JP3397626B2 - Electrostatic image developing toner and method of manufacturing toner - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image used for image formation to visualize an electrostatic latent image and a method for producing the same.

[0002]

2. Description of the Related Art US Pat.
It is known by a number of methods as described in JP-A-7,691 and JP-B-42-23910 and JP-B-43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with toner, and a direct or indirect means is used as necessary. After the toner image is transferred to a transfer material such as paper, it is fixed by heating, pressurizing, heating and pressurizing, solvent vapor or the like to obtain a copy or a print. Then, the toner remaining on the photoconductor without being transferred is cleaned by various methods as necessary, and the above steps are repeated.

The toner as described above is generally a particle whose main components are a binder resin and a colorant, and further, if necessary, a charge control agent and a fixing aid. Usually, the particle size is in the range of several to several tens of microns. This toner is generally produced by a so-called pulverization method in which a coloring agent such as a dye, a pigment or a magnetic material is mixed and melted in a thermoplastic resin, the colorant is uniformly dispersed in the thermoplastic resin, and then pulverization and classification are performed. ing.

In recent years, image forming apparatuses using electrophotography have been
It has come to be widely used not only as a copier for office work for simply copying text originals, but also as full-color output with high image quality and high-definition output for computers. Further, along with the generalization of computers, printers have been used in the personal field as well, and accordingly, there has been a demand for lowering the fixing temperature in order to reduce power consumption.

As a result, the performance required of the toner has become higher, and excellent image formation has become unsuccessful unless performance improvement such as image quality improvement and fixing property improvement from the toner side can be achieved.

As one of means for achieving such high image quality, there is a method of reducing the particle size of the toner. Certainly, improvement in image quality and resolution has been achieved by reducing the particle size to several μm.

However, in the conventional pulverization toner, if a strong impact force is applied in order to reduce the particle diameter of the toner, the pulverized object may be fused to the pulverization device. It is difficult to reduce the particle size to less than micron, and it is also difficult to sharpen the particle size distribution to some extent due to the cohesive force of the powder when the particle size of the toner is reduced in the classification operation. As a result, it becomes difficult to control the charge amount of the toner, and problems such as image scattering and fog occur.

[0008] In order to reduce the particle size of the toner and further improve the sharpness of the particle size distribution, a toner by a polymerization method has been proposed. For example, Japanese Patent Publication No. 6-52432 and Japanese Unexamined Patent Publication No. 5-93002 disclose a method of producing particles having a sharp particle size distribution of about 1 to 10 μm. Further, Japanese Patent Publication No. 6-58543, Japanese Patent Publication No. 6-
Japanese Patent No. 58544 discloses a method for producing image forming particles having a stable particle size distribution and a coating composition comprising a colorant or a conductive agent and a binder, and having stable charge characteristics and improved functionality. Has been done.

However, such particles having a sharp particle size distribution have excellent fluidity, but on the other hand, when they are allowed to stand, they cause the problem that the toner agglomerates when they are packed closest to each other, particularly when they are left in a high temperature environment. Occurs. The particles coated with a coloring agent or a conductive agent for imparting the above-mentioned functionality have a problem that they are more likely to aggregate when they are densely packed due to the non-uniformity in the fine portion on the toner surface. When the toner or the developer aggregates, poor charging is likely to occur, resulting in a problem that the resolution of the developed image deteriorates.

This becomes more remarkable as the particle size of the toner becomes smaller, and as a significant problem when the glass transition temperature of the binder resin is lowered or the average molecular weight is lowered in order to achieve low temperature fixing. appear.

[0011]

SUMMARY OF THE INVENTION It is an object of the present invention to provide an electrostatic charge image developing toner and a method for producing the same which solve the above problems.

That is, the present invention provides a toner for developing an electrostatic charge image, which satisfies both high image quality and low-temperature fixability at the same time, is stable even at high temperature, and has a narrow particle size distribution, and a method for producing the same. To aim.

The present invention provides a toner for developing an electrostatic charge image, which does not cause toner agglomeration and developer agglomeration even when left to stand at a high temperature, has excellent fluidity, is satisfactorily charged, and can obtain a high-quality image. It is an object to provide a manufacturing method thereof.

[0014]

The above object can be achieved by the present invention described below.

That is, the present invention relates to a toner for developing an electrostatic charge image, which comprises at least a binder resin and a colorant, wherein the toner comprises (i) 100 parts by weight of the binder resin and 0.1 part by weight of the colorant. To 15 parts by weight, (ii) 0.5
a number average particle diameter of μm to 6.0 μm, (iii)
A mixed solvent soluble resin having a coefficient of variation of number distribution of 20% or less, (iv) having a capsule structure containing a surface layer and a core part, and extracted with an ethanol (EtOH) / methyl ethyl ketone (MEK) mixed solvent In the component, the maximum glass transition temperature (Tg1) of the first soluble resin component from the start of extraction to 10% by weight based on the total weight of the mixed solvent soluble resin component and the remaining second soluble resin component The present invention relates to an electrostatic charge image developing toner characterized in that the relationship of the maximum glass transition temperature (Tg2) satisfies the following expressions Tg1> Tg2 and Tg1 ≧ 50 ° C.

Further, in the present invention, the polymer which is soluble in the polymerization solvent and which is produced by the polymerization is the first polymerizable monomer which is insoluble in the polymerization solvent and the polymerization solvent. A step of preparing a polymerization reaction system by dissolving a soluble polymer composition in the polymerization solvent; setting the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction to 2.0 mg / l or less. And the step of polymerizing the first polymerizable monomer in the presence of a polymerization initiator in the polymerization reaction system; the polymerization conversion rate of the first polymerizable monomer is 50% or more. At this point, the polymer that is soluble in the polymerization solvent, is not dissolved in the polymerization solvent, and has a glass transition higher than that of the polymer synthesized by the first polymerizable monomer. A step of adding a second polymerizable monomer capable of synthesizing a polymer having a high temperature into the polymerization reaction system; Step of polymerizing a polymerizable monomer of the second in situ; to obtain a polymer particle from within the polymerization reaction system;
And a step of producing a toner from the obtained polymer particles, wherein the obtained toner contains at least a colorant and a binder resin, and the toner comprises (i) a binder. A coloring agent is added to 100 parts by weight of the coating resin.
1 to 15 parts by weight, (ii) having a number average particle diameter of 0.5 μm to 6.0 μm, and (iii) 20%
It has the following coefficient of variation of number distribution, (iv) has a capsule structure containing a surface layer and a core part, and has ethanol (Et)
OH) / methyl ethyl ketone (MEK) mixed solvent-soluble resin component extracted with a mixed solvent-soluble resin component from the start of extraction to 10% by weight based on the total weight of the mixed solvent-soluble resin component. A method for producing a toner characterized in that the relationship between the maximum glass transition temperature (Tg1) and the maximum glass transition temperature (Tg2) of the remaining second soluble resin component satisfies the following formulas Tg1> Tg2 and Tg1 ≧ 50 ° C. Regarding

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION One of the features of the present invention is that in a toner for developing an electrostatic charge image, the number average particle diameter is in the range of 0.5 μm to 6.0 μm, and the variation coefficient of the number distribution is 20.
% Or less, and further ethanol (EtOH) /
Of the mixed solvent-soluble resin components extracted with the methyl ethyl ketone (MEK) mixed solvent, the first soluble resin component from the start of extraction to 10% by weight, that is, the maximum glass transition temperature (Tg1) of the toner surface layer and the remaining The relationship between the second soluble resin component, that is, the maximum glass transition temperature (Tg2) of the core portion of the toner satisfies the following expressions Tg1> Tg2 and Tg1 ≧ 50 ° C.

According to a detailed study by the present inventor, it has been found that a toner having a fine particle diameter such as an average particle diameter of 0.5 to 6 μm can faithfully develop a latent image. Further, it has been found that in such a fine particle toner, it is necessary that the variation coefficient of the number distribution is in the range of 20% or less in order to suppress the variation in charging. Further, in a toner having such a fine particle size and uniform particle size and having a resin having a low glass transition temperature in the core portion which is also excellent in low-temperature fixability, particularly in a case where the toner is allowed to stand in a high temperature environment. In order to prevent packing and accompanying aggregation of toner, it is effective to provide a resin layer having a glass transition temperature of 50 ° C. or higher and a glass transition temperature higher than the core portion of the toner on the toner surface layer to some extent or more. I found out.

Ethanol (EtOH) / methyl ethyl ketone (MEK) mixed solvent In the mixed solvent-soluble resin component to be extracted, the first soluble component from the start of extraction to 10% by weight based on the total weight of the mixed solvent-soluble resin component. Resin component,
That is, most of the components of the toner surface layer are considered to be the binder resin of the toner surface layer, but some residual monomers, initiators and other additives are also considered to be included.

Therefore, in the present invention, ethanol (Et
OH) / methylethylketone (MEK) mixed solvent Among the glass transition temperatures of the first soluble resin component to be extracted, the glass transition temperature of the surface layer is the portion showing the maximum endothermic width,
That is, the maximum glass transition temperature (Tg1) is set. Further, the core is formed with the glass transition temperature obtained from the remaining second soluble resin component extracted from the start of extraction after 10% by weight to the end of extraction, that is, the part showing the maximum endothermic width of the core part of the toner. Maximum glass transition temperature (T
g2).

The measurement of the glass transition temperature will be described in detail in the description of the measuring method.

Further, in the present invention, the relationship between the maximum glass transition temperature (Tg1) of the surface layer portion and the maximum glass transition temperature (Tg2) of the core portion satisfies the following expression Tg1> Tg2 Tg1 ≧ 50 ° C. More preferably, by satisfying the following formula Tg1-Tg2 ≧ 20 ° C. Tg1 ≧ 50 ° C., it is possible to more preferably prevent aggregation at high temperature while maintaining low-temperature fixability.

Further, Tg2 of less than 50 ° C. is more preferable in terms of low fixing temperature and low temperature fixing property.

The capsule structure having a surface layer and a core portion in the present invention includes a capsule structure in which a surface layer covers a single core body and a plurality of core bodies dispersed in a resin constituting the surface layer. A domain-encapsulating structure having a matrix structure.

Furthermore, when the radius of the toner having the capsule structure is r1 and the distance from the toner surface to the surface portion of the core which is the shortest distance among the single or plural cores is r2, 1.1 ≦ r1 By satisfying the relational expression of / r2 ≦ 100, the low-temperature fixability becomes good while satisfying the aggregation resistance.

Further, TH of the binder resin component in the toner is
In the molecular weight distribution by GPC, the content of the F-soluble component in the molecular weight distribution of 1000 or less is 0.5% by weight, whereby the effect of maintaining stability at high temperature is enhanced.

The toner of the present invention is preferably a method of directly producing the toner by a polymerization method. Among them, a polymer that is soluble in a polymerization solvent and is produced by polymerization is a first polymerizable monomer that is insoluble in the polymerization solvent, and a polymer composition that is soluble in the polymerization solvent. Is dissolved in the polymerization solvent to prepare a polymerization reaction system; the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction is 2.0 mg / l.
A step of polymerizing the first polymerizable monomer in the presence of a polymerization initiator in the polymerization reaction system, set to the following; the polymerization conversion rate of the first polymerizable monomer is 50% or more. At this point, the polymer which is soluble in the polymerization solvent and which is produced by the polymerization does not dissolve in the polymerization solvent, and is more soluble than the polymer synthesized by the first polymerizable monomer. A step of adding a second polymerizable monomer capable of synthesizing a polymer having a high glass transition temperature to the polymerization reaction system; a step of polymerizing the second polymerizable monomer in the polymerization reaction system It is preferable that the toner is produced by a method for producing a toner, which comprises a step of obtaining polymer particles from the polymerization reaction system; and a step of producing a toner from the obtained polymer particles.

