combination of two or more.

[Carboxylic acid component (AP-ac)]
Examples of the carboxylic acid component (AP-ac) include those similar to those exemplified as the carboxylic acid component (CH-ac).
Of these, aliphatic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds are preferred from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter, and aliphatic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds are preferred. It is more preferable to use together.
As the aliphatic carboxylic acid compound, fumaric acid is preferable. The number of carbon atoms of the aliphatic dicarboxylic acid compound is preferably 2 or more, and preferably 10 or less, more preferably 6 or less, from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter. More preferably, it is 4 or less.
As the aromatic dicarboxylic acid compound, terephthalic acid is preferred. The content of the aromatic dicarboxylic acid compound, preferably terephthalic acid, in the carboxylic acid component (AP-ac) is preferably 30 mol from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and printed product bending resistance. % Or more, more preferably 40 mol% or more, still more 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 the physical properties, the alcohol component (AP-al) may appropriately contain a monovalent 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 preferable from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending 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. .

  The amorphous polyester (AP) comprises an alcohol component (AP-al) and a carboxylic acid component (AP-ac) in an inert gas atmosphere, as necessary, an esterification catalyst, an esterification cocatalyst, and a polymerization inhibitor. It can manufacture by carrying out polycondensation using etc.

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

Examples of the esterification catalyst, esterification co-catalyst, and polymerization inhibitor that are suitably used for the polycondensation reaction include those similar to those used for the production of the crystalline composite resin (CH).
The amount of the esterification catalyst used is a total amount of alcohol component (AP-al) and carboxylic acid component (AP-ac) of 100 from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous polyester (AP). Preferably, it is 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 with respect to parts by mass. Is 1.5 parts by mass or less, more preferably 1.0 part by mass or less.
The use amount of the esterification cocatalyst is 100 mass of the total amount of the alcohol component (AP-al) and the carboxylic acid component (AP-ac) from the viewpoints of reactivity, molecular weight adjustment, and physical property adjustment of the amorphous polyester (AP). Part is preferably 0.001 part by weight or more, more preferably 0.01 part by weight or more, still more preferably 0.03 part by weight or more, and preferably 0.2 part by weight or less, more preferably It is 0.15 parts by mass or less, more preferably 0.1 parts by mass or less.
From the viewpoint of reactivity, the mass ratio of the esterification cocatalyst to the esterification catalyst [esterification cocatalyst / esterification catalyst] is preferably 0.001 or more, more preferably 0.01 or more, and still more preferably 0.00. It is 05 or more, and preferably 0.5 or less, more preferably 0.3 or less, and still more preferably 0.15 or less.

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

(Amorphous composite resin (AH1)
The amorphous composite resin (AH1) used as the amorphous resin (A1) includes a polyester resin component (AH1-1) and a styrenic resin component (AH1-2), and the polyester resin component (AH1). -1), a styrene resin component (AH1-2), a component derived from a bireactive monomer capable of reacting with any of the polyester resin component (AH1-1) and the styrene resin component (AH1-2); It is preferable that it consists of. Moreover, within the range which does not inhibit the objective of this invention, you may include structural parts other than these three structural parts, but it is preferable not to include structural parts other than three structural parts.
Examples of the bireactive monomer include the same ones as the bireactive monomers that can be used in the crystalline composite resin (CH), and preferred types and amounts used are also the same.

  In the amorphous composite resin (AH1), the mass ratio of the polyester resin component (AH1-1) to the styrene resin component (AH1-2) (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 viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. 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.

  In the amorphous composite resin (AH1), the total content of the polyester resin component (AH1-1), the styrene resin component (AH1-2), and the constituent parts derived from both reactive monomers is low temperature fixability, From the viewpoints of storage stability, charge build-up property, and bending resistance of printed matter, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less. More preferably, 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 viewpoints of low-temperature fixability, storage stability, charge rise property, and bending resistance of printed matter. It is obtained by polycondensation with a carboxylic acid component (hereinafter also referred to as “carboxylic acid component (AH1-ac)”).
Examples of the alcohol component (AH1-al) and carboxylic acid component (AH1-ac) include the same components as the alcohol component (AP-al) and 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 preferable from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending 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 the physical properties, the alcohol component (AH1-al) may optionally contain a monovalent alcohol, and the carboxylic acid component (AH1-ac) suitably contains a monovalent carboxylic acid compound. It may be.

[Styrene resin component (AH1-2)]
The styrene resin component (AH1-2) is a segment made of a styrene resin.
Examples of the styrenic resin include polystyrene, a polymer of a styrene derivative, a styrene-acrylic copolymer, and the like, from the viewpoints of low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter. 1 type or more chosen from a polymer of these, and a styrene-acrylic copolymer is preferred, 1 type or more chosen from polystyrene and a styrene-acrylic copolymer is more preferred, and a styrene-acrylic copolymer is still more preferred.
As a raw material monomer of a styrene resin component (AH1-2), the same thing as the raw material monomer of the said styrene 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 production methods (1) to (3) of the crystalline composite resin (CH).

