JP2019035807A - Manufacturing method of toner - Google Patents

Abstract

To provide a manufacturing method of a toner showing an image density of an excellent printed matter and a hot offset resistance, and provide the toner.SOLUTION: [1] A manufacturing method of a toner includes: Step 1 of agglomerating resin particles X containing an amorphous resin A having a component derived from a hydrocarbon wax 1 having a hydroxyl or a carboxyl group in the presence of a wax D1, a wax D2, and a coloring agent in an aqueous medium so that the agglomerated particles are acquired; and Step 2 of fusing the agglomerated particles acquired by the Step 1. In a manufacturing method of the toner, a melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T for fusing the agglomerated particles in the Step 2 is above the temperature lower by 10°C than the melting point Tm1 of the wax D1 and is lower the temperature higher by 10°C than the melting point Tm2 of the wax D2. [2] The toner includes the amorphous resin A having the component derived from the hydrocarbon wax W1 having the hydroxyl or the carboxyl group as well as the polyester resin segment, and the wax D1, the wax D2, and the coloring agents, in which the melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2.SELECTED DRAWING: None

Description

  The present invention relates to a toner production method and toner used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.

  In the field of electrophotography, with the development of an electrophotographic system, development of a toner corresponding to high image quality and high speed is required. Corresponding to high image quality, a method of obtaining a toner having a narrow particle size distribution and a small particle size is obtained by agglomerating and fusing fine resin particles in an aqueous medium to obtain a toner. A toner is manufactured by an aggregating method or an aggregating method). In addition, in order to improve the basic characteristics of the toner such as low-temperature fixability and storage stability, it has been studied to give the resin a specific structure.

In Patent Document 1, an aqueous dispersion of a binder resin composition for toner containing a polyester resin and a wax (A), wherein the wax (A) is selected from the group consisting of an ester wax and a hydrocarbon wax. The wax (A) content is 3 to 50 parts by mass with respect to 100 parts by mass of the polyester resin, and the polyester resin has a melting point of 60 to 110 ° C. An aqueous dispersion of a binder resin composition for toner having 1 to 20% by mass of a constituent site derived from a hydrocarbon wax (B) having a hydroxyl group and / or a carboxy group having a molecular weight of 400 or more is described. Thus, it is described that a toner excellent in filming resistance, low-temperature fixability and hot offset resistance can be obtained.
In Patent Document 2, a polycondensation of a polyhydric alcohol component and a polycarboxylic acid component is performed in the presence of a hydrocarbon wax (W1) having a hydroxyl group or a carboxy group, and the component derived from the hydrocarbon wax (W1). And a step (1) of obtaining an amorphous resin (A) having a polyester resin segment, a step of dispersing the obtained amorphous resin (A) in an aqueous medium to obtain an aqueous dispersion of resin particles (X) (2) Step (3) of obtaining the aggregated particles by aggregating the obtained resin particles (X) in the presence of the crystalline polyester (B) in an aqueous medium, and melting the obtained aggregated particles. A method for producing a toner for developing an electrostatic charge image is described, which comprises the step (4) of applying. It is described that the toner thus obtained is excellent in low-temperature fixability and charging characteristics and excellent in image density of printed matter.

Japanese Patent Laid-Open No. 2015-210277 Japanese Patent Laid-Open No. 2006-136249

The toner production methods described in Patent Documents 1 and 2 contain highly hydrophobic components such as waxes and colorants, particularly with good dispersibility in the production of toners by the emulsion aggregation method in which shearing force cannot be applied. It is a technique that can be made.
However, with the methods of Patent Documents 1 and 2, it is difficult to say that a toner that sufficiently satisfies the two conflicting characteristics of excellent printed image density and offset resistance can be obtained.

  The present invention relates to a toner production method and toner that exhibit excellent printed image density and hot offset resistance.

  The inventors of the present invention have examined the constituent components of the toner. As a result, using two or more kinds of waxes having a specific structure and two or more types of waxes having a specific melting point simultaneously achieves two contradictory properties such as excellent printed image density and excellent hot offset resistance. I found it effective to do.

That is, the present invention relates to the following [1] and [2].
[1] Step 1: Resin particles X containing a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and an amorphous resin A having a polyester resin segment are mixed in an aqueous medium with wax D1, wax D2, And agglomerating in the presence of a colorant to obtain aggregated particles;
Step 2: fusing the aggregated particles obtained in Step 1 above,
A toner production method comprising:
The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T at which the aggregated particles are fused in Step 2 is 10 ° C. lower than the melting point Tm1 of the wax D1, and the melting point Tm2 of the wax D2 A method for producing toner, wherein the temperature is 10 ° C. or higher.
[2] A constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a colorant, and a melting point Tm1 of the wax D1 Is a toner having a melting point Tm2 lower than that of the wax D2.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the toner which shows the image density of the printed matter excellent in hot offset resistance, and a toner can be provided.

[Toner Production Method]
The method for producing the toner of the present invention includes:
Step 1: Resin particles X containing a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and an amorphous resin A having a polyester resin segment are mixed in an aqueous medium with a wax D1, a wax D2, and a colorant. Agglomerating in the presence of to obtain aggregated particles;
Step 2: fusing the aggregated particles obtained in Step 1 above,
including.
In the toner manufacturing method, the melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and the temperature T at which the aggregated particles are fused in Step 2 is 10 ° C. lower than the melting point Tm1 of the wax D1. The temperature is not higher than 10 ° C. above the melting point Tm2 of the wax D2.
According to the production method, a toner exhibiting excellent image density of printed matter and resistance to hot offset can be obtained. The reason is not clear, but it can be considered as follows.

The toner obtained by the production method of the present invention contains a component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and an amorphous resin A having a polyester resin segment, and at least two types of wax D1 and wax D2. The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2.
In the manufacturing method of this invention, the amorphous resin A which has the structural component derived from the hydrocarbon wax W1 which has a hydroxyl group or a carboxy group, and a polyester resin segment is used. In the aqueous medium, the resin particles X containing the amorphous resin A are formed so that the constituent component derived from the hydrocarbon wax W1 exists inside as a hydrophobic group and the more hydrophilic polyester resin segment exists outside. The
The resin particles X are aggregated in the presence of at least two kinds of wax D1 and wax D2 and a colorant, and the wax D1, wax D2, and colorant are included in the aggregated particles. The agglomerated particles are heat-fused at a temperature not lower than 10 ° C. than the melting point Tm1 of the wax D1 and not higher than 10 ° C. higher than the melting point Tm2 of the wax D2. Furthermore, the colorant is finely dispersed in the fused particles by further interacting with the components derived from the hydrocarbon wax W1 in the resin. On the other hand, the wax D2, which has a high melting point and is difficult to melt, forms a moderately sized domain without being excessively finely dispersed in the fused particles. For this reason, it is considered that the obtained toner has not only excellent image density of the printed matter but also excellent hot offset resistance because the wax can effectively act during development.

Definitions of various terms and the like in this specification are shown below.
Whether the resin is crystalline or amorphous is determined by the crystallinity index. The crystallinity index is defined by the ratio between the softening point of the resin and the maximum endothermic peak temperature (softening point (° C.) / Maximum endothermic peak temperature (° C.)) in the measurement methods described in the examples described later. The crystalline resin is one having a crystallinity index of 0.6 or more and 1.4 or less. An amorphous resin is one having a crystallinity index of less than 0.6 or greater than 1.4. The crystallinity index 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.
In the specification, the carboxylic acid component of the polyester includes not only the compound but also an anhydride that decomposes during the reaction to generate an acid, and an alkyl ester of each carboxylic acid (an alkyl group having 1 to 3 carbon atoms). included.
In the specification, “binder resin” is a general term for resin components contained in a toner including the amorphous resin A and the crystalline resin B.
Hereinafter, each process etc. of the manufacturing method of this invention are demonstrated.

[Step 1]
In step 1, resin particles X containing amorphous resin A having a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group (hereinafter also simply referred to as “hydrocarbon wax W1”) and a polyester resin segment are treated with water. In this process, the particles are aggregated in the presence of wax D1, wax D2, and a colorant to obtain aggregated particles.
Aggregation is preferably performed in the presence of the crystalline resin B. The crystalline resin B, the wax D1, the wax D2, and the colorant may be contained in the resin particles X or may be aggregated using these dispersions.

Step 1 may include the following steps 1-1 to 1-3.
Step 1-1: Step of obtaining amorphous resin A having a constituent component derived from hydrocarbon wax W1 having a hydroxyl group or a carboxy group and a polyester resin segment Step 1-2: Amorphous resin obtained in Step 1-1 Step 1-3 for obtaining an aqueous dispersion of resin particles X containing A: The resin particles X obtained in Step 1-2 are aggregated in an aqueous medium in the presence of wax D1, wax D2, and a colorant. Step of obtaining aggregated particles The details of step 1-1 are based on the method shown in the method for producing amorphous resin A described later.
The details of step 1-2 are based on the method shown in the method for producing resin particle X described later.
Hereinafter, each component used in step 1 will be described.

<Amorphous resin A>
Amorphous resin A has a component derived from hydrocarbon wax W1 having a hydroxyl group or a carboxy group and a polyester resin segment from the viewpoint of obtaining a toner exhibiting image density of printed matter and hot offset resistance. The amorphous resin A is, for example, a resin obtained by polycondensation of an alcohol component and a carboxylic acid component in the presence of a hydrocarbon wax W1 having a hydroxyl group or a carboxy group.
The amorphous resin A has a constituent component derived from the hydrocarbon wax W1 having a hydroxyl group or a carboxy group, and a polyester resin segment from the viewpoint of further improving the image density and hot offset resistance of the printed matter of the toner, preferably further It has an addition polymerization resin segment.

(Constituent component derived from hydrocarbon wax W1)
The constituent component derived from the hydrocarbon wax W1 is, for example, a hydrocarbon wax W1 in which a hydroxyl group or a carboxy group is reacted and covalently bonded to a polyester resin segment.
The hydrocarbon wax W1 has a hydroxyl group or a carboxy group. The hydrocarbon wax W1 may have either one or both of a hydroxyl group and a carboxy group, but is preferably a hydroxyl group from the viewpoint of improving the image density of the printed material and the hot offset resistance. And having a carboxy group.
The hydrocarbon wax W1 is obtained, for example, by modifying an unmodified hydrocarbon wax by a known method. Examples of the raw material of the hydrocarbon wax W1 include paraffin wax, Fischer-Tropsch wax, microcrystalline wax, polyethylene wax, and polypropylene wax. Among these, paraffin wax and Fischer-Tropsch wax are preferable.
Examples of commercially available paraffin waxes and Fischer-Tropsch waxes that are the raw materials for the hydrocarbon wax W1 include “HNP-11”, “HNP-9”, “HNP-10”, “FT-0070”, and “HNP-51”. "," FNP-0090 "(manufactured by Nippon Seiwa Co., Ltd.).

