JP2008268366A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which can attain an image having high glossiness even upon low temperature fixation and has high durability even under severe usage circumstances. <P>SOLUTION: The toner has: toner particles obtained by dispersing and granulating a polymerizable monomer composition which includes at least polymerizable monomer, colorant, polar resin A, polar resin B, polar resin C and releasing agent into aqueous medium to form particles and polymerizing the polymerizable monomer in the particles; and an inorganic fine powder. The polar resin A is a polymer obtained by polymerizing at least styrene or a styrene derivative, of which the weight average molecular weight (Mw) measured by gel permeation chromatography is 1,500 to 6,000, and is used with an addition amount in the range of 5.0 pts.mass to 65.0 pts.mass per 100.0 pts.mass of the polymerizable monomer. The polar resin B is a polymer or a copolymer having a sulfonic group, a sulfonate group or a sulfonic acid ester group. The polar resin C is a polyester type resin. The toner satisfies the following relations: 0.5≤Va≤15.0, 10.0≤Vb≤40.0, 5.0≤Vc≤30.0, Va<Vb and Va<Vc, wherein the acid value of the polar resin A is Va(mgKOH/g); the acid value of the polar resin B is Vb(mgKOH/g) and the acid value of the polar resin C is Vc(mgKOH/g). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner used for developing an electrostatic latent image in electrophotography and electrostatic recording. More specifically, the present invention relates to a toner used in an image recording apparatus that can be used in a copying machine, a printer, or a facsimile.

In recent years, printer technology trends have progressed toward smaller, faster, and energy-saving machines. Due to increasing demand for printers, they are also being used for mass printing in harsh environments such as hot and humid areas. It was. Even under such severe usage conditions, the image quality required for printers is increasing year by year, and in particular, the demand for images with high glossiness has increased as photo printing with printers has become common. Yes.
In order to satisfy these demands, it is necessary to improve the performance of the toner. That is, there is a demand for a toner that can realize an image with high glossiness even when the amount of heat applied to the toner at the time of fixing is reduced by increasing the speed and energy of the machine. Furthermore, there is a demand for a highly durable toner that can provide a stable image without causing image degradation even in the case of severe printing environments such as high-speed machines and high-temperature and high-humidity environments. Various studies have been made.

In general, in order to obtain a high gloss level, it is necessary to add a certain amount or more of a release agent to the toner. However, if a release agent is present on the toner surface, the durability tends to deteriorate, thus overcoming the above problems. Therefore, a toner production method by a suspension polymerization method has been proposed. (For example, refer to Patent Documents 1 and 2).
In the suspension polymerization method, a polymerizable monomer, a colorant, a polymerization initiator, and, if necessary, a crosslinking agent, a charge control agent, and other additives are uniformly dissolved or dispersed to form a monomer composition. Then, this monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using an appropriate stirrer, and the polymerizable monomer is polymerized to obtain a toner. In this method, since the release agent is processed in an aqueous medium, it is possible to make it difficult to expose the release agent having high hydrophobicity to the toner surface.
With this method, it became possible to add a release agent to a certain amount, but with that alone, the reduction in fixing temperature and the speeding up of the machine are accelerating. It was difficult to fully satisfy both of these requirements.

Therefore, in order to achieve high gloss at low temperatures, methods such as lowering the molecular weight in the toner binder resin and lowering the toner viscosity are conceivable. However, simply using both of these methods makes the toner durable. In particular, image deterioration is likely to occur when a large amount of printing is performed in a high-temperature and high-humidity environment (see, for example, Patent Document 3). On the other hand, in order to improve durability, a method of keeping the melt viscosity within a certain range by incorporating a polyfunctional crosslinking agent in the polymerizable monomer and creating a high molecular weight component in the toner particles can be considered. In general, if the crosslinking agent is added too much, the entire toner binder resin becomes hard, and the durability of the toner is improved, but the glossiness tends to decrease (see, for example, Patent Document 4).
Therefore, there is still a demand for a toner that can realize an image with high glossiness at the time of low-temperature fixing and has high durability even under severe use conditions.
Japanese Patent Publication No. 36-10231 Japanese Patent Publication No. 51-14895 JP 07-225492 A Japanese Patent Laid-Open No. 11-024307

  An object of the present invention is to provide a toner that solves the above problems.

As a result of intensive studies, the present inventors have found that the above problem can be solved by the following configuration, and have completed the present invention.
That is, the present invention comprises dispersing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin A, a polar resin B, a polar resin C, and a release agent in an aqueous medium. In a toner having toner particles obtained by granulating to form particles and polymerizing a polymerizable monomer in the particles and inorganic fine powder, the polar resin A polymerizes at least styrene or a styrene derivative. The weight average molecular weight (Mw) measured by gel permeation chromatography of a tetrahydrofuran (THF) soluble content is 1500 to 6000, and the addition amount of the polar resin A is 5.0 parts by mass to 65.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer, and the polar resin B is a polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group. The polar resin C is a polyester resin, the acid value of the polar resin A is Va (mgKOH / g), the acid value of the polar resin B is Vb (mgKOH / g), When the acid value of the polar resin C is Vc (mgKOH / g), 0.5 ≦ Va ≦ 15.0, 10.0 ≦ Vb ≦ 40.0, 5.0 ≦ Vc ≦ 30.0, Va <Vb And a toner satisfying the relationship Va <Vc.

  According to the present invention, it is possible to provide a toner having high glossiness at low temperature fixing and having high durability even under severe conditions.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention.
In the toner of the present invention, a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin A, a polar resin B, a polar resin C, and a release agent is dispersed in an aqueous medium. In the toner particles obtained by granulating to form particles and polymerizing the polymerizable monomer in the particles and the toner having inorganic fine powder, the polar resin A is obtained by polymerizing at least styrene or a styrene derivative. In the obtained polymer, the weight average molecular weight (Mw) measured by gel permeation chromatography of tetrahydrofuran (THF) soluble content is 1500 to 6000, and the addition amount of the polar resin A is the polymerizable property. 5.0 parts by mass to 65.0 parts by mass with respect to 100.0 parts by mass of the monomer, and the polar resin B is a polymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. The polar resin C is a polyester resin, the acid value of the polar resin A is Va (mgKOH / g), the acid value of the polar resin B is Vb (mgKOH / g), and the polar resin C is a polymer. When the acid value of Vc (mgKOH / g) is 0.5 ≦ Va ≦ 15.0, 10.0 ≦ Vb ≦ 40.0, 5.0 ≦ Vc ≦ 30.0, Va <Vb, and Va <Vc is satisfied.