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

[Esterification catalyst, esterification cocatalyst, polymerization inhibitor]
Examples of the esterification catalyst, esterification co-catalyst, and polymerization inhibitor suitably used for the polycondensation reaction include esterification catalyst, esterification co-catalyst, and polymerization inhibitor used for the production of the amorphous polyester (AP). The same thing is mentioned, A preferable aspect is also the same.

[Softening point]
The softening point of the amorphous composite resin (AH1) is preferably 60 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably, from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending 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, and further preferably 40 ° C. or higher, from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and printed paper folding resistance. 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 value]
The acid value of the amorphous composite resin (AH1) is preferably 0 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. The amount is preferably 15 mgKOH / g or more, and preferably 40 mgKOH / g or less, more preferably 30 mgKOH / g or less, and further preferably 25 mgKOH / 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 production conditions such as the type and ratio of the raw material monomers, reaction temperature, reaction time, and cooling rate.

In the production method of the present invention, in addition to the crystalline resin (C) and the amorphous resin (A1), a known resin used for the toner, for example, other than the crystalline resin (C) and the amorphous resin (A1). 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 a crystalline resin (C), an organic solvent, and a neutralizing agent to obtain a mixture Step 2: Mixing the mixture obtained in Step 1 with at least water to form a crystalline resin (C) Step 3: Obtaining an aqueous dispersion of resin particles (X) containing crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2 Step 4: The resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A1) are aggregated 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 an organic solvent, from the viewpoint of solubility, alcohol solvents such as isopropanol and isobutanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diethyl ketone; ether solvents such as dibutyl ether and dioxane; ethyl acetate Preferred are acetate ester solvents such as isopropyl acetate. Among these, from the viewpoints of low-temperature fixability, storage stability, bending resistance, and charge rising property, a ketone solvent is more preferable, and methyl ethyl ketone is more preferable.
In step 1, the mass ratio of the organic solvent to the crystalline resin (C) [organic solvent / crystalline resin (C) (total amount of crystalline polyester resin (CP) and crystalline composite resin (CH))] is From the viewpoint of low-temperature fixability, storage stability, charge build-up property, and bending 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.

<Neutralizing agent>
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. A base. Among these, metal hydroxide and ammonia are preferable, metal hydroxide is more preferable, alkali metal hydroxide is more preferable, one or more selected from sodium hydroxide and potassium hydroxide is still more preferable, Sodium oxide is even more preferred.
The degree of neutralization of the crystalline resin (C) by the neutralizing agent is adjusted by adjusting the volume-median particle size (D ₅₀ ) of the resin particles (X) obtained in Step 3, and the low-temperature fixability, storage stability, and charge rising property From the viewpoint of improving the bending resistance of the printed material, it is preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, and from the same viewpoint, preferably 150 mol%. Below, more preferably 120 mol% or less, still more preferably 100 mol% or less, and still more preferably 80 mol% or less.
In addition, the neutralization degree (mol%) of resin can be calculated | required by a following formula.
Degree of neutralization = {[mass of neutralizer (g) / equivalent of neutralizer] / [[acid value of resin (mgKOH / g) × mass of resin (g)] / (56 × 1000)]} × 100

<Surfactant>
In step 1, it is preferable to use a surfactant from the viewpoints of low-temperature fixability, storage stability, charge rising property of the toner obtained, and bending resistance of the printed matter.
Surfactants include nonionic surfactants, anionic surfactants and cationic surfactants. Among these, nonionic surfactants and / or anionic surfactants are preferable from the viewpoint of emulsion stability of the resin, and anionic surfactants are more preferable.
Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl aryl ethers such as polyoxyethylene lauryl ether or polyoxyethylene alkyl ethers, polyethylene glycol monolaurate, Examples include polyoxyethylene fatty acid esters such as polyethylene glycol monostearate and polyethylene glycol monooleate, and oxyethylene / oxypropylene block copolymers. Among these, from the viewpoint of emulsion stability of the resin, polyoxyethylene alkyl ethers Is preferred.
Examples of the anionic surfactant include alkylbenzene sulfonates such as sodium alkylbenzene sulfonate, alkyl sulfates such as sodium alkyl sulfate, and alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate. From the viewpoint of emulsion stability, sodium alkylbenzene sulfonate and alkyl ether sulfate are preferable, and alkyl ether sulfate is more preferable.
Examples of the cationic surfactant include alkyltrimethylammonium chloride and dialkyldimethylammonium chloride.
Among these, from the viewpoint of emulsion stability of the binder resin, polyoxyethylene alkyl ethers and alkyl ether sulfates are preferable, and polyoxyethylene alkyl ether sulfates are more preferable. The polyoxyethylene alkyl ether sulfate is preferably a sodium salt from the same viewpoint.

The polyoxyethylene alkyl ether sulfate preferably contains polyoxyethylene alkyl ether sulfate (EO2) having an addition mole number of ethylene oxide of 2 mol.
In the anionic surfactant, the content of polyoxyethylene alkyl ether sulfate is preferably 80% by mass or more, more preferably from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. Is 85% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 100% by mass or less.