The hydrocarbon wax having a hydroxyl group is obtained, for example, by modifying a hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax by oxidation treatment. Examples of the oxidation treatment method include methods described in JP-A Nos. 62-79267 and 2010-197979. Specifically, there is a method of liquid phase oxidation of hydrocarbon wax with a gas containing oxygen in the presence of boric acid.
Examples of commercially available hydrocarbon waxes having a hydroxyl group include “Unilin 700”, “Unilin 425”, “Unilin 550” (manufactured by Baker Petrolite).

Examples of the hydrocarbon wax having a carboxy group include acid-modified hydrocarbon waxes.
The acid-modified hydrocarbon wax can be obtained, for example, by introducing a carboxy group into a hydrocarbon wax such as paraffin wax or Fischer-Tropsch wax by acid modification. Examples of the acid modification method include the methods described in JP-A-2006-328388 and JP-A-2007-84787. Specifically, the reaction is performed by adding an organic peroxide such as dicumyl peroxide and a carboxylic acid compound having an unsaturated bond as a reaction initiator to the raw material hydrocarbon wax melt. Groups can be introduced.
Examples of commercially available hydrocarbon waxes having a carboxy group include maleic anhydride-modified ethylene-propylene copolymer “High Wax 1105A” (manufactured by Mitsui Chemicals, Inc.).

The hydrocarbon wax having a hydroxyl group and a carboxy group can be obtained, for example, by the same method as the oxidation treatment of a hydrocarbon wax having a hydroxyl group.
Examples of commercially available hydrocarbon waxes having a hydroxyl group and a carboxy group include “Paracol 6420”, “Paracol 6470” and “Paracol 6490” (manufactured by Nippon Seiwa Co., Ltd.).

  The hydroxyl value of the hydrocarbon wax W1 is preferably 35 mgKOH / g or more, more preferably 40 mgKOH / g or more, and even more preferably 50 mgKOH / g, from the viewpoint of improving the image density of the printed material and improving the hot offset resistance. Or more, more preferably 70 mgKOH / g or more, still more preferably 90 mgKOH / g or more, and preferably 180 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less, even more preferably. Is 100 mg KOH / g or less.

  The acid value of the hydrocarbon wax W1 is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more, and further preferably 5 mgKOH / g, from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. As described above, it is more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, and preferably 30 mgKOH / g or less, more preferably 25 mgKOH / g or less, and further preferably 20 mgKOH / g or less.

  The total of the hydroxyl value and the acid value of the hydrocarbon wax W1 is preferably 40 mgKOH / g or more, more preferably 60 mgKOH / g or more, further from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. It is preferably 80 mgKOH / g or more, more preferably 90 mgKOH / g or more, and preferably 210 mgKOH / g or less, more preferably 175 mgKOH / g or less, still more preferably 140 mgKOH / g or less, and even more preferably 120 mgKOH / g. It is as follows.

The number average molecular weight of the hydrocarbon wax W1 is preferably 500 or more, more preferably 600 or more, still more preferably 700 or more, and preferably 2000 or less, more preferably 1700, from the viewpoint of improving the image density of the printed matter. Hereinafter, it is more preferably 1500 or less.
The method for measuring the hydroxyl value, acid value, and number average molecular weight of the hydrocarbon wax W1 is according to the method described in the examples.

(Polyester resin segment)
A polyester resin segment is a segment which consists of a polyester resin which is a polycondensate of an alcohol component and a carboxylic acid component, for example.

Hereinafter, each component of the polyester resin segment of the amorphous resin A will be described.
Examples of the alcohol component include aromatic diols, linear or branched aliphatic diols, alicyclic diols, and trihydric or higher polyhydric alcohols. Among these, aromatic diols are preferable.
The aromatic diol is preferably an alkylene oxide adduct of bisphenol A, more preferably of formula (I):

(In the formula, OR and RO are oxyalkylene groups, R is each independently an ethylene group or a propylene group, x and y are the average number of moles of alkylene oxide added, each being a positive number, The sum of y is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 4 or less).
Examples of the alkylene oxide adduct of bisphenol A include a polyoxypropylene adduct of bisphenol A [2,2-bis (4-hydroxyphenyl) propane] and a polyoxyethylene adduct of bisphenol A. One or more of these are preferably used.
The content of the alkylene oxide adduct of bisphenol A is preferably at least 70 mol%, more preferably at least 80 mol%, even more preferably at least 90 mol%, even more preferably at least 95 mol% in the alcohol component, And it is 100 mol% or less, More preferably, it is 100 mol%.

Examples of the linear or branched aliphatic diol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. 2,3-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, , 12-dodecanediol.
Examples of the alicyclic diol include hydrogenated bisphenol A [2,2-bis (4-hydroxycyclohexyl) propane], hydrogenated bisphenol A alkylene oxide having 2 to 4 carbon atoms (average added mole number of 2 to 12). The following).
Examples of the trihydric or higher polyhydric alcohol include glycerin, pentaerythritol, trimethylolpropane, and sorbitol.
These alcohol components can be used alone or in combination of two or more.

Examples of the carboxylic acid component include dicarboxylic acids and trivalent or higher polyvalent carboxylic acids.
Examples of the dicarboxylic acid include aromatic dicarboxylic acid, linear or branched aliphatic dicarboxylic acid, and alicyclic dicarboxylic acid. Among these, at least one selected from aromatic dicarboxylic acids and linear or branched aliphatic dicarboxylic acids is preferable.
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, and terephthalic acid. Among these, isophthalic acid and terephthalic acid are preferable, and terephthalic acid is more preferable.
The amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, and preferably 95 mol% or less, more preferably It is 90 mol% or less, More preferably, it is 80 mol% or less.

The carbon number of the linear or branched aliphatic dicarboxylic acid is preferably 2 or more, more preferably 3 or more, and preferably 30 or less, more preferably 20 or less.
Examples of linear or branched aliphatic dicarboxylic acids include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, dodecanedioic acid, azelaic acid And succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms. Examples of the succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms include dodecyl succinic acid, dodecenyl succinic acid, and octenyl succinic acid. Among these, fumaric acid, succinic acid substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms is preferable, and fumaric acid is more preferable.
The amount of the linear or branched aliphatic dicarboxylic acid is preferably 1 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, and preferably 30 mol% in the carboxylic acid component. Hereinafter, it is more preferably 20 mol% or less, and still more preferably 10 mol% or less.

The trivalent or higher polyvalent carboxylic acid is preferably a trivalent carboxylic acid, for example, trimellitic acid.
In the case of containing a trivalent or higher polyvalent carboxylic acid, the amount of the trivalent or higher polyvalent carboxylic acid is preferably 3 mol% or more, more preferably 5 mol% or more, still more preferably 10 mol% in the carboxylic acid component. And more preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less.
These carboxylic acid components can be used alone or in combination of two or more.

  The ratio of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably Is 1.2 or less.

(Addition polymerization resin segment)
The addition polymerization resin segment is preferably an addition polymerization product of a raw material monomer containing a styrene compound from the viewpoint of improving the image density of the printed matter.

Examples of the styrenic compound include substituted or unsubstituted styrene. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, an alkoxy group having 1 to 5 carbon atoms, a sulfonic acid group, or a salt thereof.
Examples of the styrene compound include styrene, methyl styrene, α-methyl styrene, β-methyl styrene, tert-butyl styrene, chlorostyrene, chloromethyl styrene, methoxy styrene, styrene sulfonic acid or a salt thereof. Of these, styrene is preferred.
From the viewpoint of improving the image density of the printed matter, the content of the styrene compound in the raw material vinyl monomer of the addition polymerization resin segment is preferably 40% by mass or more, more preferably 50% by mass or more, and further preferably 60% by mass. More preferably, the content is 70% by mass or more, and preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 87% by mass or less, and still more preferably 85% by mass or less.

Examples of raw material monomers other than styrene compounds include (meth) acrylic acid esters such as alkyl (meth) acrylate, benzyl (meth) acrylate, and dimethylaminoethyl (meth) acrylate; ethylene, propylene, butadiene and the like. Olefins; Halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as vinyl methyl ether; Vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone It is done. Among these, (meth) acrylic acid esters are preferable and alkyl (meth) acrylates are more preferable from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance.
The number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1 or more, more preferably 6 or more, and still more preferably from the viewpoint of further improving the image density of the printed material and the hot offset resistance. 10 or more, and preferably 24 or less, more preferably 22 or less, and still more preferably 20 or less.
Examples of the alkyl (meth) acrylate include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (meth) acrylate (iso or tertiary) butyl, (meth ) Acrylic acid (iso) amyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, (meth) acrylic acid ( (Iso) dodecyl, (meth) acrylic acid (iso) palmityl, (meth) acrylic acid (iso) stearyl, (meth) acrylic acid (iso) behenyl. Among these, 2-ethylhexyl acrylate and stearyl methacrylate are preferable, and stearyl methacrylate is more preferable.
In addition, “(iso or tertiary)” means normal, iso or tertiary, and “(iso)” means normal or iso.
“(Meth) acrylic acid” means at least one selected from acrylic acid and methacrylic acid.

  From the viewpoint of improving the image density of the printed material, the raw material monomer of the addition polymerization resin segment is preferably made of styrene or contains styrene and (meth) acrylic acid ester, more preferably styrene and (meth) acrylic acid. It contains an ester, and more preferably includes styrene and an alkyl (meth) acrylate having an alkyl group having 6 to 20 carbon atoms.

From the viewpoint of improving the image density of the printed matter, the content of the (meth) acrylic acid ester in the raw material vinyl monomer of the addition polymerization resin segment is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably. It is 15% by mass or more, more preferably 17% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
The total content of the styrene compound and the (meth) acrylic acid ester in the raw material monomer of the addition polymerization resin segment is preferably 80% by mass or more, more preferably 90% by mass from the viewpoint of further improving the image density of the printed matter. More preferably, it is 95% by mass or more, and 100% by mass or less, and still more preferably 100% by mass.