Thus, by starting the polymerization in a state where the amount of dissolved oxygen at the start of the polymerization reaction is 2.0 mg / l or less, (i) the glass transition temperature is set to a desired value (Tg is less than 50 ° C.). When set to 2, two polymerizable monomers of the polymerizable monomer A and the polymerizable monomer B are used as the first polymerizable monomer for forming the core part, and The monomers A and B are set to a weight ratio of 1: 1 for copolymerization, and the resin composition as the core part thereof is made to have a copolymerization weight ratio of 1: 1 as set, and ( T1) It becomes possible to make the particle size distribution within the range of the present invention. At the same time, a second polymerizable monomer capable of synthesizing a polymer having a glass transition temperature higher than that of the polymer synthesized by the first polymerizable monomer when the polymerization conversion rate becomes 50% or more. By forming the surface layer by adding, the adhesion between the soft inside and the hard surface layer is finally good, and the surface property becomes very uniform. It is considered that this also makes it easier to prevent packing at high temperatures without deteriorating the fixability.

The configuration of the present invention will be described in detail.

In the present invention, it is important that the number average particle diameter of the toner is 0.5 μm to 6.0 μm, preferably 1.0 μm to 5.0 μm. This is necessary to obtain a high-definition image, and if the number average particle diameter is smaller than 0.5 μm, it becomes difficult to handle as dry powder. If it exceeds 6.0 μm, it becomes impossible to faithfully develop an extremely small dot latent image, and thus reproducibility of extremely highlight becomes particularly low.

Further, in the present invention, the variation coefficient of the number distribution of toner is 20% or less, preferably 18% or less.

The variation coefficient of the toner number distribution is calculated by the following equation.

(Formula) Coefficient of variation (%) = [(standard deviation of number distribution) / (number average particle size)] × 100

In the present invention, in addition to the average particle size of the toner, the broadening of the particle size distribution greatly contributes to the image reproducibility particularly in the transfer step. That is, when the coefficient of variation exceeds 20%, even if the average particle diameter is within the range of the present invention, the development is satisfactorily performed, but on the other hand, there is toner scattered during transfer or untransferred due to variations in charging, so that halftone is particularly generated. Reproducibility decreases.

In the present invention, the glass transition temperature (Tg1) of the first soluble resin component extracted as the surface layer,
The remaining second soluble resin component, that is, the relationship between the maximum glass transition temperature (Tg2) and (Tg1)> (Tg2) of the nucleus portion is satisfied, and the maximum glass transition temperature (Tg of the nucleus portion) (Tg).
1) is preferably 50 ° C. or higher.

When the maximum glass transition temperature (Tg1) of the first soluble resin component is lower than the maximum glass transition temperature (Tg2) of the second soluble resin component, that is, Tg1≤Tg2.
In such a case, the toner surface becomes too soft and the developability and blocking property at high temperature cannot be satisfied.

When the maximum glass transition temperature (Tg1) of the first soluble resin component is less than 50 ° C., it becomes difficult to sufficiently prevent the aggregation of toner particles.

In the present invention, the relationship between the maximum glass transition temperature (Tg1) of the first soluble resin component and the maximum glass transition temperature (Tg2) of the second soluble resin component is further expressed by the following formula Tg1- It is preferable that Tg2 ≧ 20 ° C. and Tg1 ≧ 50 ° C. are satisfied, and it is more preferable that the following relationships 80 ° C. ≧ Tg1−Tg2 ≧ 30 ° C. and Tg1 ≧ 50 ° C. are satisfied.

The maximum glass transition temperature of the first soluble resin component in the toner of the present invention is preferably 50 ° C. to 1
It is preferable that the temperature is from 50 ° C., more preferably from 60 ° C. to 120 ° C., since the effects of low-temperature fixability and packing prevention can be sufficiently exhibited.

When the temperature exceeds 150 ° C., although it is effective in preventing aggregation and packing, the low temperature fixability may not be sufficiently satisfied.

In the present invention, the maximum glass transition temperature (Tg2) of the second soluble resin component is preferably less than 50 ° C. from the viewpoint of low temperature fixability.

The toner of the present invention has a molecular weight of 1000 in the molecular weight distribution by GPC of the THF soluble component of the toner.
The content of the following components is 0.5% by weight or less,
It is preferable because it is possible to further improve blocking resistance and cohesiveness in a high temperature environment during long-term use, and at the same time, it is possible to further satisfy low temperature fixing property.

The molecular weight of the THF-soluble component of the toner is 10
When the content of the components of 00 or less exceeds 0.5% by weight, the toner particles may easily aggregate when packed.

The toner of the present invention has a capsule structure having a core portion and a surface layer covering the core portion, and this capsule structure has a single capsule structure as shown in FIG. A form in which the surface layer covers the nucleolus and a domain in which the surface layer covers a plurality of nucleolus as shown in FIG.
It may be in any form having a matrix structure.

In the present invention, when the radius of the toner having the capsule structure is r1, and the distance from the toner surface of the single nucleus or a plurality of the nucleus to the surface portion of the nucleus which is the shortest distance is r2. Preferably, the following formula 1.1 ≦ r1 / r2 ≦ 100 is satisfied, more preferably the following formula 2.0 ≦ r1 / r2 ≦ 50 is satisfied, and further preferably the following formula 5 is satisfied. It is preferable that 0.0 ≦ r1 / r2 ≦ 40 is satisfied because the aggregation resistance is satisfied and the low temperature fixing property is also improved.

When r1 / r2 is less than 1.1, sufficient low-temperature fixability cannot be obtained, and when r1 / r2 exceeds 100, it is sufficiently satisfactory to suppress agglomeration due to packing in a high temperature environment. It may not be possible.

In the present invention, the toner capsule structure is confirmed and r1 and r2 are measured by, for example, slicing a toner powder hardened with an epoxy resin with a microtome, dyeing it with a dye such as osmic acid, and then using TEM.
Observe at a magnification of 10,000 to 100,000 times, and judge from the photograph. It should be noted that the magnifying power is such that the toner particles are 1 in one field of view.
Set so that one to two can be entered.

As a method for producing the toner of the present invention, the following method is mentioned as a preferred embodiment. The toner of the present invention is soluble in a polymerization solvent, and the polymer produced by the polymerization is soluble in the first polymerizable monomer that is not soluble in the polymerization solvent and the polymerization solvent. Dissolving a certain polymer composition in the polymerization solvent to prepare a polymerization reaction system; setting the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction to 2.0 mg / l or less, A step of polymerizing the first polymerizable monomer in the polymerization reaction system in the presence of a polymerization initiator; at a time point when the polymerization conversion rate of the first polymerizable monomer becomes 50% or more, The polymer that is soluble in the polymerization solvent, is not dissolved in the polymerization solvent, and has a higher glass transition temperature than the polymer synthesized by the first polymerizable monomer. A step of adding a second polymerizable monomer capable of synthesizing a polymer into the polymerization reaction system; It is better to be produced by the method for producing a toner having; generating a toner and from the resulting polymer particles; polymerizable monomer to the polymerization process; obtaining a polymer particle from in the polymerisation reaction system.

In the above production method, the amount of dissolved oxygen in the polymerization reaction system is successively monitored using a dissolved oxygen meter (dissolved oxygen meter Model 3600 manufactured by Orvisfair Laboratories).

Further, in the present invention, the start of the polymerization reaction is defined as the time when the polymerization conversion rate is 5% or less.

The polymerization conversion rate is calculated by gas chromatography (GC) as the rate of change of the integral value of the monomer peak. The measuring method will be described later.

In the present invention, when a toner is produced by this production method, the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction is very important for the sharpness of the particle size distribution, the homogeneity of the composition and the like. is there. When the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction exceeds 2.0 mg / l, the copolymer composition of the binder resin is such that the toner glass transition temperature is set to a certain value in order to obtain the desired fixability. However, not only the production stability that the copolymerization ratio cannot be polymerized as it is cannot be obtained, but also the generation of fine particles of 1 μm or less may occur. Therefore, the amount of dissolved oxygen in the polymerization reaction system at the start of the reaction is preferably 2.0 mg / l or less, and more preferably 1.0 mg / l or less. As a method for removing dissolved oxygen, a method of substituting it with an insoluble gas such as various gases, preferably nitrogen or argon, is preferable, and it is also preferable to bubble the gas by sucking the gas into the liquid. Further, the method of deoxidizing by ultrasonic waves may be performed alone instead of the above gas replacement method, or may be performed in combination with the above gas replacement method.

In the present invention, in addition to the control of the amount of dissolved oxygen in the above-mentioned polymerization reaction system, in the polymerization reaction system when the conversion of the first polymerizable monomer reaches 50% or more. Polymer which is soluble in the solvent for polymerization, is not dissolved in the solvent for polymerization, and has a higher glass transition temperature than the polymer synthesized by the first polymerizable monomer. By forming the surface layer by adding the second polymerizable monomer capable of synthesizing the polymer into the polymerization reaction system, the adhesion between the very soft inside and the hard surface layer is finally good. , And the surface becomes very uniform.

It is considered that the use of these manufacturing methods also makes it easier to prevent packing at high temperature without deteriorating the fixing property. It is more preferable to add the second polymerizable monomer to the polymerization reaction system when the conversion rate of the first polymerizable monomer reaches 60% to 95%. Even when the conversion rate of polymerization of the first polymerizable monomer is less than 50% and the second polymerizable monomer is added to the polymerization reaction system, each set of resins for the core portion and the surface layer Although it may be possible depending on the combination, generally, the low temperature fixing property is deteriorated.

In the above production method, specific examples of the polymer composition for preparing the polymerization reaction system by dissolving it in the polymerization solvent include polyhydroxystyrene, polystyrene sulfonic acid, vinylphenol- (meth) acrylic acid. Polystyrene derivatives such as ester copolymers, styrene-vinylphenol- (meth) acrylic acid ester copolymers; poly (meth) acrylic acid, poly (meth) acrylamide, polyacrylonitrile, polyethyl (meth) acrylate, polybutyl (meth) Poly (meth) acrylic acid derivatives such as acrylates; Polyvinyl alkyl ether derivatives such as polymethyl vinyl ether, polyethyl vinyl ether, polybutyl vinyl ether, polyisobutyl vinyl ether; Cellulose, cellulose acetate, cellulose nitrate, Mud carboxymethyl cellulose, hydroxypropyl cellulose, cellulose derivatives such as carboxymethyl cellulose; polyvinyl alcohol,
Polyvinyl acetate derivatives such as polyvinyl butyral, polyvinyl formal, polyvinyl acetate; nitrogen-containing polymer derivatives such as polyvinyl pyridine, polyvinyl pyrrolidone, polyethylene imine, poly-2-methyl-2-oxazoline; polyvinyl chloride, polyvinylidene chloride, etc. Mention may be made of polyvinyl halide derivatives, siloxane derivatives such as polydimethylsiloxane; or copolymers thereof, or mixtures thereof.

In the present invention, the above polymer composition is
A weight average molecular weight of 3,000 to 300,000 is preferable in order to make the particle size distribution uniform. The weight average molecular weight of the polymer composition can be calculated from the molecular weight distribution measured according to the method for measuring the molecular weight distribution of the toner described below.

The weight average molecular weight of the polymer composition is 3000
If it is less than, the particle size distribution of the toner becomes broad,
It is outside the scope of the present invention.

If it exceeds 300,000, the viscosity in the polymerization reaction system becomes too high at the time of polymerization and uniform stirring cannot be carried out, which may also cause a broad particle size distribution.

The amount of the above-mentioned polymer composition used is preferably 0.1% by weight to 50% by weight, more preferably 0.5% by weight to 30% by weight, and still more preferably based on the weight of the solvent for polymerization. Is preferably 1% by weight to 20% by weight in order to make the particle size distribution sharp within the average particle size range of the present invention.

