JP6722019B2 - Toner manufacturing method - Google Patents

Description

The present invention relates to a method for producing a toner used in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method and a toner jet method.

In recent years, printers and copiers are required to have high image quality and to lower the frequency of cartridge replacement and toner replenishment (prolonging the life of the cartridge and toner). Specifically, it has excellent coloring power that can obtain high image density even when the amount of toner on the image is small, and excellent durability and narrow charging that can maintain stable image quality for a long time even when printing at high speed. A toner having a quantity distribution is desired.

Patent Document 1 describes a toner containing a polyester resin having an alicyclic structure in at least one of a polycarboxylic acid and/or a polyhydric alcohol and defining a particle size distribution and a circularity distribution of toner particles. Has been done.
Patent Document 2 describes the relationship between the mass of the oxycarboxylic acid extracted from 1 g of the toner with methanol and the mass of the oxycarboxylic acid extracted from the 1 g of the toner with a 0.1 mol/liter sodium hydroxide aqueous solution. The specified toner is described.
Patent Document 3 describes a toner containing a crystalline polyester, an amorphous polyester resin containing a constitutional unit derived from a polyvalent carboxylic acid having an adamantane skeleton or a derivative thereof, and a release agent.

JP, 2000-305320, A JP, 2001-034016, A JP, 2005-040912, A

The toner described in Japanese Patent Laid-Open Publication No. 2004-242242 has obtained a high image density, but sometimes the charge amount distribution of the toner becomes wide. Therefore, image defects such as image fogging and density unevenness at the image center and image edge portion due to poor regulation may occur.
Although the toner described in Patent Document 2 is excellent in environmental stability and charging characteristics, a high image density could not be obtained when the amount of toner on the image was small. Further, the durability was insufficient, and improvement was needed.
Although the toner described in Patent Document 3 has a high charging stability, it has a wide charge amount distribution, and therefore may cause image defects such as fog and density unevenness at the image center and the image edge due to poor regulation. It was
The present invention provides a method for producing a toner that solves the above problems. That is, an object of the present invention is to provide a method for producing a toner having high coloring power, high durability and a narrow charge amount distribution.

According to the present invention, there is provided a method for producing a toner having toner particles having a binder resin, a polyester resin, and a colorant,
The manufacturing method is
Forming particles of a polymerizable monomer composition containing the polymerizable resin capable of forming the binder resin, the polyester resin, and the colorant in an aqueous medium containing hardly water-soluble inorganic fine particles. , A granulation step to obtain a suspension,
In the suspension, a polymerization step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain resin particles, and
The aqueous medium in which the resin particles are dispersed, by heating at the glass transition temperature (Tg) of from 15 ℃ or higher temperature of the polyester resin having a heat treatment step of obtaining the toner particles in this order,
The binder resin is a copolymer of a styrene monomer and an unsaturated carboxylic acid ester,
The polymerizable monomer is a styrenic monomer and an unsaturated carboxylic acid ester,
The pH of the aqueous medium in the heat treatment step is 6.0 or more and 12.0 or less,
The polyester resin is the main chain and / or side chain, the production method of the toner and having a unit derived from alcohol represented by the following formula (1) is provided.

(In the formula _(1), at least two of R 1 ~ _{R 6} are each independently rest of the .R ₁ ~ R ₆ showing -OH, or -R ₇ -O H is Each independently represents a hydrogen atom, a halogen atom, or an alkyl group, and R ₇ represents an alkylene group.)

According to the present invention, it is possible to provide a method for producing a toner having high tinting strength, high durability and a narrow charge amount distribution.

It is a flow figure showing an outline of a manufacturing method of a toner of the present invention.

In the present invention, the present inventors presume the reason why high coloring power, high durability and narrow charge distribution can be achieved as follows.
First, in order to obtain high coloring power, it is necessary to control the adsorption of the polyester resin and the pigment. When a polyester resin that is easily adsorbed on a pigment is used, inter-pigment crosslinking occurs, which is a phenomenon in which one molecule of polyester resin is adsorbed on two or more pigment particles. When the inter-pigment cross-linking occurs, the pigments agglomerate and the coloring power decreases. Therefore, in order to obtain high coloring power, it is effective to use a polyester resin that is difficult to be adsorbed on the pigment.

In order for the polyester resin to be adsorbed on the pigment, the resin needs to have an attractive interaction with the pigment, and the resin must have the flexibility to be deformed along the surface of the pigment. Therefore, it is possible to obtain a high tinting strength by using a polyester resin which does not interact with the pigment and has a rigid structure.

A π-π interaction works between the polyester resin and the pigment. The pigment has a conjugated structure for color development, and the conjugated structure causes a π-π interaction with the aromatic structure present in the polyester resin. Therefore, in order to suppress the interaction between the polyester resin and the pigment, it is effective to introduce an aliphatic structure that does not cause the π-π interaction into the resin.
Further, in order to make a rigid structure, it is effective to introduce a cyclic structure, which is a structure in which molecular chains are constrained.
From the above, by introducing an alicyclic structure into the polyester resin, it becomes difficult for the polyester resin to be adsorbed on the pigment, and high tinting strength can be obtained.

Next, in order to obtain high durability, it is necessary that the resin is not largely deformed by the external force and is not destroyed by the external force.
In order to prevent the resin from being largely deformed by an external force, it is necessary to reduce the intermolecular mobility when the external force is applied. Specifically, in a linear structure, molecular chains are less likely to be entangled with each other, and thus resistance to external force is small and deformation is easy. On the other hand, when the cyclic structure is introduced, the molecular chains are likely to be entangled with each other, so that resistance to external force can be increased and deformation due to external force is less likely to occur.

Further, in order to prevent the resin from being destroyed by an external force, it is necessary to deform it in the molecule to cope with the external force. Specifically, a structure in which the movement of molecules such as aromatic compounds is completely restrained lacks flexibility with respect to external force and is therefore easily broken. On the other hand, the alicyclic structure can be flexibly dealt with by changing the conformation with respect to an external force, and thus is not easily broken.
As described above, by introducing the alicyclic structure into the resin, the resin is not largely deformed by the external force, and at the same time, is not destroyed by the external force, so that high durability can be obtained.

On the other hand, since the alicyclic structure has a low charging property, if the alicyclic structure is exposed on the toner surface, the charging property of the exposed portion is deteriorated. Therefore, a difference in charge amount occurs between the toner having many exposed portions of the alicyclic structure and the toner having few exposed portions. As a result, it has become clear that when a polyester resin having an alicyclic structure is used in a toner, the charge amount distribution becomes wider.
In order to solve the above problems, the inventors of the present invention have earnestly studied, and as a result,
By performing heat treatment under the condition that "the carboxylic acid of the polyester resin is dissociated and the molecular chain of the polyester resin can move in the aqueous medium", the carboxylic acid is oriented on the toner surface, and the alicyclic structure is formed. It has been found that is difficult to be exposed to the toner surface.

Specifically, it is possible to dissociate the carboxylic acid of the polyester resin by setting the pH of the aqueous medium to 6.0 or more and 12.0 or less. In addition, the molecular chain mobility of the polyester resin can be sufficiently increased by setting the temperature of the aqueous medium to a temperature higher than the glass transition temperature (Tg) of the polyester resin by 15° C. or more.
From the above, when a polyester having an alicyclic structure is used by performing heat treatment in an aqueous medium having a temperature higher than the glass transition temperature of the polyester resin by 15° C. or more and a pH of 6.0 or more and 12.0 or less. Also in, the narrow charge amount distribution can be obtained.

However, even in the case of performing the heat treatment step, the charge amount distribution may not be improved depending on the type of alicyclic structure. Therefore, the present inventors have conducted further studies,
"A unit derived from an alcohol or a carboxylic acid represented by any of the following formulas (1) to (4) (hereinafter, referred to as a unit having a specific alicyclic structure) is easy to move by heat treatment, and Because of the large polarity difference with the carboxylic acid, the distribution of charge amount is significantly improved."
I found that.

(In the formula (1), at least two members out of R ₁ to R ₆ each independently represent —OH, —COOH, —R ₇ —OH, or —R ₈ —COOH. COOH or —R ₈ —COOH may be an acyl halide derivatized with a carboxy group, an ester, an acid anhydride, or may form an acid anhydride in the molecule, among R ₁ to R ₆ . The rest independently represent a hydrogen atom, a halogen atom, or an alkyl group. R ₇ and R ₈ represent an alkylene group.)