When the amorphous resin A has an addition polymerization resin segment, the amorphous resin A is preferably a structural unit derived from an amphoteric monomer bonded to the polyester resin segment and the addition polymerization resin segment via a covalent bond. Have
The “structural unit derived from both reactive monomers” means a unit in which the functional group and unsaturated bond site of both reactive monomers are reacted.
Examples of both reactive monomers include addition polymerizable monomers having at least one functional group selected from a hydroxyl group, a carboxy group, an epoxy group, a primary amino group, and a secondary amino group in the molecule. . Among these, from the viewpoint of reactivity, an addition polymerizable monomer having a hydroxyl group or a carboxy group is preferable, and an addition polymerizable monomer having a carboxy group is more preferable.
Examples of the both reactive monomers include acrylic acid, methacrylic acid, fumaric acid, maleic acid and the like. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is more preferable from the viewpoint of the reactivity of both the polycondensation reaction and the addition polymerization reaction.
The amount of the structural unit derived from both reactive monomers is preferably 1 mol part or more, more preferably 5 mol part or more, and still more preferably 8 with respect to 100 mol parts of the alcohol component of the polyester resin segment of the amorphous resin A. It is at least 30 parts by mole, more preferably at most 25 parts by mole, still more preferably at most 20 parts by mole.

  The amount of the constituent component derived from the hydrocarbon wax W1 in the amorphous resin A is preferably 1% by mass or more, more preferably from the viewpoint of further improving the image density of the printed matter and the hot offset resistance. Is 2% by mass or more, more preferably 3% by mass or more, and preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 10% by mass or less.

  In the amorphous resin A, the amount of the polyester resin segment is preferably 40% by mass or more, more preferably 50% by mass or more, from the viewpoint of further improving the image density of the printed material and the hot offset resistance. More preferably 60% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 99% by mass or less, more preferably When the addition polymerization resin segment described later is included, it is preferably 80% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less.

  In the amorphous resin A, the amount of the addition polymerization resin segment is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, from the viewpoint of further improving the image density of the printed matter. Still more preferably, it is 25 mass% or more, More preferably, it is 35 mass% or more, Preferably it is 60 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 45 mass% or less.

  In the amorphous resin A, the amount of the structural unit derived from both reactive monomers is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more. And preferably it is 10 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 3 mass% or less.

  The total amount of the structural component derived from the hydrocarbon wax W1, the polyester resin segment, the addition polymerization resin segment, and the structural unit derived from both reactive monomers is preferably 80% by mass or more in the amorphous resin A. Preferably it is 90 mass% or more, More preferably, it is 93 mass% or more, More preferably, it is 95 mass% or more, and it is 100 mass% or less, Preferably it is 99 mass% or less.

  The above amount is calculated based on the ratio of the amount of the raw material monomer of the polyester resin segment, the addition polymerization resin segment, the bireactive monomer, and the radical polymerization initiator, and excludes the amount of dehydration due to polycondensation in the polyester resin segment. When a radical polymerization initiator is used, the mass of the radical polymerization initiator is calculated by including it in the addition polymerization resin segment.

(Manufacture of amorphous resin A)
The amorphous resin A is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component in the presence of a hydrocarbon wax W1 having a hydroxyl group or a carboxy group.
If necessary, an esterification catalyst such as di (2-ethylhexanoic acid) tin (II), dibutyltin oxide, titanium diisopropylate bistriethanolamate is added to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. 0.01 parts by mass or more and 5 parts by mass or less, 0% of the esterification promoter such as gallic acid (same as 3,4,5-trihydroxybenzoic acid) is 100 parts by mass with respect to 100 parts by mass of the alcohol component and the carboxylic acid component. Polycondensation may be performed using 0.001 part by mass or more and 0.5 part by mass or less.
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 230 ° C or lower. The polycondensation may be performed in an inert gas atmosphere.

When the amorphous resin A has an addition polymerization type resin segment, for example, the step A of the polycondensation reaction with the alcohol component and the carboxylic acid component, and the addition polymerization reaction with the raw material monomer and the both reactive monomers of the addition polymerization resin segment You may manufacture by the method containing process B.
Step B may be performed after step A, step A may be performed after step B, or step A and step B may be performed simultaneously.
In Step A, a part of the carboxylic acid component is subjected to a polycondensation reaction, and then Step B is performed. Then, the reaction temperature is increased again, and the remainder of the polyvalent carboxylic acid component is added to the polymerization system. A method of further proceeding the condensation reaction and, if necessary, the reaction with both reactive monomers is more preferable.

The conditions for the polycondensation reaction are as described above.
Examples of the radical polymerization initiator for the addition polymerization reaction include peroxides such as dibutyl peroxide, persulfates such as sodium persulfate, and azo compounds such as 2,2′-azobis (2,4-dimethylvaleronitrile). Is mentioned.
The amount of radical polymerization initiator used is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the raw material monomer.
The temperature of the addition polymerization reaction is preferably 110 ° C. or higher, more preferably 130 ° C. or higher, and preferably 220 ° C. or lower, more preferably 200 ° C. or lower, and further preferably 180 ° C. or lower.
In the addition polymerization reaction, a radical polymerization inhibitor of preferably 0.001 part by mass or more and 0.5 part by mass or less may be used as required with respect to 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. . Examples of the radical polymerization inhibitor include 4-tert-butylcatechol.

(Physical properties of amorphous resin A)
The softening point of the amorphous resin A is preferably 70 ° C. or higher, more preferably 90 ° C. or higher, and still more preferably 100 ° C. from the viewpoint of further improving the image density of the printed matter and the hot offset resistance. As described above, it is more preferably 110 ° C. or more, and preferably 140 ° C. or less, more preferably 135 ° C. or less, and further preferably 130 ° C. or less.

  The glass transition temperature of the amorphous resin A is preferably 30 ° C. or higher, more preferably 35 ° C. or higher, and still more preferably 40 from the viewpoint of further improving the image density of the printed material and the hot offset resistance. And is preferably 80 ° C. or lower, more preferably 70 ° C. or lower, and further preferably 65 ° C. or lower.

  From the viewpoint of further improving the image density of the printed matter, the acid value of the amorphous resin A is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 16 mgKOH / g or more, and preferably It is 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.

The softening point, glass transition temperature and acid value of the amorphous resin A 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. A value is calculated | required by the method as described in an Example.
In addition, when using 2 or more types of amorphous resin A in mixture, it is preferable that the softening point, glass transition temperature, and acid value which were obtained as those mixtures are in the above-mentioned range, respectively.

<Crystalline resin B>
Examples of the crystalline resin B include a crystalline polyester resin.
Crystalline polyester is a polycondensate of an alcohol component and a carboxylic acid component.

As the alcohol component, α, ω-aliphatic diol is preferable.
The carbon number of the α, ω-aliphatic diol is preferably 2 or more, more preferably 4 or more, still more preferably 6 or more, and preferably 16 or less, more preferably 14 or less, still more preferably 12 or less. is there.
Examples of the α, ω-aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol Can be mentioned. Among these, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol are preferable, and 1,10-decanediol is more preferable.

  The amount of α, ω-aliphatic diol is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more in the alcohol component, and It is 100 mol% or less, More preferably, it is 100 mol%.

  The alcohol component may contain another alcohol component different from the α, ω-aliphatic diol. Examples of other alcohol components include aliphatic diols other than α, ω-aliphatic diols such as 1,2-propylene glycol and neopentyl glycol; aromatic diols such as alkylene oxide adducts of bisphenol A; glycerin and penta Examples include trihydric or higher alcohols such as erythritol and trimethylolpropane. These alcohol components can be used alone or in combination of two or more.

As the carboxylic acid component, an aliphatic dicarboxylic acid is preferable.
The carbon number of the aliphatic dicarboxylic acid is preferably 4 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 14 or less, more preferably 12 or less.
Examples of the aliphatic dicarboxylic acid include fumaric acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Among these, sebacic acid and dodecanedioic acid are preferable, and sebacic acid is more preferable. These carboxylic acid components can be used alone or in combination of two or more.

  The amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and 100 It is less than mol%, and more preferably 100 mol%.

  The carboxylic acid component may contain another carboxylic acid component different from the aliphatic dicarboxylic acid. Examples of other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; and trivalent or higher polyvalent carboxylic acids. These carboxylic acid components can be used alone or in combination of two or more.

  The ratio of the carboxyl group of the carboxylic acid component to the hydroxyl group of the alcohol component [COOH group / OH group] is preferably 0.7 or more, more preferably 0.8 or more, and preferably 1.3 or less, more preferably Is 1.2 or less.

The crystalline resin B is obtained, for example, by polycondensation of an alcohol component and a carboxylic acid component.
The conditions for the polycondensation reaction are as shown in the method for producing the amorphous resin A described above.

(Physical properties of crystalline resin B)
The softening point of the crystalline resin B is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, from the viewpoint of improving the image density of the printed material. From the viewpoint of improving the offset property, it is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower.

  The melting point of the crystalline resin B is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 65 ° C. or higher, and preferably 100 ° C. or lower, more preferably, from the viewpoint of improving the image density of the printed matter. Is 90 ° C. or lower, more preferably 80 ° C. or lower.

  The acid value of the crystalline resin B is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, from the viewpoint of improving the dispersion stability of the resin particles Y described later. , Preferably 35 mgKOH / g or less, more preferably 30 mgKOH / g or less, and even more preferably 25 mgKOH / g or less.

The softening point, melting point, and acid value of the crystalline resin B 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. It is determined by the method described in the examples.
In addition, when using 2 or more types of crystalline resin B in mixture, it is preferable that the value of the softening point, melting | fusing point, and acid value which were obtained as those mixtures is in the said range, respectively.

<Wax D1 and Wax D2>
In step 1, two types of waxes, wax D1 and wax D2, are used. The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2.
Examples of the wax D1 and the wax D2 include hydrocarbon wax, ester wax, silicone wax, and fatty acid amide.
Examples of the hydrocarbon wax include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax, and sazol wax.
Examples of the ester wax include carnauba wax, montan wax, deoxidized wax thereof, and fatty acid ester wax. These can use 1 type (s) or 2 or more types.

As the wax D1, hydrocarbon wax and ester wax are preferable, hydrocarbon wax is more preferable, and paraffin wax is still more preferable.
The melting point Tm1 of the wax D1 is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, further preferably 70 ° C. or higher, and preferably 100 ° C. or lower, more preferably, from the viewpoint of further improving the image density of the printed matter. Is 90 ° C. or lower, more preferably 80 ° C. or lower.