When the amount of the polymer composition used is less than 0.1% by weight based on the weight of the polymerization solvent, the produced toner particles cannot be kept stable in the polymerization reaction system and the particles are May not be possible.

If it exceeds 50% by weight, the viscosity in the polymerization reaction system may be too high, and the particle size distribution may be broad.

Examples of the polymerization solvent used in the above-mentioned production method of the present invention include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, ter.
t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 1-hexanol, 2-methyl 1-pentanol, 4 Alcohols such as -methyl-2-pentanol, 2-ethylbutanol, 1-heptanol, 2-heptanol, 3-heptanol, 2-octanol, 2-ethyl 1-hexanol, benzyl alcohol, cyclohexanol; methyl cellosolve, cellosolve , Ether alcohols such as isopropyl cellosolve, butyl cellosolve and diethylene bricol monobutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, pro Esters such as ethyl onate and cellosolve acetate; pentane, 2-methylbutane, n-hexane, cyclohexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, n-octane, isooctane, 2, 2,
3-trimethylpentane, decane, nonane, cyclopentane, methylcyclopentane, methylcyclohexane,
Aliphatic or aromatic hydrocarbons such as ethylcyclohexane, p-menthane, bicyclohexyl, benzene, toluene, xylene, ethylbenzene; carbon tetrachloride; halogenated hydrocarbons such as trichloroethylene, chlorobenzene, tetrapromethane; ethyl ether, Ethers such as dimethyl ether and trioxane tetrahydrofuran, acetals such as methylal and diethyl acetal; fatty acids such as formic acid, acetic acid and propionic acid; nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylformamide,
Mention may be made of sulfur such as dimethylsulfoxide; nitrogen-containing organic compounds; and water.

In the present invention, examples of the first and second polymerizable monomers used in the above production method include styrene, o-methylstyrene, m-methylstyrene and p-.
Styrene-based monomers such as methoxystyrene, p-ethylstyrene, p-tertiarybutylstyrene, acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, n-propyl acrylate, isobutyl acrylate, acrylic Octyl acid, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate,
2-chloroethyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid 2 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminomethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, benzyl methacrylate, crotonic acid, isocrotonic acid, acid phosphooxyethyl methacrylate, acid phosphooxypropyl methacrylate, Acroylmorpholine, 2-hydroxyethyl acrylate, 2
-Acrylic acid monomers such as hydroxyethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl ether, isobutyl ether, β-chloroethyl vinyl ether, phenyl vinyl ether, p-methylphenyl Ether, p-chlorophenyl ether, p-bromophenyl ether, p-nitrophenyl vinyl ether, p
Vinyl ether type monomers such as methoxyphenyl vinyl ether and butadiene; dibasic acid type monomers such as itaconic acid, maleic acid, fumaric acid, monobutyl itaconate and monobutyl maleate: 2-vinylpyridine, 3-vinylpyridine, Heterocyclic monomers such as 4-vinylpyridine, N-vinylpyrrolidone, 2-vinylimidazole, N-methyl-2-vinylimidazole and N-vinylimidazole can be mentioned.

These polymerizable monomers may be used alone or in combination of two or more, and the polymerizable monomer may be used so as to obtain a suitable polymer composition so that preferable characteristics can be obtained. A monomer can be selected appropriately.

In the toner of the present invention, it is necessary to change the composition of the above-mentioned polymerizable monomer between the core portion and the surface layer portion. For example, it becomes a surface layer obtained by the polymerization of the second polymerizable monomer which is added midway from the glass transition temperature of the resin which becomes the core portion given by the polymerization of the first polymerizable monomer. It is important that the glass transition temperature of the resin is high, and it is preferable that the difference is 20 ° C. or more.

Specifically, in the binder resin for copolymerizing styrene and n-butyl acrylate, the mixing ratio of the first polymerizable monomer is set to styrene: n-butyl acrylate = 60: 40. The mixing ratio of styrene: n-butyl acrylate = 6 as the second polymerizable monomer (composition) added when the polymerization reaction proceeds by 50% or more.
A combination such as 1:39 to 100: 0 or a mixture ratio of styrene: methyl methacrylate = 60: 40 to 10 as the second polymerizable monomer (composition) added later.
This can be achieved by changing the composition ratio such that it is set to 0: 0 or changing the type of the polymerizable monomer.

In the toner of the present invention, a high molecular weight component or a gel component can be contained in the core portion or the surface layer, preferably in the surface layer portion. The introduction of such a high molecular weight component or gel component is achieved by using a crosslinking agent having two or more polymerizable double bonds per molecule.

Examples of the crosslinking agent used in the present invention include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene, ethylene glycol diacrylate,
Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,
4-butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol tetramethacrylate, glycerol acryloxydimethacrylate, N, Examples thereof include N-civinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone, which may be used alone or in a suitable mixture of two or more kinds.

This crosslinking agent can be mixed with the polymerizable monomer in advance, and is preferably added during the polymerization reaction of the polymerizable monomer.

In the present invention, the polymer particles obtained by the above-mentioned production method are subjected to a washing step for removing the polymer composition, monomers, oligomers, initiators and other additives remaining in the polymerization reaction system. Good to go through.

The washing method in this washing step can be carried out, for example, by repeating decantation, centrifugal pressure filtration, vacuum filtration and the like, ultrasonic agitation in a solvent, mechanical stirring and the like.

Further, the washed toner is dried and used as a toner, but the drying step is not particularly limited, and the toner can be obtained by a conventionally used drying method.

The toner of the present invention may be classified after drying if necessary.

In the present invention, any known colorant can be used. Regarding the method of coloring the toner with the colorant, a method of adding the colorant together with the polymerizable monomer into the polymerization reaction system and containing the colorant in the toner at the same time as the polymerization, or by obtaining the polymer particles in a warm solvent, etc. Coloring can be performed by any means such as a method of dyeing with a dye. However, in the present invention, a coloring method of depositing a colorant onto a toner surface by applying a mechanical impact force after producing the polymer particles is not preferable. This is because if hygroscopic particles such as a colorant are present on the surface of the toner, they tend to agglomerate when packed due to non-uniformity in the fine portion.

Examples of the colorant used in the present invention include carbon black, known organic colorants, C.I. I. Direct Red 1, C.I. I. Basic Red 1, C.I.
I. Mordant Red 30, C.I. I. Direct Blue 1, C.I. I. Direct Blue 2, C.I. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Mordant Blue 7, C.I.
I. Direct Green 6, C.I. I. Basic Green 4, C.I. I. Dyes such as Basic Green 6, Cadmium Yellow, Mineral First Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Tartrazine Lake, Molybdenum Orange GTR, Benzidine Orange G, Cadmium Red 4R, Watching Red Calcium Salt , Brilliant Carmine 3B, Fast Violet B, Methyl Violet Rake, Cobalt Blue,
Alkali Blue Lake, Victoria Blue Lake, Quinacridone, Rhodamine Lake, Phthalocyanine Blue,
Pigments such as Fest Sky Blue, Pigment Green B, Macalite Green Lake, Final Yellow Green G, C.I. I. Solvent Yellow 6, C.I. I. Solvent Yellow 9, C.I. I. Solvent yellow 1
7, C.I. I. Solvent Yellow 31, C.I. I. Solvent Yellow 35, C.I. I. Solvent yellow 10
0, C.I. I. Solvent Yellow 102, C.I. I. Solvent Yellow 103, C.I. I. Solvent yellow 1
05, C.I. I. Solvent Orange 2, C.I. I. Solvent Orange 7, C.I. I. Solvent Orange 13,
C. I. Solvent Orange 14, C.I. I. Solvent Orange 66, C.I. I. Solvent Red 5, C.I. I.
Solvent Red 16, C.I. I. Solvent Red 1
7, C.I. I. Solvent Red 18, C.I. I. Solvent Red 19, C.I. I. Solvent Red 22, C.I.
I. Solvent Red 23, C.I. I. Solvent Red 143, C.I. I. Solvent Red 145, C.I. I. Solvent Red 146, C.I. I. Solvent Red 14
9, C.I. I. Solvent Red 150, C.I. I. Solvent Red 151, C.I. I. Solvent Red 157,
C. I. Solvent Red 158, C.I. I. Solvent Violet 31, C.I. I. Solvent Violet 3
2, C.I. I. Solvent Violet 33, C.I. I. Solvent Violet 37, C.I. I. Solvent Blue 22, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I.
I. Solvent Blue 84, C.I. I. Solvent Blue 85, C.I. I. Solvent Blue 86, C.I. I. Solvent Blue 104, C.I. I. Solvent Blue 191,
C. I. Solvent Blue 194, C.I. I. Solvent Blue 195, C.I. I. Solvent Green 24, C.I.
I. Solvent Green 25, C.I. I. Solvent Brown 3, C.I. I. Solvent Brown 9 can be mentioned.
Commercially available dyes include, for example, Mitsubishi Kasei's dialyzin Ye
low-3G, Yellow-F, Yellow-H
2G, Yellow-HG, Yellow-HC, Ye
low-HL, Orange-HS, Orange-
G, Red-GG, Red-S, Red-HS, Red
-A, Red-K, Red-H5B, Violet-
D, Blue-J, Blue-G, Blue-N, Bl
ue-K, Blue-P, Blue-H3G, Blue
-4G, Green-C, Brown-A; Hodogaya Chemical's indigo dye SOT dye, Yellow-1, Yellow
-3, Yellow-4, Orange-1, Oran
ge-2, Orange-3, Scarlet-1, R
ed-1, Red-2, Red-3, Brown-2,
Blue-1, Blue-2, Violet-1, Gr
een-1, Green-2, Green-3, Bla
ck-1, Black-4, Black-6, Blac
k-8; BASF sudan dye Yellow-1
46, Yellow-150, Orange-220,
Red-290, Red-380, Red-460, B
lue-670; Orient Chemical Industry oil black, oil color Yellow-3G, Yellow
-GG-S, Yellow- # 105, Orange-
PS, Orange-PR, Orange- # 201,
Scarlet- # 308, Red-5B, Brown
-GR, Brown- # 416, Green-BG, G
reen- # 502, Blue-BOS, Blue-I
IN, Black-HBB, Black- # 803, B
black-EB, Black-EX; Sumitomo Chemical's Sumiplast Blue GP, Blue OR, Red-FB,
Red-3B, Yellow FL7G, Yellow GC; Nippon Kayaku's Kayaron Polyester Black EX-SF30
0, Kayaset Red-B, and Blue A-2R.

In the toner having a fine particle diameter of the present invention, the amount of the colorant used is the binder resin 10 of the toner.
With respect to 0 parts by weight, preferably 0.1 parts by weight to 15 parts by weight, more preferably 1.0 parts by weight to 10 parts by weight,
More preferably, it is 2 to 8 parts by weight.

When the content of the above dye or pigment is less than 0.1% by weight with respect to 100 parts by weight of the binder resin of the toner, the hiding power of the toner tends to be insufficient.
If it exceeds 5 parts by weight, it may be O depending on the kind of colorant.
The HP becomes inferior in transparency.

Further, in the present invention, a magnetic toner can be prepared by using a magnetic material as a colorant.
In this case, the amount of the magnetic substance used is 5 times the content of the dye or pigment (the specific gravity of the dye or pigment is about 1 g / cm 2).
³ (while the specific gravity of the magnetic material is about 5 g / cm ³ ), an amount range is preferably used.

The polymerization initiator that can be used in the present invention includes
Any known in the art can be used. As the polymerization initiator, a radical-polymerizable initiator or an ionic-polymerizable initiator can be used.