Although the specific mechanism is not clarified, the toner having the above characteristics is dispersed in the aqueous medium because the acid values of the polar resin A, the polar resin B, and the polar resin C have a specific relationship. It is considered that the core-shell particles are formed from the difference in polarity of the resin. That is, the low molecular weight component of the polar resin A that enables high glossiness at the time of low-temperature fixing is from the inside of the polar resins B and C that are the shell portions of the toner particles, the binder resin and the release agent having a small polarity, and the like. It is predicted to exist near the interface of the core part.
Therefore, since the low molecular weight component derived from the polar resin A that enables high glossiness is selectively present in the vicinity of the shell in the toner of the present invention, high glossiness can be obtained even at a low fixing temperature. It is thought that. Furthermore, since it becomes easy to encapsulate the release agent having high hydrophobicity in the core central portion, it is considered that high durability is obtained even in use in a harsh environment.

  The toner particles used in the present invention are prepared by dispersing a polymerizable monomer composition in an aqueous medium, such as suspension polymerization and suspension granulation, and granulating to form particles. It is characterized in that it is obtained by a production method in which a polymerizable monomer is polymerized. The toner particles synthesized by these production methods are easy to synthesize with a core-shell structure, and even when a large amount of the release agent component is added to the toner particles, the release agent component does not exist on the toner particle surface. Since it can be encapsulated, it is possible to achieve both high durability and high glossiness during low-temperature fixing.

The acid values (mgKOH / g) of the polar resin A and the polar resin B satisfy the relationship Va <Vb. When Vb ≦ Va, since the polar resin A which is a low molecular weight component exists on the surface of the toner particles, the durability of the toner tends to be lowered. For the same reason, Va <Vc.
The acid value Va (mgKOH / g) of the polar resin A is 0.5 ≦ Va ≦ 15.0, preferably 1.0 ≦ Va ≦ 7.0, and more preferably 1.0 ≦ Va ≦ 4. .0. When Va is less than 0.5, the presence of the core portion and the polar resin A when the core-shell structure is formed tends to be non-uniform, making it difficult to obtain sufficient effects of the present invention. When Va is larger than 15.0, the existence state of the shell portion and the polar resin A is likely to be non-uniform, so that the durability is deteriorated. The acid value of the polar resin A can be controlled by a generally known method.

The acid value in the present invention is measured according to the measuring method described in JIS K0070. Measuring apparatus: Automatic potentiometric titrator AT-400 (manufactured by Kyoto Electronics Co., Ltd.)
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 25 ° C
Sample preparation: 1.0 g of polar resin is added to 120 ml of toluene and dissolved by stirring with a magnetic stirrer at room temperature (25 ° C.) for 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
Measurement operation:
1) Accurately weigh 1.0 g of polar resin into a 200 ml beaker. 120 ml of toluene is added to this and stirred and dissolved. After stirring for 10 hours, 30 ml of ethanol is added to form a mixed solution of toluene and ethanol. At the same time, a mixed solution consisting only of the same amount of toluene and ethanol is prepared for the blank test.
2) A blank test is performed using an ethanol solution of 0.1 mol / l potassium hydroxide. The amount of potassium hydroxide solution used at this time is B (ml).
3) Next, the sample solution is titrated. The amount of potassium hydroxide solution used at this time is S (ml).
4) Calculate the acid value according to the following formula.
Acid value (mgKOH / g) = {(SB) × f × 5.61}} / W
f: Factor of KOH W: Amount of sample accurately weighed (g)

The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polar resin A soluble in tetrahydrofuran (THF) is 1500 to 6000. When the weight average molecular weight (Mw) is smaller than 1500, the durability of the toner tends to deteriorate. When the weight average molecular weight (Mw) is larger than 6000, it is not possible to obtain a sufficient effect of increasing the glossiness due to the addition of the low molecular polar resin.

The molecular weight of the resin soluble in tetrahydrofuran (THF) by GPC is measured as follows. Using a GPC measuring device (HLC-8120GPC manufactured by Tosoh Corporation), a molecular weight distribution chart of THF-soluble matter is measured under the following measurement conditions, and various molecular weights are calculated therefrom.
Column (manufactured by Showa Denko KK): Shodex GPC KF-801, Shodex GPC KF-802, Shodex GPC KF-803, Shodex GPC KF-804, Shodex GPC KF-805, Shodex GPC KF-806, G Seven series of 807 (diameter 8.0 mm, length 30 cm).
・ Temperature: 40 ℃
・ Flow rate: 0.6ml / min
・ Detector: RI
Sample concentration: 10 μl of 0.1% by mass sample
The sample is prepared by placing a resin sample to be measured in tetrahydrofuran (THF) and allowing it to stand for 6 hours, after which it is sufficiently shaken (until the sample is no longer integrated), and is allowed to stand for one more day. And let what passed the sample processing filter (pore size 0.45 micrometer) be a sample for GPC measurement. The calibration curve uses a molecular weight calibration curve created with a monodisperse polystyrene standard sample.

  The addition amount of the polar resin A is 5.0 to 65.0 parts by mass, preferably 15.0 to 55.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. Part. If the amount of the polymerizable monomer is less than 5.0 parts by mass, the effect of adding a low molecular weight resin is small, and it is difficult to achieve high glossiness at low temperature fixing. When the amount exceeds 65.0 parts by mass, the strength of the toner particles themselves becomes weak and the durability becomes low.

The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography of the tetrahydrofuran (THF) soluble matter of the polar resin A is 1.0 <Mw / Mn <5. Of 0.0, more preferably 1.0 <Mw / Mn <3.0, and still more preferably 1.0 <Mw / Mn <2.0. When Mw / Mn is 5.0 or more, it becomes difficult to obtain a remarkable effect of improving the glossiness at low temperature fixing by adding the polar resin A.

  The glass transition point (Tg) of the polar resin A is preferably 30 ° C. to 100 ° C., more preferably 50 ° C. to 75 ° C. When the Tg is less than 30 ° C., the strength of the entire toner particles is lowered, and the transferability and development characteristics are liable to be lowered during the durability test of a large number of sheets. On the other hand, when the glass transition point is 100 ° C. or higher, it is difficult to obtain high gloss at a low temperature.