(In the formula (2), at least two of R ₁ to R ₁₀ each independently represent —OH, —COOH, —R ₁₁ —OH, or —R ₁₂ —COOH. COOH or —R ₁₂ —COOH may be an acyl halide derivatized with a carboxy group, an ester, or an acid anhydride, and may form an acid anhydride in the molecule, among R ₁ to R ₁₀ . The rest independently represent a hydrogen atom, a halogen atom, or an alkyl group. R ₁₁ and R ₁₂ represent an alkylene group.)

(In formula (3), at least two of R ₁ to R ₆ each independently represent —OH, —COOH, —R ₇ —OH, or —R ₈ —COOH. COOH or —R ₈ —COOH may be an acyl halide derivatized with a carboxy group, an ester, an acid anhydride, or may form an acid anhydride in the molecule, among R ₁ to R ₆ . The rest independently represent a hydrogen atom, a halogen atom, or an alkyl group. R ₇ and R ₈ represent an alkylene group.)

(In formula (4), at least two of R ₁ to R ₄ each independently represent —OH, —COOH, —R ₅ —OH, or —R ₆ —COOH. COOH or —R ₆ —COOH may be an acyl halide derivatized with a carboxy group, an ester, an acid anhydride, or may form an acid anhydride in the molecule, among R ₁ to R ₄ . The rest independently represent a hydrogen atom, a halogen atom, or an alkyl group. R ₅ and R ₆ represent an alkylene group.)

The method for producing the toner of the present invention will be described in more detail below.

In the present invention, first, resin particles having a polyester resin having a unit having a specific alicyclic structure in the main chain and/or side chain and a colorant are produced. Thereafter, a step of heat-treating the resin particles in an aqueous medium having a temperature higher than the glass transition temperature of the polyester resin by 15° C. or more and a pH of 6.0 or more and 12.0 or less is performed to obtain toner particles (of the toner particles). Water dispersion). Further, if necessary, steps such as filtration, washing, drying, classification and external addition are carried out to obtain a toner.

(Heat treatment process)
In the heat treatment step (step S130 in FIG. 1) in the toner manufacturing method of the present invention, the temperature of the aqueous medium needs to be higher than the glass transition temperature of the polyester resin by 15° C. or more. At the above temperature, the molecular chains of the polyester resin can move freely. More preferably, the temperature of the aqueous medium is higher than the glass transition temperature of the polyester resin by 20° C. or more. Further, the upper limit of the temperature of the aqueous medium is 100° C. under normal pressure because the aqueous medium is used, and therefore the upper limit is preferably 100° C. or lower. It is possible to further raise the temperature by setting the pressure. From the viewpoint of suppressing the hydrolysis reaction of the polyester resin, it is preferably 120° C. or lower.

In the heat treatment step, the pH of the aqueous medium is 6.0 or more and 12.0 or less. Within the above range, the carboxylic acid of the polyester resin can be dissociated. The pH of the aqueous medium is more preferably 7.0 or more and 10.0 or less. When the pH of the aqueous medium is 7.0 or higher, the dissociation of carboxylic acid is further promoted. Further, when the pH of the aqueous medium is 10.0 or less, the hydrolysis reaction of the polyester resin is suppressed, and the durability and heat resistance can be further improved.

The pH of the aqueous medium can be adjusted by a known method.
For example, when the pH is raised, an alkali metal such as lithium, sodium and potassium or an aqueous solution thereof, an alkali metal salt or an aqueous solution thereof, an alkaline earth metal such as calcium or magnesium or an aqueous solution thereof, an alkaline earth metal salt or an aqueous solution thereof. Can be adjusted by adding. More specifically, a method of adding lithium hydroxide aqueous solution, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution, magnesium hydroxide aqueous solution, lithium carbonate aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution, etc. Can be given.
For example, when lowering the pH, it can be adjusted by adding an acid such as hydrochloric acid, sulfuric acid, carbonic acid, acetic acid or phosphoric acid, an aqueous solution thereof, or a salt or aqueous solution thereof.

(Polyester resin)
The polyester resin used in the method for producing a toner of the present invention is derived from an alcohol-derived unit having a specific alicyclic structure or a carboxylic acid having a specific alicyclic structure in the main chain and/or side chain. Have a unit to
The side chain of the polyester resin is defined as “branch, side chain, pendant molecular chain” in the following definition (Source: Glossary of Polymer Society of Japan) and does not include “pendant group, side group”. The description of the Glossary of Terms of the Polymer Society of Japan is as follows.

1.53 branch, side chain, pendant molecular chain This refers to an oligomer-like or high-molecular weight branch extending from the molecular chain of a polymer.
Polymer Society of Japan Glossary, 1.56 Pendant group, side group Refers to the side branch originating from the main chain that is neither an oligomer molecular chain nor a polymer molecular chain.

That is, the side chain in the present invention has a repeating unit like the main chain.
When the content ratio of the unit derived from the alcohol having a specific alicyclic structure or the unit derived from the carboxylic acid having a specific alicyclic structure is 0.1 mol% or more and 50.0 mol% or less, the coloring power is improved. It is possible and preferable.

Specific examples of the compound (alcohol or carboxylic acid) represented by the formula (1) include the following. 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 4-(2-hydroxyethyl)cyclohexanol, 4-(hydroxymethyl)cyclohexanol, 1 , 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methyl, 1,2-cyclohexanedicarboxylic acid and the like.

Specific examples of the compound (alcohol or carboxylic acid) represented by the formula (2) include the following 4,4′-bicyclohexanol and bicyclohexane-4,4′-dicarboxylic acid.
Specific examples of the compound (alcohol or carboxylic acid) represented by the formula (3) include the following. 2-cyclohexene-1,4-diol, 4-cyclohexene-1,2-dimethanol, 4-cyclohexene-1,2-dicarboxylic acid, 1-cyclohexene-1,2-dicarboxylic acid, 6-methyl-4-cyclohexene -1,2,3-tricarboxylic acid and the like.

Specific examples of the compound (alcohol or carboxylic acid) represented by the formula (4) include 5-norbornene-2,3-dimethanol, 5-norbornene-2,3-diol and 5-norbornene-2 shown below. , 3-dicarboxylic acid and the like.
It is more preferable that the unit having a specific alicyclic structure is a diol having a specific alicyclic structure. Since the carboxylic acid unit is oriented on the toner surface, the use of a diol makes it possible to separate the alicyclic structure having a low chargeability from the toner surface, thereby improving the chargeability. In addition, since there is a portion having a low chargeability immediately below the toner surface, the charge is less likely to move from the toner surface to the inside of the toner, and a higher chargeability can be obtained with a smaller charge. Starts up faster.

The acid value of the polyester resin is preferably 2.0 mgKOH/g or more and 15.0 mgKOH/g or less. Within this range, the carboxylic acid can sufficiently cover the surface during heat treatment, and the charge distribution can be narrowed.
The glass transition temperature of the polyester resin is preferably 60° C. or higher and 90° C. or lower. Within this range, the heat resistance of the toner can be improved while maintaining the molecular chain mobility during heat treatment.

The weight average molecular weight of the polyester resin is preferably 5,000 or more and 50,000 or less. Within this range, the heat resistance of the toner can be improved while maintaining the molecular chain mobility during heat treatment.
The polyester resin may be used alone as a binder resin, or may be mixed with another resin described below and used as a binder resin. When mixed and used, the polyester resin may be contained in the binder resin in an amount of 1% or more and 60% or less.

(Colorant)
As the colorant, conventionally known pigments and dyes can be used without particular limitation. Above all, it is preferable to use an organic pigment because it hardly transfers to the aqueous phase or the toner surface during heat treatment and hardly affects the charging property.
Specifically, the following black pigments, yellow pigments, magenta pigments, cyan pigments, etc. are used.

Examples of black pigments include carbon black.
Examples of yellow pigments include monoazo compounds; disazo compounds; condensed azo compounds; isoindolinone compounds; isoindoline compounds; benzimidazolone compounds; anthraquinone compounds; azo metal complexes; methine compounds; allylamide compounds. Specifically, C.I. I. Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185 and the like.

Examples of magenta pigments include monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; basic dye lake compounds; naphthol compounds: benzimidazolone compounds; thioindigo compounds; perylene compounds. Specific examples include the following. C. I. Pigment Red 2,3,5,6,7,23,48:2,48:3,48:4,57:1,81:1,122,144,146,150,166,169,177,184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Violet 19 etc.