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

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

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, inorganic composite oxide, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliantamine 3B, Brilliantamine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Green Oxalate, etc. Various pigments: acridine, xanthene, azo, benzoquinone, azine, anthraquinone, indico, Indigo dyes, phthalocyanine, aniline black, polymethine, triphenylmethane dyes, diphenylmethane dyes, thiazine, and include various dyes of thiazole, and the like. These can be used alone or in combination of two or more.
From the viewpoint of improving the image density of the toner, the amount of the colorant used is preferably 0.1 parts by mass or more with respect to 100 parts by mass in total of the crystalline resin (C) and the amorphous resin (A1). Preferably it is 0.5 mass part or more, More preferably, it is 1.0 mass part or more, Preferably it is 40 mass parts or less, More preferably, it is 20 mass parts or less, More preferably, it is 10 mass parts 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 with respect to 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. Preferably it is 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 as follows.

(Release agent)
Release agents include polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, jojoba Plant waxes such as oil; animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax, which are used alone or in combination of two or more Can be mixed and used.
From the viewpoint of resin dispersibility, the release agent is preferably used in an amount of 0.1 parts by mass or more, more preferably 0.1 parts by mass relative to the total of the crystalline resin (C) and the amorphous resin (A1). 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 obtaining a dispersion of the crystalline resin (C) by mixing at least water with the mixture obtained in Step 1.
In this step, by adding an aqueous medium to the mixture, first, a W / O phase is formed, and then the phase is inverted to the O / W phase. Whether or not phase inversion has occurred can be confirmed, for example, by visual observation or electrical conductivity.
The phase inversion step can be adjusted by the addition rate and amount of the aqueous medium as described later.

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

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

  From the viewpoint of obtaining resin particles having a small particle size, 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 the phase inversion is completed. More preferably 1 part by mass / min or more, further preferably 3 parts by mass / min or more, still more preferably 4 parts by mass / min or more, and preferably 50 parts by mass / min or less, more preferably 30 parts by mass. / 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 restriction | limiting in the addition rate of the aqueous medium after phase inversion.

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

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

  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 5% by mass or more by adding water as appropriate from the viewpoints of stability and ease of handling of the aqueous dispersion. It is preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

The volume median particle size (D ₅₀ ) of the resin particles (X) obtained in this step is preferably 30 nm or more, more preferably from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and printed material bending resistance. Is 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, and still more preferably 130 nm or less.
In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size.

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

Step 4-1: The resin particles (X) containing the crystalline resin (C) obtained in Step 3 and the resin particles (Y) containing the amorphous resin (A1) are aggregated in an aqueous medium. Step of obtaining aggregated particles (1) Step 4-2: Aggregate the resin particles (Z) containing the amorphous resin (A2) to 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 Hereinafter, steps 4-1 to 4-3 will be described. .

(Step 4-1)
In Step 4-1, the resin particles (X) containing the crystalline resin (C) obtained in Step 3 and the resin particles (Y) containing the amorphous resin (A1) are aggregated in an aqueous medium. This is a step of obtaining aggregated particles (1).

The resin particles (Y) are preferably obtained as an aqueous dispersion of the resin particles (Y). By using an amorphous resin (A1) as the binder resin, the resin particles (Y) are similar to the aqueous dispersion of the resin particles (X). It can manufacture by the method of.
The volume median particle size (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, More preferably, it is 130 nm or less.
The solid content concentration of the aqueous dispersion of the resin particles (Y) is preferably 3% by mass or more, more preferably 5% by mass or more, by appropriately adding water from the viewpoint of stability of the dispersion and ease of handling. More preferably, it is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

  In Step 4-1, the aqueous dispersion of resin particles (X) and the aqueous dispersion of resin particles (Y) are mixed, and the resin particles (X) and the resin particles (Y) are mixed to agglomerate. It is preferable to make it. In Step 4-1, it is preferable to add a flocculant in order to efficiently perform the aggregation.

As the flocculant, a quaternary salt cationic surfactant, an organic flocculant such as polyethyleneimine; and an inorganic flocculant such as inorganic metal salt and inorganic ammonium salt are used. From the viewpoint of toner particle size distribution and heat-resistant storage stability, inorganic flocculants are preferable, and inorganic metal salts are particularly preferable.
Examples of the inorganic metal salt include sodium sulfate, sodium chloride, calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, and aluminum chloride. The valence of the central metal of the inorganic metal salt is preferably 2 or more from the viewpoint of the particle size distribution of the toner and the heat resistant storage stability.
When adding a flocculant, the addition amount is preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, with respect to 100 parts by mass in total of the resin particles (X) and the resin particles (Y). More preferably, it is 0.1 parts by mass or more, and preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and still more preferably 1 part by mass or less.
The flocculant is preferably added after being dissolved in an aqueous medium, and it is preferable that the flocculant is sufficiently stirred at the time of addition of the flocculant and after the addition.