Production methods for the polar resin A include bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and ionic polymerization, but solution polymerization is preferable from the viewpoint of operability.
The polar resin A is a polymer obtained by polymerizing at least styrene or a styrene derivative. A polymer obtained by polymerizing styrene or a styrene derivative is easily encapsulated inside the polar resin C, which is a polyester resin.

The polar resin A may be a homopolymer or a copolymer.
As the polar resin A, an amino group, a carboxylic acid group, a hydroxyl group, a sulfonic acid group, a glycidyl group, a nitrile group, a generally known monomer component containing a hydrophilic functional group, and a random vinyl compound such as styrene or a styrene derivative Examples thereof include a copolymer, a block copolymer, and a graft copolymer. These can be used alone or in combination. Specific examples of the polar resin A include low molecular weight styrene-acrylic acid copolymers and styrene maleic acid copolymers.

In the polar resin A, a chain transfer agent component may be used as a softening temperature and a molecular weight adjusting agent. Examples of the chain transfer agent component include α-methylstyrene dimer, n-dodecyl mercaptan, thioglycolic acid ester, and n-octyl mercaptan.

The production method of the polar resin B includes bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and ionic polymerization, but solution polymerization is preferable from the viewpoint of operability.
The polar resin B is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. When this is used, a stable image can be provided even during mass printing at high temperature and high humidity.
The acid value Vb (mgKOH / g) of the polar resin B is 10.0 ≦ Vb ≦ 40.0, and preferably 12.0 ≦ Vb ≦ 30.0. If it is less than 10.0, density unevenness tends to occur when printing in large quantities in a high-temperature and high-humidity environment. Easy to cause.
The polar resin B is preferably 0.5 parts by mass to 15.0 parts by mass, and 1.0 parts by mass to 10.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. More preferably. If the content of the resin B is less than 0.5 parts by mass, the presence state of the polar resin in the toner particles tends to be non-uniform, and if it exceeds 15.0 parts by mass, the average circularity decreases, and developability and transfer It is easy to cause image degradation due to a decrease in property.
The weight average molecular weight Mw of the polar resin B is preferably 10,000 ≦ Mw ≦ 50000, more preferably 15000 ≦ Mw ≦ 30000. When the weight average molecular weight Mw of the polar resin B is less than 10,000, the durability is lowered. In addition, when Mw exceeds 50000, it takes time to dissolve in the monomer, and an appropriate glossiness cannot be obtained at low temperature fixing.
The glass transition point (Tg) of the polar resin B is preferably in the range of 60 ° C. to 100 ° C., more preferably 75 ° C. to 90 ° C. When the glass transition point is less than 60 ° C., the external additive is easily embedded in the toner surface, which may make it difficult to output a stable image during mass printing under high temperature and high humidity. On the other hand, when the glass transition point exceeds 100 ° C., the image gloss at the time of low-temperature fixing tends to be inferior.

  As a monomer which has a sulfonic acid group for manufacturing polar resin B used for this invention, the vinyl-type monomer containing a sulfonic acid group is preferable, and the following are mentioned. Styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, methacrylsulfonic acid, maleic acid amide derivatives, maleimide derivatives, and styrene derivatives having the following structures.

The polar resin B used in the present invention may be a homopolymer of the monomer, but may be a copolymer of the monomer and another monomer. As a monomer that forms a copolymer with the monomer, there is a vinyl polymerizable monomer, and a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.
Of these monomers, sulfonic acid group-containing (meth) acrylamide is more preferable in terms of providing a stable image without being affected by the environment.

Examples of the monofunctional polymerizable monomer include the following. 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 styrene, 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 -Acrylic polymerizable monomers such as nonyl 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, Diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as til methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, vinyl Vinyl ethers such as isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.
The following are mentioned as a polyfunctional polymerizable monomer. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-buty Lenglycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis ( 4-methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

  In the polar resin B, as a monomer that can be used in combination with a monomer having a sulfonic acid group, the above-described monomers can be used, and styrene or a styrene derivative is a particularly preferable monomer. The reason is that it is particularly important in maintaining stable image quality during mass printing in a hot and humid environment. Furthermore, (meth) acrylic acid ester is a particularly preferable component in controlling the glass transition point described later.

Moreover, as polar resin B, the polymer which has a sulfonate group which has the following structure can also be illustrated.
X (SO ₃ ⁻ ) n · mY ^{k +}
(X represents a polymer site derived from the polymerizable monomer, Y ^{k +} represents a counter ion, k is a valence of the counter ion, m and n are integers, and n = k × m is there.)
In this case, the counter ions are preferably hydrogen ions, sodium ions, potassium ions, calcium ions, and ammonium ions.
Furthermore, as the polar resin B, a polymer having a sulfonate group having the following structure can also be exemplified.
X-SO ₃ -R
(X: represents a polymer site derived from the polymerizable monomer, and R represents a linear or branched alkylene group having 1 to 15 carbon atoms which may be substituted.)
The amount of the monomer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group used when polymerizing the polar resin B used in the present invention is 2. The range of 0 to 14.0% by mass, preferably 4.0 to 10.0% by mass is preferable in that a stable image can be supplied even in a severe environment.

The polar resin C is a polyester resin. By using a polyester-based resin as the polar resin C, it is possible to provide a stable image even in a harsh environment with little member contamination.
The acid value Vc (mgKOH / g) of the polar resin C is 5.0 ≦ Vc ≦ 30.0, and preferably 8.0 ≦ Vc ≦ 15.0.
If it is less than 5.0, density unevenness is likely to occur when printing in large quantities in a high temperature and high humidity environment. If it exceeds 30.0, image deterioration such as density reduction due to deterioration in transferability due to reduction in circularity of toner particles will occur. Easy to cause.
The weight average molecular weight Mw of the polar resin C is preferably 5000 ≦ Mw ≦ 25000, and more preferably 5000 ≦ Mw ≦ 15000. When the weight average molecular weight Mw of the polar resin C is less than 5000, the durability tends to decrease. On the other hand, when Mw exceeds 25,000, it takes a long time to dissolve in the monomer, and it tends to be inferior in image gloss at low temperature fixing.
The glass transition point (Tg) of the polar resin C is preferably in the range of 50 ° C. to 100 ° C., more preferably 62 ° C. to 90 ° C. When the glass transition point is less than 50 ° C., the external additive is easily embedded in the toner surface, which may make it difficult to output a stable image during mass printing under high temperature and high humidity. On the other hand, when the glass transition point exceeds 100 ° C., the image gloss at the time of low-temperature fixing tends to be inferior.