Examples of cyan pigments include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.
The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the resin in the toner.

(Release agent)
The toner produced by the production method of the present invention may further contain a release agent. Specific examples include the following. Esters of monohydric alcohols and monocarboxylic acids represented by behenyl behenate, stearyl stearate, palmityl palmitate and the like; esters of divalent carboxylic acids and monoalcohol represented by dibehenyl sebacate and the like; hexanediol dibe Esters of dihydric alcohols represented by henates and monocarboxylic acids; esters of acid alcohols represented by glycerin tribehenates and monocarboxylic acids; pentaerythritol tetrastearate, pentaerythritol tetra Esters of tetrahydric alcohols and monocarboxylic acids represented by palmitate and the like; Esters of hexavalent alcohols and monocarboxylic acids represented by dipentaerythritol hexastearate and dipentaerythritol hexapalmitate and the like; poly Esters of polyfunctional alcohols represented by glycerin behenate and monocarboxylic acids; natural ester waxes represented by carnauba wax and rice wax; petroleum hydrocarbons such as paraffin wax, microcrystalline wax, petrolatum Wax and its derivative; Hydrocarbon wax and its derivative by Fischer-Tropsch method; Polyolefin hydrocarbon wax and its derivative such as polyethylene wax and polypropylene wax; Higher aliphatic alcohol; Fatty acid such as stearic acid and palmitic acid; Acid amide wax and the like ..

Among these, esters of monohydric alcohols and monocarboxylic acids, esters of dihydric carboxylic acids and monoalcohols, esters of dihydric alcohols and monocarboxylic acids, and hydrocarbon waxes are preferable. The reason is that the releasability and the low temperature fixability can be improved without lowering the charging property and the heat resistance.
When the release agent is present in the vicinity of the surface layer of the toner, the release property and the low temperature fixability can be improved, but when it is exposed on the toner surface, the chargeability and heat resistance are deteriorated. Therefore, it is difficult to achieve both releasability and low-temperature fixability as well as chargeability and heat resistance.

In the present invention, due to the heat treatment step, the alicyclic portion of the polyester resin is not exposed on the toner surface and is present in the vicinity of the toner surface layer. Since the release agent has a polarity close to that of the alicyclic portion of the polyester resin, it is likely to be unevenly distributed near the alicyclic portion of the polyester resin. Therefore, the release agent is also unevenly distributed in the vicinity of the toner surface layer without being exposed on the toner surface. Therefore, the releasability and low-temperature fixability can be improved without deteriorating the charging property and heat resistance due to the exposure of the release agent. From the above viewpoint, hydrocarbon waxes are more preferable.

The melting point of the release agent is preferably lower than the temperature of the heat treatment step by 10° C. or more. Within the above range, in the heat treatment step, the release agent easily moves, and the release agent exposed on the toner surface moves to the toner inner layer. Therefore, the charging property and heat resistance are further improved.
The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin because the releasability is improved. It is more preferably 5.0 parts by mass or more and 20.0 parts by mass or less.

(Other resins)
The toner produced by the production method of the present invention contains, in the main chain and/or side chain, a polyester resin having a unit derived from an alcohol or a carboxylic acid having a specific alicyclic structure, and further contains another resin. You may.
Examples of other resins include vinyl resins, polyester resins, polyamide resins, furan resins, epoxy resins, xylene resins, silicone resins and the like. Among these, it is preferable to use a vinyl resin. The following vinyl resins can be used. Styrene-based monomers such as styrene, α-methylstyrene and divinylbenzene; methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate Saturated carboxylic acid ester; unsaturated carboxylic acid such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acid such as maleic acid; unsaturated dicarboxylic acid anhydride such as maleic anhydride; nitrile vinyl monomer such as acrylonitrile; A halogen-containing vinyl monomer such as vinyl; a polymer of a monomer of a nitro vinyl monomer such as nitrostyrene, or a copolymer thereof. Above all, it is preferable to use a copolymer of a styrene-based monomer and an unsaturated carboxylic acid ester.

(Charge control agent)
The toner produced by the production method of the present invention may further contain a charge control agent. As the charge control agent used in the present invention, conventionally known charge control agents can be used without particular limitation. Specific examples of the negative charge control agent include the following. Aromatic carboxylic acid metal compounds represented by salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, etc.; polymers or copolymers having sulfonic acid groups, sulfonate groups or sulfonate ester groups; azo dyes Alternatively, metal salts or metal complexes of azo pigments; boron compounds, silicon compounds, calixarene, etc.
Examples of the positive charge control agent include the following quaternary ammonium salts, polymer type compounds having a quaternary ammonium salt in the side chain; guanidine compounds; nigrosine compounds; imidazole compounds.
The following may be used as the polymer or copolymer having a sulfonate group or a sulfonate group. Sulfonic acid group-containing vinyl monomer homopolymer represented by styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid and methacrylsulfonic acid. Alternatively, a copolymer of the vinyl-based monomer shown in the section of other resins and the above-mentioned vinyl-based monomer having a sulfonic acid group.

(External additive)
The toner produced by the production method of the present invention may further contain an external additive (external additive) for the purpose of improving the fluidity of the toner. As the external additive used in the present invention, conventionally known external additives can be used without particular limitation. Specific examples include the following. Original silica fine particles typified by wet process silica, dry process silica and the like, or silica fine particles obtained by subjecting these original silica fine particles to a surface treatment with a silane coupling agent, a titanium coupling agent, and a treatment agent typified by silicone oil; Metal oxide fine particles represented by titanium oxide fine particles, aluminum oxide fine particles, zinc oxide fine particles and the like, or metal oxide fine particles obtained by subjecting the above metal oxides to a hydrophobic treatment; represented by zinc stearate, calcium stearate, zinc stearate and the like. Fatty acid metal salt; metal complex of aromatic carboxylic acid represented by salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acid, etc.; clay mineral represented by hydrotalcite; vinylidene fluoride fine particles, polytetrafluoroethylene Fluorine-based resin particles such as particles. Among them, from the viewpoint of excellent fluidity and chargeability, it is preferable to use silica fine particles obtained by subjecting the original silica fine particles to surface treatment with a silane coupling agent, a titanium coupling agent, or a treatment agent typified by silicone oil.
The content of the external additive is preferably 0.1 part by mass or more and 5.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles.

(Method for producing resin particles)
As a method for producing resin particles in the method for producing a toner of the present invention, a conventionally known method can be used without particular limitation. Specifically, a suspension polymerization method; a dissolution suspension method; an emulsion aggregation method; a spray dry method; a pulverization method and the like can be mentioned.

Here, when employing a production method including a step of polymerizing a monomer to obtain a resin, such as a suspension polymerization method or an emulsion aggregation method, it is determined whether or not the production of resin particles has been completed. The polymerization conversion rate (mass %) of the particles is used. In the present invention, when the polymerization conversion rate reaches 99.0% or more, it is considered that the production of the resin particles is completed.
Further, when adopting a manufacturing method including a step of performing solvent removal to obtain resin particles, such as a dissolution suspension method, it is determined whether or not the manufacturing of resin particles is completed, the solvent removal rate (mass%) Done by In the present invention, it is considered that the production of resin particles is completed when the solvent removal rate reaches 99.0% or more.

Among the above-mentioned production methods, the suspension polymerization method or the dissolution suspension method is particularly preferable. When the resin particles are produced by the suspension polymerization method or the dissolution suspension method, the carboxylic acid, which is a highly polar portion of the polyester resin, is likely to be unevenly distributed near the surface of the resin particles. Therefore, the carboxylic acid can be uniformly oriented on the toner surface by the heat treatment. Therefore, the charge amount distribution can be further narrowed.

(Suspension polymerization method)
In the case of obtaining resin particles by the suspension polymerization method, a polyester resin, a polymerizable monomer capable of forming a binder resin, and a colorant are added, and polymerization is performed by melting, dissolving or dispersing these using a disperser. A polymerizable monomer composition is prepared (dissolving step S111). At this time, a release agent, a charge control agent, a crystalline resin, a chain transfer agent, and other additives can be appropriately added to the polymerizable monomer composition, if necessary. Examples of the disperser include a homogenizer, a ball mill, a colloid mill, and an ultrasonic disperser. As the polymerizable monomer, the monomers used for the vinyl-based resin described in the section of other resins can be preferably used.