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

In Step 4-1, the additives such as a coloring agent, a charge control agent, a release agent, a conductivity adjusting agent, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent are added. You may make it aggregate from.
Additives such as a colorant, a charge control agent, and a release agent may be premixed in the binder resin, or a dispersion in which each additive is separately dispersed in a dispersion medium such as water, that is, colorant fine particles. You may prepare the coloring agent dispersion containing, the charge control agent dispersion containing charge control agent microparticles | fine-particles, and the mold release agent dispersion containing release agent microparticles | fine-particles, and may use for an aggregation process.
The volume median particle size (D ₅₀ ) of the colorant fine particles is preferably 50 nm or more, more preferably 100 nm or more, and preferably 200 nm or less, more preferably 150 nm or less.
The volume median particle size (D ₅₀ ) of the charge control agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 800 nm or less, more preferably 500 nm or less.
The volume median particle size (D ₅₀ ) of the release agent fine particles is preferably 100 nm or more, more preferably 300 nm or more, and preferably 1000 nm or less, more preferably 700 nm or less.

(Step 4-2)
Step 4-2 is a step in which the aggregated particles (1) obtained in Step 4-1 are aggregated with the resin particles (Z) containing the amorphous resin (A2) to obtain aggregated particles (2). is there.

(Amorphous resin (A2))
The amorphous resin (A2) is a resin having a crystallinity index exceeding 1.4 or less than 0.6, preferably exceeding 1.5, or 0.5 or less, more preferably 1. It is 6 or more and 0.5 or less.
Examples of the amorphous resin (A2) include amorphous polyester, amorphous styrene resin, amorphous composite resin (AH2) containing a polyester resin component (AH2-1) and a styrene resin component (AH2-2). From the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter, amorphous composite resin (AH2) is preferable.

[Amorphous composite resin (AH2)]
The amorphous composite resin (AH2) includes a polyester resin component (AH2-1) and a styrene resin component (AH2-2). The polyester resin component (AH2-1) and the styrene resin component ( AH2-2) and a constituent part derived from a bireactive monomer capable of reacting with any of the polyester resin component (AH2-1) and the styrene resin component (AH2-2) are preferred. Moreover, within the range which does not inhibit the objective of this invention, you may include structural parts other than these three structural parts, but it is preferable not to include structural parts other than three structural parts.
Examples of the bireactive monomer include the same ones as the bireactive monomers that can be used in the crystalline composite resin (CH), and preferred types and amounts used are also the same.

  In the amorphous composite resin (AH2), the mass ratio of the polyester resin component (AH2-1) to the styrene resin component (AH2-2) (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 viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending 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.

  In the amorphous composite resin (AH2), the total content of the polyester resin component (AH2-1), the styrene resin component (AH2-2), and the constituent parts derived from both reactive monomers is low temperature fixability, From the viewpoints of storage stability, charge build-up property, and bending resistance of printed matter, it is preferably 90 mol% or more, more preferably 95 mol% or more, still more preferably 99 mol% or more, and preferably 100 mol% or less. More preferably, 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 fixability, storage stability, charge rising property, and bending resistance of printed matter. It is obtained by polycondensation with 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, The kind and content of a preferable resin are also the same.
Examples of the carboxylic acid component (AH2-ac) include those similar to the carboxylic acid component (AP-ac), and preferred resin types are also the same.
The content of the aromatic dicarboxylic acid compound, preferably terephthalic acid, in the carboxylic acid component (AH2-ac) is preferably 40 mol from the viewpoint of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. % Or more, more preferably 55 mol% or more, still more 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 contain a monovalent alcohol as appropriate, and the carboxylic acid component (AH2-ac) contains a monovalent carboxylic acid compound as appropriate. 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 viewpoints of low-temperature fixability, storage stability, charge rising property, and bending 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 styrene resin and the raw material monomer constituting the styrene resin component (AH2-2) are the same as the styrene resin component (CH-2) and the raw material monomer constituting the crystalline composite resin (CH). The types and contents of preferable monomers are the same.

  The amorphous composite resin (AH2) can be produced by the same method as the amorphous composite resin (AH1). The conditions for the polycondensation reaction and the addition polymerization reaction, as well as the esterification catalyst, esterification promoter, The same applies to the type and amount of the polymerization inhibitor, and the preferred embodiment thereof.

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

The resin particles (Z) are preferably obtained as an aqueous dispersion of the resin particles (Z). By using an amorphous resin (A2) as the binder resin, the resin particles (Z) are similar to the aqueous dispersion of the resin particles (X). It can manufacture 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, More preferably, it is 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 stability of the dispersion and ease of handling. More preferably, it is 15% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less.

In Step 4-2, the resin particles (Z) are further adhered to the aggregated particles (1) by adding an aqueous dispersion of the resin particles (Z) to the above-described dispersion of the aggregated particles (1), thereby aggregating the aggregated particles (1). It is preferable 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. Further, when the aqueous dispersion of the resin particles (Z) is added to the dispersion of the aggregated particles (1), the coagulant is added in order to efficiently attach the resin particles (Z) to the aggregated particles (1). It may be used in the process.

  The temperature at which the aqueous dispersion of the resin particles (Z) is added is preferably 40 ° C. or more, more preferably from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and printed paper bending resistance of the obtained toner. Is 45 ° C. or higher, more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, more preferably 70 ° C. or lower, still more preferably 65 ° C. or lower.