For the polar resin C used in the present invention, for example, one or both of a saturated polyester resin and an unsaturated polyester resin is appropriately selected in order to control physical properties such as durability and fixability of toner obtained from toner particles. Can be used.
The alcohol component and acid component which comprise the said polyester resin are illustrated below. As alcohol components, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexane Diol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, and bisphenol derivatives represented by the following general formula (I):

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２乃至１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  Alternatively, a hydrogenated compound of the compound of the general formula (I), a diol represented by the following general formula (II),

Or the diol of the hydrogenated compound of the compound of Formula (II), and also polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenol resins.

Examples of the divalent carboxylic acid include the following. Benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or its anhydride, alkyl dicarboxylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid or its anhydride, and further 6 to 18 carbon atoms. Succinic acid substituted with alkyl or alkenyl groups or anhydrides thereof, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid or anhydrides thereof, trimellitic acid, pyromellitic acid, 1 , 2,3,4-butanetetracarboxylic acid, polyvalent carboxylic acids such as benzophenone tetracarboxylic acid and their anhydrides.

A preferable addition amount of the polar resin C is 1 with respect to 100.0 parts by mass of the polymerizable monomer.
. It is 0 to 30.0 parts by mass, and more preferably 2.0 to 20.0 parts by mass. If the amount is less than 1.0 part by mass, the presence state of the polar resin in the toner particles tends to be non-uniform, while if it exceeds 30.0 parts by mass, the average circularity of the toner particles decreases, and the developability and transferability deteriorate. It is easy to cause image degradation by.

The toner of the present invention preferably has a viscosity at 100 ° C. (also simply referred to as 100 ° C. viscosity) of 1.0 × 10 ^{4 to} 4.5 × 10 ⁴ Pa · s, more preferably, by a flow tester heating method. It is 3.0 × 10 ^{4 to} 4.0 × 10 ⁴ Pa · s. When the viscosity at 100 ° C. is smaller than 1.0 × 10 ⁴ Pa · s, the durability of the obtained toner is remarkably deteriorated, and when it is larger than 4.5 × 10 ⁴ Pa · s, the obtained toner has a low temperature. Glossiness at fixing tends to decrease.
The viscosity at 100 ° C. can be adjusted to the above range by a generally known method such as appropriately changing the addition amount of the polar resin A, the addition amount of the polymerization initiator, or the polymerization temperature.

  The glass transition point (Tg) of the toner of the present invention is preferably 40 ° C. to 100 ° C., more preferably 45 ° C. to 80 ° C., and particularly preferably 50 ° C. to 70 ° C. When the glass transition point is less than 40 ° C., the durability of the toner is lowered. When the glass transition point exceeds 100 ° C., the glossiness at the time of low-temperature fixing of the toner tends to decrease.

  The toner of the present invention has an average circularity of 0.960 to 0.995 as measured by a flow type particle image analyzer to reduce a physical load applied to the toner and improve durability. This is preferable because a stable image can be provided.

Hereinafter, the most suitable suspension polymerization method for obtaining the toner particles used in the present invention will be exemplified and the production method of the toner particles will be described. Polymerizer, colorant, polar resin A, polar resin B, polar resin C, mold release agent and other additives as required are dispersed in a homogenizer, ball mill, colloid mill, ultrasonic disperser, etc. Thus, the polymerization initiator is dissolved or dispersed uniformly, and the polymerization initiator is dissolved therein to prepare a polymerizable monomer composition. Next, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer and granulated to form particles, and toner particles are produced by polymerizing the polymerizable monomer in the particles. To do. The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before the polymerizable monomer composition is dispersed in the aqueous medium. . Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.
When a polar resin is added during the polymerization reaction from the dispersion step to the polymerization step of the polymerizable monomer composition, it is added according to the balance of the polarity exhibited by the polymerizable monomer composition that becomes toner particles and the aqueous dispersion medium. The presence state of the polar resin can be controlled, for example, the formed polar resin forms a resin layer corresponding to the polarity in the toner particles. That is, by adding a polar resin, functional separation according to the resin layer is possible. Further, the toner particles obtained by the suspension polymerization method are preferable because they have a complete capsule structure in which a release agent component is encapsulated.

Examples of the binder resin used in the toner of the present invention include commonly used styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, and styrene-butadiene copolymers. As the polymerizable monomer constituting the binder resin, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

  The following are mentioned as a polymerizable monomer for producing | generating a binder resin. Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, Ether-based monomers; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, such as ene-based monomers methacrylamide.

  These polymerizable monomers are used alone or in general, and have a theoretical glass transition point (Tg) described in publication polymer handbook 2nd edition III-p139 to 192 (John Wiley & Sons) of 40 ° C. to A polymerizable monomer is appropriately mixed and used so as to exhibit 75 ° C. When the theoretical glass transition point is less than 40 ° C., a problem is likely to occur from the viewpoint of the durability stability of the toner, whereas when it exceeds 75 ° C., the glossiness at low temperature fixing is lowered.

In the present invention, a crosslinking agent may be used when the binder resin is synthesized in order to increase the mechanical strength of the toner particles and to control the molecular weight of the THF soluble component of the toner.
Examples of the bifunctional crosslinking agent include the following. 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 dimethacrylate instead of diacrylate Thing.

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 to 10.00 parts by mass, more preferably 0.10 to 5.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer. is there.

The release agent used in the present invention is preferably a hydrocarbon-based release agent, and the content of the release agent component is preferably 4.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. Part to 25.0 parts by weight, more preferably 7.0 parts by weight to 15.0 parts by weight. If the release agent content is less than 4.0 parts by mass, sufficient glossiness cannot be obtained at low temperature fixing. On the other hand, if it is larger than 25.0 parts by mass, the durability is lowered.
Further, the release agent preferably has a maximum endothermic peak temperature in a range of 40 ° C. to 110 ° C. in a DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) device,
More preferably, it is 45 ° C to 90 ° C. When the maximum endothermic peak temperature is less than 40 ° C., the durability of the toner decreases. On the other hand, when the maximum endothermic peak temperature exceeds 110 ° C., the glossiness at the time of low-temperature fixing decreases.