As the wax D2, hydrocarbon wax and ester wax are preferable, hydrocarbon wax and carnauba wax are more preferable, hydrocarbon wax is more preferable, and Fischer-Tropsch wax is still more preferable.
The melting point Tm2 of the wax D2 is preferably 60 ° C. or higher, more preferably 70 ° C. or higher, further preferably 80 ° C. or higher, still more preferably 85 ° C. or higher, from the viewpoint of further improving the hot offset resistance. Preferably it is 110 degrees C or less, More preferably, it is 100 degrees C or less, More preferably, it is 95 degrees C or less.
The difference | Tm1−Tm2 | between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 is preferably 5 ° C. or higher, more preferably 8 ° C. or higher, from the viewpoint of further improving the image density and hot offset resistance of the printed matter. Preferably it is 10 degreeC or more, More preferably, it is 15 degreeC or more, Preferably it is 30 degrees C or less, More preferably, it is 25 degrees C or less, More preferably, it is 20 degrees C or less.

<Colorant>
Examples of the colorant include pigments and dyes, and pigments are preferable from the viewpoint of improving the image density of printed matter.
Examples of the pigment include a cyan pigment, a yellow pigment, a magenta pigment, and a black pigment. The cyan pigment is preferably a phthalocyanine pigment, and more preferably copper phthalocyanine. The yellow pigment is preferably a monoazo pigment, an isoindoline pigment, or a benzimidazolone pigment. The magenta pigment is preferably a soluble azo pigment such as a quinacridone pigment or a BONA lake pigment, or an insoluble azo pigment such as a naphthol AS pigment. The black pigment is preferably carbon black.
Examples of the dye include an acridine dye, an azo dye, a benzoquinone dye, an azine dye, an anthraquinone dye, an indigo dye, a phthalocyanine dye, and an aniline black dye.
A coloring agent can be used individually or in combination of 2 or more types.

<Resin particles X>
The resin particle X contains at least the amorphous resin A.
The resin particle X may contain a crystalline resin B, a colorant, a wax D1, and a wax D2.
The resin particles X are obtained as an aqueous dispersion of the resin particles X by dispersing the amorphous resin A and, if necessary, optional components such as a crystalline resin B and a colorant in an aqueous medium.
Dispersion can be carried out using a known method, but it is preferably dispersed by a phase inversion emulsification method. Examples of the phase inversion emulsification method include a method of phase inversion emulsification by adding an aqueous medium to an organic solvent solution of a resin or a molten resin.

The organic solvent used for phase inversion emulsification is not particularly limited as long as the resin is dissolved, and examples thereof include methyl ethyl ketone.
It is preferable to add a neutralizing agent such as a basic substance to the organic solvent solution. Examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; nitrogen-containing basic substances such as ammonia, trimethylamine and diethanolamine.
The use equivalent (mol%) of the neutralizing agent with respect to the acid groups of the resin is preferably 10 mol% or more, more preferably 30 mol% or more, and preferably 150 mol% or less, more preferably 120 mol% or less. More preferably, it is 100 mol% or less.
In addition, the use equivalent (mol%) of a neutralizing agent can be calculated | required by a following formula. In addition, the usage equivalent of a neutralizing agent is synonymous with a neutralization degree, when it is 100 mol% or less.
Equivalent (mole%) of neutralizing agent = [{added mass of neutralizing agent (g) / equivalent of neutralizing agent} / [{weighted average acid value of resin constituting resin particle X (mgKOH / g) × Mass of resin constituting resin particle X (g)} / (56 × 1000)]] × 100

While stirring the organic solvent solution or the molten resin, the aqueous medium is gradually added to invert the phase.
From the viewpoint of improving the dispersion stability of the resin particles X, the organic solvent solution temperature when adding the aqueous medium is preferably not less than the glass transition temperature of the resin constituting the resin particles X, more preferably not less than 50 ° C., and still more preferably Is 60 ° C. or higher, more preferably 70 ° C. or higher, and preferably 85 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 75 ° C. or lower.
After the phase inversion emulsification, the organic solvent may be removed from the obtained dispersion by distillation or the like, if necessary.

The volume median particle size (D ₅₀ ) of the resin particles X in the dispersion is preferably 0.05 μm or more, more preferably 0.08 μm or more, from the viewpoint of obtaining a toner capable of obtaining a high-quality image. The thickness is preferably 0.8 μm or less, more preferably 0.4 μm or less, and still more preferably 0.3 μm or less.
The coefficient of variation (hereinafter also simply referred to as “CV value”) (%) of the particle size distribution of the resin particles X is preferably 5% or more, more preferably from the viewpoint of improving the productivity of the dispersion of the resin particles X. From the viewpoint of obtaining a toner capable of obtaining a high-quality image, it is preferably 50% or less, more preferably 40% or less, and still more preferably 35% or less.
The volume median particle size (D ₅₀ ) and the CV value are determined by the method described in the examples described later.

<Resin particles Y>
The crystalline resin B may be contained in a resin particle Y different from the resin particle X. In that case, in Step 1, the resin particles X and the resin particles Y are aggregated in an aqueous solvent in the presence of the wax D1, the wax D2, and the colorant to obtain aggregated particles.
The resin particles Y are obtained, for example, by the same method as the resin particles X described above. The volume median particle size (D ₅₀₎ and CV value is the same as the above-mentioned examples.

<Wax D1 particles and wax D2 particles>
The wax D1 is preferably added as wax D1 particles. Similarly, the wax D2 is preferably added as wax D2 particles. Hereinafter, description common to the wax D1 and the wax D2 will be simply referred to as “wax”.
The method for producing wax particles is, for example, a method in which a wax and an aqueous medium are dispersed using a disperser in the presence of a surfactant or the like at a temperature equal to or higher than the melting point of the wax, the wax, the resin particles Z, and an aqueous And a method of dispersing the medium at a temperature equal to or higher than the melting point of the wax using a disperser. Of these, the latter method is preferred. By preparing wax particles using the wax and the resin particles Z, the wax particles are stabilized by the resin particles Z, and the wax can be dispersed in the aqueous medium without using a surfactant. The wax particle dispersion is considered to have a structure in which a large number of resin particles Z adhere to the surface of the wax particles.

Examples of the disperser used for dispersing the wax include a homogenizer, an ultrasonic disperser, and a high-pressure disperser.
Examples of the ultrasonic disperser include an ultrasonic homogenizer. Examples of the commercially available products include “US-150T”, “US-300T”, “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.), “SONIFIER (registered trademark) 4020-400”, “SONIFIER (registered trademark). ) 4020-800 "(manufactured by Branson).
Examples of commercially available high-pressure dispersers include a high-pressure wet atomizer “Nanomizer (registered trademark) NM2-L200-D08” (manufactured by Yoshida Kikai Kogyo Co., Ltd.).

The resin constituting the resin particles Z in which the wax is dispersed is preferably a polyester resin, and more preferably a polyester resin segment and an addition polymerization resin segment from the viewpoint of improving the dispersibility of the wax in the aqueous medium. A composite resin.
The polyester resin segment and the addition polymerization resin segment of the composite resin are the same as those exemplified for the amorphous resin A described above.
The softening point of the composite resin is preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and preferably 140 ° C. or lower, more preferably 120 ° C. or lower, and even more preferably 100 ° C. or lower.
The other preferred ranges of the resin characteristics of the composite resin, the preferred examples of the raw material monomers constituting the resin, and the like are the same as the examples shown for the amorphous resin A. The dispersion of resin particles Z can be obtained, for example, by the above-described phase inversion emulsification method.

  The solid content concentration of the wax particle dispersion is preferably 5% by mass or more, more preferably 10% by mass or more, from the viewpoint of improving the productivity of the toner and the dispersion stability of the wax particle dispersion. The amount is preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less.

The volume median particle size (D ₅₀ ) of the wax particles is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably from the viewpoint of obtaining uniform aggregated particles and improving the image density of the printed material. It is 0.3 μm or more, and preferably 1 μm or less, more preferably 0.8 μm or less, and further preferably 0.6 μm or less.

The CV value of the wax particles is preferably 10% or more, more preferably 25% or more from the viewpoint of improving toner productivity, and preferably 50% or less from the viewpoint of obtaining uniform aggregated particles. Preferably it is 45% or less, More preferably, it is 42% or less.
The volume median particle size (D ₅₀ ) and CV value of the wax particles are specifically determined by the method described in the examples.

<Colorant particles>
The colorant is preferably added as colorant particles.
Examples of the method for producing the colorant particles include a method in which the colorant and the aqueous medium are dispersed using a disperser in the presence of a surfactant or the like. Examples of the disperser include the above-described homogenizer and ultrasonic disperser. A preferred embodiment of the aqueous medium is the same as the aqueous medium used for the aqueous dispersion of the resin particles X.
The surfactant is preferably a compound represented by the following formula (1) (hereinafter also simply referred to as “Compound 1”). That is, the colorant particles are preferably obtained by mixing a colorant and a compound represented by the following formula (1).

[Wherein, R ¹ is an alkanediyl group having 1 to 12 carbon atoms, m represents an average number of substitutions, the value of m is 1 to 4 and R ² is a hydrogen atom or a methyl group, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of added moles of alkylene oxide, and the value of n is 5 or more and 100 or less. ]

R ¹ is preferably an alkanediyl group having 1 to 4 carbon atoms, more preferably an alkanediyl group having 1 to 2 carbon atoms. The plurality of R ¹ may be the same or different but are preferably the same.
Examples of R ¹ include a methanediyl group (also referred to as a methylene group), an ethane-1,1-diyl group, and an ethane-1,2-diyl group (hereinafter, as a comprehensive concept, “ethanediyl group” or “ethylene group”). Propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,1-diyl group, butane-1,2-diyl group, butane A -1,3-diyl group, a butane-1,4-diyl group, and a butane-2,3-diyl group can be mentioned. Among these, a methanediyl group and an ethanediyl group are preferable, and an ethanediyl group is more preferable.
The value of m is preferably 2 or more and 3 or less.
R ² is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
A ¹ is preferably an ethylene group, or an ethylene group and a propylene group, and more preferably an ethylene group.
The value of n is preferably 6 or more, more preferably 9 or more, still more preferably 11 or more, still more preferably 12 or more, and is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less. is there.