The addition amount of the resin particles (Z) is such that the resin particles (Z), the resin particles (X), and the resin particles (from the viewpoint of low-temperature fixability, storage stability, charge build-up property, and printed paper bending resistance of the resulting toner ( The mass ratio [shell (resin particles (Z)) / core (resin particles (X) and resin particles (Y))] with respect to Y) is preferably 0.05 or more, more preferably 0.1 or more, still more preferably Is 0.15 or more, and preferably 1 or less, more preferably 0.5 or less, still more preferably 0.3 or less, even more preferably 0.25 or less.
Further, resin particles (X) containing a crystalline resin (C), resin particles (Y) containing an amorphous resin (A1), and resin particles (Z) containing an amorphous resin (A2) The total mass ratio of [(resin particles (X)) / (resin particles (Y) and resin particles (Z))] is from the viewpoint of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. Preferably it is 3/97 or more, more preferably 5/95 or more, still more preferably 7/93 or more, still more preferably 10/90 or more. From the same viewpoint, it is preferably 40/60 or less, more preferably 30 / 70 or less, more preferably 20/80 or less, even more preferably 17/83 or less, and even more preferably 15/85 or less.

The volume-median particle size (D ₅₀ ) of the obtained aggregated particles (2) is determined from the viewpoint of obtaining a toner capable of obtaining a high-quality image, as well as the low-temperature fixability, storage stability, charge build-up property 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 aggregation may be stopped when the toner particles have grown to an appropriate particle size.
Examples of the method for stopping the aggregation include a method of cooling the dispersion, a method of adding an aggregation stopper, and a method of diluting the dispersion. From the viewpoint of reliably preventing unnecessary aggregation, a method of stopping aggregation by adding an aggregation stopper is preferable.
A surfactant is preferably used as the aggregation terminator, and an anionic surfactant is more preferably used. Of the anionic surfactants, it is more preferable to use one or more selected from alkyl ether sulfates, alkyl sulfates, and linear alkylbenzene sulfonates, and it is more preferable to use alkyl ether sulfates.

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

The toner for electrophotography of the present invention can be suitably obtained by 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 as appropriate.
In the washing step, it is preferable to completely remove the added nonionic surfactant by washing, and washing with an aqueous solution below the cloud point of the nonionic surfactant is preferred. The washing is preferably performed a plurality of times.
In the drying step, any method such as a vibration type fluidized drying method, a spray drying method, a freeze drying method, a flash jet method, or the like can be employed. The water content after drying of the toner is preferably adjusted to 1.5% by mass or less, more preferably 1.0% by mass or less from the viewpoint of chargeability.

[Electrophotographic toner]
The electrophotographic toner of the present invention is an electrophotographic toner obtained by the production method of the present invention.
An external additive may be used in the toner of the present invention in order to improve transferability. As the external additive, inorganic fine particles are preferably used. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide, and zinc oxide. Among these, silica is preferable. As the silica, hydrophobic silica that has been subjected to a hydrophobic treatment is preferable from the viewpoint of transferability of the toner.
Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Among these, hexamethyldisilazane is preferable.

The average particle diameter of the external additive is preferably 10 nm or more, more preferably 15 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoints of chargeability, fluidity, and transferability of the toner. Preferably it is 100 nm or less, More preferably, it is 50 nm or less.
The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and still more preferably 0.3 parts by mass with respect to 100 parts by mass of the toner before processing with the external additive. And preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and still more preferably 3 parts by mass or less.
In the electrophotographic toner 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. From the viewpoints of heat resistance, bending resistance, and charge rising property, 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 still more preferably. From the same viewpoint, it is preferably 40/60 or less, more preferably 30/70 or less, still more preferably 20/80 or less, and still more preferably 17/83 or less.

The toner for electrophotography of the present invention preferably has a core-shell structure, the core portion contains a crystalline resin (C) and an amorphous resin (A1), and the shell portion contains an amorphous resin (A2). More preferably.
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). The mass ratio of the crystalline resin (C) to the amorphous resin (A1) and the amorphous resin (A2) [crystalline resin (C) / [amorphous resin (A1) + amorphous resin. (A2)]] is preferably 3/97 or more, more preferably 5/95 or more, and even more preferably 7/93 or more, from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. From the same viewpoint, it is preferably 40/60 or less, more preferably 30/70 or less, still more preferably 20/80 or less, even more preferably 17/83 or less, and more. 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). The mass ratio of the crystalline resin (C) and amorphous resin (A1) contained in the core part to the amorphous resin (A2) contained in the shell part [shell part (amorphous resin (A2) ) / Core part [crystalline resin C + amorphous resin (A1)]] is preferably 5/100 or more, more preferably from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. Is 10/100 or more, more preferably 15/100 or more. From the same viewpoint, it is preferably 100/100 or less, more preferably 50/100 or less, still more preferably 30/100 or less, still more preferably 25/100 or less. 100 or less

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3.0 μm or more, more preferably 3.5 μm, from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and bending resistance of printed matter. More preferably, it is 4.0 μm or more, 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, and still more preferably 7.5 μm or less.