Next, the polymerizable monomer composition is put into an aqueous medium, and a suspension is prepared using a high speed disperser such as a high speed stirrer or an ultrasonic disperser (granulation step FIG. 1, step S112). At this time, it is preferable to contain the poorly water-soluble inorganic fine particles in the aqueous medium for the purpose of suppressing the coalescence of the suspension. After that, the polymerizable monomer in the suspension is polymerized to obtain an aqueous dispersion of resin particles (polymerization step S113). Then, the toner particles are obtained through the heat treatment process (step S130).

The polymerization initiator may be mixed with other additives when preparing the polymerizable monomer composition, or may be mixed with the polymerizable monomer composition immediately before being suspended in the aqueous medium. Good. In addition, during granulation or after completion of granulation, that is, immediately before starting the polymerization reaction, it can be added in a state of being dissolved in a polymerizable monomer or another solvent, if necessary.

(Polymerization initiator)
As the polymerization initiator, a known polymerization initiator can be used without particular limitation. Specific examples include the following. 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis Azo- or diazo-type polymerization initiators represented by -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc.; benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, t -Butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators represented by peroxides and lauroyl peroxide.

(Slightly water-soluble inorganic fine particles)
The poorly water-soluble inorganic fine particles preferably include a compound in which a cation and an anion are ionically bonded. The cation is preferably at least one cation selected from the group consisting of calcium ion, magnesium ion, and aluminum ion. The anion is preferably at least one anion selected from the group consisting of carbonate ion, hydroxide ion, and phosphate ion.

More preferably, it is at least one selected from the group consisting of a calcium phosphate compound, an aluminum phosphate compound, a magnesium phosphate compound, a calcium hydroxide compound, an aluminum hydroxide compound and a magnesium hydroxide compound. More preferably, it is a calcium phosphate compound.

(Dissolution suspension method)
When obtaining resin particles by the dissolution suspension method, first, a polyester resin and a colorant are dissolved or dispersed in an organic solvent to prepare a resin solution (dissolution step S121). At this time, other resins, mold release agents, charge control agents, crystalline resins, plasticizers, chain transfer agents, and other additives can be appropriately added to the resin solution, if necessary. Next, the resin solution is dispersed in an aqueous medium and granulated to obtain a suspension (granulation step S122). At this time, it is preferable to contain the above-mentioned hardly water-soluble inorganic fine particles in the aqueous medium for the purpose of suppressing the coalescence of the suspension. Then, an aqueous dispersion of resin particles is obtained through a solvent removal step (step S123) of removing the organic solvent contained in the granulated particles. Then, the toner particles are obtained through the heat treatment process (step S130).

As the organic solvent for obtaining the resin particles by the dissolution suspension method, it is preferable to use a solvent which is immiscible with water and which is easily removed by heating. For example, ethyl acetate may be mentioned.
Next, the measuring method used in the present invention will be described in detail below.

<Weight average molecular weight Mw of polyester resin>
The weight average molecular weight Mw of the polyester resin is measured by gel permeation chromatography (GPC) as follows.
First, the polyester resin is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholydisc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the THF-soluble component is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.

Device: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805, 806, and 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min Oven temperature: 40.0°C
Sample injection volume: 0.10mL

In calculating the molecular weight of the sample, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F- 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corp., is used for the molecular weight calibration curve.

<Acid value of polyester resin>
The acid value of the polyester resin is measured by the following method. The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the polyester resin is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.

(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95 vol%), and ion-exchanged water is added to 100 mL to obtain a phenolphthalein solution. 7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95 vol%) is added to make 1 L. The solution is placed in an alkali-resistant container so that it does not come into contact with carbon dioxide gas, left standing for 3 days, and then filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali resistant container. The factor of the above potassium hydroxide solution is that 25 mL of 0.1 mol/L hydrochloric acid is placed in an Erlenmeyer flask, a few drops of the above phenolphthalein solution is added, and titration is performed with the above potassium hydroxide solution. Calculated from the amount of potassium solution. As the above 0.1 mol/L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of a crushed polyester resin sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene/ethanol (2:1) is added, and dissolved for 5 hours. Next, a few drops of the above-mentioned phenolphthalein solution is added as an indicator, and titration is performed using the above-mentioned potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for 30 seconds.
(B) Blank test The same titration as the above operation is performed except that the sample is not used (that is, only the mixed solution of toluene/ethanol (2:1) is used).

(3) The acid value is calculated by substituting the obtained result into the following formula.
A=[(CB)×f×5.61]/S
Here, A: acid value (mgKOH/g), B: amount of potassium hydroxide solution added in blank test (mL), C: amount of potassium hydroxide solution added in main test (mL), f: potassium hydroxide Solution factor, S: sample (g).

<Glass transition temperature of polyester resin>
The glass transition temperature of the polyester resin is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments).
The melting point of indium and zinc is used to correct the temperature of the device detection unit, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, 2 mg of polyester resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, and a temperature rising rate of 10°C/ Measure in minutes. In this temperature rising process, a specific heat change is obtained in the temperature range of 40°C to 100°C.
The straight line extending the baseline before the specific heat change at this time is the first straight line, and the straight line extending the baseline after the specific heat change is the second straight line, the first straight line and the second straight line. A straight line that is equidistant from the straight line in the vertical axis direction is referred to as a third straight line. The temperature at the intersection of the third straight line and the differential thermal curve (so-called midpoint glass transition temperature) is the glass transition temperature (Tg) of the polyester resin.

<Method for measuring the weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube by a pore electrical resistance method is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with the number of effective measurement channels of 25,000.

The electrolytic aqueous solution used for the measurement may be prepared by dissolving special grade sodium chloride in ion-exchanged water so that the concentration becomes 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).
Before the measurement and analysis, the dedicated software was set as follows.

On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to "standard particles 10.0 μm" (Beckman -Set the value obtained using Coulter Co., Ltd. The threshold and noise level are automatically set by pressing the "Threshold/noise level measurement button". Further, the current is set to 1600 μA, the gain is set to 2, and the electrolytic solution is set to ISOTON II, and a check is put in “Flash of aperture tube after measurement”.
On the "pulse-to-particle size conversion setting" screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measuring method is as follows.

(1) 200 mL of the above electrolytic aqueous solution is put into a glass 250 mL round-bottom beaker for exclusive use of Multisizer 3, set on a sample stand, and stirring of a stirrer rod is performed counterclockwise at 24 rotations/second. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flush" function of the dedicated software.
(2) Put 30 mL of the above electrolytic solution into a 100 mL flat-bottom beaker made of glass. In this, as a dispersant, "Contaminone N" (a nonionic surfactant, anionic surfactant, a 10 mass% aqueous solution of a neutral detergent for washing precision measuring instruments of pH 7 comprising an organic builder, Wako Pure Chemical Industries, Ltd. (3) was diluted 3 times with ion-exchanged water and 0.3 mL of a diluted solution was added.

(3) Prepare two ultrasonic dispersers "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electric output of 120 W, which incorporates two oscillators with an oscillation frequency of 50 kHz with a phase shift of 180 degrees. .. 3.3 l of ion-exchanged water is put in the water tank of the ultrasonic disperser, and 2 mL of Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker becomes maximum.

(5) While the electrolytic aqueous solution in the beaker of (4) is being irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10°C or higher and 40°C or lower.
(6) To the round-bottom beaker of (1) installed in the sample stand, the aqueous solution of the electrolyte of (5) in which the toner is dispersed is dropped using a pipette, and the concentration is adjusted to 5%. Then, the measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed by the above-mentioned dedicated software attached to the apparatus to calculate the weight average particle diameter (D4). The "average diameter" on the "Analysis/volume statistical value (arithmetic mean)" screen when the graph/volume% is set in the dedicated software is the weight average particle diameter (D4).