Examples of the radical-polymerizable initiator include 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,
1,1′-azobis- (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis-4-methoxy2,4-dimethylvaleronitrile Such azo or diazo polymerization initiators; 2,2'-azobis (2-aminodipropane) dihydrochloride, 2,2'-azobis (N, N '
-Dimethylene isobutylamidine), 2,2'-azobis (N, N'-dimethyleneisobutylamidine) dihydrochloride, such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, Examples thereof include peroxide type polymerization initiators such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide; and persulfide type initiators such as potassium vortex sulfate and ammonium persulfate.

Examples of the anionically polymerizable initiator include SrR2, CaR2, K, KR, Na, NaR, Li,
LiR, ketyl, R-MgR, R-ONa, R-OK,
Examples include strong alkalis such as R-OLi, sodium hydroxide and potassium hydroxide; weak alkalis such as pyridine and ammonia; R-O-R (where R represents an alkyl group); and water.

Examples of the cationically polymerizable initiator include SnC1 ₄ , BF ₃ , AlC1 ₃ and TiC1 ₃ . These polymerization initiators can be used alone or in combination of two or more kinds.

The concentration of the polymerization initiator used in the production of the toner of the present invention includes the molecular weight of the produced polymer,
Although it can be adjusted appropriately in consideration of the yield, it is preferably 0.1 based on the total amount of the polymerizable monomers used.
Wt% to 15 wt%, more preferably 0.5 wt%
It is preferable that it is from 12 to 12% by weight.

When the concentration of the polymerization initiator is less than 0.1% by weight, it becomes difficult to sufficiently generate radicals,
Polymerization may not proceed.

When it exceeds 15% by weight, many radicals are generated, so that the molecular weight does not increase, and the glass transition temperature of the resulting resin does not increase, depending on the polymerizable monomer used.

In the present invention, a polymerization reaction may be carried out by adding a chain transfer agent to the above production method.

Examples of the chain transfer agent include halogenated carbonization such as carbon tetrachloride, carbon tetrabromide, ethyl dibromide acetate, ethyl acid bromide acetate, ethyl dibromide benzene, ethane dibromide and ethane dichloride. Hydrocarbons such as hydrogen, diazothioether, benzene, ethylbenzene, and isopropylbenzene, mercaptans such as tertiary decyl mercaptan and n-dodecyl mercaptan, and disulfides such as diisopropyl xanthogen disulfide can also be added.

The toner of the present invention may contain a chargeability control agent for the purpose of controlling chargeability. As the charge control agent, any of a positive charge control agent or a negative charge control agent which is usually used for toner can be used. Examples of charge control agents include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts,
Examples thereof include amine-based or imine-based compounds, metal compounds of salicylic acid or alkylsalicylic acid, metal-containing monoazo dyes, compounds having a carboxylyl group or a sulfoalkyl group, humic acids such as nitrohumin, and humic salts.

In the present invention, for the toner having a single capsule structure in the core portion, the above-mentioned polymerization method of the toner can be most preferably used.

When a toner having a capsule structure having a domain-matrix structure having a plurality of cores is produced, a good toner can be obtained by using the following production method.

That is, it is a method for producing by applying the porous glass membrane emulsification method.

First, the binder resin A having a desired molecular weight distribution and a low glass transition temperature is dissolved in a good solvent such as toluene. Further, the solution is reprecipitated in a poor solvent such as methanol or ethanol to obtain a binder resin from which low molecular weight components and residual monomers have been removed. The obtained binder resin is redissolved in a good solvent to prepare a low Tg resin solution A. Further, this low Tg resin solution A is passed through a tubular first phase-separated glass porous body having uniform pores, and an aqueous solution containing a surfactant (first
(Continuous phase) of oil / water (O / W)
Prepare the emulsion.

Secondly, the binder resin B having a desired molecular weight distribution and a high glass transition temperature is dissolved in a good solvent such as toluene. Further, the solution is reprecipitated in a poor solvent such as methanol or ethanol to obtain a binder resin from which low molecular weight components and residual monomers have been removed. Each of the obtained binder resins is redissolved in a good solvent to prepare a high Tg solution B. This high Tg solution B
A polymerizable monomer, a crosslinkable monomer and a polymerization initiator are dissolved therein to prepare a second continuous phase.

The above-mentioned O / W emulsion is passed through a second phase-separated glass porous body which has pores larger than those of the above-mentioned first phase-separated glass porous body and is subjected to a hydrophobization treatment, Directly dispersed in the continuous phase of oil / water / oil (O /
W / O) Prepare emulsion.

Thirdly, the above O / W / O emulsion is passed through a third phase-separated glass porous body having pores larger than those of the aforementioned second phase-separated glass porous body, and a surfactant is added. An oil / water / oil / water (O / W / O / W) emulsion is prepared by dispersing in an aqueous solution (third continuous phase) containing the emulsion.

Fourthly, a toner having a capsule structure exhibiting a domain-matrix structure can be produced by polymerizing in this state, recovering powder from the obtained slurry and drying.

Various external additives may be externally added to the toner of the present invention for the purpose of improving fluidity and chargeability.
Examples of the external additive include fine powders such as silica, titanium oxide, and alumina. The external additive preferably used in the toner of the present invention has a BET surface area of 300.
Those having m ² / g or more can be mentioned. BET specific surface area is 3
It can be used even if it is less than 00 m ² / g, but in addition to the fine particle size, in order to maintain a uniform surface state of the toner with a sharp particle size distribution, to perform good charging and to embed an external additive in a long-term use. An external additive having a specific surface area of 300 m ² / g or more is also preferable in order to prevent the above and to stabilize the image for a long period of time. Preferably, by using a toner having a specific surface area of 350 m ² / g or more, especially in combination with a toner having a fine particle diameter, it is possible to more stably maintain the fluidity and the chargeability even in the long-term use.

The toner of the present invention can be used as a one-component type developer or a two-component type developer mixed with carrier particles. As the carrier, conventionally used carriers such as iron powder, magnetite, ferrite and magnetic substance dispersed resin carrier can be used. It is preferable that the number average particle diameter of the carrier is 30 μm or less in order to give a sufficient charge to the toner.

The methods for measuring various physical properties in the present invention will be described below.

(1) Formation of soluble resin by mixed solvent of toner
Extraction of the soluble resin component is extracted under normal temperature and normal humidity environment by the extractor shown in FIG.

10 parts of toner powder 1 was precisely weighed as a sample,
Toner powder 1 is put into a cylindrical filter paper 2 with an inner diameter B of 24 mmφ.
A circular filter paper 3 having the same diameter as the inner diameter of the cylindrical filter paper 2 is put on the top.
The cylindrical filter paper 2 is set in the extraction tube 4 having an inner diameter A of 33 mmφ.

Next, ethanol (EtOH) / methyl ethyl ketone (MEK) (2:
1) The mixed solvent 10 is dropped using the liquid feed pump 11.
At this time, the cock 6 of the extraction tube 4 is closed and the cylindrical filter paper 2
The toner powder 1 therein is uniformly wet, and the mixed solvent 10 is filled so that the liquid level 5 is located at a position 5 mm higher than the circular filter paper 3 covered with the toner powder 1 in the cylindrical filter paper 2. As the liquid feed pump 11, a digital pump 7524-10 (manufactured by Masterflex Co.) was used, and a pump head 3
2S (manufactured by Masterflex) 12 and silicone tube 32SL (manufactured by Masterflex) 13 are combined. The digital pump can drop a fixed amount of the mixed solvent 10 in the graduated cylinder 9 from the silicon tube 13 into the extraction pipe 4 per unit time, and the dropping amount can be appropriately adjusted.

In this state, the cock 6 of the extraction pipe 4 is immediately opened to drop the extraction liquid 8 from the extraction pipe 4 into the first container 7, and the liquid feed pump 11 is operated to operate the graduated cylinder 9.
The mixed solvent 10 therein is added dropwise. At this time, the liquid feed pump 11 is adjusted so that the amount of the drop of the extract liquid 8 from the extraction pipe 4 and the amount of the drop of the mixed solvent 10 in the graduated cylinder 9 by the liquid feed pump 11 become the same amount, and it is always constant. The amount of the mixed solvent 10 is present in the extraction tube 4, that is, the liquid surface 5 in the extraction tube 4 is kept constant. As a result, the extraction liquid (mixed solvent-soluble resin component) 8 sequentially dissolved and extracted from the surface of the toner particles is accumulated in the first container 7.

The dropping amount of the extraction liquid 8 from the extraction pipe 4 and the dropping amount of the mixed solvent 10 in the graduated cylinder 9 by the liquid feed pump 11 are, for example, 12 ml / min.

When the weight of the mixed solvent-soluble resin component in the extract liquid 8 accumulated in the first container 7 from the start of extraction became 10% by weight based on the total weight of the mixed solvent-soluble resin component of the sample. , The cock 6 of the extraction tube 4 is closed, the liquid feed pump 11 is stopped, the dropping of the mixed solvent 10 in the measuring cylinder 9 is stopped, and the first container 7 is replaced with an empty second container. At this time, the extract liquid 8 accumulated in the first container 7 is used as the first extract liquid.

Next, the cock 6 of the extraction pipe 4 is opened again to drop the extraction liquid from the extraction pipe 4 into the second container, and the liquid feed pump 11 is operated to operate the mixed solvent 1 in the measuring cylinder 9.
0 is dropped again. At this time, the dropping amount of the extraction liquid from the extraction pipe 4 and the dropping amount of the mixed solvent 10 in the measuring cylinder 9 by the liquid feeding pump 11 are both the same as those at the time of the extraction of the first extraction liquid (for example, (12 ml / min), and extraction is carried out until the mixed solvent-soluble resin component of the sample is gone (extraction is completed). The obtained extract solution in the second container is referred to as a second extract solution.

The solvent component is distilled off from the obtained first extract under reduced pressure, and the glass transition temperature (Tg1) of the obtained extract powder (first soluble resin component) is measured.

Similarly, the solvent component is distilled off from the obtained second extract under reduced pressure, and the glass transition temperature (Tg2) of the obtained extract powder (second soluble resin component) is measured. .

From the start of extraction, when the weight of the mixed solvent-soluble resin component in the extract liquid 8 accumulated in the first container 7 becomes 10% by weight based on the total weight of the mixed solvent-soluble resin component,
And at the end of extraction when the mixed solvent soluble resin component is exhausted,
A calibration curve showing the relationship between the dropped amount of the mixed solvent and the dissolved amount of the mixed solvent-soluble resin component of the sample is prepared in advance by a pre-test, and the calibration curve is used to determine the dropped amount of the mixed solvent. It is necessary to perform the pre-test for creating this calibration curve immediately before performing the main test for extracting the mixed solvent-soluble resin component from the sample, and to match the environmental conditions of the pre-test and the main test.

(2) Measurement of glass transition temperature The glass transition temperature of the soluble resin component was measured by a DSC measuring device (M
-DSC TA-manufactured by Instruments). The measurement sample accurately weighs 6 mg. Put this in an aluminum pan, use an empty aluminum pan as a reference,
In the measurement temperature range of 20 ° C to 200 ° C, the heating rate is 4 ° C /
The measurement is performed at room temperature and normal humidity in minutes. At this time, the modulation amplitude is ± 0.6 ° C. and the frequency is 1 / min. The maximum glass transition temperature (Tg1, Tg2) is calculated from the obtained reversing heat flow curve. In the calculation, the glass transition temperature is defined as the intersection of the tangents of the baseline and the endothermic curve. In this case, when there are a plurality of endothermic curves, the glass transition temperature obtained from the portion showing the maximum endothermic width among them is the maximum glass transition point.
An example of DSC measurement is schematically shown in FIG. The solid line part is the reversing heat flow curve of the first soluble resin component, and the broken line is the reversing heat flow curve of the remaining second soluble resin component. Both curves are curves having two types of glass transition temperatures. Explaining the broken line curve, when comparing the heat absorption (a) on the low temperature side and the heat absorption (b) on the high temperature side, it is (a) that the heat absorption is large. Therefore, the maximum glass transition temperature (T
g2) is the part (a). Similarly, regarding the solid line, when the maximum glass transition temperature is obtained, Tg1 in the figure is obtained.