The release agent used in the present invention is particularly preferably a release agent having a small polar component such as a hydrocarbon-based release agent in that it is easily encapsulated in the toner particle central part. Examples of other mold release agents include the following. Amide waxes, higher fatty acids, long chain alcohols, ketone waxes, ester waxes, and derivatives such as these graft compounds and block compounds. If necessary, two or more release agents may be used in combination.
The following are mentioned as said hydrocarbon type mold release agent. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolatum; Fischer-Tropsch wax and derivatives thereof by the Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further examples include hydrogenated castor oil and derivatives thereof, vegetable waxes and animal waxes. These waxes can be used alone or in combination of two or more. Note that an antioxidant may be added to these hydrocarbon release agents as long as the chargeability of the toner is not affected.

The following are mentioned as a polymerization initiator used for the toner of the present invention. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide, lauroyl peroxide, tert-butyl-peroxypivalate.
The amount of these polymerization initiators used varies depending on the desired degree of polymerization, but is generally 3 to 20 parts by mass with respect to 100 parts by mass of the polymerizable vinyl monomer. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  The toner of the present invention contains a colorant as an essential component in order to impart coloring power. Examples of the colorant preferably used in the present invention include the following organic pigments, organic dyes, and inorganic pigments.

  Examples of organic pigments or organic dyes as cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment blue.

Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I
. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  Examples of the organic pigment or organic dye as the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

Examples of the black colorant include carbon black and those prepared by using the yellow colorant / magenta colorant / cyan colorant toned to black.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.
The colorant is preferably used by adding 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

In the present invention, when toner particles are obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase migration property of the colorant, and preferably, a hydrophobic treatment with a substance that does not inhibit polymerization is performed. It is better to apply it to the colorant. In particular, since dye-based colorants and carbon black have many polymerization inhibiting properties, care must be taken when using them. In addition, as a method for suppressing the polymerization inhibitory property of the dye-based colorant, a method of polymerizing a polymerizable monomer in the presence of these dyes in advance can be mentioned, and the obtained colored polymer is composed of a polymerizable monomer composition. Add to product.
Moreover, about carbon black, you may process with the substance (for example, polyorganosiloxane etc.) which reacts with the surface functional group of carbon black besides the process similar to the said dye.

As the dispersion stabilizer used when preparing the aqueous medium, known inorganic and organic dispersion stabilizers can be used.
Specifically, the following are mentioned as an example of an inorganic dispersion stabilizer. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina . Examples of the organic dispersant include the following. Polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, starch.
Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.
As the dispersion stabilizer used in preparing the aqueous medium used in the toner of the present invention, an inorganic poorly water-soluble dispersion stabilizer is preferable, and it is preferable to use a poorly water-soluble inorganic dispersion stabilizer that is soluble in acid. .
In the present invention, when an aqueous medium is prepared, the amount of these dispersion stabilizers used is 0.2 to 2.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer. Preferably there is. In the present invention, it is preferable to prepare an aqueous medium using 300 parts by mass to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

  In the present invention, when preparing an aqueous medium in which the above dispersion stabilizer is dispersed, a commercially available dispersion stabilizer may be used as it is. In order to obtain particles of a dispersion stabilizer having a fine uniform particle size, an aqueous medium may be prepared by generating a dispersion stabilizer in a liquid medium such as water under high-speed stirring. For example, when tricalcium phosphate is used as a dispersion stabilizer, a preferred dispersion stabilizer can be obtained by mixing sodium phosphate aqueous solution and calcium chloride aqueous solution under high speed stirring to form fine particles of tricalcium phosphate. Can do.

In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.
As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and a small amount of solubilized products in an aqueous medium is particularly preferable.
Examples of the charge control agent that control the toner to be negatively charged include the following. Organic metal compounds and chelate compounds are effective, and monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.
Examples of the charge control agent that controls the toner to be positively charged include the following. Nigrosine-modified products such as nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; resin charge control agent.
The toner of the present invention can contain these charge control agents alone or in combination of two or more.
A preferable blending amount of the charge control agent is 0.01 to 20.00 parts by mass, more preferably 0.50 to 10.00 parts by mass with respect to 100.00 parts by mass of the polymerizable monomer. . However, it is not essential to add a charge control agent to the toner of the present invention, and it may be appropriately selected depending on the machine configuration.

The toner of the present invention is a toner having toner particles and inorganic fine powder.
Examples of the inorganic fine powder include fine powder such as silica fine powder, titanium oxide fine powder, alumina fine powder, and double oxide fine powder thereof. Among the inorganic fine powders, silica fine powder and titanium oxide fine powder are preferable.
Examples of the silica fine powder include dry silica or fumed silica produced by vapor phase oxidation of silicon halide, and wet silica produced from water glass. As the inorganic fine powder, there are few silanol groups on the surface and inside the silica fine powder, and Na ₂ O,
Dry silica with less SO ₃ ²⁻ is preferred. The dry silica may be a composite fine powder of silica and another metal oxide by using a metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound in the production process.
The inorganic fine powder is externally added to the toner particles in order to improve the fluidity of the toner and to make the charge of the toner particles uniform. By hydrophobizing the inorganic fine powder, it is possible to adjust the charge amount of the toner, improve the environmental stability, and improve the characteristics in a high-humidity environment. It is preferable to use it. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner decreases, and the developability and transferability tend to decrease, and the durability in a harsh environment tends to decrease.
Non-modified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds are used as hydrophobic treatment agents for inorganic fine powders. Can be mentioned. These treatment agents may be used alone or in combination.
Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, when the inorganic fine powder is hydrophobized with a coupling agent, or after the hydrophobization treatment, the hydrophobized inorganic fine powder treated with silicone oil maintains a high charge amount of toner particles even in a high humidity environment, and is stable. The point which can provide the done image is good.

Hereinafter, various measurement methods according to the present invention will be described.
<Measurement of viscosity at 100 ° C. of toner by flow tester heating method>
The viscosity at 100 ° C. of the toner by the flow tester temperature rising method was measured under the following conditions using a flow tester CFT-500D (manufactured by Shimadzu Corporation) according to the operation manual of the apparatus.
Sample: 1.0 g of toner is weighed and molded by pressing it with a pressure molding machine having a diameter of 1 cm at a load of 20 kN for 1 minute.
-Die hole diameter: 1.0mm
-Die length: 1.0mm
・ Cylinder pressure: 9.807 × 10 ⁵ (Pa)
Measurement mode: Temperature rising method Temperature rising rate: 4.0 ° C./min
By the method described above, the viscosity (Pa · s) of the toner at 50 ° C. to 200 ° C. was measured to obtain the viscosity (Pa · s) at 100 ° C.