<Measurement method of polymerization conversion rate or solvent removal rate of resin particles>
The polymerization conversion rate or desolvation rate of the resin particles is measured by gas chromatography (GC) as follows.
500 mg of the resin particle dispersion liquid is precisely weighed and put in a sample bottle. After adding 10 g of precisely weighed acetone to the lid and mixing with a lid, the mixture was mixed well with a tabletop ultrasonic cleaner (trade name "B2510J-MTH", manufactured by Branson) having an oscillation frequency of 42 kHz and an electric output of 125 W. Irradiate with ultrasonic waves for 30 minutes. Then, filtration is carried out using a solvent-resistant membrane filter "Mysholydisk" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 µm, and 2 µL of the filtrate is analyzed by gas chromatography. Then, the "residual amount" of the remaining polymerizable monomer or solvent is calculated from the calibration curve prepared using the previously used polymerizable monomer or solvent. Then, the polymerization conversion rate (mass %) or the solvent removal rate (mass %) of the resin particles is defined according to the following formula.
(Formula) 100×(1-(residual amount)/(total amount of polymerizable monomer or solvent used))

<Method for measuring volume average particle diameter of polyester resin fine particles, colorant fine particles, etc.>
The polyester resin fine particles used in the present invention, and resin particles such as release agent fine particles, and the volume-based median diameter of colorant fine particles are measured according to JIS Z8825-1 (2001). Specifically, it is as follows.
As the measuring device, a laser diffraction/scattering particle size distribution measuring device “LA-920” (manufactured by Horiba Ltd.) is used. For setting the measurement conditions and analyzing the measurement data, dedicated software "HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02" attached to the LA-920 is used.
The measurement procedure is as follows.

(1) Attach the batch type cell holder to LA-920.
(2) A predetermined amount of ion-exchanged water is put in a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) Stir the inside of the batch type cell using a dedicated stirrer chip.
(4) Press the "Refractive index" button on the "Display condition setting" screen and select the appropriate refractive index for each material.
(5) In the "display condition setting" screen, the particle size reference is the volume reference.
(6) After warming up for 1 hour or more, the optical axis is adjusted, the optical axis is finely adjusted, and the blank measurement is performed.
(7) The dispersion liquid to be measured is immediately added little by little to a batch type cell while being careful not to let air bubbles enter, and the transmittance of the tungsten lamp is adjusted to 90% to 95%. Then, the particle size distribution is measured. The volume-based median diameter (D50) is calculated based on the obtained volume-based particle size distribution data.

The present invention will be specifically described with reference to the following examples. However, this does not limit the invention in any way. The toner and the method for producing the toner will be described below. All "parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

[Production Example of Polyester Resin]
<Production Example of Polyester Resin 1>
To a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, 100.0 parts of a mixture obtained by mixing the raw material monomers in a molar ratio shown in Table 1 was added, and the temperature was maintained with stirring. Heated to 120°C. Then, 0.50 part of di(2-ethylhexanoic acid)tin was added as an esterification catalyst, and the temperature was raised to 190° C. to carry out polycondensation until a desired molecular weight was obtained to obtain polyester resin 1.
Polyester resin 1 had a weight average molecular weight of 19,600, an acid value of 6.1 mgKOH/g, and a glass transition temperature of 72°C.

<Production Examples of Polyester Resins 2 to 8 and Polyester Resin 10>
The polyester resin 2 to 8 and the polyester resin 10 were manufactured by performing the same operation as the polyester resin 1 under the raw material monomer mixing amount and the temperature condition of the polycondensation reaction in Table 1. Table 2 shows the physical properties of the polyester resins 2 to 8 and the polyester resin 10.

<Production Example of Polyester Resin 9>
-Bisphenol A (PO 2.2 mol adduct): 27.3 mol%
-Bisphenol A (EO2.2 mol adduct): 9.1 mol%
・Terephthalic acid: 31.8 mol%
・Dodecenyl succinic anhydride: 4.5 mol%
Fumaric acid: 9.1 mol%
-Glycerin: 9.1 mol%
*1,3-adamantanedicarboxylic acid: 9.1 mol%

In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, a dehydration tube, and a decompression device, in addition to fumaric acid and glycerin among the above monomer components, tin dioctanoate was added to 0 parts per 100 parts of the above components. .25 parts were charged. After reacting at 235° C. for 6 hours in a nitrogen gas stream, the temperature was lowered to 200° C., and the fumaric acid was added and reacted for 30 minutes. Further, the above glycerin was added and reacted for 30 minutes. Then, the temperature was further raised to 220° C. over 4 hours, and polymerization was performed under a pressure of 10 kPa to obtain polyester resin 9. Table 2 shows the physical properties of the polyester resin 9.

※ＥＧ：エチレングリコール、ＢＰＡ−ＰＯ：ビスフェノールＡ ＰＯ付加物、ＴＭＡ：トリメリット酸、ＴＰＡ：テレフタル酸

*EG: ethylene glycol, BPA-PO: bisphenol A PO adduct, TMA: trimellitic acid, TPA: terephthalic acid

<Preparation Example of Polyester Resin Fine Particle Dispersion 1>
While maintaining a jacketed 3 liter reaction tank (BJ-30N manufactured by Tokyo Rika Kikai Co., Ltd.) equipped with a condenser, a thermometer, a water dropping device, and an anchor blade at 40° C. in a water circulation type constant temperature bath, the following mixing was performed. A solvent was added and 300 parts of the polyester resin 1 was added.
-Mixed solvent: a mixed solvent of 160 parts of ethyl acetate and 100 parts of isopropyl alcohol Then, the mixture was stirred at 150 rpm using a three-one motor and dissolved to obtain an oil phase. To this stirring oil phase, 14 parts of 10 mass% aqueous ammonia solution was added dropwise for 5 minutes, and after mixing for 10 minutes, 900 parts of ion-exchanged water was further added dropwise at a rate of 7 parts per minute for phase inversion. Then, an emulsion was obtained.

Immediately, 800 parts of the obtained emulsion and 700 parts of ion-exchanged water were placed in a 2-liter eggplant flask and set in an evaporator (Tokyo Rikakikai Co., Ltd.) equipped with a vacuum control unit via a trap ball. While rotating the eggplant flask, the mixture was heated in a hot water bath at 60° C., and the solvent was removed by reducing the pressure to 7 kPa while paying attention to bumping. When the solvent recovery amount reached 1,100 parts, the pressure was returned to normal pressure, and the eggplant flask was water-cooled to obtain a dispersion liquid. There was no solvent odor in the obtained dispersion. The volume-based median diameter of the polyester resin fine particles in this dispersion was 130 nm. Then, ion-exchanged water was added to prepare a solid content concentration of 20% by mass, which was designated as Polyester Resin Fine Particle Dispersion Liquid 1.

<Preparation example of polyester resin fine particle dispersion 2>
Polyester resin fine particle dispersion 2 is prepared in the same manner as in the synthesis example of polyester resin dispersion 1 except that the polyester resin used is changed from polyester resin 1 to polyester resin 8 in the preparation example of polyester resin fine particle dispersion 1. did.

<Preparation Example of Polyester Resin Fine Particle Dispersion Liquid 3>
Polyester resin fine particle dispersion liquid 3 was prepared in the same manner as in the synthesis example of polyester resin dispersion liquid 1 except that the polyester resin used was changed from polyester resin 1 to polyester resin 9 in the preparation example of polyester resin fine particle dispersion liquid 1. did.

<Preparation Example of Colorant Fine Particle Dispersion>
C. I. Pigment Red 122
(Dainichi Seika Kogyo Co., Ltd., trade name "Chromofine Magenta 6886"): 100 parts Polyoxyethylene nonylphenol ether (anionic surfactant) (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen R): 15 parts Ion-exchanged water: 900 parts or more are mixed, dissolved, and dispersed for 1 hour using a high-pressure impact disperser Ultimaizer (manufactured by Sugino Machine Co., Ltd., HJP30006) to disperse the colorant, thereby dispersing fine particles of the colorant. A liquid was prepared. The volume-based median diameter of the colorant particles in the colorant particle dispersion was 130 nm, and the colorant particle concentration was 25% by mass.

<Example of Preparation of Release Agent Fine Particle Dispersion Liquid 1>
-Behenyl behenate (melting point 71°C): 270 parts-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., trade name "Neogen RK"): 13.5 parts-Ion-exchanged water: 21.6 parts

After mixing the above components and using a pressure discharge homogenizer (Gorin homogenizer manufactured by Gorin Co., Ltd.) to dissolve the mold release agent at an internal liquid temperature of 120° C., a dispersion treatment was carried out at a dispersion pressure of 5 MPa for 120 minutes, and then, Dispersion treatment was performed at 40 MPa for 360 minutes. Then, it cooled and obtained the release agent fine particle dispersion liquid 1. The volume-based median diameter of fine particles in this release agent fine particle dispersion was 225 nm. Then, ion-exchanged water was added to adjust the solid content concentration to 20.0% by mass.

<Preparation Example of Release Agent Fine Particle Dispersion Liquid 2>
In the preparation example of the release agent fine particle dispersion liquid 1, the same as the preparation example of the release agent fine particle dispersion liquid 1 except that the release agent used is changed from behenyl behenate to butanediol dibehenate (melting point 81° C.). Then, the release agent fine particle dispersion liquid 2 was prepared.