Examples of the compound 1 include polyoxyethylene (styrenated phenyl) ether, polyoxyethylene (distyrenated phenyl) ether, polyoxyethylene (distyrenated methylphenyl) ether, polyoxyethylene (tristyrenated phenyl) ether, poly Oxypropylene (styrenated phenyl) ether, polyoxypropylene (distyrenated phenyl) ether, polyoxypropylene (distyrenated methylphenyl) ether, polyoxypropylene (tristyrenated phenyl) ether, polyoxyethylene (benzylphenyl) ether, Polyoxyethylene (dibenzylphenyl) ether, polyoxyethylene (tribenzylphenyl) ether, polyoxypropylene (benzylphenyl) ether, poly Carboxymethyl propylene (dibenzyl) ether, polyoxypropylene (tribenzyl phenyl) ether.
Among these, polyoxyethylene (distyrenated phenyl) ether is preferable from the viewpoint of improving the image density of the printed matter. The average number of added moles of the polyoxyethylene group is preferably in the range of n described above.

  Examples of commercially available products of Compound 1 include polyoxyethylene (distyrenated phenyl) ether “Emulgen A-60” (average addition mole number 13, manufactured by Kao Corporation), polyoxyethylene (distyrenated phenyl) ether “Emulgen A” -90 "(average added mole number 18, produced by Kao Corporation), polyoxyethylene (tribenzylphenyl) ether" Emulgen B-66 "(average added mole number 15, produced by Kao Corporation).

  When mixing the colorant and the compound 1, the amount of the compound 1 is preferably 10 parts by mass or more, more preferably 20 parts by mass or more with respect to 100 parts by mass of the colorant, from the viewpoint of further improving the image density of the printed matter. More preferably, it is 25 parts by mass or more, more preferably 30 parts by mass or more, and preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and still more preferably 40 parts by mass or less.

For mixing the colorant and the compound 1, for example, the colorant, the compound 1, and the aqueous medium are preferably mixed using a disperser to disperse the colorant. By dispersing the colorant with Compound 1 to obtain colorant particles, the affinity between the colorant and the composite resin A is increased during aggregation and fusion, and the image density of the printed matter can be further improved. .
Examples of the disperser include a homomixer, a homogenizer, and an ultrasonic disperser. Examples of suitable commercially available dispersers include homomixer “TKAGI HOMOMIXER 2M-03” (manufactured by Tokushu Kika Kogyo Co., Ltd.), high-pressure homogenizer “Microfluidizer M-110EH” (manufactured by Microfluidics), Ultra A sonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusho Co., Ltd.) can be mentioned.

  The solid content concentration of the colorant particle dispersion is preferably 5% by mass or more, more preferably 10% by mass from the viewpoint of improving the productivity of the toner and the dispersion stability of the colorant particle dispersion. % Or more, more preferably 15% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.

The volume median particle size (D ₅₀ ) of the colorant particles is preferably 0.050 μm or more, more preferably 0.080 μm or more, and further preferably 0.10 μm or more from the viewpoint of obtaining a toner capable of obtaining a high-quality image. And preferably 0.50 μm or less, more preferably 0.30 μm or less, and still more preferably 0.20 μm or less.

The CV value of the colorant particles is preferably 10% or more, more preferably 25% or more from the viewpoint of improving toner productivity, and preferably 50% or less from the viewpoint of obtaining uniform aggregated particles. More preferably, it is 45% or less, More preferably, it is 42% or less.
The volume median particle size (D ₅₀ ) and CV value of the colorant particles are specifically determined by the method described in the examples.

<Conditions for Step 1>
In step 1, the resin particles X are preferably mixed with the wax D1 particles, the wax D2 particles, and the colorant particles in an aqueous medium and aggregated to obtain aggregated particles.
An aqueous dispersion of resin particles X, a dispersion of wax D1 particles, a dispersion of wax D2 particles, a dispersion of colorant particles, and other optional components such as a surfactant, if necessary, are mixed in an aqueous medium. Thus, it is preferable to obtain a mixed dispersion. Then, the particles in the mixed dispersion liquid are aggregated to obtain aggregated particles.

The amount of each component in the mixed dispersion in Step 1 is as follows.
The blending amount of the resin particles X is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more from the viewpoint of improving the image density of the printed matter. From the viewpoint of obtaining aggregated particles having a desired particle size, it is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.

The blending amount of the amorphous resin A is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and preferably 95% by mass or less in the binder resin. Preferably it is 90 mass% or less, More preferably, it is 80 mass% or less.
The blending amount of the crystalline resin B is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less in the binder resin. Is 40% by mass or less, more preferably 30% by mass or less.
The total amount of the amorphous resin A and the crystalline resin B in the binder resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and still more preferably 98% by mass. % Or more and 100 mass% or less.

  The blending amount of the wax D1 is preferably 2 parts by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. More preferably, it is 6 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

  The blending amount of the wax D2 is preferably 2 parts by mass or more, more preferably 5 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. More preferably, it is 6 parts by mass or more, and preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and still more preferably 10 parts by mass or less.

  The total blending amount of the wax D1 and the wax D2 is preferably 4 parts by mass or more, more preferably 100 parts by mass with respect to 100 parts by mass of the binder resin from the viewpoint of improving the image density of the printed matter and improving the hot offset resistance. Is 10 parts by mass or more, more preferably 12 parts by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.

  The mass ratio of the wax D1 and the wax D2 (wax D1 / wax D2) is preferably 0.1 or more, more preferably 0.3 or more, from the viewpoint of further improving the image density and hot offset resistance of the printed matter. Preferably it is 0.5 or more, and preferably 3.5 or less, more preferably 2 or less, and still more preferably 1.5 or less.

  The blending amount of the colorant is preferably 4 parts by mass or more, more preferably 10 parts by mass with respect to 100 parts by mass of the binder resin, from the viewpoint of improving the image density of the printed material and the hot offset resistance. As mentioned above, More preferably, it is 12 mass parts or more, Preferably it is 30 mass parts or less, More preferably, it is 20 mass parts or less, More preferably, it is 15 mass parts or less.

  The mixing temperature of each dispersion is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, from the viewpoint of obtaining aggregated particles having a desired particle size by controlling aggregation. Is 40 ° C. or lower, more preferably 30 ° C. or lower.

<Flocculant>
From the viewpoint of efficiently aggregating each particle, it is preferable to add an aggregating agent.
As the flocculant, for example, a cationic surfactant of a quaternary ammonium salt, an organic flocculant such as polyethyleneimine; an inorganic metal salt such as sodium sulfate, sodium nitrate, sodium chloride, calcium chloride, calcium nitrate; ammonium sulfate, Examples include inorganic ammonium salts such as ammonium chloride and ammonium nitrate; inorganic flocculants such as divalent or higher metal complexes. From the viewpoint of improving the cohesiveness and obtaining uniform aggregated particles, monovalent to pentavalent inorganic flocculants are preferred, monovalent to divalent inorganic metal salts and inorganic ammonium salts are more preferred, and inorganic ammonium salts are preferred. More preferably, ammonium sulfate is even more preferable.

  Using a flocculant, for example, 5 to 50 parts by mass of a flocculant with respect to 100 parts by mass of the binder resin is added to a mixed dispersion containing resin particles X of 0 to 40 ° C. X is aggregated in an aqueous medium to obtain aggregated particles. Furthermore, from the viewpoint of promoting aggregation, it is preferable to increase the temperature of the dispersion after adding the aggregating agent.

<Aggregated particles>
The volume median particle size (D ₅₀ ) of the aggregated particles 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 8 μm or less, and even more preferably 6 μm. It is as follows. The volume-median particle size of the aggregated particles is determined by the method described in the examples described later.

  After obtaining the agglomerated particles, resin particles containing an amorphous resin may be further added to obtain agglomerated particles obtained by adhering the resin particles to the agglomerated particles. Examples of the amorphous resin include amorphous polyester which is a polycondensate of the alcohol component and the carboxylic acid component exemplified in the amorphous resin A described above. Through this step, toner particles having a core-shell structure are obtained.

In step 1, the aggregation may be stopped when the aggregated particles have grown to an appropriate particle size as a toner.
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.

<Aggregation stop agent>
Examples of the aggregation terminator include a surfactant. As the surfactant, an anionic surfactant is more preferable. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate, alkyl ether sulfate, and polyoxyalkylene alkyl ether sulfate. An aggregation terminator can be used individually or in combination of 2 or more types. The aggregation terminator may be added as an aqueous solution.
The addition amount of the aggregation terminator is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, with respect to 100 parts by mass of the binder resin, from the viewpoint of reliably preventing unnecessary aggregation. From the viewpoint of reducing residual toner, it is preferably 15 parts by mass or less, more preferably 10 parts by mass or less.

  The temperature at which the aggregation terminator is added is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, still more preferably 50 ° C. or higher, and preferably 80 ° C. or lower, from the viewpoint of improving toner productivity. Preferably it is 70 degrees C or less, More preferably, it is 65 degrees C or less.

[Step 2]
Step 2 is a step of fusing the aggregated particles obtained in Step 1.
In the aggregated particles, the particles that are mainly physically attached to each other are fused and united to form toner particles.

The temperature T at which the agglomerated particles are fused in Step 2 is not less than a temperature 10 ° C. lower than the melting point Tm1 of the wax D1 and 10 ° C. than the melting point Tm2 of the wax D2 from the viewpoint of obtaining a toner exhibiting the image density and hot offset resistance of the printed matter. From the viewpoint of further improving the image density of the printed material, the temperature is preferably 5 ° C. lower than the melting point Tm1 of the wax D1, more preferably 3 ° C. lower than the melting point Tm1 of the wax D1, more preferably Is at least 1 ° C. lower than the melting point Tm1 of the wax D1, more preferably at least 1 ° C. higher than the melting point Tm1 of the wax D1, and from the viewpoint of further improving the hot offset resistance, preferably the melting point of the wax D2 Below 5 ° C higher than Tm2, more preferably 3 ° C above melting point Tm2 of wax D2 A temperature lower than the melting point Tm2 of the wax D2, more preferably a temperature lower than the melting point Tm2 of the wax D2, even more preferably a temperature lower than the melting point Tm2 of the wax D2, even more preferably a temperature lower than 5 ° C. The temperature is 10 ° C. or lower than the melting point Tm2 of the wax D2.
The temperature T means the temperature around the aggregated particles. For example, the temperature T means a temperature measured by inserting a thermometer into the dispersion to be fused.