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

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

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

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

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

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

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

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

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

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

[Thermal storage stability of toner under high humidity]
A 25 mL container (diameter: about 3 cm) was charged with 5 g of toner and allowed to stand for 72 hours in an environment at a temperature of 55 ° C. and a humidity of 90%. The degree of 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 during which no agglomeration is observed, the better the heat resistant storage stability at high humidity.
(Evaluation criteria)
A: Aggregation is not observed even after 72 hours.
B: Aggregation is not observed after 60 hours, but aggregation is observed after 72 hours.
C: Aggregation is not observed after 36 hours, but aggregation is observed after 48 hours.
D: Aggregation is not observed after 24 hours, but aggregation is observed after 36 hours.
E: Aggregation is observed after 24 hours.

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

[Charge rising property of toner]
At 25 ° C. and 50% RH, 2.1 g of toner and 27.9 g of silicone ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd., average particle size: 40 μm) are placed in a 50 ml cylindrical polypropylene bottle (manufactured by Nikko Corporation). The mixture was shaken 10 times vertically and horizontally, and then mixed using a tumbler mixer. The charge amount at the mixing time of 1 minute and 10 minutes was measured using a q / m meter (manufactured by EPPING) to obtain the respective charge amount. From the 1 min value of the charge amount (charge amount at a mixing time of 1 minute) and the 10 min value of charge amount (charge amount at a mixing time of 10 minutes), the charge rising property was measured. The closer to (1 min value of charge amount) / (10 min value of charge amount) is, the closer the charging is, the better the rising property of charging.
Measurement equipment, settings, etc. are as follows.
・ Measuring equipment: “q / m-meter” (manufactured by EPPING)
Setting: Mesh size: 635 mesh (opening: 24 μm, made of stainless steel)
・ Soft blow: Blow pressure (600V)
Suction time: 90 seconds Charge amount (μC / g) = total amount of electricity after 90 seconds (μC) / amount of toner sucked (g)

[Production of crystalline resin]
Synthesis Examples 1-8, 10-13
(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 the alcohol component, half the amount of the carboxylic acid component, the esterification catalyst, 10 equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen introduction tube The mixture was placed in a liter four-necked flask, heated in a mantle heater in a nitrogen atmosphere from 135 ° C. to 160 ° C. over 6 hours, and then reacted at 160 ° C. Thereafter, it was confirmed that the reaction rate reached 95% or more, and a mixed solution of the raw material monomer of the styrene resin component, the both reactive monomers and the radical polymerization initiator shown in Table 1 was added dropwise over 1 hour. Thereafter, after maintaining at 160 ° C. for 30 minutes, the remaining carboxylic acid component was added, the temperature was raised from 135 ° C. to 200 ° C. over 8 hours, and further reacted for 2 hours under a reduced pressure of 8 kPa. -1 to C-8 and C-10 to C-13 were obtained. Table 1 shows the physical properties of the resin. In addition, the reaction rate in this invention means the value of production | generation reaction water amount (mol) / theoretical production | generation water amount (mol) x100.

Synthesis Example 9
(Production of crystalline polyester C-9)
Of the raw material components of the polyester resin component shown in Table 1, the total amount of the alcohol component, the total amount of the carboxylic acid component, the esterification catalyst, 10 liters equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen introduction tube 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, and then reacted at 200 ° C. for 2 hours. The reaction rate reached 95% or more. It was confirmed. Furthermore, it was made to react under reduced pressure of 8 kPa for 2 hours, and crystalline polyester C-9 was obtained. Table 1 shows the physical properties of the resin.

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

Synthesis Example 15
(Production of amorphous polyester A-2)
BPA-PO, terephthalic acid, esterification catalyst and esterification co-catalyst shown in Table 3 were placed in a 10 liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and nitrogen was added. The temperature was raised to 235 ° C. over 2 hours in a mantle heater in the atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Then, it cooled to 190 degreeC, the radical polymerization inhibitor and the remaining carboxylic acid component were added, and it heated up to 210 degreeC over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 3 was reached, and amorphous polyester A-2 was obtained. Table 3 shows the physical properties.

Synthesis Examples 16 and 17
(Production of amorphous composite resins A-3 and A-4)
BPA-PO, terephthalic acid, esterification catalyst and esterification co-catalyst shown in Table 3 were placed in a 10 liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and nitrogen was added. The temperature was raised to 235 ° C. over 2 hours in a mantle heater in the atmosphere. Thereafter, it was confirmed that the reaction rate reached 95% or higher at 235 ° C., cooled to 160 ° C., and a mixed solution of the raw material monomer of the styrenic resin component, the both reactive monomers and the radical polymerization initiator shown in Table 3 was obtained. The solution was added dropwise over 1 hour. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., further reacted for 1 hour under a reduced pressure of 8 kPa, and then cooled to 180 ° C. Thereafter, a radical polymerization inhibitor and the remaining carboxylic acid component were added, and the temperature was raised to 210 ° C. over 2 hours. Then, after reacting at 210 ° C. for 1 hour, the reaction was performed at 40 kPa until the softening point shown in Table 3 was reached, and amorphous composite resins A-3 and A-4 were obtained. Table 3 shows the physical properties.

