JP5078642B2 - toner - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic image in an image forming method such as electrophotography and electrostatic printing, or a toner for forming a toner image in a toner jet type image forming method.

Conventionally, in image forming methods such as electrophotography and electrostatic printing, frictionally charged toner particles are configured to develop an electrostatic latent image on a drum by an electrostatic force corresponding to a potential difference on the photosensitive drum. Yes. At this time, the frictional charging of the toner is caused by friction between the toner and the toner, between the toner and the carrier, and further with the regulating blade. For this reason, in addition to the particle size and particle size distribution of the toner, it is important to control the tribocharging property.
Particularly in recent years, demands for higher speed and higher stability of printers and copiers have led to demands for more rapid tribocharging characteristics and toner triboelectric characteristics that are less susceptible to environmental changes. In addition, since the characteristics must be maintained for a long period of time, it is not possible to add an excessive share to the toner, and it is more difficult to obtain the desired frictional charging characteristics as described above.

In order to control the triboelectric charging property of the toner, the triboelectric charging characteristic of the binder resin itself can be used, but the triboelectric charging characteristic of the binder resin generally used for the toner is often low, and its composition It is not easy to control the triboelectric charging property. Therefore, in general, a charge control agent that imparts triboelectric chargeability is added.
Conventionally, as the negatively chargeable charge control agent, there are metal complex salts of monoazo dyes, metal compounds of dialkyl salicylic acid, boron compounds, urea compounds, silicon compounds, calixarenes, sulfonated copper phthalocyanine pigments, and chlorinated paraffins. Many charge control agents containing these dyes and pigments have a complicated structure, are not constant in properties, and are poor in stability, and the triboelectric chargeability is particularly likely to change due to changes in temperature and humidity. Others may be altered by heat kneading during toner preparation.
Furthermore, the charge control agent added to these toners must be present on the toner surface to some extent in order to impart frictional charging ability. As a result, friction between the toners, collision with the carrier, conveyance sleeve or roller, regulating blade, and friction with the photosensitive drum cause these additives to fall off the toner surface, causing contamination of the carrier, developing member, and photosensitive drum. May cause contamination. As a result, as the number of durable sheets increases, the triboelectric chargeability decreases, and at the same time, deterioration due to contamination progresses, which easily causes problems such as a change in image density and a decrease in image quality.

As described above, it can be seen that there are very few charge control agents that can stably provide a toner with sufficient triboelectric chargeability for a long period of time. In addition, in order to apply to a full-color toner, it is preferable that what is added to the toner is colorless, and very few can be put to practical use.
Considering the background described above, studies for improving the triboelectric charging characteristics of toners have been actively conducted.In particular, due to environmental considerations, demands for more stable triboelectric charging properties, and manufacturing costs in recent years. Thus, a proposal has been made to use a resin having a charge control function as a toner raw material (see Patent Documents 1 to 3). Here, a toner containing a styrene resin and a sulfonic acid group-containing copolymer is proposed. Further, a proposal has been made to improve the triboelectric charging characteristics by fixing resin fine particles having a sulfonic acid group to the surface of the toner base particles, but further improvement is required (see Patent Document 4).
For the purpose of obtaining insufficient triboelectric charging performance in a high-speed printer that requires high-speed triboelectric charging, it is conceivable to increase the unit amount of 2-acrylamido-2-methylpropanesulfonic acid, which is an example of a triboelectric charging unit of resin. Problems easily occur in toner preparation. For example, when resin fine particles having a high concentration of the triboelectrically charged unit in an aqueous medium are to be fixed to the surface of the toner base particles, the acid value of the fine particles is very high, and the resin fine particles are hydrophilic. It is difficult to obtain the stability of fine particles, and it becomes difficult to control the particle size distribution due to aggregation of fine particles, and it becomes difficult to obtain the fixing strength with the mother particles, and a large number of printing operations and copying operations are required. In some printers and copiers, it may be difficult to obtain image stability.
Japanese Patent Publication No. 8-012467 Japanese Patent No. 2666316 Japanese Patent No. 2807955 JP-A-6-332229

  The object of the present invention is that the rise of frictional charging is good, stable density and image quality can be obtained even in various environmental changes, and image output excellent in image quality can be stably obtained even by a large number of copying operations. To obtain a toner having excellent durability and stability.

（式１中、Ｒ_１は環状構造をとっても良い炭化水素基を示し、該Ｒ_１は置換基を有していてもよく、Ｒ_２はメチル基、エチル基又はイソプロピル基を示す。） The present invention is a toner having toner particles in which a surface layer B is formed by fixing fine particles containing at least resin fine particles b on the surface of mother particles A containing at least a binder resin, a colorant and a release agent. Thus, the mass of the resin forming the surface layer B is 2.0 to 20.0% by mass with respect to the mass of the base particle A, and the resin fine particle b is a sulfone represented by the following formula (1). A resin fine particle containing a resin having at least a polyester unit obtained by polycondensation of a unit having an acid substituent and a polyhydric alcohol and a polyvalent carboxylic acid, and the number average particle diameter of the resin fine particle b is 10 to 150 nm. The acid value of the resin forming the resin fine particles b is 5.0 to 40.0 mgKOH / g, and the ratio of the sulfur element amount to the acid value in the resin forming the resin fine particles b (S / AV )But A toner which is a 0.02 to 0.30 mmol / mg KOH.

(In the formula 1, R ₁ represents a very good hydrocarbon group a cyclic structure, said R ₁ may have a substituent, R ₂ represents a methyl group, an ethyl group or an isopropyl group.)

  According to a preferred embodiment of the present invention, it is possible to provide a toner having a good rise in frictional charge, a stable image density and image quality even in various environmental changes, and excellent durability stability.

（式１中、Ｒ_１は環状構造をとっても良い炭化水素基を示し、該Ｒ_１は置換基を有していてもよく、Ｒ_２はメチル基、エチル基又はイソプロピル基を示す。） A preferred embodiment of the present invention will be described.
The toner of the present invention is a toner having toner particles in which a surface layer B is formed by fixing fine particles containing at least resin fine particles b on the surface of mother particles A containing at least a binder resin, a colorant and a release agent. The mass of the resin forming the surface layer B is 2.0 to 20.0% by mass with respect to the mass of the base particle A, and the resin fine particles b are represented by the following formula (1). Resin fine particles containing a resin having at least a polyester unit obtained by polycondensation of a unit having a sulfonic acid substituent and a polyhydric alcohol and a polyvalent carboxylic acid, and the number average particle diameter of the resin fine particles b is 10 The acid value of the resin forming the resin fine particles b is 5.0 to 40.0 mgKOH / g, and the ratio of the amount of sulfur element in the resin forming the resin fine particles b to the acid value (S / V), characterized in that a 0.02 to 0.30 mmol / mg KOH.

(In the formula 1, R ₁ represents a very good hydrocarbon group a cyclic structure, said R ₁ may have a substituent, R ₂ represents a methyl group, an ethyl group or an isopropyl group.)

  As described above, the present invention relates to a toner that has both triboelectric charging characteristics and durability stability by concentrating units having sulfonic acid-based substituents on the surface layer of toner particles and forming a strong surface state. .

Various means can be considered as means for concentrating the unit having a sulfonic acid substituent on the surface of the toner particle. Most preferably, it is fixed to the surface of the base particle.
For example, when a resin containing a high concentration of the unit having the sulfonic acid-based substituent is added together with the polymerizable monomer in the suspension polymerization method, the polymerizable monomer composition is added to the aqueous medium to add toner particles. In the granulation step of dispersing in the diameter, the stability of the droplets of the polymerizable monomer composition cannot be obtained, and it becomes difficult to obtain a desired particle size. Furthermore, a resin containing a unit having a sulfonic acid type substituent is compatible with the toner binder, and a desired triboelectric unit density may not be obtained on the toner surface.

  In the present invention, the resin fine particles b are resin fine particles containing a resin having at least a unit having a sulfonic acid substituent. Then, by fixing the fine particles containing the resin fine particles b to the toner base particles A as the surface layer B, the density of the unit having the sulfonic acid-based substituent can be further improved and the triboelectric charging characteristics can be improved. all right.

  In the present invention, the resin fine particles b are resin fine particles containing a resin having at least a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid, thereby obtaining further triboelectric charging characteristics. I found out that Although the details are not clear, the resin fine particles b having a polyester unit are easily fixed uniformly to the mother particle A, and the action of confining a compound that adversely affects the frictional charging property such as wax contained in the mother particle A inside the particle. It can be considered excellent.

In the present invention, a known method can be used to obtain resin fine particles b containing a resin containing a high concentration of the unit having a sulfonic acid substituent.
Specifically, the following methods are mentioned. There is a method in which fine particles are obtained by synthesizing a resin containing a unit having a sulfonic acid-based substituent and then emulsifying in a water-based medium. By producing fine particles in an aqueous medium, uniform fine particles having a small particle size and a narrow particle size distribution can be obtained, which is a preferred embodiment. At that time, if the acid value of the resin is too high, the water-solubility of the resin is expressed and it becomes difficult to obtain fine particles. In order to improve the density of units having a sulfonic acid-based substituent while suppressing the acid value, it is necessary that at least the unit having the sulfonic acid-based substituent has a structure having no acid value. Specifically, the sulfonic acid group is esterified to form a structure in which acid dissociation hardly occurs in an aqueous medium.

The acid value of the resin forming the resin fine particles b is 5.0 to 40.0 mg KOH / g, so that the resin fine particles b can be uniformly fixed to the mother particles A. The acid value of the resin is preferably 7.0 to 30.0 mgKOH / g, and more preferably 9.0 to 20.0 mgKOH / g.
When the acid value is less than 5.0 mgKOH / g, the fixing strength with the mother particle A may be lowered. On the other hand, when the acid value is larger than 40.0 mgKOH / g, the water-soluble tendency of the resin fine particles b becomes strong, so that the fixing process may be difficult in a wet manufacturing method.
A known method can be used to adjust the acid value of the resin. For example, a method of controlling the amount ratio of acid monomers in resin production, or preparing an acid value by transesterification of a sulfonic acid ester portion represented by the above formula (1) after resin production can be mentioned.