(3) Measurement of Toner Molecular Weight Distribution The toner molecular weight distribution is measured by a GPC measuring device (HLC-81).
It is measured under the following measurement conditions using 20GPC Tosoh Corporation.

Measurement conditions Column: TSKgel HM-M (6.0 ^* 15 cm) double temperature: 40 ° C. Solvent: THF Flow rate: 0.6 ml / min Detector: RI Sample concentration: 10 μl of 0.1% sample

For the sample preparation, the sample is placed in tetrahydrofuran (THF), left for several hours, shaken sufficiently (until the coalescence of the samples disappears), and left still for 12 hours. Sample processing filter (pore size 0.45μ
What passed m) is made into a GPC sample.

As the calibration curve, a molecular weight calibration curve prepared from monodisperse polystyrene standard samples is used. The maximum molecular weight is determined from the obtained logarithmic curve (logM). Further, from the cumulative curve of the molecular weight of 1000 or less, the TH of the toner is
An extremely low molecular weight component contained in the F soluble component is calculated. In the present invention, the molecular weight is based on weight.

(4) Measurement of Particle Size of Toner Particles The particle size of toner particles used in the present invention is measured by a laser scanning type particle size distribution measuring device (CIS-100 GALA).
(Manufactured by Mfg. Co., Ltd.) is used in the range of 0.4 μm to 60 μm. The sample is a cubic cell containing a magnetic stirrer after adding 0.5 to 2 mg of toner to a solution prepared by adding 0.2 ml of a surfactant (alkylbenzene sulfonate) to 100 ml of water and dispersing with an ultrasonic disperser for 2 minutes. About 80% of water is put in and the ultrasonically dispersed sample is added by 1 or 2 drops with a pipette. The number average particle diameter Dn and standard deviation S. D. Based on the above, the number average particle size and the coefficient of variation are determined.

For the toner having a number average particle diameter of 1 μm or less obtained by the above measuring method, the number average particle diameter obtained by the following measuring method is taken as the number average particle diameter of the toner.

The toner was scanned with a scanning electron microscope (FE-SEM).
S-800 manufactured by Hitachi, Ltd.) was used to take a 5000 times photograph, and the horizontal ferret diameter was 0.0 based on the photograph.
The particles of 5 μm or more are measured so that the cumulative number is 300 or more. The average is taken as the number average particle size. Further, the coefficient of variation is calculated from this numerical value by the same calculation formula as CIS-100.

(5) Measurement of Toner Triboelectricity Amount of toner (2)
The toner and the carrier are mixed so as to be about 15% by weight) and mixed for 180 seconds with a turbula mixer. This mixed powder (developer) is put in a metal container equipped with a conductive screen of 635 mesh at the bottom, sucked by a suction device, the weight difference before and after suction and the potential accumulated in the condenser connected to the container. Calculate the triboelectric charge amount from At this time, the suction pressure is 250 mmHg. By this method, the triboelectric charge amount is calculated using the following formula.

Q = (μC / g) = (C × V) / (W1-W2) (W1 is the weight before suction, W2 is the weight after suction, C is the capacity of the capacitor, and V is the weight after suction. Is the potential stored in the capacitor.)

The present invention will be described below with reference to examples, but the present invention is not limited to the examples. All "parts" used in the examples are "parts by weight".

[0121]

【Example】   (Example 1)   600 parts of methanol   Polyvinylpyrrolidone 60 parts   Styrene 65 parts   35 parts of n-butyl acrylate   Carbon black 5 parts   Di-t-butyl salicylate metal compound 1 part   2,2'-azobis (2-methylbutyronitrile) 8.5 parts

The mixture of the above materials was placed in a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and the mixed solution was well mixed for 30 minutes while bubbling nitrogen at 400 ml / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 0.8 mg / l. Then, nitrogen is set to 40 ml / min, and the temperature of the oil bath is set to 6
The polymerization reaction was carried out at 5 ° C. while sequentially monitoring the consumption of styrene by GC. Styrene consumption is 80
%, A mixture of 30 parts of styrene and 2 parts of n-butyl acrylate is charged into the reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted 5 times. The resulting slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.73 μm and a number distribution variation coefficient of 11.0%.

The obtained toner particles are treated with ethanol (EtO).
H) / methyl ethyl ketone (MEK) (2: 1) mixed solvent was used for extraction for 2 hours (mixed solvent dropping amount 1440 ml) using the modified Soxhlet extractor shown in FIG.
As a result of measuring the maximum glass transition temperature (Tg1) of the first soluble resin component from the start of extraction to 10% by weight based on the total weight of the mixed solvent soluble resin component using DSC,
Tg1 was 76.2 ° C. Furthermore, the maximum glass transition temperature (Tg2) of the remaining second soluble resin component was measured by DSC, and as a result, Tg2 was 45.0 ° C.

After the obtained toner particles were hardened with epoxy, an ultrathin section was prepared with a microtome and stained with osmic acid. When this was observed with a TEM at a magnification of 15,000 times, a two-layer structure of one nuclear part and a surface layer was observed. The average value of the radius r1 of the toner and the shortest distance r2 from the surface to the core inside the toner was calculated from the difference in the density of dyeing, and r1 / r2 was 13.8.

As a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution was 20500, and the component having a molecular weight of 1000 or less was 0.35% by weight in the toner particles.

To 100 parts by weight of the obtained toner particles (toner), 2.0 parts of crushed hydrophobic silica having a BET value of 360 m ² was added by external mixing by mixing with a Henschel mixer.

To 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was placed in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component developer.

The triboelectric charge amount of the toner in this two-component developer was -35.1 μC / g.

This two-component developer is a full-color laser copier copying machine CLC-500 modified by Canon (developing).
Matting was performed so that the surface roughness of the developer carrying member of was Rz = 10. Furthermore, in order to precisely evaluate the halftone reproducibility, the usual laser spot diameter was reduced by 20%).
The image was evaluated by forming a solid image and a halftone image with an extremely small spot.

The solid image was formed into a strip having a width of 2 cm and a length of 10 cm to obtain an unfixed image on plain paper.
This unfixed image was subjected to a fixing test with an external fixing device having the same fixing device configuration as CLC-500. As a fixing test, the plain paper on which the unfixed strip-shaped solid image is formed is passed through the external fixing device along the length direction of the strip while monitoring the temperature of the upper roller of the external fixing device. The lowest temperature at which no offset was found at the rear of the strip was defined as the fixing start temperature. As a result, the fixing start temperature was 125 ° C.

The image density of the fixed solid image was 1.52 as measured by a Macbeth reflection densitometer.

As a method of evaluating the reproducibility of the halftone formed by the extremely small spots, the reproducibility of the toner with respect to the very small spots can be measured by the multi-valued recording by the pulse width modulation (PWM) of the laser within one pixel. By observing the surface with a microscope, it was evaluated based on the following evaluation criteria.

(Evaluation Criteria) A: Dots are not disturbed and very small dots are reproduced. Very good. B: No scatter and dot shapes are slightly variable, but C: Scatter and dot shapes are uneven. , Practically no problem D: Scattering, dot shape has significant variation E: Dot is not developed where there should be dots, or scattering is severe

As a result, the halftone reproducibility due to the extremely small spots was very good.

Furthermore, under high temperature and high humidity (30 ° C., 80 RH
%), The cohesiveness after the toner was left for 7 days and the halftone reproducibility due to the minimal spots left were evaluated.

The cohesiveness was evaluated by placing 3 g of the toner in a 50 cc glass bottle container, leaving it in a high temperature and high humidity environment for 7 days, and evaluating it based on the following evaluation criteria.

(Evaluation Criteria) A: No packing, very smooth, and very good B: Some packing occurred, but it became smooth by shaking, and good C: Shaking, but shaking It became dry and there was no problem in practical use D: Packing occurred, some aggregation was observed, unsuitable E: Aggregation did not loosen, lumps were seen, unsuitable

As a result, the toner after being left under high temperature and high humidity is
It was very fluid.

Further, the evaluation of halftone reproducibility by an extremely small spot of the toner after being left under high temperature and high humidity was carried out by mixing the toner after being left with the same carrier as that used for preparing the above two-component developer. After the component-based developer was prepared, a halftone image was formed with an extremely small spot by a CLC-500 remodeling machine in the same manner as the above image evaluation, and the halftone image was evaluated with the extremely small spot.

As a result, the halftone reproducibility due to the extremely small spots was very good as in the initial stage. The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.

[0142]   (Example 2)   600 parts of methanol   Polyvinylpyrrolidone 40 parts   Styrene 65 parts   35 parts of n-butyl acrylate   Carbon black 5 parts   Di-t-butyl salicylate metal compound 1 part   2,2'-azobis (2-methylbutyronitrile) 10.2 parts

As in Example 1, the mixture of the above materials was placed in a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and the mixed solution was bubbled with nitrogen at 400 ml / min. Mix well for 20 minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.1 mg / l. Then, nitrogen was set to 40 ml / min, the temperature of the oil bath was set to 65 ° C., and the polymerization reaction was carried out while successively monitoring the consumption of styrene by GC. When the consumption of styrene reaches 80%, 30 parts of styrene n
A mixture of 2 parts of butyl acrylate is charged into this reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted 5 times. The resulting slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 5.82 μm and a number distribution variation coefficient of 15.9%.

The obtained toner particles were extracted with an EtOH / MEK mixed solvent in the same manner as in Example 1 to obtain the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 74.4 ° C and Tg2 was 4
It was 6.3 ° C.

Further, when the obtained toner particles were observed by TEM in the same manner as in Example 1, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 15.1.

Further, as a result of measuring the molecular weight of the toner particles, Mp of the molecular weight distribution is 18100, and the molecular weight is 10
The amount of the components below 00 was 0.40% by weight in the toner particles.

The obtained toner particles (toner) were externally added by mixing 1.0 part of crushed hydrophobic silica having a BET value of 360 m ² with a Henschel mixer.

With respect to 10% by weight of this toner, 90% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was put in a plastic bottle and mixed and stirred by a Turbula mixer to prepare a two-component type developer.

The triboelectric charge amount of the toner in this two-component developer was -27.8 μC / g.

Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and the fixing start temperature and the solid image are formed in the same manner as in Example 1. The density, the reproducibility of a halftone image with an extremely small spot, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of a halftone image with an extremely small spot were evaluated.

The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.
Shown in.

[0153]   (Example 3)   600 parts of methanol   Polyvinylpyrrolidone 100 parts   Styrene 65 parts   35 parts of n-butyl acrylate   Carbon black 5 parts   Di-t-butyl salicylate metal compound 1 part   2,2'-azobis (2-methylbutyronitrile) 7.0 parts

In the same manner as in Example 1, the mixture of the above materials was put into a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and the mixed solution was bubbled with nitrogen at 400 ml / min. Mix well for 25 minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.0 mg / l. Then, nitrogen was set to 40 ml / min, the temperature of the oil bath was set to 65 ° C., and the polymerization reaction was carried out while successively monitoring the consumption of styrene by GC. When the consumption of styrene reaches 80%, 30 parts of styrene,
A mixture of 2 parts of n-butyl acrylate was charged into the reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction container was cooled to room temperature, and the dispersion was washed with methanol and decanted seven times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 1.40 μm and a variation coefficient of number distribution of 13.9%.