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

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

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

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

Production Examples 2 to 28
(Production of aqueous dispersions c-2 to c-28 of binder resin particles)
In Production Example 1, the aqueous dispersions c-2 to c of binder resin particles were produced in the same manner as in Production Example 1, except that the resin type and the production conditions of the aqueous dispersion were changed as shown in Tables 4 and 5. -28 was obtained. Tables 4 and 5 show the volume median particle size of the binder resin particles in the obtained aqueous dispersion.

Production Example 29
(Production of aqueous dispersion c-29 of binder resin particles)
In Production Example 1, anionic surfactant “Emar E27C” (manufactured by Kao Corporation) is not added in Step 1, and ion exchange is performed so that the solid content concentration of the aqueous dispersion is 20% by mass after Step 3. After adding water, the same procedure as in Production Example 1 was conducted except that 16.7 g (4.5% by mass based on 100 g of resin) of the anionic surfactant “Emar E27C” (manufactured by Kao Corporation) was added. Thus, an aqueous dispersion c-29 of binder resin particles was obtained. Table 5 shows the volume-median particle size of the binder resin particles in the obtained aqueous dispersion.

Production Example 30
(Production of aqueous dispersion a-1 of binder resin particles)
100 g of amorphous styrene resin A-1, 100 g of methyl ethyl ketone, 16.7 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation) (4.5% by mass with respect to 100 g of resin) at 25 ° C. And dissolved at 73 ° C. for 2 hours. The obtained solution was mixed with 600 g of ion-exchanged water at 73 ° C. and subjected to a dispersion treatment at an output of 350 W for 30 minutes using an ultrasonic homogenizer (trade name: “UP-400S” manufactured by Dr. Heelscher). Thereafter, ethyl acetate was distilled off under reduced pressure at 70 ° C. to obtain an aqueous dispersion a-1 of binder resin particles. Table 5 shows the volume-median particle size of the binder resin particles in the obtained aqueous dispersion.

Production Examples 31-33
(Production of aqueous dispersions a-2 to a-4 of binder resin particles)
In Production Example 1, the aqueous dispersions of binder resin particles a-2 to a-4 were produced 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. Got.

[Manufacture of toner for electrophotography]
Example 1
(Manufacture 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 styrene resin A-1, 8 g of the colorant dispersion, 20 g of the release agent dispersion, and charging 2 g of the control agent dispersion and 52 g of deionized water are placed in a 2 L container, and 150 g of a 0.1 mass% calcium chloride aqueous solution at 20 ° C. with stirring of 100 r / min (peripheral speed 31 m / min) with an anchor type stirrer. Was added dropwise over 30 minutes. Then, it heated up to 50 degreeC, stirring. It was held 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 dispersed by stirring. Then, a dilute solution obtained by diluting 4.2 g of anionic surfactant “Emar E27C” (manufactured by Kao Corporation, solid content: 27 mass%) with 37 g of deionized water was added as an aggregation terminator. Next, the temperature was raised to 80 ° C., and after maintaining at 80 ° C. for 1 hour from the time when the temperature reached 80 ° C., the heating was terminated. As a result, fused particles were formed, and then slowly cooled to 20 ° C., filtered through a 150 mesh (mesh 150 μm) wire mesh, suction filtered, washed, and dried to obtain toner particles.

(External addition process)
Hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., number average particle diameter 40 nm) 1.0 part by mass, hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd.) A 10 L Henschel mixer equipped with ST and A0 stirring blades (number average particle diameter 16 nm) 0.6 parts by mass, titanium oxide “JMT-150IB” (manufactured by Teika Co., Ltd., number average particle diameter 15 nm) Toner A was obtained by stirring at 3000 rpm for 2 minutes. Table 6 shows the evaluation results of the toner.

Examples 2-28, Comparative Examples 1-3
(Manufacture of toners B to Z and AA to AE)
In Example 1, the type of the aqueous dispersion and the mass ratio of the crystalline resin and the amorphous resin in the core were changed to the types and mass ratios shown in Tables 6 and 7 in the same manner as in Example 1. Thus, 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 that in Example 1 (300 g). The evaluation results of the obtained toner are shown in Tables 6 and 7.