The object of the present invention is when the ratio of the sulfur element amount and the acid value (sulfur element amount [S] / acid value [AV]) in the resin forming the resin fine particles b is 0.02 to 0.30 mmol / mg KOH. Is achieved. The amount of sulfur element [S] / acid value [AV] is preferably 0.05 to 0.25 mmol / mg KOH, more preferably 0.10 to 0.20 mmol / mg KOH.
This value indicates that the amount of units having a sulfonic acid-based substituent contained in the resin fine particles b is larger than that in the case where a conventional friction charging resin is used as the fine particles. The measurement of the amount of sulfur element will be described later.
If the value of the sulfur element amount [S] / acid value [AV] is smaller than 0.02 mmol / mg KOH, the triboelectric charge control function is difficult to be exhibited, or there may be a problem in toner production. On the other hand, when it exceeds 0.30 mmol / mg KOH, the compatibility with the mother particle A is lowered from the composition surface, and it may be difficult to obtain the fixing strength. The amount of sulfur element [S] / acid value [AV] satisfies the above range by adjusting the unit ratio of sulfonic acid groups, sulfonic acid ester groups, carboxyl groups, etc. in the resin forming the fine particles. Is possible.

  In the present invention, a known method can be used to form the surface layer B on the surface of the base particle A. For example, a method of adding a share by mixing fine particles containing base particles A and resin fine particles b, or adding fine particles containing resin fine particles b forming the surface layer B in an aqueous medium containing the mother particles A A method of forming the surface layer B by controlling the temperature, pH, time, or changing the conditions for adding an aggregating agent to the electrolyte can be given.

In the present invention, in order to form the surface layer B by fixing the fine particles containing the resin fine particles b uniformly and firmly on the surface of the base particles A, the following configuration is important.
That is, in order to obtain the film uniformity of the surface layer B, the number average particle diameter of the resin fine particles b is 10 to 150 nm. This makes it possible to obtain uniform triboelectric charging characteristics and film strength, which are the objects of the present invention. The smaller the particle size of the resin fine particles b, the easier it is to obtain film uniformity. However, if the particle size is less than 10 nm, the composition distribution tends to occur in the individual fine particles, and there is concern about uneven distribution of the triboelectric charging unit. A decrease in rate may occur. Further, when the number average particle diameter is larger than 150 nm, the toner surface after fixing may be uneven, and the image characteristics may be deteriorated due to the release of these fine particles. The number average particle diameter is preferably 30 to 120 nm, more preferably 50 to 100 nm.
The number average particle diameter of the resin fine particles b can satisfy the above range by adjusting the granulation conditions at the time of producing the fine particles. Specifically, the solid-liquid ratio in the aqueous medium, the pH of the aqueous medium, the stirring speed, and the like can be mentioned.

In the present invention, the mass of the resin forming the surface layer B is 2.0% with respect to the mass of the base particle A.
It is thru | or 20.0 mass%, Preferably it is 2.5 to 10.0 mass%, More preferably, it is 3.0 to 7.0 mass%. When the above range is satisfied, the unit having the sulfonic acid substituent represented by the above formula (1) can easily form the surface layer B in a uniform and high density state, and the object of the present invention can be achieved. If the amount is less than 2.0% by mass, the base particle A may not be uniformly covered, and the effect is difficult to obtain. On the other hand, if the amount is more than 20.0% by mass, the fine particles may be partially peeled off.

The resin fine particle b used in the present invention contains a resin having at least a unit having a sulfonic acid substituent represented by the following formula (1) and a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. Resin fine particles. The resin fine particle b is a resin fine particle containing a resin having at least a unit having a sulfonic acid-based substituent represented by the following formula (1) and a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. This can be analyzed using FT-IR spectrum, ¹ H-NMR, and ¹³ C-NMR as described later. The resin forming the resin fine particles b preferably contains 5 to 25% by mass of the unit having the sulfonic acid-based substituent with respect to the total amount of the resin.

（式１中、Ｒ_１は環状構造をとっても良い炭化水素基を示し、該Ｒ_１は置換基を有していてもよく、Ｒ_２はメチル基、エチル基又はイソプロピル基を示す。）

上記式（１）中のＲ_２はメチル基、エチル基、又はイソプロピル基である。イソプロピル基よりも炭素数の大きな脂肪族基を導入した場合には該エステル基自体の安定性が低下し、トナー作製時にエステル基が遊離するなどして所望の摩擦帯電性能が得られない場合があり好ましくない。

(In the formula 1, R ₁ represents a very good hydrocarbon group a cyclic structure, said R ₁ may have a substituent, R ₂ represents a methyl group, an ethyl group or an isopropyl group.)

R ₂ in the above formula (1) is a methyl group, an ethyl group, or an isopropyl group. When an aliphatic group having a carbon number larger than that of an isopropyl group is introduced, the stability of the ester group itself is lowered, and the desired triboelectric charging performance may not be obtained due to liberation of the ester group during toner preparation. There is not preferable.

  Examples of the unit having a sulfonic acid substituent include the following units.

（式２中、Ｒ_１ａは置換基を有していてもよい芳香族基を示し、Ｒ_２はメチル基、エチル基又はイソプロピル基を示す。） The resin fine particles b include a resin having at least a unit having an aromatic sulfonic acid substituent represented by the following formula (2) and a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. Fine particles are preferred. Resin fine particles containing a resin in which the resin fine particles b have at least a unit having an aromatic sulfonic acid substituent represented by the following formula (2) and a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid It can be analyzed using FT-IR spectrum, ¹ H-NMR, ¹³ C-NMR as described later.

(In Formula 2, R _1a represents an aromatic group which may have a substituent, and R ₂ represents a methyl group, an ethyl group or an isopropyl group.)

In the unit represented by the above formula (1) or (2), a known synthesis method can be used for the synthesis method of the sulfonate ester.
That is, for example, when preparing the vinyl-based unit represented by the above (Structural Formula 5), 2-acrylamido-2-methylpropanesulfonic acid is copolymerized with styrene and (meth) acrylic acid ester as shown below. After obtaining (A), a method of esterifying the side chain sulfonic acid group may be used. On the other hand, after the side chain sulfonic acid group of 2-acrylamido-2-methylpropanesulfonic acid is methyl esterified to obtain (B), (B) and a vinyl monomer may be copolymerized. As a method for obtaining (B), a known method can be used.

On the other hand, as a method of methyl esterifying the side chain of the copolymer (A), for example, the following method can be used. 10 parts by mass of the copolymer (A) is put into a reaction vessel, 350 parts by mass of chloroform and 87.5 parts by mass of methanol are added and dissolved, and the temperature is cooled to 0 ° C. To this, 20 mL of a 2 mol / liter trimethylsilyldiazomethane-hexane solution (for example, manufactured by Aldrich) is added and stirred for 4 hours. Thereafter, the solvent is distilled off by distillation.
Furthermore, 350 parts by mass of toluene and 100 parts by mass of 2-butanone are added to redissolve the polymer, and the solvent is distilled off by distillation. This re-dissolution / distillation operation is repeated three times and dried at a temperature of 50 ° C. under reduced pressure. The obtained solid is pulverized to obtain the compound of the above (Structural Formula 5).

As described above, the resin fine particles b are particularly preferably resin fine particles containing a resin having a unit having an aromatic sulfonic acid substituent represented by the above formula (2). As a result, the adhesiveness with the mother particles derived from the high triboelectric chargeability is strengthened, and the toner becomes more durable. As the structure of the unit, as represented by the above formula (2), R _1a is a unit containing an aromatic group having an aromatic ring such as a phenyl group or a naphthyl group which may have a substituent. It is a preferred embodiment.
Specific examples include units containing the following aromatic groups.

As described above, the resin fine particles b are resin fine particles containing a resin having at least a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid.
The resin having the polyester unit means that it contains at least a polyester structure formed by polycondensation of a polyhydric alcohol component and a polyvalent carboxylic acid component.

The following are mentioned as a polyhydric alcohol component which can be used by this invention.
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2. 0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) alkylene oxide adducts of bisphenol A such as -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, neopentyl glycol, 1,4-butenediol Dihydric alcohol components such as 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A .
Sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol Trivalent or higher alcohol components such as 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxymethylbenzene.

Examples of the polyvalent carboxylic acid component include the following.
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides; substituted with an alkyl group having 6 to 12 carbon atoms Succinic acid or anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or anhydrides thereof.

  Among them, a carboxylic acid component (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, etc.) comprising a bisphenol derivative as an alcohol component and a divalent or higher carboxylic acid or acid anhydride thereof, or a lower alkyl ester thereof. , Terephthalic acid, trimellitic acid, pyromellitic acid, etc.) as an acid component, and a polyester unit obtained by condensation polymerization of these can be preferably used. The resin forming the resin fine particles b preferably contains 30 to 80% by mass of the polyester unit with respect to the total amount of the resin.

The object of the present invention can be achieved more suitably by the resin fine particles b being resin fine particles containing a hybrid resin having units formed from styrene. Here, the hybrid resin means a resin having both a vinyl resin structure and a polyester structure in the molecule.
The unit having a sulfonic acid-based substituent is preferably present in the hybrid resin. When the unit having the sulfonic acid-based substituent is present in the hybrid resin, the adhesiveness of the surface layer B to the mother particles A is enhanced, and a uniform surface layer B is easily formed.

In the hybrid resin, the styrene modification ratio is preferably 10.0 to 90.0%, and more preferably 20.0 to 60.0% from the viewpoint of the production method.
In addition, a known method can be used to adjust the vinyl modification ratio in the hybrid resin.
Specifically, an arbitrary modification ratio can be prepared by changing the charged amount ratio of the polyester component and the vinyl monomer component to be used. In the present invention, the unit having a sulfonic acid substituent may be present in either a vinyl resin unit or a polyester unit, and may be present in a side chain or a terminal.

The hybrid resin contained in the resin fine particles b may contain a known vinyl unit in addition to the unit formed from styrene.
Examples of the vinyl monomer that can be used in the hybrid resin include the following monomers.
Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; C such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride Vinyl esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as dodecyl acid, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid Propyl, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic Acrylic esters such as phenyl oxalate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N- N-vinyl compounds such as vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid Unsaturated dibasic acids such as acid, fumaric acid, mesaconic acid; unsaturated dibasic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride; Methyl half ester, ethyl maleate half ester, butyl maleate half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester, methyl fumarate Half ester, half ester of unsaturated dibasic acid such as methyl mesaconic acid half ester; unsaturated dibasic acid ester such as dimethyl maleic acid, dimethyl fumaric acid; α, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid β-unsaturated acid; α, β-unsaturated acid anhydride such as crotonic acid anhydride, cinnamic acid anhydride, anhydride of α, β-unsaturated acid and lower fatty acid; alkenylmalonic acid, alkenylglutaric acid, Alkenyl adipic acid, these acids Monomers having a carboxyl group such as anhydrides and monoesters thereof; acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy A monomer having a hydroxyl group such as -1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

  Furthermore, the weight average molecular weight Mw of the resin forming the resin fine particles b is preferably 5000 to 50000, more preferably 7000 to 30000, in order to achieve the object of the present invention.