The obtained toner particles were extracted with an EtOH / MEK mixed solvent in the same manner as in Example 1 to obtain the maximum glass transition temperature (Tg1) of the first soluble resin component and the second soluble resin component.
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 77.7 ° C and Tg2 was 4
It was 7.8 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 14.1.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 26800, and the molecular weight is 10
The amount of components of 00 or less was 0.21% by weight in the toner particles.

To 100 parts of the obtained toner particles (toner), 3.5 parts of crushed hydrophobic silica having a BET value of 360 m ² was added externally by mixing with a Henschel mixer.

With respect to 3.5% by weight of this toner, 96.5% by weight of a carrier in which a ferrite core having an average particle diameter of 35 μm is coated with a silicone resin is put in a plastic bottle and mixed and stirred by a Turbula mixer to prepare a two-component developer. Was prepared.

The triboelectric charge amount of the toner in this two-component developer was -43.9 μC / g.

Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and the fixing start temperature and the image of the solid image are obtained in the same manner as in Example 1. The density, the reproducibility of a halftone image with an extremely small spot, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of a halftone image with an extremely small spot were evaluated.

The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.
Shown in.

(Example 4) 600 parts of methanol 100 parts of polymethyl vinyl ether 60 parts of styrene 40 parts of n-butyl acrylate Carbon black 5 parts Di-t-butyl salicylate metal compound 1 part 2,2'-azobisisobutyronitrile 9.6 parts

As in Example 1, the mixture of the above materials was charged into a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and a mixed solution was prepared while bubbling nitrogen at 400 ml / min. Mix well for 30 minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.0 mg / l. Then, nitrogen was set to 40 ml / min, the temperature of the oil bath was set to 65 ° C., and the polymerization reaction was carried out while successively monitoring the consumption of styrene by GC. When the consumption of styrene reaches 90%, 40 parts of styrene is charged into this reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction container was cooled to room temperature, and the dispersion was washed with methanol and decanted five times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.56 μm and a variation coefficient of number distribution of 14.5%.

The obtained toner particles were extracted with an EtOH / MEK mixed solvent in the same manner as in Example 1 to obtain the maximum glass transition temperature (Tg1) of the first soluble resin component and the second soluble resin component.
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 92.1 ° C and Tg2 was 3
It was 4.0 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 5.93.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 21600, and the molecular weight is 10
The amount of the components below 00 was 0.32% by weight in the toner particles.

Hydrophobic titanium oxide having a BET value of 360 m ² was obtained by crushing the obtained toner particles (toner).
The parts were externally added by mixing with a Henschel mixer.

With respect to 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was placed in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component developer.

The triboelectric charge amount of the toner in this two-component developer was -36.8 μC / g.

Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and fixing start temperature and solid image are formed in the same manner as in Example 1. The density, the reproducibility of a halftone image with an extremely small spot, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of a halftone image with an extremely small spot were evaluated.

The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.
Shown in.

Example 5 A mixture having the same formulation as in Example 4 was placed in the same reaction vessel as in Example 4, and the mixed solution was well mixed for 30 minutes while bubbling nitrogen at 400 ml / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.0 mg / l. Then 40m nitrogen
The polymerization reaction was carried out while setting the oil bath temperature to 65 ° C. and the styrene consumption to be monitored successively by GC. When the consumption of styrene reaches 90%, a mixture of 32 parts of styrene and 8 parts of 2-ethylhexyl acrylate is charged into the reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and then the dispersion was washed with methanol and decanted five times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.40 μm and a number distribution variation coefficient of 17.0%.

The obtained toner particles were extracted with an EtOH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 67.0 ° C and Tg2 was 3
It was 5.0 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 5.99.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 21100, and the molecular weight is 10
The amount of the components below 00 was 0.38% by weight in the toner particles.

Hydrophobic titanium oxide having a BET value of 360 m ² was obtained by crushing the obtained toner particles (toner).
The parts were externally added by mixing with a Henschel mixer.

To 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was placed in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component developer. .

The triboelectric charge amount of the toner in this two-component developer was -35.0 μC / g.

Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and the fixing start temperature and the solid image are formed in the same manner as in Example 1. The density, the reproducibility of a halftone image with an extremely small spot, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of a halftone image with an extremely small spot were evaluated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

(Example 6) Styrene-butyl acrylate copolymer (monomer composition weight ratio 65:35, molecular weight Mp
25000) was dissolved in toluene to a concentration of 20%, and the insoluble matter which was not dissolved was filtered to prepare a solution. 10 ml / min of this solution in stirring methanol
Was added dropwise at a rate of 1, and the precipitate was recovered and sufficiently dried under reduced pressure to obtain a reprecipitated styrene-butyl acrylate copolymer.

On the other hand, polystyrene (molecular weight Mp2140
0) was dissolved in toluene so as to have a concentration of 20%, and insoluble matter which was not dissolved was filtered to prepare a solution. This solution was added dropwise to stirring methanol at a rate of 10 ml / min, and the precipitate was recovered and sufficiently dried under reduced pressure to obtain reprecipitated polystyrene.

Using the reprecipitated styrene-butyl acrylate copolymer obtained and the reprecipitated polystyrene, toner particles were produced by the following porous glass film emulsification method.

[0188] 100 parts of deionized water Sodium dodecylbenzene sulfate 0.05 parts

The above materials were charged into a first container to prepare a first continuous phase.

[0190] Toluene 50 parts 20 parts of the above styrene-butyl acrylate copolymer Oil red part 2

On the other hand, the above materials were mixed to prepare a solution.

Nitrogen gas pressure 120KP
In step a), the first phase-separated glass porous body was used to directly extrude and disperse in the above-mentioned first continuous phase to disperse the first dispersed phase of the above-mentioned solution in the first continuous phase. A / W emulsion was obtained.

[0193]   Toluene 300 parts   10 parts of polystyrene subjected to the reprecipitation operation described above   Styrene monomer 1 part   Divinylbenzene 0.5 part   2,2'-azobis (2,4-dimethylvaleronitrile) 0.03 parts

Next, the above materials were put into a second container and mixed to prepare a second continuous phase.

The above-mentioned O / W emulsion was extruded directly into the above-mentioned second continuous phase through the second phase-separated glass porous body which had been subjected to the hydrophobizing treatment under the pressure of nitrogen gas of 32 KPa to disperse the second O-W emulsion. In the continuous phase, the second phase-separated phase of the above O / W emulsion was dispersed O / W / O (oil / water /
An oil) emulsion was obtained.

[0196] Ion-exchanged water 1000 parts Polyvinyl alcohol 1 part Sodium dodecylbenzene sulfate 0.1 part

Next, the above materials were put into a third container and mixed to prepare a third continuous phase.

The above O / W / O emulsion was extruded directly into the above third continuous phase through a third phase-separated glass porous body at a nitrogen gas pressure of 7.5 KPa to disperse the third O / W / O emulsion. An O / W / O / W (oil / water / oil / water) emulsion was obtained in which the above O / W / O emulsion was dispersed in the continuous phase.

The O / W / O / W emulsion was subjected to a polymerization reaction at a reaction temperature of 50 ° C. under a nitrogen atmosphere for 6 hours. After the reaction, the temperature was raised with stirring the emulsion to volatilize the toluene. After that, wash with water, filter and dry,
Toner particles are obtained.

The toner particles obtained have a number average particle diameter (D
n) was 5.88 μm, and the variation coefficient of the number distribution was 18.9%. The toner particles thus obtained were treated in the same manner as in Example 1 to obtain E
Extraction was performed with a toH / MEK mixed solvent, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the maximum glass transition temperature (Tg2) of the second soluble resin component were measured. As a result, tg1 was 101.0 ° C and Tg2 was 4
It was 7.2 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a domain matrix island structure having a plurality of core portions and the sea of the surface layer was observed. When the average value of the radius r1 of the toner and the shortest distance r2 from the toner surface to the core inside the toner was calculated from the difference in the density of dyeing, r1 / r2 was 12.73.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 25500, and the molecular weight is 10
The amount of the components below 00 was 1.3% by weight in the toner particles.

To 100 parts of the obtained toner particles (toner), 1.0 part of crushed hydrophobic titanium oxide having a BET value of 360 m ² was externally added by mixing with a Henschel mixer.

To 20% by weight of this toner, 90% by weight of a carrier in which a ferrite core having an average particle diameter of 35 μm was coated with a silicone resin was placed in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component type developer.

The triboelectric charge amount of the toner in this two-component developer was −26.3 μc / g.

Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and the fixing start temperature and the solid image are formed in the same manner as in Example 1. The density, the reproducibility of a halftone image with an extremely small spot, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of a halftone image with an extremely small spot were evaluated.

The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.
Shown in.

[0208]   (Example 7)   600 parts of methanol   Polyvinylpyrrolidone 60 parts   67 parts of styrene   n-Butyl acrylate 33 parts   Carbon black 5 parts   Di-t-butyl salicylate metal compound 1 part   2,2'-azobis (2-methylbutyronitrile) 8.5 parts

As in Example 1, the mixture of the above materials was put into a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and the mixed solution was bubbled with nitrogen at 400 ml / min. Mix well for 20 minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.1 mg / l. Then, nitrogen was set to 40 ml / min, the temperature of the oil bath was set to 65 ° C., and the polymerization reaction was carried out while successively monitoring the consumption of styrene by GC. When the consumption of styrene reaches 80%, 30 parts of styrene,
A mixture of 4 parts of n-butyl acrylate is charged into this reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and then the dispersion was washed with methanol and decanted five times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.41 μm and a variation coefficient of number distribution of 12.0%.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 67.0 ° C and Tg2 was 4
It was 9.1 ° C.

Further, when the obtained toner particles were observed by TEM in the same manner as in Example 1, a two-layer structure of one core portion and a surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 13.2.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 21,800, and the molecular weight is 10
The amount of the components below 00 was 0.46% by weight in the toner particles.

Hydrophobic titanium oxide having a BET value of 360 m ^{2 and} obtained by crushing the obtained toner particles (toner) 2.0
The parts were externally added by mixing with a Henschel mixer.

With respect to 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was put in a plastic bottle and mixed and stirred by a turbuler mixer to prepare a two-component developer. .

The frictional charge of the toner in this two-component developer was -38.2 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

Example 8 A mixture having the same formulation as in Example 7 was placed in the same reaction vessel as in Example 1, and the mixed solution was well mixed for 30 minutes while bubbling nitrogen at 400 ml / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.1 mg / l. Then 40m nitrogen
The polymerization reaction was carried out while setting the oil bath temperature to 65 ° C. and the styrene consumption to be monitored successively by GC. When the consumption of styrene reaches 80%, a mixture of 30 parts of styrene and 1 part of n-butyl acrylate is charged into the reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted 5 times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.39 μm and a variation coefficient of number distribution of 11.8%.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 74.2 ° C and Tg2 was 4
It was 9.3 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 24.9.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 20,700, and the molecular weight is 10
The amount of the components below 00 was 0.5% by weight in the toner particles.

To the obtained toner particles (toner), 2.0 parts of crushed BET 360 m ² of hydrophobic titanium oxide was mixed with a Henschel mixer and externally added.

With respect to 6% by weight of this toner, 94% by weight of a carrier in which a ferrite core having an average particle diameter of 35 μm is coated with a silicone resin is put in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component developer. .