<Measurement of glass transition point of polar resin or toner>
The glass transition point of the polar resin or toner was measured under the following conditions using a differential scanning calorimeter (DSC) (manufactured by M-DSC TA-Instruments) according to the operation manual of the apparatus. Weigh accurately 6 mg of polar resin or toner (sample). This was put in an aluminum pan, and an empty aluminum pan was used as a reference, and measurement was performed at a temperature rising rate of 1.0 ° C./min and a normal temperature and normal humidity within a measurement temperature range of 20 ° C. to 200 ° C. At this time, the modulation amplitude is ± 0.5.
The temperature and the frequency were set to 1 / min. The glass transition point Tg (° C.) was determined from the obtained reversing heat flow curve. For Tg, the central value of the intersection of the baseline before and after the endotherm and the tangent to the endothermic curve was defined as Tg (° C.).

<Measurement of weight average particle diameter (D4) of toner>
The weight average particle diameter (D4) of the toner is a precision particle size distribution measuring apparatus “Coulter Counter Multisizer by pore electrical resistance method equipped with an aperture tube of 100 μm.
3 ”(registered trademark, manufactured by Beckman Coulter) and attached dedicated software“ Beckman Coulter Multisizer 3 Version 3.51 ”(manufactured by Beckman Coulter, Inc.) for measurement condition setting and measurement data analysis, Measurement was performed with 25,000 effective measurement channels, and 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.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, dirt and bubbles in the aperture tube are 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 is added.
(3) In an aquarium of an ultrasonic disperser “Ultrasonic Dispense System Tetora150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W and containing two oscillators with an oscillation frequency of 50 kHz, with a phase shifted by 180 degrees. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) Into the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement sample concentration is adjusted to about 5%. To do. The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is 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).

<Measurement of average circularity of toner>
The average circularity of the toner was calculated using the following formula by measuring the following items using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Toa Medical Electronics Co., Ltd.) according to the operation manual of the device.

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The degree of circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical, and the degree of circularity becomes smaller as the surface shape becomes more complicated.

  The average circularity C, which means the average value of the circularity frequency distribution, was calculated from the following equation, where ci was the circularity (center value) at the dividing point i of the particle size distribution and m was the number of measured particles.

  As a specific measuring method, first, 10 ml of ion-exchanged water from which impure solids were removed in advance was prepared in a container. After adding a surfactant, preferably an alkylbenzene sulfonate, as a dispersant, 0.02 g of a toner (measurement sample) was further added and dispersed uniformly (the toner concentration at the time of measurement was 3000 to 10,000). / Μl is preferred). As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios) was used for dispersion treatment for 2 minutes to obtain a dispersion for measurement. The dispersion was measured so that 1000 or more toners could be measured, and data with an equivalent circle diameter of less than 2 μm was cut to determine the average circularity of the toner. During dispersion of the dispersion, cooling was appropriately performed so that the temperature of the dispersion did not exceed 40 ° C. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocusing was performed using 2 μm latex particles every 2 hours.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the examples. In addition, all the parts used in an Example show a mass part.

[Production of Polar Resin A (1)]
1-methoxypropyl-2 was added to a reactor equipped with a dropping funnel, a Liebig condenser and a stirrer.
-300.0 mass parts of acetate was put and it heated up to 135 degreeC. A mixture of 99.90 parts by mass of styrene monomer, 0.10 parts by mass of acrylic acid and 10.00 parts by mass of t-butyl-peroxybenzoate was charged into the dropping funnel, and 1-methoxypropyl-
The solution was added dropwise to 2-acetate over 2 hours. Further, the solution polymerization was completed under reflux of 1-methoxypropyl-2-acetate (140 ° C.), and 1-methoxypropyl-2-acetate was removed to obtain polar resin A (1). The obtained polar resin A (1) has a weight average molecular weight (Mw) of 3.
500, Mw / Mn was 1.7, and the acid value (Va) was 1.2 mgKOH / g.

[Production of Polar Resin A (2), Polar Resin A (4) to Polar Resin A (8), Polar Resin A (10)]
Same as polar resin A (1) except that styrene monomer, acrylic acid, α-methylstyrene dimer, t-butyl-peroxybenzoate and 1-methoxypropyl-2-acetate were used in the amounts shown in Table 1. The polar resin A (2), polar resin A (4) to polar resin A (8), and polar resin A (10) were produced using the production method described above. The α-methylstyrene dimer is added to the styrene monomer mixture. Table 1 shows the weight average molecular weight (Mw), Mw / Mn, acid value (Va) and the like of the obtained polar resin.

[Production of Polar Resin A (3) and Polar Resin A (9)]
Polar resin A (1) except that the amount of addition shown in Table 1 is styrene monomer, acrylic acid, t-butyl-peroxybenzoate, and xylene, and the solvent is changed from 1-methoxypropyl-2-acetate to xylene. The polar resin A (3) and the polar resin A (9) were produced using the same production method. Table 1 shows the weight average molecular weight (Mw), Mw / Mn, acid value (Va) and the like of the obtained polar resin.

[Production of Polar Resin B (1)]
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 60.0 parts by mass of methanol as a solvent, 81.0 parts by mass of styrene as a monomer, 2-ethylhexyl 13.0 parts by mass of acrylate and 6.0 parts by mass of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature with stirring. 2.0 parts by mass of dimethyl 2,2′-azobis as a polymerization initiator was added, and stirring was continued for 5 hours. Further, 2.0 parts by mass of dimethyl 2,2′-azobis was added and further stirred for 5 hours to complete the polymerization. Further, 500 parts by mass of deionized water was added while maintaining the temperature, and after stirring for 2 hours at 90 rpm so that the interface between the organic layer and the aqueous layer was not disturbed, the mixture was allowed to stand for 30 minutes and separated. The aqueous layer was discarded, and anhydrous sodium sulfate was added to the organic layer for dehydration.
Next, the polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. The obtained polymer having a sulfonic acid group had Tg = 81 ° C., Mw = 28,500, and an acid value (Vb) of 22.3 mgKOH / g, and this was designated as polar resin B (1).

[Production of Polar Resins B (2) to (5)]
Polar resin B (2) using the same production method as polar resin B (1) except that styrene monomer, 2-ethylhexyl acrylate, and 2-acrylamido-2-methylpropanesulfonic acid were used in the addition amounts shown in Table 2. ) To (5) were produced. Table 2 shows the weight average molecular weight (Mw), Mw / Mn, glass transition point (Tg), and acid value (Vb) of the obtained polar resins B (2) to (5).