Various known methods can be used as a method for producing the resin for forming the resin fine particles b. In the case where the resin having a polyester unit is a polyester resin, the following method is exemplified. (1) A method of converting to a unit having a sulfonic acid-based substituent by an organic reaction using a reaction residue of a carboxyl group or a hydroxyl group contained in a polyester unit. (2) A method for producing a polyester using a polyhydric alcohol or a polycarboxylic acid having a unit having a sulfonic acid-based substituent. (3) A method in which a functional group that facilitates introduction of a sulfonic acid-based substituent is previously introduced into a polyhydric alcohol or polycarboxylic acid.
In addition, when the resin having a polyester unit is a hybrid resin, the following method is exemplified. (4) A method of hybridizing a polyester resin containing a unit having a sulfonic acid substituent with a vinyl monomer. (5) A method in which a resin having a carboxyl group such as (meth) acrylic acid is used as a vinyl monomer, and then the acid group is converted into a unit having a sulfonic acid substituent by an organic reaction. (6) A method of hybridizing a polyester resin using a vinyl monomer having a unit having a sulfonic acid-based substituent.

As a method for hybridizing a polyester resin with a vinyl monomer containing styrene, a known method can be used, which is effective as the method (4).
Specific examples include a method of producing a hybrid resin by performing vinyl modification of a polyester with a peroxide-based initiator or graft-modifying a polyester resin having an unsaturated group.

  Examples of (5) include the following methods. A carboxyl group present in the resin is amidated using a compound having an amino group and a sulfonic acid group such as aminomethanesulfonic acid or aminoethanesulfonic acid (taurine), and the sulfonic acid is esterified with a known esterifying agent. how to.

The method for preparing the resin fine particles b is not particularly limited, and examples thereof include a method in which a resin is dissolved or melted in a solvent to be liquefied and suspended or phase-inverted in an aqueous medium. At this time, known surfactants and dispersants can be used, and the resin forming the resin fine particles b can be made self-emulsifying.

Although there is no restriction | limiting in particular as a solvent which can be used when melt | dissolving the said resin in a solvent and preparing microparticles | fine-particles, The following can be mentioned.
Hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane; ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate; ether solvents such as diethyl ether; Ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane; alcohol solvents such as methanol, ethanol and butanol.

The toner base particles A that can be used in the present invention contain at least a binder resin, a colorant, and a release agent.
Although the weight average particle diameter of the mother particle A depends on the film thickness of the surface layer B, 3 to 10 μm is preferably used.

  Further, as the binder resin constituting the mother particle A, a known resin can be used, and examples thereof include the following. Styrene resin, acrylic resin (including methacrylic resin), styrene-acrylic resin (including methacrylic resin), polyethylene resin, polyethylene-vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenol resin, polyurethane resin, Polybutyral resin, polyester resin, and hybrid resin in which those resins are arbitrarily combined. Those resins may have a crosslinked structure as required.

Moreover, a well-known thing can be utilized as a coloring agent which can be used for the mother particle A.
The toner of the present invention may be either a magnetic toner or a nonmagnetic toner.
When used as a magnetic toner, the following magnetic materials are preferably used when the mother particles A are produced.
Examples of the magnetic material contained in the magnetic toner include the following.
Iron oxide such as magnetite, maghemite, ferrite, or iron oxide containing other metal oxides; metals such as Fe, Co, Ni, or these metals and Al, Co, Cu, Pb, Mg, Ni, Sn , Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, alloys with metals such as V, and mixtures thereof.
Specific examples include the following. Iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), iron yttrium oxide (Y ₃ Fe ₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), copper iron oxide (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₁₂ O ₁₉ ), nickel iron oxide (NiFe ₂ O ₄ ), neodymium iron oxide (NdFe ₂ O ₃ ), iron barium oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (Fe) , Cobalt powder (Co), nickel powder (Ni).
The magnetic materials described above are used alone or in combination of two or more. A magnetic material particularly suitable for the purposes of the present invention is a fine powder of iron trioxide or γ-iron trioxide.

The magnetic material preferably has a number average particle size of 0.1 to 2.0 μm (more preferably 0.1 to 0.3 μm). Moreover, the magnetic material has a coercive force (Hc) of 1.6 to 12 kA / m (20 to 150 oersted) and a saturation magnetization (σs) as magnetic characteristics when 795.8 kA / m (10K oersted) is applied. 5 to 200 Am ² / kg (5 to 200 emu / g) (more preferably 50 to 100 / Am ² / kg), and residual magnetization (σr) is ^{2 to 20} Am ² / kg ( ^{2 to 20} emu / g). Is preferred.
The content of the magnetic material in the mother particle A is preferably 10 to 200 parts by mass, and more preferably 20 to 150 parts by mass with respect to 100 parts by mass of the binder resin.

On the other hand, as a colorant for use as a non-magnetic toner, known colorants such as various conventionally known dyes and pigments can be used.
Examples of the magenta color pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207, 209, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.
The magenta pigment may be used alone or in combination with a dye and a pigment.

  Examples of the magenta dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Oil-soluble dyes such as Disperse Violet 1; I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

  Examples of the color pigment for cyan include the following. C. I. Pigment blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  Examples of the color pigment for yellow include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 65, 73, 83, 180, C.I. I. Bat yellow 1, 3, 20

  Examples of the black colorant include the following. Carbon black, aniline black, acetylene black, and toned to black using the yellow, magenta, and cyan colorants shown above. The content of the colorant in the mother particle A varies depending on the kind of the colorant, but is 0.1 to 50% by mass, preferably 0.5 to 40% by mass with respect to the mother particle A.

Since the toner of the present invention improves the offset property to the fixing device at the time of fixing, the mother particle A contains a release agent. There are no particular restrictions on the release agent that can be used in the toner of the present invention, and known ones can be used. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymers of aliphatic hydrocarbon waxes; Waxes mainly composed of fatty acid esters such as carnauba wax, sazol wax, and montanic acid ester wax; A partially esterified product of a monohydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and fats.
The amount of the release agent added to the base particle A is preferably 2.0 to 30.0% by weight, and more preferably 2.5 to 20.0% by weight with respect to the base particle A.

The mother particle A may contain an organometallic compound. For example, the metal compound of the aromatic oxycarboxylic acid derivative shown below is mentioned.

上記式中のＭ_２は２価の金属原子であり、Ｍｇ^２＋、Ｃａ^２＋、Ｓｒ^２＋、Ｐｂ^２＋、Ｆｅ^２＋、Ｃｏ^２＋、Ｎｉ^２＋、Ｚｎ^２＋、Ｃｕ^２＋が挙げられる。Ｍ_３は３価の金属原子であり、Ａｌ^３＋、Ｃｒ^３＋、Ｆｅ^３＋、Ｎｉ^３＋が挙げられる。Ｍ_４は４価の金属原子であり、Ｚｒ^４＋、Ｈｆ^４＋、Ｍｎ^４＋、Ｃｏ^４＋が挙げられる。これらの金属原子の中で好ましいのはＡｌ^３＋、Ｆｅ^３＋、Ｃｒ^３＋、Ｚｒ^４＋、Ｈｆ^４＋、Ｚｎ^２＋である。
また、式（ａ）乃至（ｊ）中、Ｒ_１〜Ｒ_４は同一または異なる基を示し、水素原子、炭
素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、−ＯＨ、−ＮＨ_２、−ＮＨ（ＣＨ_３）、−Ｎ（ＣＨ_３）_２、−ＯＣＨ_３、−Ｏ（Ｃ_２Ｈ_５）、−ＣＯＯＨまたは−ＣＯＮＨ_２を示す。好ましいＲ_１としては、ヒドロキシル基、アミノ基及びメトキシ基が挙げられるが、中でもヒドロキシル基が好ましい。

M ₂ in the above formula is a divalent metal atom, and examples thereof include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ and Cu ²⁺ . M ₃ is a trivalent metal atom, and examples thereof include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Ni ³⁺ . M ₄ is a tetravalent metal atom, and examples thereof include Zr ⁴⁺ , Hf ⁴⁺ , Mn ⁴⁺ , and Co ⁴⁺ . Among these metal atoms, Al ³⁺ , Fe ³⁺ , Cr ³⁺ , Zr ⁴⁺ , Hf ⁴⁺ and Zn ²⁺ are ^preferable .
In the formulas (a) to (j), R _{1 to} R ₄ represent the same or different groups, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, —OH, — _{NH 2, -NH (CH 3)} , - N (CH 3) 2, -OCH 3, -O (C 2 H 5), - shows a COOH or -CONH _2. Preferable R ₁ includes a hydroxyl group, an amino group, and a methoxy group, and among them, a hydroxyl group is preferable.

As a method for producing the mother particle A in the present invention, a known method can be used.
For example, the following method is mentioned. (1) A method in which toner particles are prepared by melt-kneading a binder resin, a colorant, and a release agent, finely pulverizing, and, if necessary, a pulverizing method. (2) A method of producing in an aqueous medium such as suspension polymerization method, dissolution suspension method, interfacial polymerization method, dispersion polymerization method, emulsion aggregation method.

In the present invention, the mother particles A are preferably particles obtained in an aqueous medium.
When the mother particles A are produced in an aqueous medium, the surface of the mother particles A tends to be relatively hydrophilic compared to those produced by a dry process. Accordingly, when the surface layer B is formed, the fine particles can be easily aggregated on the surface of the base particle, and a uniform film can be easily formed, whereby the fine particles can be firmly fixed.
Furthermore, it is more preferable in terms of productivity that the mother particle A is a particle obtained by a suspension polymerization method or a particle obtained by aggregating emulsified resin particles.

Specific examples for producing the mother particles A by the suspension polymerization method are shown below.
A monomer composition is prepared by uniformly dissolving or dispersing a polymerizable monomer, a colorant, and a release agent (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, a resin, and other additives). Then, the monomer composition is dispersed in a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer by using a suitable stirrer and simultaneously subjected to a polymerization reaction, whereby mother particles having a desired particle size are obtained. A can be obtained. The mother particles A obtained by this polymerization method are preferable because each particle shape is almost spherical and the distribution of the triboelectric charge amount is relatively uniform, so that it has high transferability.