From Tables 6 and 7, the toners of Examples 1 to 28 of the present invention have an excellent balance of low-temperature fixability, storage stability, charge rising property, and printed paper folding resistance as compared with the toners of Comparative Examples 1 to 3. You can see that
A comparison of Examples 1, 4, 5 and Comparative Examples 1 and 2 shows that the toner of Example 1 using tetradecanedioic acid as a raw material monomer for the polycondensation resin component of the crystalline composite resin has low temperature fixability and storage. It can be seen that it is excellent in the property, the rising property of charging and the bending resistance of the printed matter.
Comparing Examples 1 to 3, the toner of Example 1 using 1,4-butanediol as a raw material monomer for the alcohol component of the polycondensation resin component of the crystalline composite resin has a low-temperature fixability, storage stability, It can be seen that the charge rising property and the bending resistance of the printed matter are excellent.
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 bending resistance of printed matter. I understand that.
When Examples 1, 9, and 10 are compared, the mass ratio of the polycondensation resin component to the styrene resin component [polycondensation resin component / styrene resin component] in the crystalline composite resin is 80/20. It can be seen that the toner of Example 1 is excellent in low-temperature fixability, storage stability, charge rising property, and printed paper folding resistance.
Comparing Example 1 and Example 8, it can be seen that the toner of Example 1 using a crystalline composite resin is excellent in low-temperature fixability, storage stability, charge rising property, and bending resistance of printed matter.
Comparing Examples 1 and 12 to 15, the toner of Example 1 in which the volume average particle diameter (D ₅₀ ) of the aqueous dispersion of the crystalline composite resin is 102 nm is low temperature fixability, storage stability, charge rising property, It can also be seen that the printed material is excellent in bending resistance.
A comparison of Examples 1, 16, and 17 shows that the toner of Example 1 using methyl ethyl ketone as the organic solvent used in the production of the aqueous dispersion of the crystalline composite resin has low temperature fixability, storage stability, charge rising property, and It can be seen that the printed material has excellent bending resistance.
A comparison of Examples 1, 18, and 19 shows that the toner of Example 1 using polyoxyethylene alkyl ether sulfate as the surfactant used in the production of the aqueous dispersion of the crystalline composite resin has low temperature fixability and storage. It can be seen that it is excellent in the property, the rising property of charging and the bending resistance of the printed matter.
When Examples 1, 20, and 21 were compared, the amount of the surfactant used during the production of the aqueous dispersion of the crystalline composite resin was 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 printed matter bending resistance.
Comparing Examples 1, 23, and 24, the toner of Example 1 in which the mass ratio of the organic solvent to the crystalline composite resin [organic solvent / crystalline composite resin] is 1.0 is low temperature fixability and storage stability. It can be seen that it is excellent in charge rising property and bending resistance of printed matter.
Comparing Examples 1 and 25, the neutralizing agent used to neutralize the crystalline composite resin in Step 1 is from the viewpoint of low-temperature fixability, storage stability, charge build-up property, and printed sheet bending resistance. It can be seen that Aralkali metal hydroxide is preferred.
Comparing Examples 1, 27, and 28, it is found that the core amorphous resin is preferably a styrene resin from the viewpoints of low-temperature fixability, storage stability, charge build-up property, and printed material bending resistance.

Claims (9)

A method for producing an electrophotographic toner 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,
The polycondensation resin constituting the crystalline polyester resin (CP) and the polycondensation resin component (CH-1) is an alcohol component containing an aliphatic diol of 80 mol% or more and 100 mol% or less, and a carbon number of 14 or more. A method for producing an electrophotographic toner, which is a resin obtained by polycondensation of a carboxylic acid component containing 20 mol% or less of an aliphatic dicarboxylic acid compound of 80 mol% or less and 100 mol% or less.
Step 1: Step of mixing a crystalline resin (C), an organic solvent, and a neutralizing agent to obtain a mixture Step 2: Mixing the mixture obtained in Step 1 with at least water to form a crystalline resin (C) Step 3: Obtaining an aqueous dispersion of resin particles (X) containing crystalline resin (C) by removing the organic solvent from the dispersion obtained in Step 2 Step 4: The resin particles (X) containing the crystalline resin (C) obtained in step 3 and the resin particles (Y) containing the amorphous resin (A1) are aggregated and fused in an aqueous medium. Process   The carbon number of the aliphatic diol which is a raw material monomer of the polycondensation resin constituting the crystalline polyester resin (CP) and the polycondensation resin component (CH-1) is 2 or more and 6 or less. A method for producing the electrophotographic toner according to claim.   The crystalline resin (C) contains a crystalline composite resin (CH), and the mass ratio of the polycondensation resin component (CH-1) to the styrene resin component (CH-2) (polycondensation resin component (CH— The method for producing an electrophotographic toner according to claim 1, wherein 1) / styrene resin component (CH-2)) is 60/40 or more and 98/2 or less.   The method for producing an electrophotographic toner according to claim 1, wherein the acid value of the crystalline composite resin (CH) is 5 mgKOH / g or more and 40 mgKOH / g or less.   The amorphous resin (A1) is selected from an amorphous composite resin (AH1) having an amorphous styrene resin (AS) and a polyester resin component (AH1-1) and a styrene resin component (AH1-2) The method for producing an electrophotographic toner according to claim 1, comprising at least one resin.   6. The method for producing an electrophotographic toner according to claim 1, wherein the resin particles (X) containing the crystalline resin (C) have a volume median particle size of 30 nm or more and 250 nm or less. The method for producing an electrophotographic toner according to claim 1, wherein step 4 includes the following steps 4-1 to 4-3.
Step 4-1: The resin particles (X) containing the crystalline resin (C) obtained in Step 3 and the resin particles (Y) containing the amorphous resin (A1) are aggregated in an aqueous medium. Step of obtaining aggregated particles (1) Step 4-2: Aggregate the resin particles (Z) containing the amorphous resin (A2) to 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 amorphous resin (A2) includes an amorphous composite resin (AH2) having a polyester resin component (AH2-1) and a styrenic resin component (AH2-2). A method for producing the electrophotographic toner according to claim.   An electrophotographic toner obtained by the production method according to claim 1.