[Production of Polar Resin C (1)]
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
-Terephthalic acid: 24.0 parts by mass-Isophthalic acid: 24.0 parts by mass-Bisphenol A-propylene oxide 2-mole adduct: 87.5 parts by mass-Bisphenol A-propylene oxide 3-mole adduct: 20.5 parts by mass Bisphenol A-ethylene oxide 2 mol adduct: 2.5 parts by mass Neopentyl glycol: 1.0 part by mass Potassium oxalate titanate: 0.035 part by mass, 210 ° C under nitrogen atmosphere and normal pressure Then, 0.005 parts by mass of potassium oxalate titanate was added, reacted at 220 ° C. for 1.0 hour, and further reacted under reduced pressure of 15 mmHg for 1.5 hours. Thereafter, the temperature was lowered to 180 ° C., 0.10 parts by mass of trimellitic anhydride was added, and the mixture was reacted at 180 ° C. for 1.5 hours to obtain a polar resin C (1). The physical properties of the obtained polar resin C (1) are as follows: weight average molecular weight (Mw) is 9900, Mw / Mn is 2.5, glass transition point (Tg) is 70 ° C., acid value (Vc) is 9.1 mgKOH / g.

[Production of Polar Resin C (2)]
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
Dimethyl terephthalate: 40.0 parts by mass Bisphenol A-propylene oxide 2-mole adduct: 39.0 parts by mass Bisphenol A-propylene oxide 3-mole adduct: 68.0 parts by mass Dibutyltin oxide: 0.02 parts by mass The reaction was carried out at 200 ° C. for 5 hours under a nitrogen atmosphere and at normal pressure, and then reacted at 220 ° C. for 1.5 hours to obtain Polar Resin C (2). The physical properties of the obtained polar resin C (2) are as follows: weight average molecular weight (Mw) is 5600, Mw / Mn is 3.3, glass transition point (Tg) is 64 ° C., acid value (Vc) is 5.8 mgKOH / g.

[Production of Polar Resin C (3)]
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
-Terephthalate: 20.0 parts by mass-Isophthalate: 20.0 parts by mass-Bisphenol A-propylene oxide 2-mole adduct: 59.0 parts by mass-Bisphenol A-propylene oxide 3-mole adduct: 37.0 parts by mass Potassium oxalate titanate: 0.025 part by mass was charged, and the reaction was carried out at 220 ° C. for 22 hours under a nitrogen atmosphere and normal pressure, and further for 2 hours under a reduced pressure of 15 mmHg. Thereafter, the temperature was lowered to 190 ° C., 1.50 parts by mass of trimellitic anhydride was added, and the mixture was reacted at 190 ° C. for 1.5 hours to obtain a polar resin C (3). Regarding the physical properties of the obtained polar resin C (3), the weight average molecular weight (Mw) is 6750, Mw / Mn is 2.6,
The glass transition point (Tg) was 61 ° C. and the acid value (Vc) was 18.0 mgKOH / g.

[Production of Polar Resin C (4)]
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
-Terephthalate: 20 parts by mass-Isophthalate: 20 parts by mass-Bisphenol A-propylene oxide 2-mole adduct: 59 parts by mass-Bisphenol A-propylene oxide 3-mole adduct: 37 parts by mass-Bisphenol A-ethylene oxide 2-mole addition Product: 2 parts by mass-Tetrabutoxy titanate: 0.025 part by mass was charged, and reacted at 200 ° C for 5 hours under a nitrogen atmosphere and at normal pressure. Then, 0.010 parts by mass of tetrabutoxy titanate was added, and at 220 ° C. The reaction was performed for 3 hours, and further, the reaction was performed for 2 hours under a reduced pressure of 15 mmHg to obtain a polar resin C (4). Regarding the physical properties of the obtained polar resin C (4), the weight average molecular weight (Mw) is 6000, Mw / Mn is 2.1, and the glass transition point (Tg) is 6.
The acid value (Vc) at 6 ° C. was 3.0 mgKOH / g.

[Production of Polar Resin C (5)]
In the production example of the polar resin C (3), except that the reaction was stopped when the acid value reached 32.0 [mgKOH / g], using the same method as in the production example of the polar resin C (3), Polar resin C (5) was obtained. The physical properties of the obtained polar resin C (5) are as follows: the weight average molecular weight (Mw) is 5350, the Mw / Mn is 2.4, the glass transition point (Tg) is 60 ° C., and the acid value (Vc) is 31.3 mgKOH / g.

<Example 1>
In a four-necked vessel, 355 parts by mass of ion-exchanged water and 425 parts by mass of 0.1 mol / liter aluminum phosphate aqueous solution were added, and the mixture was stirred at 12,000 rpm using a high-speed stirring device TK-homomixer, and 65 ° C. Held on. Here, 42.5 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was added at a time to prepare an aqueous dispersion medium containing a fine hardly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ .

Styrene monomer 78.0 parts by mass n-butyl acrylate 22.0 parts by mass C.I. I. Pigment Blue 15: 3 8.0 parts by mass Polar resin A (1) 25.0 parts by mass Polar resin B (1) 0.5 parts by mass Polar resin C (1) 12.5 parts by mass Negative charge control agent (3, Aluminum compound of 5-di-tertiary butylsalicylic acid (Orient Chemical Industries, Ltd .: Bontron E88))
0.5 parts by weight wax (Fischer-Tropsch wax (manufactured by Nippon Seiwa): HNP-10)
12.5 parts by mass

The material is dispersed at 5,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and then heated to 65 ° C. to uniformly dissolve and disperse the polymerizable monomer composition. Was prepared. After adding 7.5 parts by mass of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate (75% toluene solution) as a polymerization initiator to the polymerizable monomer composition, Charged into dispersion medium. And it granulated for 5 minutes, maintaining the rotation speed of a stirrer at 12,000 rpm. Thereafter, the high-speed stirrer was changed to a propeller stirrer, the internal temperature was raised to 67 ° C., and the reaction was allowed to proceed for 5 hours with slow stirring.
Next, the temperature in the container was raised to 80 ° C. and maintained for 40 minutes, and the vessel was gradually cooled to 30 ° C. at a cooling rate of 1 ° C. per minute, whereby slurry 1 was obtained. Dilute hydrochloric acid was added to the container containing the slurry 1 to remove the dispersion stabilizer. Further, the toner particles 1 having a weight average particle diameter of 5.7 μm were obtained by filtration, washing and drying.
With respect to 100 parts by mass of the toner particles, 1.5 parts by mass of hydrophobic silica fine powder (number average primary particle size: 7 nm) surface-treated with hexamethyldisilazane was used using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The toner 1 of the present invention was obtained by dry-mixing for 5 minutes at a rotation speed of 4000 rpm. Table 4 shows the physical property values of Toner 1 thus obtained.