<Preparation Example of Release Agent Fine Particle Dispersion Liquid 3>
In the preparation example of the release agent fine particle dispersion 1, a release agent fine particle dispersion 1 is prepared, except that the release agent used is changed from behenyl behenate to pentaerythritol tetrabehenate (melting point: 82° C.). Similarly, a release agent fine particle dispersion liquid 3 was prepared.

[Production Example of Toner 1]
-Styrene: 60.0 parts-C.I. I. Pigment Red122
(Dainichi Seika Kogyo Co., Ltd., trade name "Chromofine Magenta 6886"): 8.0 parts The above materials were put into an Attritor (Mitsui Miike Kakoki Co., Ltd.) and further zirconia particles with a diameter of 1.7 mm. Was dispersed at 220 rpm for 5 hours to obtain a pigment dispersion liquid.

The following materials were added to the above pigment dispersion.
-Styrene: 14.1 parts-n-butyl acrylate: 20.9 parts-Polyester resin 1: 5.0 parts-Paraffin wax (Nippon Seiwa Co., Ltd., trade name "HNP-9" melting point 75°C): 6.0 parts The above materials were kept at 65° C. and uniformly dissolved and dispersed at 500 rpm using TK Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). 4.4 parts by mass of t-butylperoxy-2-ethylhexanoate (trade name “Perbutyl O”, manufactured by NOF CORPORATION) was dissolved in this to prepare a polymerizable monomer composition.

On the other hand, 850 parts of 0.1 mol/L-Na ₃ PO ₄ aqueous solution and 8.0 parts of 10% hydrochloric acid were added to a container equipped with a high-speed stirrer Clearmix (manufactured by M Technique Co., Ltd.), and the rotation speed was It was adjusted to 15,000 rpm and heated to 60°C. Here was added 1.0mol / L-CaCl ₂ aqueous solution 68 parts, to prepare an aqueous medium containing a calcium phosphate compound. 5 minutes after the polymerization initiator was added to the polymerizable monomer composition, the polymerizable monomer composition at 60° C. was added to the aqueous medium heated to 60° C., and CLEARMIX was 15,000 rpm. Granulate for 15 minutes while rotating with.

After that, the stirrer was changed from a high speed stirrer to a propeller stirrer, the mixture was reacted at 60° C. for 5 hours while refluxing, then the liquid temperature was adjusted to 80° C., and further reacted for 5 hours. Here, a part of the dispersion liquid was extracted, and the temperature was cooled to 20° C. while continuing stirring to obtain resin particles (aqueous dispersion of resin particles). When the polymerization conversion rate of the resin particles contained in the extracted dispersion liquid was measured, it was 100.0 (mass %), and it was confirmed that the polymerization step was completed.

Then, the pH of the aqueous medium was adjusted to 9.0, the liquid temperature was raised to 98° C., and a heat treatment step was further performed for 3 hours. After completion of the heat treatment step, the liquid temperature was lowered to 20° C., diluted hydrochloric acid was added to adjust the pH of the aqueous medium to 3.0 or less, and the poorly water-soluble dispersant was dissolved. Further, washing and drying were performed to obtain toner particles.

After that, the following fluidity improver was added to 100.0 parts by mass of the toner particles, and the mixture was mixed at 3,000 rpm for 15 minutes using a Mitsui Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to prepare toner 1. Obtained. Physical properties of Toner 1 are shown in Table 3.
Flowability improver: Hydrophobized silica fine powder (number average particle diameter of primary particles: 10 nm) treated with dimethyl silicone oil (20% by mass) and frictionally charged to the same polarity (negative polarity) as the toner particles. , BET specific surface area: 170 m2/g) 2.0 parts

[Production Example of Toners 2 to 10]
Toners 2 to 10 were obtained in the same manner as in the toner 1 production example except that the combination of the materials used and the production conditions were changed to those shown in Table 3. Table 3 shows the physical properties of Toners 2 to 10.

[Production Example of Toner 11]
A dissolved and suspended toner was manufactured by the following method.
(Production example of wax dispersion)
Behenyl behenate (100.0 parts) crushed to an average particle size of 20 μm was put into methanol (100.0 parts), stirred at a rotation speed of 150 rpm for 10 minutes to wash, and then filtered. After repeating this 3 times, it was filtered and dried to collect the wax.
The obtained wax: 100.0 parts and ethyl acetate: 100.0 parts were placed in an attritor containing zirconia beads having a diameter of 20 mm and dispersed at 150 rpm for 2 hours. The zirconia beads were separated to obtain a wax dispersion liquid.

(Production example of colorant dispersion)
C. I. Pigment Red122
(Chromofine magenta 6886): 20.0 parts by mass-Ethyl acetate: 80.0 parts by mass The above materials were placed in an attritor containing zirconia beads having a diameter of 1.7 mm and rotated at a rotation speed of 200 rpm for 5 hours. .. The zirconia beads were separated to obtain a colorant dispersion liquid.

(Example of toner production)
-Vinyl resin Styrene-n-butyl acrylate copolymer: 95.0 parts (styrene-n-butyl acrylate copolymerization ratio=78.0:22.0, Mp=22,000, Mw=35,000 , Mw/Mn=2.4, Tg=55° C.)
-Polyester resin 1: 5.0 parts-Wax dispersion: 12.0 parts-Colorant dispersion: 40.0 parts The above materials were uniformly mixed to form a toner composition.

On the other hand, 850 parts of 0.1 mol/L-Na3PO4 aqueous solution and 8.0 parts of 10% hydrochloric acid were added to a container equipped with a high-speed stirrer Clearmix, the rotation speed was adjusted to 15,000 rpm, and the mixture was heated to 60°C. did. 68 parts of 1.0 mol/L-CaCl2 aqueous solution was added here, and the aqueous medium containing a calcium phosphate compound was prepared.

While maintaining the aqueous medium at 30° C. and maintaining the rotation speed at 15,000 rpm, the above toner composition was charged into the aqueous medium and granulated for 2 minutes.
Then, 500 parts of ion-exchanged water was added. The propeller stirrer was changed to an ordinary propeller stirrer, the aqueous medium was maintained at 30 to 35° C., the stirrer was rotated at 150 rpm, the pressure in the container was reduced to 52 kPa, and ethyl acetate was distilled off. Here, a part of the dispersion liquid was extracted, and the temperature was cooled to 20° C. while continuing stirring to obtain resin particles (aqueous dispersion of resin particles). The solvent removal rate of the resin particles contained in the extracted dispersion was measured and found to be 100.0 (mass %), confirming that the solvent removal step was completed.

Next, the pH of the aqueous medium was adjusted to 9.0, the temperature was raised to 90° C., and the heat treatment step was performed for 3 hours. After the heat treatment process was completed, this was cooled to 25° C. at a cooling rate of 0.15° C./min. While maintaining the internal temperature at 20.0 to 25.0°C, dilute hydrochloric acid was added to the aqueous dispersion medium to dissolve the hardly water-soluble dispersant. Further, washing and drying were performed to obtain toner particles. A fluidity improver was added to the obtained toner particles in the same manner as in the production example of Toner 1 to obtain Toner 11. Table 3 shows the physical properties of Toner 11.

[Production Example of Toner 12]
Toner 12 was obtained in the same manner as in the toner 11 production example except that the polyester resin 1 was changed to the polyester resin 8. Table 3 shows the physical properties of Toner 12.

[Production Example of Toner 13]
Toner 13 was obtained in the same manner as in the toner 11 production example except that the vinyl resin was not used and the amount of the polyester resin 1 was changed to 100.0 parts. Table 3 shows the physical properties of Toner 13.

[Production Example of Toner 19]
Toner 19 was obtained in the same manner as in the toner 11 production example except that the polyester resin 1 was changed to the polyester resin 10. Table 3 shows the physical properties of Toner 19.

[Production Example of Toner 20]
Toner 20 was obtained in the same manner as in the toner 12 production example except that the pH in the heat treatment step was set to 5.5. Table 3 shows the physical properties of Toner 20.

[Production Example of Toner 21]
Manufacturing Example of Toner 20 is the same as Manufacturing Example of Toner 20, except that 1.0 part of a charge control agent (manufactured by Orient Chemical Co., Ltd., trade name “Bontron E-84”) is added to the toner composition. To obtain a toner 21. Table 3 shows the physical properties of Toner 21.