The frictional charge of the toner in this two-component developer was -38.6 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

[0227]   (Example 9)   600 parts of methanol   Polyvinylpyrrolidone 60 parts   60 parts of styrene   40 parts of n-butyl acrylate   Carbon black 5 parts   Di-t-butyl salicylate metal compound 1 part   2,2'-azobis (2-methylbutyronitrile) 8.5 parts

As in Example 1, the mixture of the above materials was placed in a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and the mixed solution was bubbled with nitrogen at 400 ml / min. Mix well for 20 minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.0 mg / l. Then, nitrogen was set to 40 ml / min, the temperature of the oil bath was set to 65 ° C., and the polymerization reaction was carried out while successively monitoring the consumption of styrene by GC. When the consumption of styrene reached 70%, 25 parts of styrene,
A mixture of 7 parts of n-butyl acrylate is charged into this reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted 5 times. The resulting slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.42 μm and a number distribution variation coefficient of 11.5%.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 57.9 ° C and Tg2 was 3
It was 6.6 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 9.3.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 21100, and the molecular weight is 10
The amount of the components below 00 was 0.42% by weight in the toner particles.

To the obtained toner particles (toner), 2.0 parts of crushed BET 360 m ² of hydrophobic titanium oxide was added by mixing with a Henschel mixer.

With respect to 6% by weight of this toner, 94% by weight of a carrier in which a ferrite core having an average particle diameter of 35 μm is coated with a silicone resin is placed in a plastic bottle and mixed and stirred by a Turbula mixer to prepare a two-component developer. .

The frictional charge of the toner in this two-component developer was -36.0 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

Example 10 A mixture having the same formulation as in Example 1 was placed in the same reaction vessel as in Example 1, and the mixed solution was well mixed for 30 minutes while bubbling nitrogen at 400 ml / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.1 mg / l. Then add 40 N
The polymerization reaction was carried out while the consumption of styrene was successively monitored by GC while the temperature of the oil bath was 65 ° C. When the consumption of styrene reaches 50%, 60 parts of styrene is charged into the reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted five times. The obtained slurry was dried to obtain toner particles having a number average particle size (Dn) of 3.49 μm and a number distribution variation coefficient of 12.1%.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 75.5 ° C and Tg2 was 4
It was 4.6 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 4.8.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 21600, and the molecular weight is 10
The amount of the components below 00 was 0.44% by weight in the toner particles.

To the obtained toner particles (toner), 2.0 parts of crushed BET 360 m ² of hydrophobic titanium oxide was added externally by mixing with a Henschel mixer.

With respect to 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was placed in a plastic bottle and mixed and stirred by a turbuler mixer to prepare a two-component developer. .

The frictional charge of the toner in this two-component developer was -37.5 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

(Example 11) A mixture having the same formulation as in Example 1 was placed in a reaction vessel similar to that in Example 1 with nitrogen.
While bubbling at 00 ml / min, mix solution to 30
Mix well for minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.3 mg / l. Then 40 ml of nitrogen /
The polymerization reaction was carried out while the consumption of styrene was sequentially monitored by GC while the temperature was set to min and the oil bath temperature was set to 65 ° C. When the consumption of styrene reaches 98%, a mixture of 10 parts of styrene and 1 part of n-butyl acrylate is charged into the reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted 5 times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.32 μm and a variation coefficient of number distribution of 12.3%.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 73.2 ° C and Tg2 was 4
It was 4.9 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 46.0.

Furthermore, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 22000 and the molecular weight is 10
The amount of the components below 00 was 0.40% by weight in the toner particles.

Hydrophobic titanium oxide having a BET value of 360 m ^{2 and} obtained by crushing the obtained toner particles (toner) 2.0
The parts were externally added by mixing with a Henschel mixer.

To 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was placed in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component developer. .

The frictional charge of the toner in this two-component developer was -35.9 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

[0255]   (Example 12)   600 parts of methanol   Polyvinylpyrrolidone 60 parts   71 parts of styrene   29 parts of n-butyl acrylate   Carbon black 5 parts   Di-t-butyl salicylate metal compound 1 part   2,2'-azobis (2-methylbutyronitrile) 8.5 parts

As in Example 1, the mixture of the above materials was charged into a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube, and a mechanical stirrer, and the mixed solution was bubbled with nitrogen at 400 ml / min. Mix well for 20 minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.1 mg / l. Then, nitrogen was set to 40 ml / min, the temperature of the oil bath was set to 65 ° C., and the polymerization reaction was carried out while successively monitoring the consumption of styrene by GC. When the consumption of styrene reached 80%, 27 parts of styrene,
A mixture of 8 parts of n-butyl acrylate is charged into this reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted five times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.53 μm and a number distribution variation coefficient of 12.3%.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 60.3 ° C and Tg2 was 5
It was 5.2 ° C.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 12.15.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 22600, and the molecular weight is 10
The amount of the components below 00 was 0.41% by weight in the toner particles.

Hydrophobic titanium oxide having a BET value of 360 m ² obtained by crushing the obtained toner particles (toner) 2.0
The parts were externally added by mixing with a Henschel mixer.

To 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was placed in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component developer. .

The frictional charge of the toner in this two-component developer was -36.5 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

(Comparative Example 1) A mixture having the same formulation as in Example 1 was placed in the same reaction vessel as in Example 1, and the mixed solution was well mixed for 10 minutes while bubbling nitrogen at 200 ml / min. The amount of dissolved oxygen at the start of polymerization was measured and found to be 3.5 mg / l. Then, a polymerization reaction was carried out in the same manner as in Example 1.

After completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted seven times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.87 μm and a number distribution variation coefficient of 21.7%. During decantation, many fine particles having a size of 1 μm or less were observed from the decantation deposition liquid.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 72.0 ° C and Tg2 was 4
It was 9.2 ° C. From this, the first styrene and n-
It is expected that the consumption of styrene was earlier than the amount charged with butyl acrylate.

Further, the obtained toner particles were observed by TEM in the same manner as in Example 1. As a result, a two-layer structure of one core portion and the surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 15.9.

Furthermore, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 18200, and the molecular weight is 10
The amount of the components below 00 was 0.42% by weight in the toner.

Hydrophobic titanium oxide having a BET value of 360 m ² obtained by crushing the obtained toner particles (toner) 2.0
The parts were externally added by mixing with a Henschel mixer.

With respect to 6% by weight of this toner, 94% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was put in a plastic bottle and mixed and stirred by a turbuler mixer to prepare a two-component developer.

The frictional charge of the toner in this two-component developer was -33.5 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

As a result, the halftone reproducibility due to the extremely small spot was not a problem in practical use although there was some scattering in the reproducibility of the fine dots having the extremely small spot diameter developed on the surface of the photosensitive drum. After being left under high humidity, the toner was in a state of being packed and slightly hardened, but it was returned to the state before being left by shaking. Regarding the reproducibility of halftone due to the extremely small spots of the toner after being left, the scattering was slightly worse than that before being left, and the dot reproducibility was deteriorated.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

(Comparative Example 2) 600 parts of water SDS (sodium dodecylbenzene sulfate) 1 part Polyvinyl alcohol 5 parts Styrene 85 parts n-Butyl acrylate 15 parts Carbon black 5 parts Di-t-butyl salicylate metal compound 1 part 2,2'-azobisisobutyronitrile 8 parts

A mixture of the above materials was placed in a reaction vessel,
Granulation was carried out by stirring with a TK homomixer at 10,000 rpm for 10 minutes. Then, add 40 argon to the reaction vessel.
The solution was mixed well for 30 minutes with displacement at 0 ml / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 30 mg.
It was / l. Then, the temperature of the oil bath was set to 70 ° C., and the polymerization was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was repeatedly decanted and washed with water. This operation was repeated 5 times, the obtained slurry was dried, and the number average particle diameter (Dn) was 5.13 μm.
m, toner particles having a number distribution variation coefficient of 30.5% were obtained. During decantation, many fine particles having a size of 1 μm or less were observed from the decantation deposition liquid.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 62.4 ° C and Tg2 was 6
It was 3.1 ° C., and it was found that the particles had a substantially uniform structure.

Further, when the obtained toner particles were observed by TEM in the same manner as in Example 1, no capsule structure was observed.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 21,200, and the molecular weight is 10
The amount of the components below 00 was 5.33% by weight in the toner particles.

The obtained toner particles (toner) were externally added by mixing 1.0 part of crushed hydrophobic silica having a BET value of 360 m ² with a Henschel mixer.

To 10% by weight of this toner, 90% by weight of a carrier in which a ferrite core having an average particle diameter of 35 μm was coated with a silicone resin was placed in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component type developer.

The triboelectric charge amount of the toner in this two-component developer was −28.1 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

As a result, the halftone reproducibility due to the extremely small spots was slightly lower than the reproducibility of the fine dots of the extremely small spots developed on the surface of the photosensitive drum. The toner after being left under high temperature and high humidity was in a slightly hardened state,
When shaken, it almost returned to the state before leaving.

Regarding the halftone reproducibility due to the extremely small spots of the toner after being left, the halftone reproducibility due to the very small spots was slightly deteriorated as with the toner before being left. Further, as a result of the fixing test, the fixing start temperature was 138 ° C.

Physical properties of the toner are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

(Comparative Example 3) A mixture having the same formulation as in Comparative Example 2 was used, and 9000 rpm was obtained using a TK homomixer.
Granulation was performed by rotating and stirring for 10 minutes. After that, the solution was well mixed for 30 minutes while displacing the reaction vessel with argon at 400 ml / min. When the amount of dissolved oxygen at the start of polymerization was measured, it was 24 mg / l. Then, the temperature of the oil bath was set to 70 ° C., and the polymerization was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was repeatedly decanted and washed with water. This operation was repeated 5 times, the obtained slurry was dried, and the number average particle diameter (Dn) was 6.57μ.
m, a black resin particle having a number distribution variation coefficient of 28.5% was obtained. During decantation, fine particles having a size of 1 μm or less were slightly observed from the decantation deposition liquid.

The obtained black resin particles were classified using a multi-division classifier utilizing inertial force, the number average particle diameter (Dn) was 6.95 μm, and the variation coefficient of the number distribution was 18.8%.
Toner particles were obtained.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 62.0 ° C and Tg2 was 6
It was 2.2 ° C., and it was found that the particles had a substantially uniform structure.

Furthermore, when the obtained toner particles were observed by TEM in the same manner as in Example 1, no capsule structure was observed.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 20,800, and the molecular weight is 10
The amount of components of 00 or less was 6.19% by weight in the toner particles.

The obtained toner particles (toner) were externally added by mixing 0.7 parts of crushed hydrophobic silica having a BET value of 360 m ² with a Henschel mixer.

With respect to 12% by weight of this toner, 88% by weight of a carrier obtained by coating a ferrite core having an average particle diameter of 35 μm with a silicone resin was placed in a plastic bottle and mixed and stirred with a Turbula mixer to prepare a two-component developer.

The triboelectrification amount of the toner in this two-component developer was −22.7 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

As a result, the halftone reproducibility due to the extremely small spots was slightly inferior to the reproducibility of the fine dots of the extremely small spots developed on the surface of the photosensitive drum, and there was scattering. The toner after being left under high temperature and high humidity had a good cohesiveness, but the halftone reproducibility due to the extremely small spots of the toner after being left was similar to that of the toner before being left, and the reproducibility of fine dots was a little. It was falling.

Toner physical properties are shown in Table 1, and evaluation results are shown in Table 2.
Shown in.

[0298]   (Comparative example 4)   600 parts of methanol   Polyvinylpyrrolidone 60 parts   80 parts of styrene   20 parts of n-butyl acrylate   Carbon black 5 parts   Di-t-butyl salicylate metal compound 1 part   2,2'-azobis (2-methylbutyronitrile) 8.5 parts

In the same manner as in Example 1, the mixture of the above materials was charged into a reaction vessel equipped with a reflux condenser, a thermometer, a nitrogen inlet tube and a mechanical stirrer, and the mixed solution was bubbled with nitrogen at 400 ml / min. Mix well for 20 minutes. When the amount of dissolved oxygen at the start of polymerization was measured, it was 1.3 mg / l. Then, nitrogen was set to 40 ml / min, the temperature of the oil bath was set to 65 ° C., and the polymerization reaction was carried out while successively monitoring the consumption of styrene by GC. When the consumption of styrene reached 80%, 18 parts of styrene,
A mixture of 14 parts of n-butyl acrylate is charged into this reaction vessel at a rate of 10 parts per minute. Then, the polymerization reaction was carried out for 12 hours in a nitrogen atmosphere.