  In step 2, the temperature T at which the aggregated particles are fused is preferably higher than the glass transition temperature of the amorphous resin A from the viewpoint of improving the fusibility of the aggregated particles and improving the productivity of the toner. 2 ° C higher temperature or higher, more preferably 4 ° C higher temperature or higher, more preferably 6 ° C higher temperature or higher, and preferably 40 ° C higher than the glass transition temperature of the amorphous resin A, more preferably The temperature is not higher than 30 ° C, more preferably not higher than 25 ° C.

The volume median particle size (D ₅₀ ) of the toner particles in the dispersion obtained by fusing in Step 2 is preferably from the viewpoint of further improving the image density of the printed material and from the viewpoint of further improving the hot offset resistance. It is 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, and further preferably 6 μm or less.
The degree of circularity of the toner particles in the dispersion obtained by fusing in Step 2 is preferably 0.955 or more, more preferably 0.960 or more, and still more preferably 0.00 from the viewpoint of further improving the image density of the printed matter. 965 or more, and preferably 0.990 or less, more preferably 0.985 or less, and still more preferably 0.980 or less.

[Post-treatment process]
A post-processing step may be performed after step 2.
Examples of the post-treatment step include a step of separating toner particles from the dispersion liquid obtained in step 2.
Separation of toner particles is performed by solid-liquid separation such as suction filtration.
The toner particles are preferably further washed after solid-liquid separation. The toner particles are preferably washed with an aqueous medium below the cloud point of the surfactant from the viewpoint of removing the added surfactant. The washing is preferably performed a plurality of times.
It is preferable to dry after washing. Examples of the drying method include a vacuum low temperature drying method, a vibration type fluidized drying method, a spray drying method, a freeze drying method, and a flash jet method.

[toner]
Toner particles are obtained by the above process.
The toner particles can be used as the toner as they are, but it is preferable to use the toner particles added to the surface of the toner particles using a fluidizing agent or the like as an external additive as will be described later.

The toner includes a component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a colorant. The content of each component in the toner is the same as the preferred range of the amount of each component in Step 1 described above.
The toner is, for example, an electrostatic image developing toner. The toner for developing an electrostatic image is used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

The volume median particle size (D ₅₀ ) of the toner particles is preferably 2 μm or more from the viewpoint of improving the productivity of the toner, the image density of the printed matter, and the hot offset resistance. Is 3 μm or more, more preferably 4 μm or more, and preferably 10 μm or less, more preferably 8 μm or less, still more preferably 6 μm or less.
The CV value of the toner particles is preferably 12% or more, more preferably 14% or more, and further preferably 16% or more from the viewpoint of improving the productivity of the toner. Preferably it is 30% or less, More preferably, it is 26% or less.

Examples of the external additive include inorganic fine particles such as hydrophobic silica, titanium oxide fine particles, alumina fine particles, cerium oxide fine particles, and carbon black; polymer fine particles such as polycarbonate, polymethyl methacrylate, and silicone resin. Among these, hydrophobic silica is preferable.
The addition amount of the external additive is preferably 1 part by mass or more, more preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, and preferably 10 parts by mass or less with respect to 100 parts by mass of the toner particles. More preferably, it is 7 parts by mass or less, and still more preferably 5 parts by mass or less.

  The toner can be used as a one-component developer or a two-component developer mixed with a carrier.

  Each property value was measured by the following method. Various evaluations were performed by the following methods.

[Measurement]
[Acid value and hydroxyl value of resin and wax]
The acid value of the resin was measured according to the neutralization titration method described in JIS K 0070: 1992. However, the measurement solvent was chloroform.

[Softening point, crystallinity index, melting point and glass transition temperature of resin]
(1) Softening point Using a flow tester “CFT-500D” (manufactured by Shimadzu Corporation), a 1 g sample was heated at a temperature rising 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) Crystallinity Index Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample is weighed into an aluminum pan, and the temperature lowering rate from room temperature (20 ° C.) is 10 ° C. / Cooled to 0 ° C. in min. Next, the sample was allowed to stand still for 1 minute, and then heated to 180 ° C. at a heating rate of 10 ° C./min, and the amount of heat was measured. Of the observed endothermic peaks, the temperature of the peak with the largest peak area is defined as the maximum endothermic peak temperature (1), and (softening point (° C)) / (maximum endothermic peak temperature (1) (° C)), The crystallinity index was determined.
(3) Melting point and glass transition temperature Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and the temperature Then, it was cooled to 0 ° C. at a temperature lowering rate of 10 ° C./min. Next, the sample was heated at a temperature rising rate of 10 ° C./min, and the heat quantity was measured. Among the observed endothermic peaks, the temperature of the peak having the maximum peak area was defined as the maximum endothermic temperature (2). In the case of a crystalline resin, the peak temperature was taken as the melting point.
In the case of an amorphous resin, when a peak is observed, the temperature of the peak is measured. When a step is observed without a peak being observed, the tangent indicating the maximum slope of the curve of the step and the step The glass transition temperature was defined as the temperature at the intersection with the base line extension on the low temperature side.

[Melting point of wax]
Using a differential scanning calorimeter “Q100” (manufactured by TA Instruments Japan Co., Ltd.), 0.02 g of a sample was weighed into an aluminum pan, heated to 200 ° C., and then cooled down from 200 ° C. to 10 ° C./min. At 0 ° C. Next, the sample was heated at a temperature rising rate of 10 ° C./min, the amount of heat was measured, and the maximum peak temperature of endotherm was taken as the melting point.

[Number average molecular weight (Mn) of wax]
The number average molecular weight (Mn) was measured by the gel permeation chromatography (GPC) method shown below.
(1) Preparation of sample solution The sample was dissolved in chloroform at 25 ° C. so that the concentration was 0.5 g / 100 mL, and this solution was then added to a fluororesin filter “DISMIC, 25JP” (ADVANTEC) having a pore size of 0.2 μm. To obtain a sample solution.
(2) Measurement Using the following measuring device and analytical column, flow chloroform at an eluent at a flow rate of 1 mL / min, stabilize the column in a constant temperature bath at 40 ° C., and inject 100 μL of the sample solution therein. The molecular weight was measured. The molecular weight (weight average molecular weight Mw, number average molecular weight Mn) of the sample is the type name (Mw) of several types of monodisperse polystyrene “TSKgel standard polystyrene”: “A-500 (5.0 × 10 ² )”, “A- 1000 (1.01 × 10 ³ ) ”,“ A-2500 (2.63 × 10 ³ ) ”,“ A-5000 (5.97 × 10 ³ ) ”,“ F-1 (1.02 × 10 ⁴ ) ” ) "," F-2 (1.81 x 10 ⁴ ) "," F-4 (3.97 x 10 ⁴ ) "," F-10 (9.64 x 10 ⁴ ) "," F-20 ( 1.90 × 10 ⁵ ) ”,“ F-40 (4.27 × 10 ⁵ ) ”,“ F-80 (7.06 × 10 ⁵ ) ”,“ F-128 (1.09 × 10 ⁶ ) ” The above calculation was performed based on a calibration curve prepared in advance using “Tosoh Co., Ltd.” as a standard sample.
-Measuring device: "HLC-8220GPC" (manufactured by Tosoh Corporation)
Analytical columns: “GMHXL” and “G3000HXL” (above Tosoh Corporation)

[Volume Median Particle Size (D ₅₀ ) and CV Value of Resin Particles, Colorant Particles, and Wax 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 ) and the volume average particle size were measured at a concentration at which the absorbance was in an appropriate range. The CV value was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Solid content concentration of resin particle dispersion, colorant particle dispersion, and wax particle dispersion]
Using an infrared moisture meter “FD-230” (manufactured by Kett Scientific Laboratory Co., Ltd.), a measurement sample 5 g was dried at a temperature of 150 ° C., a measurement mode 96 (monitoring time 2.5 minutes, fluctuation range of moisture content 0.05% ), Moisture (mass%) was measured. The solid content concentration was calculated according to the following formula.
Solid content concentration (% by mass) = 100-water content (% by mass)

[Volume-median particle size of the aggregated particles _{(D 50)]}
(1) Measuring device: “Coulter Multisizer (registered trademark) III” (manufactured by Beckman Coulter, Inc.)
(2) Analysis software: “Multisizer (registered trademark) III version 3.51” (manufactured by Beckman Coulter, Inc.)
(3) Measurement conditions:
Electrolyte: “Isoton (registered trademark) II” (manufactured by Beckman Coulter, Inc.)
・ Aperture diameter: 50μm
By adding the sample dispersion to 100 mL of the above electrolyte, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured again. The unit particle size (D ₅₀ ) was determined.

[Volume Median Particle Size (D ₅₀ ) and CV Value of Toner Particles]
The measuring device, analysis software, aperture diameter, and electrolyte solution were the same as the volume median particle size (D ₅₀ ) of the aggregated particles.
(1) Sample dispersion polyoxyethylene lauryl ether “Emalgen (registered trademark) 109P” (manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance) = 13.6) was dissolved in the electrolyte solution, and the concentration was 5% by mass. A dispersion was obtained.
To 10 mL of the dried toner particle measurement sample is added to 5 mL of the above dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. Thus, a sample dispersion was prepared.
(2) Measurement conditions: After adjusting the particle size of 30,000 particles to a concentration that can be measured in 20 seconds by adding the sample dispersion to 100 mL of the electrolytic solution, 30,000 particles are measured, The volume median particle size (D ₅₀ ) and the volume average particle size were determined from the particle size distribution.
The CV value (%) was calculated according to the following formula.
CV value (%) = (standard deviation of particle size distribution / volume average particle size) × 100

[Evaluation]
[Evaluation of toner high-temperature fixability (hot offset resistance)]
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.30 ± 0. A solid image of 0.01 mg / cm ² was output without being fixed at a length of 50 mm, leaving a margin of 5 mm from the top edge of the A4 paper.
Next, the same printer having a temperature-variable fixing device was prepared, the temperature of the fixing device was set to 130 ° C., and the toner was fixed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction to obtain a printed matter. When the temperature of the fixing device was 130 ° C., it was visually confirmed that neither cold offset nor hot offset occurred.
In the same manner, the temperature of the fixing device was raised from 130 ° C. to 5 ° C. to fix the toner to obtain a printed matter, and the occurrence of hot offset was visually confirmed. This test was conducted up to the temperature at which hot offset occurred.
The cold offset refers to a phenomenon in which the toner on the unfixed image is not sufficiently melted or the releasability is not good and the toner adheres to the fixing roller when the fixing temperature is low. On the other hand, hot offset means that when the fixing temperature is high, the viscoelasticity of the toner on the unfixed image is lowered, or the releasability is not good at high temperature, so that the toner adheres to the fixing roller. Refers to the phenomenon. The occurrence of cold offset or hot offset can be judged by whether or not toner adheres to the paper again when the fixing roller makes a round. In this test, whether toner adheres to the area 87 mm from the top of the solid image. Judged by no.
The hot offset occurrence temperature refers to a temperature at which hot offset starts to occur. Here, the maximum temperature at which a hot offset does not occur at a temperature 5 ° C. lower than the hot offset occurrence temperature is defined as the hot offset occurrence temperature.
In the evaluation of the hot offset occurrence temperature, a difference in evaluation temperature of 5 ° C. clearly shows a difference in toner fixability.