[Production Example of Toner 22]
Toner 22 was obtained in the same manner as in the toner 12 production example except that the pH in the heat treatment step was set to 12.5. Table 3 shows the physical properties of Toner 22.

[Production Example of Toner 23]
A toner 23 was obtained in the same manner as in the toner 12 production example except that the heat treatment step was not performed. Table 3 shows the physical properties of Toner 23.

[Production Example of Toner 14]
An emulsion aggregation toner was manufactured by the following method.
-Polyester resin fine particle dispersion liquid 1:655 parts-Colorant fine particle dispersion liquid: 52 parts-Release agent fine particle dispersion liquid 1:130 parts-Ion-exchanged water: 325 parts-Anionic surfactant (Dowfax2A1 manufactured by Dow Chemical Co., Ltd.) )
: 6.5 copies

The above components were placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter and a stirrer, and 0.3 M nitric acid was added to adjust the pH to 3.0 at a temperature of 25° C., and then a homogenizer (IKA 130 parts of the aluminum sulfate aqueous solution (0.3% by mass) prepared above was added and dispersed for 6 minutes while being dispersed at 5,000 rpm with Japan Co., Ltd.: Ultra Tarax T50.

Then, a stirrer and a mantle heater were installed in the reaction vessel, and the temperature of the stirrer was adjusted to 0.2° C./min up to a temperature of 40° C. while adjusting the rotation speed of the stirrer so that the slurry was sufficiently stirred. After the temperature was exceeded, the temperature was raised at a heating rate of 0.05° C./min, and the particle size was measured every 10 minutes. The temperature was maintained when the volume average particle diameter reached 5.0 μm, and 350 parts of the polyester resin dispersion liquid 1 was added over 5 minutes.

After the polyester resin dispersion liquid 1 was added and held for 30 minutes, the pH was adjusted to 9.0 and an aqueous dispersion of resin particles was prepared. Then, it heated up to 90 degreeC and performed the heat processing process at 90 degreeC for 3.0 hours. Then, the container was cooled to 20° C. with cooling water.
The cooled slurry was passed through a nylon mesh having an opening of 15 μm to remove coarse powder, and nitric acid was added to the toner slurry which passed through the mesh to adjust the pH to 6.0, followed by vacuum filtration with an aspirator. Toner remaining on the filter paper is crushed into as small pieces as possible by hand, put into ion-exchanged water at a temperature of 30°C and 10 times the amount of toner, stirred and mixed for 30 minutes, and again filtered under reduced pressure with an aspirator to conduct electric conduction of the filtrate. The degree was measured. This operation was repeated until the electric conductivity of the filtrate became 10 μS/cm or less, and the toner was washed.

The washed toner was finely crushed by a wet dry sizing machine, and then vacuum dried in an oven at 35° C. for 36 hours to obtain washed toner particles. A fluidity improver was added to the obtained toner particles in the same manner as in the production example of Toner 1 to obtain Toner 14. Table 3 shows the physical properties of Toner 14.

[Production Example of Toner 15]
A toner 15 was obtained in the same manner as in the production example of the toner 14 except that the polyester resin fine particle dispersion liquid 1 was used in place of the polyester resin fine particle dispersion liquid 2 in the production example of the toner 14. Table 3 shows the physical properties of Toner 15.

[Production Example of Toner 16]
Toner 16 was obtained in the same manner as in the toner 14 production example except that the release agent fine particle dispersion liquid 2 was used in place of the release agent fine particle dispersion liquid 1. Table 3 shows the physical properties of Toner 16.

[Production Example of Toner 17]
Toner 17 was obtained in the same manner as in the toner 14 production example except that the release agent fine particle dispersion liquid 3 was used in place of the release agent fine particle dispersion liquid 1. Table 3 shows the physical properties of Toner 17.

[Production Example of Toner 18]
A toner 18 was obtained in the same manner as in the production example of the toner 14 except that the polyester resin fine particle dispersion liquid 3 was used instead of the polyester resin fine particle dispersion liquid 1 in the production example of the toner 14. Table 3 shows the physical properties of Toner 18.

※セバシン酸ジベヘニル（融点：７３℃）

*Dibehenyl sebacate (melting point: 73°C)

(Examples 1 to 17, Comparative Examples 1 to 6)
The toners 1 to 23 were evaluated with the combinations shown in Tables 4 and 5. The evaluation results are shown in Tables 4 and 5.
The evaluation method and evaluation criteria in the present invention will be described below.
Note that Examples 11 to 17 are described as reference examples.

As the image forming apparatus, a commercially available laser printer LBP-7700C (manufactured by Canon Inc.) modified machine and a commercially available process cartridge Toner cartridge 323 (magenta) (manufactured by Canon Inc.) were used. After removing the product toner from the inside of the cartridge and cleaning it by air blow, 150 g of the toner manufactured by the manufacturing method of the present invention was filled. It should be noted that the product toners were taken out from the yellow, cyan, and black stations, and yellow, cyan, and black cartridges with the remaining toner amount detection mechanism disabled were inserted and evaluated.

<1. Evaluation of tinting strength Image density>
The process cartridge filled with toner was allowed to stand for 48 hours in a normal temperature and normal humidity environment (temperature 23° C./relative humidity 50%: hereinafter, N/N environment). Using LBP-7700C (manufactured by Canon Inc.) modified to operate even when the fixing device is removed, a 10 mm×10 mm square image is transferred onto a transfer paper (GF-C081 (manufactured by Canon Inc.) A4:81. An unfixed image having an image pattern in which 9 points are evenly arranged on 4 g/m ² ) was output. The amount of toner on the transfer paper was 0.45 mg/cm ² . As the fixing device, an external fixing device was used in which the fixing device of LBP-7700C was removed to the outside so that it could be operated outside the laser beam printer. Fixing was performed under the conditions of fixing temperature: 160° C. and process speed: 240 mm/sec.

Using a "Macbeth reflection densitometer RD918" (manufactured by Macbeth) to measure the image density on a square image of 10 mm x 10 mm, and according to the instruction manual attached, the relative density with respect to the image of the white background portion where the image density is 0.00. Was measured. The obtained relative densities of 9 points were averaged to obtain an image density value. The coloring strength was evaluated according to the following criteria using the image density as an index. If the rank is C or higher, the level is such that the effect of the present invention is obtained.

A: The image density is 1.40 or more.
B: The image density is 1.30 or more and less than 1.40.
C: The image density is 1.20 or more and less than 1.30.
D: The image density is less than 1.20.

<2. Evaluation of durability Vertical stripes>
Process cartridge filled with toner, LBP-7700C (manufactured by Canon Inc.) and transfer paper (GF-C081 (manufactured by Canon Inc.)) A4: 81.4 g/modified so that the process speed is 240 mm/sec. m ² ) was left in an N/N environment for 48 hours.
After continuously outputting 1,000 images with a printing rate of 1% on a transfer paper, one solid image with a load of 0.45 mg/cm ² was output, and the developing roller was visually observed, It was confirmed whether or not streaks parallel to the rotation direction (hereinafter, streaks in the developing roller circumferential direction) were generated. Images were output in the above cycle until streaks parallel to the output direction (hereinafter referred to as vertical streaks) were generated on the solid image or until the number of output images with a print ratio of 1% reached 20,000.
The durability was evaluated according to the following criteria, using the timing of occurrence of streaks on the developing roller and the image as an index. When the rank is C or higher, the level is such that the effect of the present invention is obtained.

A: Up to 20,000 sheets, neither vertical streaks on a solid image nor streaks on the developing roller in the circumferential direction of the developing roller occur.
B: Vertical streaks do not occur on a solid image up to 20,000 sheets, and streaks in the developing roller circumferential direction do not occur on developing rollers up to 18,000 sheets.
C: Vertical streaks do not occur on a solid image up to 20,000 sheets, and streaks in the developing roller circumferential direction do not occur on developing rollers up to 16,000 sheets.
D: Vertical stripes appear on a solid image up to 20,000 sheets.

<3. Evaluation of charge amount distribution Poor regulation/fog>
<3-1 Low temperature and low humidity environment Poor regulation>
Process cartridge filled with toner, LBP-7700C (manufactured by Canon Inc.) and transfer paper (GF-C081 (manufactured by Canon Inc.)) A4: 81.4 g/modified so that the process speed is 240 mm/sec. m ² ) was allowed to stand in a low temperature and low humidity environment (temperature 15° C./10% relative humidity: hereinafter, L/L environment) for 48 hours. In the L/L environment, after continuously printing 20,000 images with a printing rate of 1% on transfer paper, outputting one halftone image with a load of 0.20 mg/cm ² and visually observing on the developing roller. It was observed and the occurrence of poor regulation was confirmed.
The durability was evaluated according to the following criteria, using the poor regulation on the developing roller and the uneven image density caused by the poor regulation as an index. When the rank is C or higher, the level is such that the effect of the present invention is obtained.