  Examples of the polymerizable monomer that can be used in the suspension polymerization method include the following vinyl polymerizable monomers. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrene derivatives such as n-hexyl styrene, pn-octyl, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene; methyl acrylate, ethyl Acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n- Propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethylphos Fate ethyl methacrylate, dibutyl phosphate ethyl Methacrylic polymerizable monomers such as acrylate; methylene aliphatic monocarboxylic acid esters; vinyl acetate, vinyl propionate, vinyl benzoate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  Examples of the release agent that can be used in the suspension polymerization method include the following. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolactam, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, polyolefin waxes and derivatives thereof typified by polyethylene, carnauba wax, can Natural wax such as delilla wax and its derivatives. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. The content of the release agent in the toner is preferably 2.0 to 30.0% by mass.

  The following are mentioned as a polymerization initiator which can be used for the said suspension polymerization method. 2,2'-azobis- (2,4-divaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyloxy carbonate, cumene hydroperoxide, 2,4-dichloro Peroxide polymerization initiators such as benzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20% by mass relative to the polymerizable monomer, and may be used alone or in combination.

  In order to control the molecular weight of the binder resin, a chain transfer agent may be added. A preferable addition amount is 0.001 to 15% by mass with respect to the polymerizable monomer.

In order to control the molecular weight of the binder resin, the following crosslinking agent may be added.
Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and the above acrylates replaced with methacrylate of.
Moreover, the following are mentioned as a polyfunctional crosslinking | crosslinked monomer. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and methacrylate thereof, 2,2-bis (4-methacryloxy-polyethoxyphenyl) propane, diacrylphthalate, Triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diaryl chlorendate. A preferable addition amount is 0.001 to 15% by mass with respect to the polymerizable monomer.

The aqueous dispersion medium used in the suspension polymerization method is preferably water containing a dispersion stabilizer.
Preferred dispersion stabilizers include the following.
Tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Fine powder of inorganic compounds such as
Moreover, the following are mentioned as an organic dispersion stabilizer. Polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salt, polymethacrylic acid and its salt, starch. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

A surfactant may be used in combination with the above substances as a dispersion stabilizer. This is for accelerating the initial action of the dispersion stabilizer, and 0.001 to 0.1 parts by mass is sufficient for 100 parts by mass of the polymer monomer.
Specific examples of the surfactant include the following. Sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium octylate, sodium stearate, calcium oleate.

In the toner of the present invention, it is also preferable to prepare the mother particles A by an emulsion aggregation method.
Since the mother particle A is a particle obtained by aggregating at least emulsified resin particles, it is possible to produce the surface layer B containing the resin fine particles b and the like in the same process, which is preferable in terms of production cost. It becomes.

  It is more preferable that the emulsified resin particles forming the mother particles A are resins containing at least a polyester structure so that not only the triboelectric charging property of the toner but also the low-temperature fixability and high-speed fixability can be achieved.

As a method for producing the mother particle A by the emulsion aggregation method, a known method can be used.
Specifically, there is a method in which the constituent material of the mother particles is dispersed in an aqueous medium in the presence of a surfactant, and the ability of the surfactant is reduced and aggregated by dropping an inorganic salt or an inorganic metal salt thereto. Can be mentioned. After that, the aggregated particles are lightly fused at a temperature slightly higher than the glass transition temperature (Tg) of the resin particles contained in the constituent material (aggregation step), and a large amount of a surfactant is added to stabilize the particles. In this method, the mother particles A are obtained by applying sufficient heat (maturation step) to completely fuse the resin particles.

The aqueous medium that can be used in the emulsion aggregation method is water or alcohols, and two or more kinds may be mixed and used.
Moreover, as the surfactant, an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be used. Specific examples include sulfonates, fatty acid salts, sulfate ester salts, phosphate ester salts, amine salts, quaternary ammonium salts, polyethylene glycols, alkylphenol ethylene oxides, and polyhydric alcohols.

  In the case of the resin particles used as the binder resin of the mother particle A, it is only necessary to disperse in an aqueous medium containing a surfactant by gentle stirring, but in the case of other constituent materials such as colorants and release agents. It is necessary to atomize the number average particle size to about 20 nm to 300 nm by applying a high shear using a known disperser. Examples of the disperser include a homogenizer, an attritor, a paint shaker, a sand mill, a dissolver, a high speed mill, a ball mill, and a dyno mill.

In the present invention, the resin forming the surface layer B further contains the resin b2, and the toluene hexane solubility index TH (b) of the resin forming the resin fine particles b and the toluene hexane solubility index TH (b2) of the resin b2 It is preferable that the relationship between and satisfies the following formula (3).
Formula (3) | TH (b) −TH (b2) | ≧ 20
It is more preferable that the following formula (4) is satisfied.
Formula (4) | TH (b) −TH (b2) | ≧ 30

The toluene-hexane solubility index defined in the present invention is defined by the amount of hexane that begins to precipitate components when hexane is added to the toluene-soluble component of the toner. The toluene-hexane solubility index is an index that relatively indicates the affinity of the resin. Therefore, the larger the difference in the toluene-hexane solubility index between the resin fine particles b and the resin b2, the greater the phase separation between them, and the easier the domain formation when mixed.

As a method for measuring the toluene-hexane solubility index, for example, a Shimadzu spectrophotometer, UV-3300 (manufactured by Shimadzu Corporation) is used, and the measurement is performed under the following measurement conditions with an apparatus capable of stirring the inside of the quartz cell. Can do.
<Measurement conditions>
Sample preparation and measurement are performed at a temperature of 25 ° C.
A toluene solution (liquid temperature 25 ° C.) in which 100.0 parts by mass of resin is dissolved in 500.0 parts by mass of toluene is prepared. The resin dissolved and allowed to stand for about 15 hours is filtered through a sample processing filter (pore size 0.45 μm) to separate toluene-insoluble matter, and the filtrate is used as a measurement sample. The measurement sample thus obtained is put in a quartz cell having an optical path length of 1 cm, and a transmitted light spectrum is measured. The transmittance of light having a wavelength of 800 nm in the measurement sample is set to 100%.
When 120.0 parts by mass of the sample for measurement was precisely weighed and n-hexane was gradually added, the value of the amount of hexane added (parts by mass) when the light transmittance at a wavelength of 800 nm reached 50% was calculated as the resin. Toluene-hexane solubility index. A typical example of the transmittance curve is shown in FIG.
The toluene-hexane solubility index can be prepared according to the type and composition of the resin, the degree of polymerization, the type and amount of the monomer forming the resin, and the polymerization conditions when forming the resin. More specifically, the following can be mentioned. Molecular weight of resin, acid value; ratio of aromatic group or aliphatic group in polyester unit; hybrid ratio of vinyl unit and polyester unit, etc.

  It was found that the object of the present invention can be achieved more preferably by satisfying the above formula (3) in the present invention. Although details are not clear, it is considered that the durability is further improved because the surface layer B tends to be firmly fixed due to the presence of the resin b2. Further, it is considered that preferable triboelectric charging characteristics can be obtained when the resin fine particles b remain in the form of particles in the resin layer b2 in the surface layer B or form a certain amount of domains.

  If the difference between the toluene-hexane solubility index of the resin fine particles b and the toluene-hexane solubility index of the resin b2 is out of the range shown in the above formula (3), the respective resins are likely to be compatible with each other, and it is difficult to form a uniform film. Or the density of the unit having a sulfonic acid-based substituent represented by the above formula (1) or (2) may be lowered, making it difficult to obtain good triboelectric charging characteristics.

  Various known methods can be used as a method of incorporating the resin b2 into the resin forming the surface layer B. For example, a method of fixing the resin fine particles b and the finely divided resin b2 to the base particles A at the same time can be mentioned. At that time, in order to leave the resin fine particles b as domains in the surface layer B, it is effective to perform the fixing step with the minimum heat for melting the finely divided resin b2. Other methods include seed polymerization of a monomer capable of forming the resin b2 after the resin fine particles b are fixed to the mother particles A, or resin b2 after the resin fine particles b are fixed to the mother particles A. Examples thereof include a spray drying method in which a liquid having dissolved therein is sprayed in a fluidized bed.

Further, the glass transition temperature (Tg) of each of the resin fine particles b and the resin b2 can be changed by selecting a radical polymerizable monomer. For example, the resin b2 includes a method of copolymerizing an acrylic monomer for lowering Tg.
The following are mentioned as a monomer used in order to form resin b2. Specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso
-Propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, Acrylic polymerizable monomers such as dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate Over DOO, n- amyl methacrylate, n- hexyl methacrylate, 2-ethylhexyl methacrylate, n- octyl methacrylate, n- nonyl methacrylate, diethyl phosphate ethyl methacrylate, such as methacrylic polymerizable monomers dibutyl phosphate ethyl methacrylate. These can be used by homopolymerization and copolymerization.

  In the present invention, a fluidity improver may be further added to the toner particles on which the surface layer B is formed. As a specific addition method, a fluidity improver and toner particles can be sufficiently mixed by a mixing machine such as a Henschel mixer to obtain a toner with improved fluidity.

Examples of the fluidity improver include the following.
Fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder by wet process, silica fine powder such as silica fine powder by dry process, these silica fine powders as silane coupling agent, titanium cup Treated silica fine powder surface-treated with a treating agent such as a ring agent or silicone oil; titanium oxide fine powder; alumina fine powder, treated titanium oxide fine powder, treated alumina oxide fine powder.
A fluidity improver having a specific surface area of 30 to 400 m ² / g, preferably 50 to 300 m ² / g by nitrogen adsorption measured by the BET method gives good results.
The fluidity improver is added in an amount of 0.01 to 8.0 parts by weight, preferably 0.1 to 4.0 parts by weight, based on 100 parts by weight of the toner particles.

In the present invention, the weight average particle diameter (D4) of the toner is preferably 3.0 to 15.0 μm, and more preferably 4.0 to 12.0 μm.
When the weight average particle diameter (D4) of the toner is less than 3.0 μm, it is difficult to achieve tribocharging stabilization when applied to an electrophotographic development system, and in a continuous development operation (endurance operation) of a large number of sheets, Fog and toner scattering are likely to occur.
On the other hand, when the weight average particle diameter (D4) of the toner exceeds 15.0 μm, the reproducibility of the halftone portion is lowered, and the obtained image tends to be a loose image, which is not preferable.

  The toner of the present invention can be used as a one-component developer obtained by mixing toner particles and the fluidity improver, or as a two-component developer obtained by mixing toner particles, the fluidity improver, and a magnetic carrier. .

  When the toner of the present invention is used for a two-component developer, the toner is used by mixing with a magnetic carrier. Examples of magnetic carriers include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, and ferrite fine particles. Can be used. Further, by using a magnetic fine particle dispersed resin carrier in which magnetic fine particles are dispersed in a resin, the triboelectric charging characteristics of the present invention can be achieved more preferably.