The toner 1 was evaluated as described later.
When the glossiness of the image was measured, it was confirmed that even a machine with a high process speed had a very high glossiness and was a glossy image.
In addition, when a large amount of printing is performed in a high-temperature and high-humidity (H / H: temperature 30 ° C., humidity 80% RH) environment in which toner deterioration is severe, the image is evaluated due to fusion and fixing of the deteriorated toner. A development streak that is a streak-like defect in a direction parallel to the paper feeding direction is hardly generated, and a stable image (density and density unevenness) is provided from the initial stage to the late stage of printing. Detailed results are shown in Table 5.

<Examples 2 to 6>
Toners 2 to 6 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 3 and the blending ratios thereof were used. The same evaluation as in Example 1 was performed using the toners 2 to 6. The results are shown in Table 5.

<Comparative Examples 1 to 8>
Toners 7 to 14 were obtained in the same manner as in Example 1 except that the raw materials shown in Table 3 and the blending ratios thereof were used. The same evaluation as in Example 1 was performed using the toners 7 to 14. The results are shown in Table 5.

The specific evaluation method is shown below.
Image evaluation was performed using a modified machine (process speed: 200 mm / sec, fixing temperature: 170 ° C.) of LBP-2510 (manufactured by Canon Inc.) as an evaluation machine. In the evaluation, 200 g of each toner shown in Table 5 was filled in a cartridge and mounted in a cyan station, and dummy cartridges were mounted in other stations.

<Evaluation of glossiness>
Using the above evaluation machine, the toner loading amount is 0.6 mg using A4 paper (X × 75 g / m ² paper) in a normal temperature and normal humidity (N / N: temperature 23.5 ° C., humidity 60% RH) environment. / Cm ^2, and a solid image having a length of 5 cm and a width of 20 cm from a position 5 cm from the tip in the longitudinal direction, and a solid white image thereafter was output. Using “PG-3D” (manufactured by Nippon Denshoku Industries Co., Ltd.), the glossiness of the fixed image at a measurement optical part angle of 75 ° was measured.
(Evaluation criteria)
A: 20 or more B: 15 or more, less than 20 C: 10 or more, less than 15
D: Less than 10

<Evaluation of image density>
Using the above evaluation machine, high temperature and high humidity (H / H: Temperature 30 ° C., 80% RH humidity) under environment and outputs the solid image on an A4 paper (Xx75g / ^{m 2} paper) the entire surface (initial image). Next, 15000 images with a printing ratio of 2% were printed out. Thereafter, A4 paper (Xx75g / ^{m 2} paper) entirely outputting a solid image (the image after 15000-sheet running). The density of these solid images was measured at 10 points (10 points measurement on a line at the center of the image parallel to the paper discharge direction for dividing the solid image into two equal parts and dividing the line into 11 equal parts) to evaluate the image density. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
(Evaluation criteria)
A: 1.40 or more B: 1.20 or more, less than 1.40 C: 1.00 or more, less than 1.20 D: less than 1.00

<Evaluation of density unevenness>
Density unevenness was evaluated using the solid image obtained by the image density measurement. Specifically, 10 points are measured for each solid image (10 points are measured on a line in the center of the image parallel to the paper discharge direction for dividing the solid image into two equal parts, and the line is divided into 11 equal parts), and the density difference is measured. (MAX-MIN) was calculated and evaluated as follows. The image density is “Macbeth reflection densitometer RD918” (
Macbeth) was used.
(Evaluation criteria)
A: Density difference is 0.05 or less, and there is no problem in image B: Density difference is more than 0.05 and 0.10 or less, and is at a level where there is no problem in image C: Density difference is 0. More than 10 with image problems

<Evaluation of development lines>
Using the evaluation machine, an image having a printing ratio of 2% was printed out using Xx75 g / m ² paper in a high temperature and high humidity (H / H: temperature 30 ° C., humidity 80% RH) environment. Every time 1000 sheets are printed, a halftone image (toner applied amount 0.30 mg / cm ² ) is output on the entire surface of A4 paper (Xx75 g / m ² paper), and a development streak (a streak in the paper discharge direction) The development streak level was evaluated on the basis of the number of sheets having three or more (image defects).
(Evaluation criteria)
A: 15000 sheets or more B: 10,000 sheets or more, less than 15000 sheets C: 5000 sheets or more, less than 10,000 sheets D: less than 5000 sheets

Claims (5)

A polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin A, a polar resin B, a polar resin C, and a release agent is dispersed in an aqueous medium and granulated. In a toner having toner particles obtained by polymerizing a polymerizable monomer in the particles and inorganic fine powder,
The polar resin A is a polymer obtained by polymerizing at least styrene or a styrene derivative, and has a weight average molecular weight (Mw) measured by gel permeation chromatography of tetrahydrofuran (THF) soluble content of 1500 to 6000. And
The addition amount of the polar resin A is 5.0 parts by mass to 65.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer,
The polar resin B is a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group,
The polar resin C is a polyester resin,
When the acid value of the polar resin A is Va (mgKOH / g), the acid value of the polar resin B is Vb (mgKOH / g), and the acid value of the polar resin C is Vc (mgKOH / g),
0.5 ≦ Va ≦ 15.0,
10.0 ≦ Vb ≦ 40.0,
5.0 ≦ Vc ≦ 30.0,
Va <Vb,
Va <Vc
A toner characterized by satisfying the following relationship: Said Va is
1.0 ≦ Va ≦ 7.0
The toner according to claim 1, wherein the following relationship is satisfied. Said Va is
1.0 ≦ Va ≦ 4.0
The toner according to claim 1, wherein the following relationship is satisfied. The weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography of the tetrahydrofuran (THF) soluble matter of the polar resin A are as follows:
1.0 <Mw / Mn <5.0
The toner according to claim 1, wherein: 5. The toner according to claim 1, wherein the toner has a viscosity at 100 ° C. of 1.0 × 10 ^{4 to} 4.5 × 10 ⁴ Pa · s according to a flow tester heating method.