After the completion of the polymerization reaction, the reaction vessel was cooled to room temperature, and the dispersion was washed with methanol and decanted five times. The obtained slurry was dried to obtain toner particles having a number average particle diameter (Dn) of 3.50 μm and a variation coefficient of number distribution of 15.3%.

The obtained toner particles were extracted with an EtoH / MEK mixed solvent in the same manner as in Example 1, and the maximum glass transition temperature (Tg1) of the first soluble resin component and the second
The maximum glass transition temperature (Tg2) of the soluble resin component of was measured. As a result, Tg1 was 50.3 ° C and Tg2 was 6
It was 5.3 ° C.

Further, when the obtained toner particles were observed by TEM in the same manner as in Example 1, a two-layer structure of one core portion and a surface layer was observed. From the difference in dyeing density, the toner radius r1 and the shortest distance r2 from the surface to the inner core
When the average value of was calculated, r1 / r2 was 14.1.

Further, as a result of measuring the molecular weight of the toner particles, the Mp of the molecular weight distribution is 21300, and the molecular weight is 10
The amount of the components below 00 was 0.51% by weight in the toner particles.

To the obtained toner particles (toner), 2.0 parts of crushed BET 360 m ² of hydrophobic silica was added externally by mixing with a Henschel mixer.

With respect to 6% by weight of this toner, 94% by weight of a carrier in which a ferrite core having an average particle diameter of 35 μm is coated with a silicone resin is put in a plastic bottle and mixed and stirred with a turbuler mixer to prepare a two-component developer. .

The triboelectric charge amount of the toner in this two-component developer was -36.6 μc / g. Using this two-component developer, a solid image and a halftone image with an extremely small spot are formed in the same manner as in Example 1, and in the same manner as in Example 1, the fixing start temperature, the image density of the solid image, and the minimum image are reduced. The reproducibility of the halftone image due to spots, the cohesiveness of the toner after being left under high temperature and high humidity, and the reproducibility of the halftone image due to extremely small spots were evaluated.

As a result, the halftone reproducibility due to the extremely small spots was excellent. After the toner was left under high temperature and high humidity, the toner did not return to the state before the toner was left because of its agglomeration. The halftone reproducibility due to the extremely small spots of toner after standing was inferior because the dots to be developed were not developed.

The physical properties of the toner are shown in Table 1, and the evaluation results are shown in Table 2.
Shown in.

[0309]

[Table 1]

[0310]

[Table 2]

[0311]

INDUSTRIAL APPLICABILITY The present invention is a toner having a fine particle diameter and a very sharp particle size distribution, and the resin of the toner surface layer has a glass transition temperature higher than that of the resin of the core portion inside. By having a structure, it is possible to provide a toner that achieves high image quality, does not aggregate even when packed in a high temperature environment, and has excellent low temperature fixability.

[Brief description of drawings]

FIG. 1 is an explanatory view of an extractor for extracting a mixed solvent-soluble resin component of a toner in the present invention.

FIG. 2 is a diagram showing DSC curves of a first soluble resin component and a second soluble resin component of toner.

FIG. 3 is a graph of the case where each of the first soluble resin component and the second soluble resin component of the toner has a glass transition temperature of 1;
The figure which shows a SC curve.

FIG. 4 is a diagram showing a DSC curve when the first soluble resin component of the toner has two glass transition temperatures and the second soluble resin component has one glass transition temperature.

FIG. 5 is a diagram showing a DSC curve when the first soluble resin component has one glass transition temperature and the second soluble resin component has two glass transition temperatures.

FIG. 6 shows a cross-sectional view of a toner having a capsule structure with a single core portion.

FIG. 7 shows a sectional view of a toner having a capsule structure having a plurality of core portions.

[Explanation of symbols]

1 sample 2 Cylindrical filter paper 3 round filter paper 4 extraction tubes 5 liquid level 6 cooks 7 containers 8 extract 9 measuring cylinder 10 Mixed solvent 11 Liquid feed pump 12 pump heads 13 Silicon tube

Front page continued (72) Inventor Hitoshi Itabashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yayoi Nagao 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Takeshi Ikeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-6-59493 (JP, A) JP-A-6-202527 (JP, A) JP-A-5-93002 (JP, A) JP-A-3-157669 (JP, A) JP-A-58-205163 (JP, A) JP-A-58-205162 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (20)

(57) [Claims] 1. An electrostatic charge image developing toner comprising at least a binder resin and a colorant, wherein the toner comprises (i) 0.1 part by weight to 15 parts by weight of the colorant with respect to 100 parts by weight of the binder resin. (Ii) having a number average particle diameter of 0.5 μm to 6.0 μm, (iii) having a coefficient of variation of number distribution of 20% or less, and (iv) a capsule containing a surface layer and a core part. Having a structure, ethanol (EtOH) / methyl ethyl ketone (M
EK) In the mixed solvent-soluble resin component extracted with the mixed solvent, the maximum glass transition temperature of the first soluble resin component from the start of extraction to 10% by weight based on the total weight of the mixed solvent-soluble resin component ( A toner for developing an electrostatic image, wherein the relationship between Tg1) and the maximum glass transition temperature (Tg2) of the remaining second soluble resin component satisfies the following formulas Tg1> Tg2 and Tg1 ≧ 50 ° C. 2. The relationship between the maximum glass transition temperature (Tg1) of the first soluble resin component and the maximum glass transition temperature (Tg2) of the second soluble resin component is expressed by the following formula Tg1-Tg2 ≧ 20 ° C. And Tg1 ≧ 50 ° C. are satisfied, the toner for developing an electrostatic charge image according to claim 1, wherein 3. The relationship between the maximum glass transition temperature (Tg1) of the first soluble resin component and the maximum glass transition temperature (Tg2) of the second soluble resin component is expressed by the following formula: 80 ° C. ≧ Tg1- The toner for developing an electrostatic image according to claim 1, wherein Tg2 ≧ 30 ° C. and Tg1 ≧ 50 ° C. are satisfied. 4. The toner for developing an electrostatic charge image according to claim 1, wherein the maximum glass transition temperature (Tg2) of the second soluble resin component is less than 50 ° C. 5. The toner comprises a THF-soluble component G of the toner.
The toner for developing an electrostatic image according to claim 1, wherein the content of a component having a molecular weight of 1000 or less is 0.5% by weight or less in the molecular weight distribution by PC. 6. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a capsule structure having a single core portion. 7. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has a capsule structure having a plurality of core portions. 8. When the radius of the toner having a capsule structure is r1 and the distance from the toner surface to the surface portion of the core which is the shortest distance is r2, r1 and r2 are expressed by the following formula 1. 8. The toner for developing an electrostatic charge image according to claim 1, which satisfies 1 ≦ r1 / r2 ≦ 100. 9. The electrostatic charge image according to claim 1, wherein the toner has an external additive externally added to toner particles containing at least a binder resin and a colorant. Toner for development. 10. The external additive has a BET specific surface area of 300.
The toner for developing an electrostatic charge image according to claim 9, which has a fine powder having m ² / g or more. 11. A polymer that is soluble in a polymerization solvent and that is produced by polymerization is soluble in a first polymerizable monomer that is insoluble in the polymerization solvent and in the polymerization solvent. A step of preparing a polymerization reaction system by dissolving a polymer composition in the polymerization solvent; setting the amount of dissolved oxygen in the polymerization reaction system at the start of the polymerization reaction to 2.0 mg / l or less, A step of polymerizing the first polymerizable monomer in the reaction system in the presence of a polymerization initiator; the polymerization conversion rate of the first polymerizable monomer is 50.
%, The polymer that is soluble in the polymerization solvent and that is produced by the polymerization does not dissolve in the polymerization solvent, and the weight of the polymer synthesized by the first polymerizable monomer is high. Second, which can synthesize polymers with a higher glass transition temperature than coalescence
The step of adding the polymerizable monomer to the polymerization reaction system; the step of polymerizing the second polymerizable monomer in the polymerization reaction system; the step of obtaining polymer particles from the polymerization reaction system; A step of producing a toner from the obtained polymer particles; wherein the obtained toner contains at least a colorant and a binder resin, and the toner comprises (i) a binder 0.1 parts by weight to 15 parts by weight of a colorant with respect to 100 parts by weight of resin, (ii) having a number average particle diameter of 0.5 μm to 6.0 μm, and (iii) a number distribution of 20% or less. (Iv) has a capsule structure including a surface layer and a core part, and has ethanol (EtOH) / methyl ethyl ketone (M
EK) In the mixed solvent-soluble resin component extracted with the mixed solvent, the maximum glass transition temperature of the first soluble resin component from the start of extraction to 10% by weight based on the total weight of the mixed solvent-soluble resin component ( A method for producing a toner, wherein the relationship between Tg1) and the maximum glass transition temperature (Tg2) of the remaining second soluble resin component satisfies the following formulas Tg1> Tg2 and Tg1 ≧ 50 ° C. 12. The amount of dissolved oxygen in the polymerization reaction system at the start of polymerization of the polymerizable monomer in the polymerization reaction system is determined by bubbling by sucking an inert gas into the polymerization reaction system. 12. The method for producing a toner according to claim 11, wherein the amount is set to 2.0 mg / l or less. 13. The amount of dissolved oxygen in the polymerization reaction system at the initiation of polymerization of the polymerizable monomer in the polymerization reaction system is deoxidized by applying ultrasonic waves to the polymerization reaction system. By
The method for producing a toner according to claim 11, wherein the amount is set to 2.0 mg / l or less. 14. The amount of dissolved oxygen in the polymerization reaction system at the time of initiation of polymerization of the polymerizable monomer in the polymerization reaction system is determined by bubbling by sucking an inert gas into the polymerization reaction system. The method for producing a toner according to claim 11, wherein the amount is set to 2.0 mg / l or less by applying ultrasonic waves to the polymerization reaction system to deoxidize the polymerization reaction system. 15. The method for producing a toner according to claim 11, wherein the polymer composition soluble in the polymerization solvent has a weight average molecular weight of 3,000 to 300,000. 16. The polymer composition soluble in the polymerization solvent is characterized by being dissolved in the polymerization solvent in an amount of 0.1 wt% to 50 wt% based on the weight of the polymerization solvent. Item 16. A method for producing a toner according to any one of items 11 to 15. 17. The first polymerizable monomer comprises a styrene monomer, an acrylic acid monomer, a vinyl ether monomer, a dibasic acid monomer and a heterocyclic monomer. The second polymerizable monomer has at least one monomer selected from the group, and the second polymerizable monomer is a styrene-based monomer, an acrylic acid-based monomer, a vinyl ether-based monomer, or a dibasic monomer. 17. The method for producing a toner according to claim 11, further comprising at least one kind of monomer selected from the group consisting of an acid monomer and a heterocyclic monomer. . 18. The colorant is added to the polymerization reaction system together with the first polymerizable monomer, and is contained in the toner by polymerization of the first polymerizable monomer. The method for producing a toner according to any one of claims 11 to 17, which is characterized in that. 19. The colorant is added to the polymerization reaction system together with the second polymerizable monomer, and is contained in the toner by polymerization of the second polymerizable monomer. The method for producing a toner according to any one of claims 11 to 17, which is characterized in that. 20. The colorant is added to the toner together with the polymer particles in a warm solvent, and the colorant is contained in the toner by dyeing the polymer particles in the warm solvent. The method for producing a toner according to claim 11.