The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particles, and a method in which the magnetic carrier core particles and the coating material are mixed with powder. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier core particles include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (more preferably 0.5 to 20% by mass) with respect to the carrier core particles. The number average particle diameter of these carriers is preferably 10 to 100 μm, and more preferably 20 to 70 μm.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  Hereinafter, methods for measuring various physical properties of the toner of the present invention will be described.

<Measurement of resin particle size>
The number average particle diameter of the resin fine particles in the present invention was determined by the following method.
Using a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), measurement was performed with a range setting of 0.001 μm to 10 μm, and the number average particle size was determined.

<Composition analysis of resin>
The structure of the produced resin was determined using the following apparatuses (1) and (2).
(1) FT-IR spectrum manufactured by Nicolet AVATAR360FT-IR
(2) ¹ H-NMR, ¹³ C-NMR
FT-NMR JNM-EX400 manufactured by JEOL (solvent: heavy chloroform)

<Resin acid value>
The acid value of the resin in the present invention was determined by the following method.
Basic operation is based on JIS K-0070.
1) Weigh accurately 0.5 to 2.0 g of pulverized sample. The mass at this time is defined as W (g).
2) Put the sample in a 300 ml beaker, and add 150 ml of a toluene / ethanol (4/1) mixture to dissolve.
3) Perform titration using a 0.1 mol / l ethanol solution of KOH using a potentiometric titrator (for example, a potentiometric titrator AT-400 (winworkstation) manufactured by Kyoto Electronics Co., Ltd.) and an ABP-410 electric burette. Automatic titration using can be used.)
4) The amount of KOH solution used at this time is S (ml). At the same time, a blank is measured, and the amount of KOH used at this time is defined as B (ml).
5) Calculate the acid value according to the following formula. f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W

<Quantification of the amount of sulfur element in the resin>
A method for determining the amount of sulfur element contained in the resin is described below. Specifically, the resin is introduced into an automatic sample combustion device (device name: AQF-100 pretreatment device for ion chromatograph, manufactured by Dia Instruments Co., Ltd.), the polymer is combusted and gas is absorbed into the absorption liquid. I let you. Next, ion chromatography (device name: ion chromatograph ICS2000
Column: IONPAC AS17, manufactured by Nippon Dionex Co., Ltd.), the amount of sulfur element in the resin (mmol / g) was calculated.

<Calculation of Sulfur Element Amount and Acid Value Ratio (S / AV)>
The S / AV value was calculated from the acid value and sulfur element content of the resin obtained by the measurement method according to the following formula.
S / AV (mmol / mg KOH) = (Sulfur element amount: mmol / g) / (Acid value: mg KOH / g)

<Weight average particle diameter of toner base particles or toner>
The weight average particle diameter (D4) of the toner base particles or toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube. And the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis. The measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, dedicated software was set up as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) The value obtained using the above was set. The threshold and noise level were automatically set by pressing the threshold / noise level measurement button. The current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and the aperture tube flash after the measurement was checked.
In the “Pulse to Particle Size Conversion Setting Screen” of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution was placed in a glass 250 ml round-bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rpm. The dirt and bubbles in the aperture tube were removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion-exchanged water was added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water was added, and about 2 ml of the above-mentioned Contaminone N was added to this water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker was maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) was irradiated with ultrasonic waves, about 10 mg of toner was added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion treatment was further continued for 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in a sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed using a pipette is dropped to prepare a measurement concentration of about 5%. . The measurement was performed until the number of measured particles reached 50000.
(7) The measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) was calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Weight average molecular weight (Mw) of resin>
The molecular weight and molecular weight distribution of the resin are calculated in terms of polystyrene by gel permeation chromatography (GPC), but the column elution rate is the amount of acid groups in the resin containing acid groups. Therefore, accurate molecular weight and molecular weight distribution are not measured. Therefore, it is necessary to prepare a sample in which an acid group is capped in advance. Methyl esterification is preferable for capping, and a commercially available methyl esterifying agent can be used. Specifically, a method of treating with trimethylsilyldiazomethane can be mentioned. Therefore, the resin containing an acid group in the resin was capped with an acid group by a conventional method as needed.
Measurement of molecular weight and molecular weight distribution of the resin by GPC was performed as follows.
The solution was added to THF (tetrahydrofuran) and allowed to stand at room temperature for 24 hours. The solution was filtered through a solvent-resistant membrane filter having a pore diameter of 0.2 μm to obtain a sample solution, and measurement was performed under the following conditions. In addition, sample preparation prepared the quantity of THF so that the density | concentration of resin might be 0.4-0.6 mass%.

Apparatus: High-speed GPC HLC8120 GPC (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804,
Seven series of 805, 806, 807 (made by Showa Denko KK)
Eluent: Tetrahydrofuran Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the weight or number average molecular weight of the sample, standard polystyrene resin (TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F- manufactured by Tosoh Corporation) was used. 20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) were used.

<Measurement of glass transition temperature (Tg) of resin>
The glass transition temperature (Tg) of the resin was measured using a DSC measuring apparatus (manufactured by M-DSC TA-Instruments). For measurement, 6 mg of a sample was precisely weighed and used. A precisely weighed measurement sample is put in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement is performed at a temperature rise rate of 2 ° C./minute at a temperature rise rate of 2 ° C./min. It was. At this time, the measurement was performed with a modulation amplitude of ± 0.6 ° C. and a frequency of 1 / min. And the glass transition temperature (Tg) was computed from the reversing heat flow curve obtained. In the calculation, the midpoint of the straight line connecting the intersections of the tangent lines of the base line and the endothermic curve was obtained, and this was defined as the glass transition temperature (Tg).

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. All parts used in the examples indicate parts by mass.
[Production example of resin fine particles b]
The resin for forming the resin fine particles b was synthesized by the method described below.

<Production Example 1 of resin for resin fine particle b>
In a reaction vessel equipped with a condenser, a stirrer, a thermometer, and a nitrogen introduction tube, 66.1 parts of bisphenol A / propylene oxide 2 mol adduct [BP-A (PO)], dimethyl terephthalic acid [DM-TPA] 33.9 parts and 2 parts of potassium titanyl oxalate as a condensation catalyst were added, and the reaction was carried out for 10 hours while distilling off the methanol generated under a nitrogen stream at an internal temperature of 220 ° C. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and it took out when the hydroxyl value became 50 or more, and obtained the polyester resin. This polyester resin had an acid value of 0.6, a hydroxyl value of 51, Tg of 53 ° C., Mn of 1890, and Mw of 4610.
To a solution obtained by dissolving 20 parts of the obtained polyester resin in 80 parts of methoxybutyl acetate, a mixture of 3.0 parts of 2-methacryloyloxyethyl isocyanate, 0.03 part of dibutyltin laurate and 10 parts of methoxybutyl acetate was added dropwise. While the progress of the reaction was monitored by IR (infrared absorption spectrum), the reaction was continued until the peak due to the isocyanate group of 2200 cm −1 disappeared. The reaction solution was added dropwise to hexane for reprecipitation purification. After filtration, it was dried under reduced pressure to obtain a polyester resin 1 having an unsaturated bond at the terminal.
Subsequently, 100 parts of xylene and 60 parts of polyester resin 1 were charged into a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and stirred at 50 ° C. in a nitrogen stream.
・ Methyl 2-acrylamido-phenylsulfonate 15.0 parts ・ Styrene 23.8 parts ・ Acrylic acid 1.2 parts ・ T-butyl peroxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts

The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane and dried at 40 ° C. under reduced pressure to obtain Resin I for resin fine particles b-1. From the result of ¹ H-NMR, the obtained resin was confirmed to have a peak derived from methyl sulfonate, and was confirmed to contain 1.95 mmol / g of sulfur element by ion chromatography elemental analysis.

<Production example 2 of resin for resin fine particle b>
In a reaction vessel equipped with a condenser, a stirrer, a thermometer, and a nitrogen inlet tube, 26.6 parts of propylene glycol [PG], 103.8 parts of terephthalic acid [TPA], adipic acid [ADA] 9
. 7 parts, 23.5 parts of maleic anhydride [MAH] and 2.0 parts of tetrastearyl titanate as a condensation catalyst were added and reacted at 230 ° C. for 6 hours while distilling off the water generated in a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg for 8 hours, and the unsaturated polyester resin 2 was obtained. This polyester resin 2 did not contain THF-insoluble matter, and had an acid value of 15.0, a hydroxyl value of 61.0, Tg of 47.2 ° C., Mn of 1900, and Mw of 3900.

Next, 100 parts of xylene and 85 parts of polyester resin 2 were charged into a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and stirred at 50 ° C. in a nitrogen stream.
・ Methyl 2-acrylamido-ethanesulfonate 15.0 parts ・ t-butyl peroxyisopropyl monocarbonate (Perbutyl I manufactured by Nippon Oil & Fats Co., Ltd.) 1.6 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature The temperature was raised to 120-125 ° C. The mixture was stirred for 6 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane and dried at 40 ° C. under reduced pressure to obtain Resin II for resin fine particles b-2. Resin II did not contain THF-insoluble matter, and had an acid value of 70.5, a hydroxyl value of 35.9, Tg of 59.5 ° C., Mn of 2800, and Mw of 8300.

<Production Example 3 of Resin for Resin Fine Particles b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 70.0 parts of bisphenol A / propylene oxide 2-mol adduct, 25 parts of terephthalic acid, 5.0 parts of trimellitic anhydride [TMAH] And 2 parts of potassium titanyl oxalate as a condensation catalyst,
The reaction was carried out for 10 hours while distilling off the water produced at 0 ° C. under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and when the acid value became 25, it took out and the polyester resin 3 was obtained. This polyester resin 3 had a THF insoluble content of 9.0%, an acid value of 24.5, a hydroxyl value of 33.0, Tg of 64 ° C., Mn of 4700, and Mw of 36200.