[Image density of printed matter]
Using a commercially available printer “Microline (registered trademark) 5400” (manufactured by Oki Data Corporation) on high-quality paper “J paper A4 size” (manufactured by Fuji Xerox Co., Ltd.), the toner adhesion amount on the paper is 0.30 mg / cm. ^A solid image of ² was output.
Next, the temperature of the fixing device was set to 130 ° C., and the toner was fixed at a speed of 1.5 seconds per sheet in the A4 longitudinal direction to obtain a printed matter.
30 sheets of high quality paper “Excellent White Paper A4 Size” (Oki Data Co., Ltd.) was laid under the printed material, and the reflected image density of the solid image portion of the printed material was measured using a colorimeter “SpectroEye” (manufactured by GretagMacbeth, Hikari Shooting conditions: standard light source D50, observation field of view 2 °, density standard DINNB, absolute white standard), and measured values of 10 arbitrary points on the image were averaged to obtain an image density. The larger the value, the better the image density.

[Production of resin]
Production Example A1 (Production of Amorphous Resin A-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3268 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1085 g of terephthalic acid, Nitrogen atmosphere containing 30 g of di (2-ethylhexanoic acid) tin (II), 3 g of 3,4,5-trihydroxybenzoic acid, and 394 g of hydrocarbon wax W1 “Paracol 6490” (manufactured by Nippon Seiwa Co., Ltd.) Under stirring, the temperature was raised to 235 ° C. and held at 235 ° C. for 8 hours, and then the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture of styrene 2138g, stearyl methacrylate 534g, acrylic acid 108g, and dibutyl peroxide 321g was dripped over 3 hours in the state which cooled to 155 degreeC and hold | maintained at 155 degreeC. Then, after maintaining at 155 ° C. for 30 minutes, the temperature was raised to 200 ° C., and the pressure in the flask was further lowered and maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it is cooled to 190 ° C., 70 g of fumaric acid, 269 g of trimellitic anhydride and 2.5 g of 4-tert-butylcatechol are added, and the temperature is raised to 210 ° C. at 10 ° C./hr. Thereafter, the reaction was carried out at 8 kPa to the desired softening point to obtain amorphous resin A-1. The physical properties are shown in Table 1.

Production Examples A2, A4 to A6 (Production of Amorphous Resin A-2, A-4 to A-6)
Amorphous resins A-2 and A-4 to A-6 were obtained in the same manner as in Production Example A1, except that the raw material composition was changed as shown in Table 1. The physical properties are shown in Table 1.

Production Example A3 (Production of Amorphous Resin A-3)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 4771 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1923 g of terephthalic acid, 30 g of di (2-ethylhexanoic acid) tin (II), 3 g of 3,4,5-trihydroxybenzoic acid, and 349 g of hydrocarbon wax W1 “Paracol 6490” (manufactured by Nippon Seiwa Co., Ltd.) are placed under a nitrogen atmosphere. While stirring, the temperature was raised to 230 ° C., held at 230 ° C. for 8 hours, cooled to 180 ° C., added with 73 g of dodecenyl succinic anhydride and 314 g of trimellitic anhydride, and increased to 220 ° C. at 10 ° C./hr. The temperature was raised, then the pressure in the flask was lowered, and the reaction was carried out at 8 kPa to the desired softening point to obtain amorphous resin A-3. The physical properties are shown in Table 1.

Production Example A7 (Production of Amorphous Resin A-7)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3290 g of a polyoxypropylene (2.2) adduct of bisphenol A, 1092 g of terephthalic acid, Add 30 g of di (2-ethylhexanoic acid) tin (II) and 3 g of 3,4,5-trihydroxybenzoic acid, heat to 235 ° C. with stirring in a nitrogen atmosphere, and hold at 235 ° C. for 8 hours. After that, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture of styrene 2152g, stearyl methacrylate 538g, acrylic acid 108g, and dibutyl peroxide 323g was dripped over 3 hours in the state which cooled to 155 degreeC and was hold | maintained at 155 degreeC. Then, after maintaining at 155 ° C. for 30 minutes, the temperature was raised to 200 ° C., and the pressure in the flask was further lowered and maintained at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, it is cooled to 190 ° C., 71 g of fumaric acid, 271 g of trimellitic anhydride and 2.5 g of 4-tert-butylcatechol are added, and the temperature is raised to 210 ° C. at 10 ° C./hr. Thereafter, the pressure in the flask was lowered and the reaction was carried out at 4 kPa to the desired softening point to obtain amorphous resin A-7. The physical properties are shown in Table 1.

Production Example A8 (Production of Amorphous Resin A-8)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 4313 g of a polyoxypropylene (2.2) adduct of bisphenol A, 818 g of terephthalic acid, 727 g of succinic acid, 30 g of di (2-ethylhexanoic acid) tin (II), and 3.0 g of 3,4,5-trihydroxybenzoic acid were added, and the temperature was raised to 235 ° C. with stirring in a nitrogen atmosphere. After holding at 235 ° C. for 5 hours, the pressure in the flask was lowered and held at 8 kPa for 1 hour. Then, after returning to atmospheric pressure, the mixture of styrene 2756g, stearyl methacrylate 689g, acrylic acid 142g, and dibutyl peroxide 413g was dripped over 1 hour in the state which cooled to 160 degreeC and was hold | maintained at 160 degreeC. Then, after maintaining at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C., the pressure in the flask was further lowered, and the reaction was carried out to a desired softening point at 8 kPa to obtain amorphous resin A-8. The physical properties are shown in Table 1.

Production Example B1 (Production of crystalline resin B-1)
The inside of a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple was purged with nitrogen, and 3416 g of 1,10-decandiol and 4084 g of sebacic acid were added and stirred. The temperature was raised to 135C, held at 135 ° C for 3 hours, and then heated from 135 ° C to 200 ° C over 10 hours. Thereafter, 23 g of di (2-ethylhexanoic acid) tin (II) was added, and further maintained at 200 ° C. for 1 hour, and then the pressure in the flask was lowered and maintained at a reduced pressure of 8 kPa for 1 hour. B-1 was obtained. The physical properties are shown in Table 2.

[Production of resin particle dispersion]
Production Example X1 (Production of resin particle dispersion X-1)
In a 3 L vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, 210 g of amorphous resin A-1, 90 g of crystalline resin B-1 and 300 g of methyl ethyl ketone were removed. 49 g of ionic water was added and the resin was dissolved at 73 ° C. over 2 hours. A 5% by mass aqueous sodium hydroxide solution was added to the resulting solution so that the degree of neutralization was 50 mol% with respect to the acid value of the resin, and the mixture was stirred for 30 minutes.
Next, while maintaining at 73 ° C., 600 g of deionized water was added over 60 minutes while stirring at 200 r / min (circumferential speed 63 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid X-1 was obtained. Table 3 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained resin particles.

Production Examples X2 to X8 (Production of Resin Particle Dispersions X-2 to X-8)
Resin particle dispersions X-2 to X-8 were obtained in the same manner as in Production Example X1, except that the resin used and the amount ratio (the total amount of the resin was the same) were changed as shown in Table 3. Table 3 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained resin particles.

Production Example X9 (Production of resin particle dispersion X-9)
A resin particle dispersion X-9 was obtained in the same manner as in Production Example X1, except that the crystalline resin was not used and 300 g of the amorphous resin A-1 and 360 g of methyl ethyl ketone were changed. Table 3 shows the volume-median particle size (D ₅₀ ) and CV value of the obtained resin particles.

Production Example Z1 (Production of resin particle dispersion Z-1)
200 g of amorphous resin A-8 and 200 g of methyl ethyl ketone were placed in a 3 L container equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen inlet tube, and the resin was added at 73 ° C. for 2 hours. Was dissolved. 5 mass% sodium hydroxide aqueous solution was added to the obtained solution so that the neutralization degree might be 60 mol% with respect to the acid value of amorphous resin A-8, and it stirred for 30 minutes.
Next, while maintaining at 73 ° C., 700 g of deionized water was added over 50 minutes while stirring at 280 r / min (peripheral speed 88 m / min), and phase inversion emulsification was performed. While maintaining the temperature at 73 ° C., methyl ethyl ketone was distilled off under reduced pressure to obtain an aqueous dispersion. Thereafter, the aqueous dispersion is cooled to 30 ° C. while stirring at 280 r / min (peripheral speed 88 m / min), and then deionized water is added so that the solid content concentration becomes 20% by mass, thereby dispersing the resin particles. Liquid Z-1 was obtained. The obtained resin particles had a volume median particle size (D ₅₀ ) of 0.09 μm and a CV value of 23%.

[Production of wax particle dispersion]
Production Example D11 (Production of Wax Particle Dispersion D1-1)
120 g of deionized water, 86 g of resin particle dispersion Z-1 and 40 g of paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd., melting point 75 ° C.) are added to a beaker having an internal volume of 1 L, and 90 to 95 ° C. The mixture was melted while maintaining the temperature and stirred to obtain a molten mixture.
The obtained molten mixture was further dispersed for 40 minutes using an ultrasonic homogenizer “US-600T” (manufactured by Nippon Seiki Seisakusyo Co., Ltd.) while maintaining the temperature at 90 to 95 ° C., until room temperature (20 ° C.). Cooled down. Deionized water was added to adjust the solid content concentration to 20% by mass to obtain a wax particle dispersion D1-1. Table 4 shows the volume median particle size D ₅₀ and CV value of the wax particles in the dispersion.

Production Examples D12, D21, D22 (Manufacture of wax particle dispersions D1-2, D2-1, D2-2)
A wax particle dispersion was obtained in the same manner as in Production Example D11 except that the type of wax used was changed as shown in Table 4. Table 4 shows the volume-median particle size (D ₅₀ ) and CV value of the wax particles in the dispersion.