A: Neither defective regulation nor uneven image density occurs on the developing roller.
B: Poor regulation on the developing roller is slightly observed, but uneven image density is not observed.
C: Poor regulation is seen on the developing roller, and a portion with slightly high image density is seen at the edge of the image.
D: The density at the edge of the image is remarkably high.

<3-2 Fog in high temperature and high humidity environment>
Process cartridge filled with toner, LBP-7700C (manufactured by Canon Inc.) and transfer paper (GF-C081 (manufactured by Canon Inc.)) A4: 81.4 g/modified so that the process speed is 240 mm/sec. m ² ) was allowed to stand in a high temperature and high humidity environment (temperature 30° C./80% relative humidity: hereinafter, H/H environment) for 48 hours. In an H/H environment, 20,000 sheets of images with a printing rate of 1% were continuously output on a transfer paper, and then left in the same environment for 72 hours. Then, one solid white image was output on a transfer paper masking the central 5 cm×5 cm area. The masking of the obtained image was removed, and the reflectance of the masking portion and the non-masking portion was measured by TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). The fog on the image was evaluated according to the following formula. When the rank is C or higher, the level is such that the effect of the present invention is obtained.
Fog (%) = reflectance of masking part (%)-reflectance of non-masking part (%)

A: Fog is 1.0% or less.
B: Fog is more than 1.0% and 2.0% or less.
C: Fog exceeds 2.0% and 3.0% or less.
D: Fog exceeds 3.0%.

In the above evaluation, when the charge amount is large, the problem of poor regulation is likely to occur, and when the charge amount is small, the problem of fog is likely to occur. Therefore, when the distribution of the charge amount is wide, adverse effects are likely to occur in the evaluation of either (or both). Therefore, the lower evaluation rank of the evaluations of 3-1 and 3-2 was taken as the evaluation rank of the charge amount distribution of each toner.

<4. Evaluation of charge buildup Transition of image density after standing>
After the evaluation of 3-2, 10 image patterns in which a square image of 10 mm×10 mm was evenly arranged in 9 points on a transfer paper (GF-C081 (manufactured by Canon Inc.) A4:81.4 g/m ² ). Output continuously. Then, 200 sheets of images with a print rate of 1% were continuously output on the transfer paper. Then, an image pattern in which a square image of 10 mm×10 mm was evenly arranged at 9 points on a transfer paper (GF-C081 (manufactured by Canon Inc.) A4:81.4 g/m ² ) was output again. The image densities of the produced images were measured, and the charge buildup was evaluated using the number of sheets output until the image density equivalent to the image density after 200 sheets were obtained as an index. When the rank is C or higher, the level is such that the effect of the present invention is obtained.

A: The same image density can be obtained up to the second sheet.
B: Equivalent image density can be obtained up to the fifth sheet.
C: Equivalent image density can be obtained up to the 10th sheet.
D: The image density is low even on the 10th sheet.

<5. Evaluation of low temperature fixability Rubbing test>
The process cartridge filled with toner was allowed to stand for 48 hours in an N/N environment. An unfixed image of an image pattern in which a square image of 10 mm x 10 mm is evenly arranged in 9 points on the entire transfer paper by using an LBP-7700C (manufactured by Canon Inc.) modified so that it operates even if the fixing device is removed. Was output. The loading amount of toner on the transfer paper was 0.70 mg/cm ² , and the fixing start temperature was evaluated. As the transfer paper, Fox River Bond (90 g/m ² ) was used. As the fixing device, an external fixing device was used in which the fixing device of LBP-7700C (manufactured by Canon Inc.) was detached to the outside so that it could be operated outside the laser beam printer. The external fixing device was capable of setting the fixing temperature arbitrarily, and the fixing was performed under the condition of process speed: 240 mm/sec.

The fixed image was rubbed with a load of 50 g/cm ² on sill-bon paper [Lenz Cleaning Paper “dasper(R)” (Ozu Paper Co. Ltd)], and the temperature at which the density decrease rate before and after rubbing became 20% or less was fixed. As a starting point, low temperature fixability was evaluated according to the following criteria. When the rank is C or higher, the level is such that the effect of the present invention is obtained.

A: The fixing start point is 120° C. or lower.
B: The fixing start point is more than 120° C. and 130° C. or less.
C: The fixing start point is more than 130° C. and 140° C. or less.
D: The fixing start point exceeds 140°C.

<6. Evaluation of releasability Winding resistance at high temperature>
Regarding the wrapping resistance at high temperature, fixing was performed under the same conditions as in the rubbing test except that the transfer paper was changed to PB PAPER GF-500 (64 g/m ² ) in the evaluation method of the rubbing test.
The releasability was evaluated according to the following criteria, using the maximum temperature at which the paper could be passed without winding as an index. When the rank is C or higher, the level is such that the effect of the present invention is obtained.

A: The maximum temperature is 200° C. or higher.
B: The maximum temperature is 190° C. or higher and lower than 200° C.
C: The maximum temperature is 180°C or higher and lower than 190°C.
D: The maximum temperature is less than 180°C.

<7. Evaluation of heat resistance Blocking>
5 g of each toner was placed in a 50 cc resin cup and left standing at a temperature of 55° C./10% relative humidity for 3 days. Using the presence or absence of aggregates as an index, heat resistance was evaluated according to the following criteria. When the rank is C or higher, the level is such that the heat resistance effect of the present invention is obtained.
A: No aggregate is generated.
B: A slight agglomerate is generated, but it can be unraveled by light shaking.
C: A slight agglomerate is generated, but it can be released by pressing lightly with a finger.
D: An agglomerate is generated, which does not collapse even if lightly pressed with a finger.

※１：規制不良又はカブリの評価のうちランクが低い方

*1: Poor regulation or fog evaluation with lower rank

※１：２００枚出力後の画像濃度と同等の画像濃度が得られるまでに出力した枚数
※２：擦り前後の濃度低下率が２０％以下になった温度
※３：巻きつき無く通紙できた最高温度
※４：所定条件下で静置後の凝集塊の有無

*1: The number of sheets output until the image density equivalent to the image density after 200 sheets is output *2: Temperature at which the density reduction rate before and after rubbing is 20% or less *3: Paper can pass without wrapping Maximum temperature *4: Presence or absence of aggregates after standing under specified conditions

Claims (4)

A method for producing a toner having toner particles having a binder resin, a polyester resin, and a colorant,
The manufacturing method is
Forming particles of a polymerizable monomer composition containing the polymerizable resin capable of forming the binder resin, the polyester resin, and the colorant in an aqueous medium containing hardly water-soluble inorganic fine particles. , A granulation step to obtain a suspension,
In the suspension, a polymerization step of polymerizing the polymerizable monomer contained in the particles of the polymerizable monomer composition to obtain resin particles, and
The aqueous medium in which the resin particles are dispersed, by heating at the glass transition temperature (Tg) of from 15 ℃ or higher temperature of the polyester resin having a heat treatment step of obtaining the toner particles in this order,
The binder resin is a copolymer of a styrene monomer and an unsaturated carboxylic acid ester,
The polymerizable monomer is a styrenic monomer and an unsaturated carboxylic acid ester,
The pH of the aqueous medium in the heat treatment step is 6.0 or more and 12.0 or less,
The polyester resin is the main chain and / or side chain, the production method of the toner and having a unit derived from alcohol represented by the following formula (1).

(In the formula _(1), at least two of R 1 ~ _{R 6} are each independently rest of the .R ₁ ~ R ₆ showing -OH, or -R ₇ -O H is Each independently represents a hydrogen atom, a halogen atom, or an alkyl group, and R ₇ represents an alkylene group.) The method for producing a toner according to claim 1, wherein the polyester resin has an acid value of 2.0 mgKOH/g or more and 15.0 mgKOH/g or less. The glass transition temperature of the polyester resin, method for producing a toner according to claim 1 or 2 is 60 ° C. or higher 90 ° C. or less. The method for producing a toner according to claim 1, wherein the styrene-based monomer is styrene, and the unsaturated carboxylic acid ester is butyl acrylate.

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