Next, 233 parts of polyester resin 3 and 38 parts of taurine were placed in a reaction vessel equipped with a cooling pipe, a stirrer, a thermometer, and a nitrogen introduction pipe, and after adding 380 parts of pyridine and stirring, triphenyl phosphite 135 parts were added and heated at 120 ° C. for 6 hours. After completion of the reaction, it was recovered by reprecipitation in 500 parts of ethanol. The obtained polymer was washed twice with 200 parts of 1N hydrochloric acid, then washed twice with 200 parts of water, and dried under reduced pressure. As a result of IR measurement, the peak at 1695 cm −1 derived from carboxylic acid decreased, and a new peak derived from an amide bond at 1658 cm −1 was confirmed. In addition, from the result of ¹ H-NMR, since the peak derived from the methylene group of taurine is shifted, it was confirmed that the obtained polymer contained a sulfonic acid substituent-containing unit.
Furthermore, 400 parts of trimethyl orthoformate was charged in a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube and heated to 80 ° C. To this, 100 parts of the polymer obtained was added in 5 minutes and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9000 parts of hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 parts of chloroform was added to the residue and dissolved. This was dropped into 7500 parts of hexane under stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 parts of methanol and further with 300 parts of water. This was dried under reduced pressure to obtain Resin III for resin fine particles b-3. Further, it was found by ion chromatography elemental analysis that the amount of sulfur element was 1.87 mmol / g.

<Production Example 4 of Resin for Resin Fine Particles b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-methacrylamide-5-methoxyphenylsulfonate 18.0 parts ・ Styrene 20.8 parts ・ Acrylic acid 1.2 parts ・ T-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried under reduced pressure at 40 ° C. to obtain a resin IV for resin fine particles b-4. From the result of ¹ H-NMR, it was confirmed that the obtained resin IV contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. It was also found by ion chromatography elemental analysis that the sulfur element content was 1.97 mmol / g.

<Production Example 5 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-acrylamide-5-methoxyphenylsulfonate 17.0 parts ・ 21.8 parts of styrene ・ 1.2 parts of acrylic acid .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried under reduced pressure at 40 ° C. to obtain a resin V for resin fine particles b-5. From the result of ¹ H-NMR, the obtained resin V was confirmed to contain a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. It was also found by ion chromatography elemental analysis that the amount of sulfur element was 1.99 mmol / g.

<Production Example 6 of resin for resin fine particle b>
Resin fine particle b-6 was prepared in the same manner as in Production Example 5 of resin for resin fine particle b except that methyl 2-acrylamido-5-methoxyphenylsulfonate was changed to methyl 2-methacrylamide-5-methylphenylsulfonate. Resin VI for was obtained. From the result of ¹ H-NMR, it was confirmed that the obtained resin VI contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. It was also found by ion chromatography elemental analysis that the amount of sulfur element was 2.08 mmol / g.

<Production Example 7 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-methacrylamide-5-methoxyphenylsulfonate 14.5 parts ・ Styrene 24.9 parts ・ Acrylic acid 0.6 parts ・ T-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane and dried at 40 ° C. under reduced pressure to obtain Resin VII for resin fine particles b-7. From the result of ¹ H-NMR, it was confirmed that the obtained resin VII contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. Further, it was found by ion chromatography elemental analysis that the amount of sulfur element was 1.63 mmol / g.

<Production Example 8 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-methacrylamide-5-methoxyphenylsulfonate 16.5 parts ・ Styrene 18.9 parts ・ Acrylic acid 4.6 parts ・ t-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane and dried at 40 ° C. under reduced pressure to obtain Resin VIII for resin fine particles b-8. From the result of ¹ H-NMR, it was confirmed that the obtained resin VIII contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. It was also found by ion chromatography elemental analysis that the amount of sulfur element was 1.77 mmol / g.

<Production Example 9 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ 2-methacrylamido-5-methoxyphenyl sulfonate 20.0 parts ・ Styrene 18.8 parts ・ Acrylic acid 1.2 parts ・ t-butyl peroxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried under reduced pressure at 40 ° C. to obtain a resin IX for resin fine particles b-9. From the results of ¹ H-NMR, it was confirmed that the obtained resin IX contained a sulfonic acid substituent-containing unit from a peak derived from ethyl sulfonate. Further, it was found by ion chromatography elemental analysis that the amount of sulfur element was 2.10 mmol / g.

<Manufacture example 10 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 13.5 parts ・ Styrene 25.3 parts ・ Acrylic acid 1.2 parts ・ t-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1 .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried under reduced pressure at 40 ° C. to obtain a resin X for resin fine particles b-10. From the result of ¹ H-NMR, it was confirmed that the obtained resin X contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. It was also found by ion chromatography elemental analysis that the amount of sulfur element was 1.95 mmol / g.

<Production Example 11 of Resin for Resin Fine Particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Isopropyl 2-acrylamido-2-methylpropanesulfonate 14.0 parts ・ Styrene 24.8 parts ・ Acrylic acid 1.2 parts ・ T-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1 .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried at 40 ° C. under reduced pressure to obtain Resin XI for resin fine particles b-11. From the result of ¹ H-NMR, it was confirmed that the obtained resin XI contained a sulfonic acid substituent-containing unit from a peak derived from isopropyl sulfonate. It was also found by ion chromatography elemental analysis that the amount of sulfur element was 1.84 mmol / g.

<Production Example 12 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-methacrylamide-n-butylsulfonate 14.0 parts ・ Styrene 24.8 parts ・ Acrylic acid 1.2 parts ・ T-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1 .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried at 40 ° C. under reduced pressure to obtain Resin XII for resin fine particles b-12. From the result of ¹ H-NMR, it was confirmed that the obtained resin XII contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. Further, it was found by ion chromatography elemental analysis that the amount of sulfur element was 1.75 mmol / g.

<Production Example 13 of Resin for Resin Fine Particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
-7.0 parts of 2-acrylamido-2-methylpropane sulfonic acid-33.0 parts of styrene-t-butyl peroxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts It was dripped at the said reaction container, and internal temperature was heated up at 120-125 degreeC. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane and dried at 40 ° C. under reduced pressure to obtain Resin XIII for resin fine particles b-13. From the result of ¹ H-NMR, it was confirmed that the obtained resin XIII contained a sulfonic acid substituent-containing unit from a peak derived from sulfonic acid. It was also found by ion chromatography elemental analysis that the sulfur element content was 1.10 mmol / g.

<Manufacture example 14 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ 2-acrylamide-2-methylpropanesulfonic acid 12.8 parts ・ styrene 27.2 parts ・ t-butyl peroxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts It was dripped at the said reaction container, and internal temperature was heated up at 120-125 degreeC. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried under reduced pressure at 40 ° C. to obtain a resin XIV for resin fine particles b-14. From the result of ¹ H-NMR, it was confirmed that the obtained resin XIV contained a sulfonic acid substituent-containing unit from a peak derived from sulfonic acid. It was also found by ion chromatography elemental analysis that the sulfur element content was 2.11 mmol / g.

<Production Example 15 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 13.0 parts ・ Styrene 21.5 parts ・ Acrylic acid 5.5 parts ・ T-butyl peroxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1 .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried under reduced pressure at 40 ° C. to obtain a resin XV for resin fine particles b-15. From the result of ¹ H-NMR, it was confirmed that the obtained resin XV contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. It was also found by ion chromatography elemental analysis that the amount of sulfur element was 1.86 mmol / g.

<Production Example 16 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 6.5 parts ・ Styrene 33.1 parts ・ Acrylic acid 0.4 parts ・ t-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1 .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane and dried at 40 ° C. under reduced pressure to obtain Resin XVI for resin fine particles b-16. From the result of ¹ H-NMR, it was confirmed that the obtained resin XVI contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. Further, it was found by ion chromatography elemental analysis that the amount of sulfur element was 0.93 mmol / g.

<Production Example 17 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 19.5 parts ・ Styrene 19.3 parts ・ Acrylic acid 1.2 parts ・ t-butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1 .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane and dried at 40 ° C. under reduced pressure to obtain Resin XVII for resin fine particles b-17. From the results of ¹ H-NMR, it was confirmed that the obtained resin XVII contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. Further, it was found by ion chromatography elemental analysis that the amount of sulfur element was 2.80 mmol / g.

<Production Example 18 of resin for resin fine particle b>
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene and 60 parts of polyester resin 1 prepared in the same manner as Resin I were charged and stirred at 50 ° C. under a nitrogen stream.
・ Methyl 2-acrylamido-2-methylpropanesulfonate 2.5 parts ・ Styrene 33.7 parts ・ Acrylic acid 3.8 parts ・ t-Butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1 .5 parts The above materials were mixed and dropped into the reaction vessel, and the internal temperature was raised to 120 to 125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Furthermore, it was filtered and washed twice with 200 parts of hexane, and dried at 40 ° C. under reduced pressure to obtain Resin XVIII for resin fine particles b-18. From the result of ¹ H-NMR, it was confirmed that the obtained resin XVIII contained a sulfonic acid substituent-containing unit from a peak derived from methyl sulfonate. Further, it was found by ion chromatography elemental analysis that the amount of sulfur element was 0.27 mmol / g.

[Production example of resin fine particles b]
Fine particles b-1 to b-18 were produced by the following method.
<Preparation Example of Resin Fine Particle b-1 Dispersion>
A solution was prepared so that the resin I prepared for the resin fine particles b-1 had a solid content ratio of 75% by mass with acetone. Next, 33 parts by mass of the solution was added dropwise to 100 parts by mass of ion-exchanged water while stirring to emulsify, and acetone was further distilled off under reduced pressure of 100 mmHg. The solid content ratio was diluted to 15% by mass to obtain a resin fine particle b-1 dispersion. It was 70 nm when the number average particle diameter in the resin fine particle b-1 dispersion was measured, and it was weight average molecular weight Mw 14000.

Hereinafter, in the production example of the resin fine particle b-1 dispersion, dispersions of the resin fine particles b-2 to b-18 were similarly prepared except that the resin I was changed to the resin II to the resin XVIII.
At that time, the resin fine particle b-14 was able to be synthesized with a resin. However, because the resin composition was biased, the particles were coalesced in the emulsification process and could not be finely divided. These results are shown in Table 1.

[Production Example of Mother Particle A]
The production example of the mother particle A used in the present invention is shown below.
<Example of production of binder resin for mother particle A-1>
(Example of polyester resin production)
-Bisphenol A-propylene oxide 2.2 mol adduct 1206 parts-Bisphenol A-ethylene oxide 2.2 mol adduct 475 parts-Terephthalic acid 249 parts-Trimellitic anhydride 192 parts-Fumaric acid 290 parts-Dibutyltin oxide 0 .1 part The above material was put into a glass 4-liter four-necked flask, and a thermometer, a stirring bar, a condenser, and a nitrogen introducing tube were attached and placed in a mantle heater. 220 ° C under nitrogen atmosphere
For 5 hours to obtain a polyester resin P.
Subsequently, 100.0 parts by mass of the polyester resin P, cyan pigment C.I. I. Pig. Blue15: 3 (copper phthalocyanine: manufactured by Dainippon Ink) 5.0 parts by mass and paraffin wax (melting point 72 ° C.) 3.0 parts by mass sufficiently mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) After that, the mixture was melt-kneaded with a twin-screw extruder, cooled, and coarsely pulverized to a particle size of about 1 to 2 mm using a hammer mill. Subsequently, it was finely pulverized by an air jet type fine pulverizer. Further, the obtained finely pulverized product was classified with a multi-division classifier to obtain toner mother particles A-1.