[Production of Colorant Particle Dispersion]
Production Example C1 (Production of Colorant Particle Dispersion C-1)
In a beaker having an internal volume of 1 L, cyan pigment “ECB-301” (manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine pigment) 100 g, polyoxyethylene (distyrenated phenyl) ether “Emulgen A-60” (manufactured by Kao Corporation, Nonionic surfactant and polyoxyethylene have an average addition mole number of 13) 35 g and deionized water 300 g, and a homomixer “TKAGI HOMOMIXER 2M-03” (manufactured by Tokushu Kika Kogyo Co., Ltd.) The mixture was dispersed at room temperature for 1 hour at a rotating speed of the stirring blade at 8000 rpm, treated with “Microfluidizer M-110EH” (manufactured by Microfluidics) for 15 PASS at a pressure of 150 MPa, passed through a 200 mesh filter, Deionization so that the solids concentration is 24% by mass To obtain a colorant particle dispersion C-1 by addition. The resulting colorant particles had a volume-median particle size (D ₅₀ ) of 0.18 μm and a CV value of 25%.

[Production of toner]
Example 1 (Production of Toner 1)
In a 2 L four-necked flask equipped with a dehydrating tube, a stirrer and a thermocouple, 500 g of resin particle dispersion X-1, 49 g of wax particle dispersion D1-1, and 49 g of wax particle dispersion D2-1 , 56 g of the colorant particle dispersion C-1 and 10 g of a 10% by weight aqueous solution of polyoxyethylene (50) lauryl ether “Emulgen 150” (manufactured by Kao Corporation, nonionic surfactant) at a temperature of 25 ° C. did. Next, while stirring the mixture, a solution adjusted to pH 8.4 by adding a 4.8 mass% potassium hydroxide aqueous solution to an aqueous solution in which 35 g of ammonium sulfate was dissolved in 512 g of deionized water was added at 25 ° C. for 5 minutes. After dropping, the mixture was heated to 60 ° C. over 2 hours, and kept at 60 ° C. until the volume-median particle size (D ₅₀ ) of the aggregated particles became 5.2 μm to obtain a dispersion of aggregated particles. .
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate “Emar E-27C” (manufactured by Kao Corporation, anionic surfactant, effective concentration: 27 mass%), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol / L sulfuric acid aqueous solution was added. Then, after heating up to 77 degreeC over 1 hour, it hold | maintained at 77 degreeC until circularity was set to 0.965, and the dispersion liquid of the fusion | melting particle | grains by which the aggregated particle was fuse | melted was obtained.
The obtained fused particle dispersion was cooled to 30 ° C., and the dispersion was subjected to suction filtration to separate the solid content, then washed with deionized water at 25 ° C., and suction filtered at 25 ° C. for 2 hours. Thereafter, using a vacuum constant temperature dryer “DRV622DA” (manufactured by ADVANTEC), vacuum drying was performed at 33 ° C. for 24 hours to obtain toner particles. Table 5 shows the physical properties of the obtained toner particles.
100 parts by mass of toner particles, 2.5 parts by mass of hydrophobic silica “RY50” (manufactured by Nippon Aerosil Co., Ltd., number average particle size: 0.04 μm), and hydrophobic silica “Cabosil® TS720” (Cabot Japan Co., Ltd.) 1.0 part by mass (manufactured by company, number average particle diameter; 0.012 μm) was put in a Henschel mixer and stirred, and passed through a 150-mesh sieve to obtain toner 1. Table 5 shows the evaluation results of the obtained toner 1.

Examples 2 to 8, 13, and 14 and Comparative Example 1 (Production of toners 2 to 8, 13, 14, and 51)
Toners 2 to 8, 13, 14, and 51 were obtained in the same manner as in Example 1 except that the type of resin particle dispersion used and the type of release agent particle dispersion were changed as shown in Table 5. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 9 (Production of Toner 9)
A toner 9 was obtained in the same manner as in Example 1 except that the amount of the wax particle dispersion D1-1 used in Example 1 was changed to 28 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 10 (Production of Toner 10)
In Example 1, a toner 10 was obtained in the same manner as in Example 1 except that the amount of the wax particle dispersion D1-1 used was changed to 14 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 11 (Production of Toner 11)
A toner 11 was obtained in the same manner as in Example 1 except that the amount of the wax particle dispersion D2-1 used in Example 1 was changed to 28 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 12 (Production of Toner 12)
Toner 12 was obtained in the same manner as in Example 1, except that the amount of wax particle dispersion D1-1 used was 28 g and the amount of wax particle dispersion D2-1 used was 28 g. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 15 (Production of Toner 15)
In the same manner as in Example 1, an aggregated particle dispersion was obtained.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate “Emar E-27C” (manufactured by Kao Corporation, anionic surfactant, effective concentration: 27 mass%), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol / L sulfuric acid aqueous solution was added. Then, after heating up to 75 degreeC over 1 hour, it hold | maintained at 75 degreeC until circularity was set to 0.965, and the dispersion liquid of the fused particle which the aggregated particle fused was obtained.
The obtained fused particle dispersion was treated in the same manner as in Example 1 to obtain toner 15. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 16 (Production of Toner 16)
In the same manner as in Example 1, an aggregated particle dispersion was obtained.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate “Emar E-27C” (manufactured by Kao Corporation, anionic surfactant, effective concentration: 27 mass%), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol / L sulfuric acid aqueous solution was added. Then, after heating up to 73 degreeC over 1 hour, it hold | maintained at 73 degreeC until circularity was set to 0.965, and the dispersion liquid of the fused particle to which the aggregated particle was fuse | melted was obtained.
The obtained fused particle dispersion was treated in the same manner as in Example 1 to obtain toner 16. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 17 (Production of Toner 17)
In the same manner as in Example 1, an aggregated particle dispersion was obtained.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate “Emar E-27C” (manufactured by Kao Corporation, anionic surfactant, effective concentration: 27 mass%), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol / L sulfuric acid aqueous solution was added. Then, after heating up to 88 degreeC over 1 hour, it hold | maintained at 88 degreeC until circularity became 0.965, and the dispersion liquid of the fused particle which the aggregated particle fused was obtained.
The obtained fused particle dispersion was treated in the same manner as in Example 1 to obtain a toner 17. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Example 18 (Production of Toner 18)
In the same manner as in Example 1, an aggregated particle dispersion was obtained.
To the obtained dispersion of aggregated particles, 53 g of sodium polyoxyethylene lauryl ether sulfate “Emar E-27C” (manufactured by Kao Corporation, anionic surfactant, effective concentration: 27 mass%), 439 g of deionized water, and 0 An aqueous solution mixed with 30 g of a 1 mol / L sulfuric acid aqueous solution was added. Then, after heating up to 90 degreeC over 1 hour, it hold | maintained at 90 degreeC until circularity was set to 0.965, and the dispersion liquid of the fused particle which the aggregated particle fused was obtained.
The obtained fused particle dispersion was treated in the same manner as in Example 1 to obtain toner 18. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Comparative Example 2 (Production of Toner 52)
In Example 1, a toner 52 was obtained in the same manner as in Example 1 except that the wax particle dispersion D1-1 was not used. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

Comparative Example 3 (Production of Toner 53)
In Example 1, a toner 53 was obtained in the same manner as in Example 1 except that the wax particle dispersion D2-1 was not used. Table 5 shows the physical properties of the obtained toner particles and the evaluation results of the toner.

  From the results of Table 5, it can be seen that the toners of Examples 1 to 18 are superior in the image density of the printed matter and the hot offset resistance as compared with the toners of Comparative Examples 1 to 3.

Claims (11)

Step 1: Resin particles X containing a constituent component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and an amorphous resin A having a polyester resin segment are mixed in an aqueous medium with a wax D1, a wax D2, and a colorant. Agglomerating in the presence of to obtain aggregated particles;
Step 2: fusing the aggregated particles obtained in Step 1 above,
A toner production method comprising:
The melting point Tm1 of the wax D1 is lower than the melting point Tm2 of the wax D2, and
The toner manufacturing method, wherein the temperature T at which the aggregated particles are fused in Step 2 is not less than a temperature 10 ° C. lower than the melting point Tm1 of the wax D1 and not more than 10 ° C. higher than the melting point Tm2 of the wax D2.   2. The toner according to claim 1, wherein the temperature T at which the aggregated particles are fused in the step 2 is not less than a temperature 3 ° C. lower than the melting point Tm 1 of the wax D 1 and not more than 3 ° C. higher than the melting point Tm 2 of the wax D 2. Production method.   The toner production method according to claim 1, wherein the step 1 is performed in the presence of the crystalline resin B.   The method for producing a toner according to claim 1, wherein the temperature T at which the aggregated particles are fused in the step 2 is equal to or higher than a temperature 1 ° C. lower than the melting point Tm1 of the wax D1.   The toner manufacturing method according to claim 1, wherein the temperature T at which the aggregated particles are fused in the step 2 is 5 ° C. or lower than the melting point Tm2 of the wax D2.   The toner production method according to claim 1, wherein the difference between the melting point Tm1 of the wax D1 and the melting point Tm2 of the wax D2 is 10 ° C. or more.   The method for producing a toner according to claim 1, wherein the wax D1 is a hydrocarbon wax.   The method for producing a toner according to claim 1, wherein the wax D2 is a hydrocarbon wax.   The crystalline resin B comprises a polyhydric alcohol component containing 80 mol% or more of an α, ω-aliphatic diol having 4 to 16 carbon atoms and an aliphatic saturated dicarboxylic acid having 8 to 16 carbon atoms in an amount of 80 mol% or more. The method for producing a toner according to claim 1, wherein the toner is obtained by polycondensation with a polyvalent carboxylic acid component. The method for producing a toner according to claim 1, wherein the colorant is a colorant particle obtained by mixing a colorant and a compound represented by the following formula (1).

[Wherein, R ¹ is an alkanediyl group having 1 to 12 carbon atoms, m represents an average number of substitutions, the value of m is 1 to 4 and R ² is a hydrogen atom or a methyl group, A ¹ O represents an oxyalkylene group, A ¹ is an ethylene group or a propylene group, n is the average number of added moles of alkylene oxide, and the value of n is 5 or more and 100 or less. ]   It contains a component derived from a hydrocarbon wax W1 having a hydroxyl group or a carboxy group and an amorphous resin A having a polyester resin segment, a wax D1, a wax D2, and a colorant, and the melting point Tm1 of the wax D1 is the wax. A toner having a melting point Tm2 lower than D2.