<Preparation example of mother particle A-2 dispersion>
A mother particle A-2 dispersion was prepared by the method described below.
(Preparation of pigment dispersion paste)
-80 parts of styrene monomer-Cyan pigment C.I. I. Pigment Blue 15: 3 13 parts (Copper phthalocyanine Dainippon Ink)
After the above material was well premixed in a container, it was dispersed in a bead mill for about 4 hours while keeping it at 20 ° C. or lower to prepare a pigment dispersion paste.
Next, 390 parts of a 0.1 mol / liter-Na ₃ PO ₄ aqueous solution was added to 1150 parts of ion-exchanged water, heated to 60 ° C., and then adjusted to 13,000 rpm using Creamix (M Technique). And stirred. To this was added 58 parts of a 1.0 mol / liter-CaCl ₂ aqueous solution to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ .
-46.5 parts of the above pigment dispersion paste-42.0 parts of styrene monomer-18.0 parts of n-butyl acrylate-10.0 parts of paraffin wax (Mw 1810, Mw / Mn 1.20, melting point 72 ° C)
-Polyester resin Q 5.0 parts (terephthalic acid-propylene oxide modified bisphenol A copolymer, acid value 13 mg KOH / g, Mw 14500)
The above material was heated to 60 ° C., dissolved and dispersed to obtain a monomer mixture. Further, while maintaining the temperature at 60 ° C., 3.0 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added and dissolved to prepare a monomer composition. The monomer composition was charged into the dispersion medium. The mixture was stirred at 13,000 rpm for 15 minutes using Claremix at 60 ° C. in a nitrogen atmosphere, and the monomer composition was granulated. Thereafter, the mixture was reacted at 60 ° C. for 5 hours while being stirred with a paddle stirring blade, then stirred at 80 ° C. for 5 hours, and cooled to room temperature to obtain a dispersion of mother particles A-2.
A part of the dispersion was weighed, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) _2, and the content of the mother particles was measured by filtration, washing and drying. Using the result, the dispersion of the mother particle A-2 was diluted with ion-exchanged water so that the mother particle content was 15% by mass.

<Preparation example of mother particle A-3>
(Preparation of resin dispersion)
-Styrene 370 parts-N-butyl acrylate 30 parts-Acrylic acid 6 parts-Dodecanethiol 24 parts-Carbon bromide 4 parts Nonionic surfactant Nonipol 400 (Sanyo Kasei Co., Ltd.) prepared by mixing and dissolving the above materials 6 parts), 10 parts of anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) dissolved in 550 parts of ion-exchanged water, dispersed and emulsified in a flask, and slowly mixed for 10 minutes, 50 parts of ion-exchanged water in which 4 parts of ammonium persulfate was dissolved was added to perform nitrogen substitution. After that, the flask was heated with an oil bath while stirring until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. As a result, a resin dispersion having a number average particle diameter of 145 nm, a glass transition temperature of 57.6 ° C., and an Mw of 12100 was obtained.
(Preparation of cyan pigment dispersion)
Cyan pigment C.I. I. Pigment Blue 15: 3 50 parts (copper phthalocyanine made by Dainippon Ink)
・ Anionic surfactant Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts ・ Ion-exchanged water 200 parts The above materials are mixed and dissolved, and dispersed by ultrasonic irradiation with a homogenizer (Ultra Tlux T50 made by IKA). A cyan pigment dispersion having a number average particle diameter of 150 nm was obtained.
(Preparation of release agent dispersion)
The following compositions were mixed, heated to 97 ° C., and then dispersed with a homogenizer (Ultra Tlux T50 manufactured by IKA). Thereafter, the mixture was dispersed with a gorin homogenizer (manufactured by Kyowa Shoji Co., Ltd.) and treated 20 times at 105 ° C. and 550 kg / cm ² to obtain a release agent dispersion having a number average particle diameter of 190 nm.
Paraffin wax 100 parts (Mw 1810, Mw / Mn 1.20, melting point 72 ° C.)
・ Anionic surfactant (Neogen SC: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts ・ Ion-exchanged water 300 parts (Preparation of mother particle A-3 dispersion)
-250 parts of the resin dispersion-25.5 parts of the cyan pigment dispersion-28.4 parts of the release agent dispersion-1.5 parts of SANISOL B50 (manufactured by Kao Corporation) 1.5 parts or more in a round stainless steel flask, After mixing and dispersing with a homogenizer (Ultra Turrax T50 manufactured by IKA), the flask was heated to 48 ° C. with stirring in an oil bath for heating. After maintaining at 48 ° C. for 30 minutes, observation with an optical microscope confirmed that about 6 μm of mother particles A-3 were produced. It diluted with ion-exchange water so that solid content ratio might be 15 mass% from the measured solid content ratio, and the dispersion liquid of mother particle A-3 was obtained.

<Preparation example of mother particle A-4>
In preparing the mother particle A-4, the same procedure was performed except that the preparation of the resin dispersion in the mother particle A-3 was changed as follows.
(Preparation of resin dispersion)
A solution was prepared by using polyester P prepared as a binder resin for the mother particles A-1 with acetone to a solid content ratio of 75% by mass. Next, 33 parts by mass of the solution was added dropwise to 100 parts by mass of ion-exchanged water while stirring to emulsify, and acetone was further distilled off under reduced pressure of 100 mmHg. The resin dispersion was obtained by diluting the solid content ratio to 15% by mass. When the number average particle diameter in the resin dispersion was measured, it was 110 nm, the glass transition temperature was 61.7 ° C., and the Mw was 23600.

(Preparation of mother particle A-4 dispersion)
・ 250 parts of said resin dispersion ・ 25.5 parts of cyan pigment dispersion (prepared in the same manner as mother particle A-1) ・ 28.4 parts of release agent dispersion (prepared in the same manner as mother particle A-1) ・ Sanisol B50 (manufactured by Kao Co., Ltd.) 1.5 parts or more in a round stainless steel flask, mixed and dispersed with a homogenizer (IKA Ultra Turrax T50), and then stirred up to 48 ° C. while stirring the flask in an oil bath for heating. Heated. After maintaining at a temperature of 48 ° C. for 30 minutes, observation with an optical microscope confirmed that about 6 μm of mother particles A-4 were produced. It diluted with ion-exchange water so that solid content ratio might be 15 mass% from the measured solid content ratio, and the dispersion liquid of mother particle A-4 was obtained.

[Production example of toner particles]
An example of producing toner particles used in the present invention is shown below. The toner particle formulation is shown in Table 3.
(Preparation of toner particles 1)
-5 parts of the dispersion of resin fine particles b-1 is slowly added to 100 parts of the mother particle A-2 dispersion, and 1N hydrochloric acid is dropped into the system while taking care that the pH in the system gradually changes. The pH was adjusted to 1.5. Further, the temperature of the heating oil bath was raised and held at 62 ° C. for 2 hours. When observed with an optical microscope, toner particles of about 7 μm were confirmed. The obtained dispersion was filtered, washed with ion-exchanged water, dried and classified to obtain toner particles 1.

(Preparation of toner particles 2-12 and 17-23)
Toner particles 2 to 12 and 17 to 23 were prepared in the same manner as toner particles 1 except that the formulation shown in Table 3 was followed.

(Preparation of toner particles 13)
In the toner particles 13, in addition to the resin fine particles b-7, the fine particles b2-1 described below were used as the resin for forming the surface layer B. Fine particles b2-1 were prepared as follows.

[Production Example of Resin b2 Fine Particle b2-1 Dispersion]
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer and a nitrogen introduction tube, 75.0 parts of bisphenol A / ethylene oxide 2 mol adduct [BP-A (EO)], 25 parts of terephthalic acid and a condensation catalyst 2 parts of potassium titanyl oxalate was added and reacted at 230 ° C. for 10 hours while distilling off the water generated under a nitrogen stream. Subsequently, it was made to react under reduced pressure of 5-20 mmHg, and when the acid value became 25, it took out and the polyester resin 4 was obtained. This polyester resin 4 had a THF insoluble content of 3.2%, an acid value of 14.4, a hydroxyl value of 25.0, a Tg of 61 ° C., an Mn of 3200, and an Mw of 7500.
The obtained resin was again dissolved in acetone to prepare a solid content ratio of 75% by mass. Then, the mixture was added dropwise to 100 parts by mass of ion-exchanged water with stirring, emulsified, and acetone was further distilled off under reduced pressure of 100 mmHg. The solid content ratio was diluted to 15% to obtain a dispersion of fine particles b2-1. It was 70 nm when the number average particle diameter of the fine particles b2-1 was measured. The dispersion of fine particles b2-1 was dried and the toluene hexane solubility index TH (b2) was measured and found to be 14.

  Next, a mixture of 2.5 parts of the dispersion of resin fine particles b-7 and 2.5 parts of the dispersion of fine particles b2-1 is slowly added to 100 parts of the base particle A-2 dispersion, and 1N hydrochloric acid is added thereto. Was added dropwise while taking care that the pH in the system gradually changed, and the pH was adjusted to 1.5. Further, the temperature of the heating oil bath was raised and held at 62 ° C. for 2 hours. When observed with an optical microscope, toner particles of about 7 μm were confirmed. The obtained dispersion was filtered, washed with ion exchange water, dried and classified to obtain toner particles 13.

(Production Example of Toner Particle 14)
In the toner particles 14, the following fine particles b2-2 are used as the resin for forming the surface layer B in addition to the resin fine particles b-8. The fine particles b2-2 were prepared as follows.

[Production Example of Fine Particle b2-2 Dispersion of Resin b2]
In a reaction vessel equipped with a cooling tube, a stirrer, a thermometer, and a nitrogen introduction tube, 100 parts of xylene was charged and stirred at 50 ° C. under a nitrogen stream.
・ Styrene 99.0 parts ・ Acrylic acid 1.0 part ・ t-Butylperoxyisopropyl monocarbonate (Perbutyl I: manufactured by NOF Corporation) 1.5 parts The above materials were mixed and dropped into the reaction vessel, The temperature was raised to 120-125 ° C. The mixture was stirred for 4 hours under reflux conditions and cooled to room temperature. Then, it was dripped at 600 parts of hexane, and refinement | purification by reprecipitation and filtration was performed. Further, it was filtered and washed twice with 200 parts of hexane, and dried at 40 ° C. under reduced pressure to obtain a resin for fine particles b2-2.
The obtained resin was again dissolved in acetone to prepare a solid content ratio of 75% by mass. Then, the mixture was added dropwise to 100 parts by mass of ion-exchanged water with stirring, emulsified, and acetone was further distilled off under reduced pressure of 100 mmHg. The solid content ratio was diluted to 15% to obtain a dispersion of fine particles b2-2. It was 50 nm when the number average particle diameter of the fine particles b2-2 was measured. The dispersion liquid of fine particles b2-2 was dried and the toluene hexane solubility index TH (b2) was measured and found to be 93.

  Next, a mixture of 18.0 parts of the resin fine particle b-8 dispersion and 2.0 parts of the fine particle b2-2 dispersion is slowly added to 100 parts of the mother particle A-2 dispersion, and 1N hydrochloric acid is added thereto. Was added dropwise while taking care that the pH in the system gradually changed, and the pH was adjusted to 1.5. Further, the temperature of the heating oil bath was raised and held at 62 ° C. for 2 hours. When observed with an optical microscope, toner particles of about 7 μm were confirmed. The obtained dispersion was filtered, washed with ion exchange water, dried and classified to obtain toner particles 14.

(Example of preparation of toner particles 15)
To 100 parts of the obtained base particle A-3 dispersion, 5.0 parts of the dispersion of resin fine particles b-1 was slowly added, and the temperature of the heating oil bath was raised and held at 62 ° C. for 1 hour. When observed with an optical microscope, it was confirmed that aggregated particles of about 7 μm were formed. Then, after adding 3 parts of Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) here, the stainless steel flask was sealed, heated to 105 ° C. with stirring using a magnetic seal, and held for 3 hours. . After cooling, it was filtered, sufficiently washed with ion exchange water, dried and classified to obtain toner particles 15.

(Example of preparation of toner particles 16)
To 100 parts of the obtained mother particle A-4 dispersion, 5.0 parts of the dispersion of resin fine particles b-1 was slowly added, and the temperature of the heating oil bath was raised and held at 62 ° C. for 1 hour. When observed with an optical microscope, it was confirmed that aggregated particles of about 7 μm were formed. Then, after adding 3 parts of Neogen SC (Daiichi Kogyo Seiyaku Co., Ltd.) here, the stainless steel flask was sealed, heated to 105 ° C. with stirring using a magnetic seal, and held for 3 hours. . After cooling, it was filtered, sufficiently washed with ion exchange water, dried and classified to obtain toner particles 16.

(Example of preparation of toner particles 24)
4 parts of resin fine particles b-1 were added to 100 parts of toner base particles A-1, mixed well, and then sheared three times with a hybridizer to obtain toner particles 24 to which the fine particles were fixed.

[Production example of toner and two-component developer]
Using the toner particles obtained above, a toner and a two-component developer were prepared by the following method. Toner particles 1 to 24 were each externally added by a Henschel mixer to 1.2 parts of hydrophobic silica fine powder (R972, manufactured by Nippon Aerosil Co., Ltd.) with respect to 100 parts of toner particles. Further, the toner and a magnetic fine particle dispersed resin carrier (number average particle diameter 35 μm) surface-coated with a silicone resin were mixed so that the toner concentration became 8.0% by mass to obtain a two-component developer. The magnetic fine particle-dispersed resin carrier obtains core particles by polymerizing phenols and aldehydes in the presence of a basic catalyst in an aqueous medium and polymerizing them. Further, the obtained core was stirred while continuously applying a shearing stress, and the silicone resin solution was gradually added to volatilize the solvent to form a coating layer on the core surface to obtain a magnetic fine particle dispersed resin carrier.

The above toners 1 to 24 were evaluated as follows. The results are shown in Table 4.
<Environmental evaluation of toner triboelectric charge>
The triboelectric charge amount is measured by separating 50 g of each two-component developer, and at room temperature and normal humidity (23 ° C./60%), low temperature and low humidity (15 ° C./15%), and high temperature and high humidity (30 ° C.). / 80%) in each environment for 3 days and nights, and then placed in a 50 cc plastic container, shaken 200 times over 1 minute, and measured using the apparatus of FIG. Evaluation was made by measuring the absolute value of the difference in triboelectric charge amount between low temperature and low humidity and high temperature and high humidity, and judged according to the following criteria.
Rank A: Difference in triboelectric charge amount 0 or more and less than 20 μC / g Rank B: Difference in triboelectric charge amount 20 or more and less than 30 μC / g Rank C: Difference in triboelectric charge amount 30 μC / g or more (Method for measuring triboelectric charge amount) )
About 0.5 g of a two-component developer whose frictional charge is to be measured is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as Wl (g). Next, in the suction device 1 (at least the portion in contact with the measurement container 2) is suctioned from the suction port 7 and the air volume control valve 6 is adjusted to set the pressure of the vacuum gauge 5 to 250 mmAq. In this state, suction is sufficiently performed, preferably for 2 minutes, and the toner is removed by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (μF). The mass of the entire measurement container after the suction is weighed and is defined as W2 (g). The triboelectric charge amount (μC / g) of the toner is calculated as follows.
Triboelectric charge (μC / g) = (C × V) / (W1−W2)

<Evaluation of rising of triboelectric charge>
450g of each two-component developer is allowed to stand for 7 days under high temperature and high humidity (30 ℃ / 80%), and then left for another 3 days under normal temperature and humidity (23 ℃ / 60%) to reset the triboelectric charge due to initial mixing. did. The images were evaluated for evaluation in a color copier CLC5500 remodeled machine (manufactured by Canon) in a room temperature and humidity environment (23 ° C./60%). The CLC5500 increased the process speed to the normal 135%. Each developer was charged into the developing unit, 50 solid A4 images were output without preliminary rotation, and the reflectance of the solid white portion of the image was measured. Further, the reflectance of the unused paper was measured and subtracted from the reflectance of the solid white portion of the image to obtain the fog density. The reflectance was measured with TC-6DS (manufactured by Tokyo Denshoku).
(Evaluation criteria)
Rank A: 10 sheets or less and fog density is less than 1.0% Rank B: 11 to 20 sheets and fog density is less than 1.0% C rank: 21 to 30 sheets and fog density is less than 1.0% D rank: Cover density of 31 sheets is 1.0% or more

<Evaluation of toner durability>
Subsequent to the rising evaluation of the frictional charge amount, one solid black image with an image ratio of 25% is output. Further, 2000 images with an image area ratio of 1% are output. Thereafter, a solid black image with an image ratio of 25% was output again, the image density was compared with the former, and the density reduction rate was evaluated according to the following criteria.
(Evaluation criteria)
A: Solid density ratio with respect to initial at 2000 sheets is 95% or more B: Solid density ratio with respect to initial at 2000 sheets is 85% to less than 95% C: Solid density ratio with respect to initial at 2000 sheets is 80% or more and 85% Less than D: The solid density ratio relative to the initial value at 2000 sheets is less than 80%

The results of the above evaluation are shown in Table 4.
As a result, in Examples 1 to 17 according to the present invention, the change in the triboelectric charge amount due to the environmental change is less than in Comparative Examples 1 to 7, and the triboelectric charge amount in a normal temperature and normal humidity environment (23 ° C./60%). It was found that the solid white portion was well fogged by uniform frictional charging. Further, it was found that the density change at the initial stage and at the time of outputting 2000 images was smaller in Examples 1 to 17 than in Comparative Examples 1 to 7, the toner strength was high, and the image stability was excellent. Therefore, it was shown that the toners of the examples have both triboelectric charging characteristics and durability.

It is a figure which shows the structure of the apparatus used for the measurement of the triboelectric charge amount of the developing agent using the toner of this invention. It is an example of toluene hexane solubility index measurement of resin used for the toner of the present invention. FIG. 2 is an example of a transmittance curve when hexane is gradually added to a toluene solution of a resin.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Suction machine 2 Measuring container 3 Screen 4 Lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (9)

A toner having toner particles in which a surface layer B is formed by fixing fine particles containing at least resin fine particles b on the surface of mother particles A containing at least a binder resin, a colorant and a release agent,
The mass of the resin forming the surface layer B is 2.0 to 20.0% by mass with respect to the mass of the base particle A,
The resin fine particles b are resin fine particles containing a unit having a sulfonic acid-based substituent represented by the following formula (1) and a resin having at least a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. Yes,
The number average particle diameter of the resin fine particles b is 10 to 150 nm,
The acid value of the resin forming the resin fine particles b is 5.0 to 40.0 mg KOH / g, and the ratio of the sulfur element amount to the acid value (S / AV) in the resin forming the resin fine particles b is A toner characterized by 0.02 to 0.30 mmol / mg KOH.

(In the formula 1, R ₁ represents a very good hydrocarbon group a cyclic structure, said R ₁ may have a substituent, R ₂ represents a methyl group, an ethyl group or an isopropyl group.) The resin fine particle b includes a resin having at least a unit having an aromatic sulfonic acid substituent represented by the following formula (2) and a polyester unit obtained by polycondensation of a polyhydric alcohol and a polyvalent carboxylic acid. The toner according to claim 1, wherein the toner is fine particles.

(In Formula 2, R _1a represents an aromatic group which may have a substituent, and R ₂ represents a methyl group, an ethyl group or an isopropyl group.)   3. The toner according to claim 1, wherein the resin fine particles b are resin fine particles containing a hybrid resin having a unit formed from styrene.   4. The toner according to claim 1, wherein the resin forming the resin fine particles b has a weight average molecular weight Mw of 5000 to 50000. 5. The resin forming the surface layer B further contains the resin b2, and the relationship between the toluene hexane solubility index TH (b) of the resin forming the resin fine particles b and the toluene hexane solubility index TH (b2) of the resin b2 is The toner according to claim 1, wherein the toner satisfies the following formula (3).
Formula (3) | TH (b) −TH (b2) | ≧ 20   The toner according to claim 1, wherein the base particles A are particles obtained in an aqueous medium.   The toner according to claim 6, wherein the mother particle A is a particle obtained by a suspension polymerization method.   The toner according to claim 6, wherein the base particle A is a particle obtained by aggregating at least emulsified resin particles.   The toner according to claim 8, wherein the resin forming the emulsified resin particles has at least a polyester structure.

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