JPH0792736A - Electrostatic charge image developing toner and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide an electrostatic charge image developing toner which has excellent flow property, provides images of a high density and excellent fine-line reproducibility and highlight gradation, allows a good onset of charge even with a small charge-controller content, and therefore, provides stable images immediately after it has used, a method of manufacture of the toner. CONSTITUTION:In the electrostatic charge image developing toner having toner particles obtained by the polymerizaiton of a polymerizable monomer composition having at least a polymerizable monomer, the toner particles contain (i) a denatured polyester resin by 0.1 to 9.0wt.% with units of styrenic monomer, acrylic monomer or methacylic monomer; (ii) wax whose melting point is between 50 and 95 deg.C by 16 to 50wt.%; and (iii) a charge controller by 0.01 to 5.0wt.%, and, the resin component of the toner particles has weight-average molecular weight of 5000 to 45000 and the toner particles have a water absorption rate of 300 to 5000ppm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a toner for developing an electrostatic latent image and a method for producing the toner. In particular,
Toner for developing electrostatic image comprising toner particles produced by polymerizing a polymerizable monomer composition having at least a polymerizable monomer, and a polymerizable monomer having at least a polymerizable monomer The present invention relates to a method for producing a toner by polymerizing a composition and obtaining toner particles.

[0002]

2. Description of the Related Art The electrophotographic method is described in US Pat. No. 2,297,
As described in Japanese Patent No. 691 etc., a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means. Is developed with toner, the toner image is transferred to a recording material such as paper, if necessary, and then fixed by heating, pressure, solvent vapor or the like to obtain a copy. As a method of developing with a toner or a method of fixing a toner image, various methods have been conventionally proposed, and a method suitable for each image forming process is adopted.

In recent years, high-speed copying and high image quality have been required for electrophotography.

Generally, as a method for producing a toner, a thermoplastic resin is melt-mixed with a coloring agent such as a dye or a pigment and an additive such as a charge control agent, and the mixture is uniformly dispersed, followed by a fine pulverizer and a classifier. There is known a method for producing a toner having a desired particle size by pulverizing and classifying by a method, that is, a pulverizing method.

In the toners obtained by the pulverization method, there is a limitation in adding a releasing material such as wax.
That is, in order to obtain a sufficient level of dispersibility of the release material, it is necessary to maintain a certain degree of viscosity at the kneading temperature with the resin, and the content of the release material should be about 5 parts by weight or less. To do. Due to such restrictions, there is a limit to the fixability of the toner by the pulverization method.

On the other hand, suspension polymerization, that is, a toner produced by a polymerization method (hereinafter, polymerized toner) does not have the above-mentioned restrictions, and in addition, a wax can be encapsulated therein, so that a good fixing property and good resistance can be obtained. Offset property can be obtained.

However, in the past, high-speed copying was realized,
It has not been sufficiently studied the fixing property in consideration of high image quality and full color, and it cannot be said that the characteristics of the polymerized toner are sufficiently brought out.

Particularly, in the case of the polymerized toner having the conventional constitution, the blocking resistance may be poor when a large amount of wax is contained, and there is room for improvement. For example, in Japanese Patent Laid-Open No. 2-273758, the promotion of pseudo-capsule properties is promoted, but it has become clear that there is room for improvement in the case where a large amount of wax is included.

Further, the inclusion of such a low melting point wax is required to increase the amount of the wax in order to improve the fixing property. In such a case, it is difficult to completely encapsulate the wax, the blocking property is maintained to some extent, and the fluidity of the toner is insufficient.

Regarding the fluidity and the cohesiveness of the toner, JP-A-56-116042 and JP-A-56-1160 are used.
Japanese Patent Laid-Open No. 43-43 proposes a reactive polyester-containing polymerized toner, and Japanese Patent Application Laid-Open No. 60-238846 proposes a saturated polyester-containing polymeric toner.

Toners obtained by these methods can solve the fluidity to some extent, but when a large amount of wax is contained, the fluidity of the toner is still insufficient, and further, the blocking property is deteriorated and the granulation property is deteriorated. The problem of decrease in

This is because the granulation system becomes an unstable system because the compatibility between the polyester resin and the wax is poor,
It is considered that a phenomenon occurs in which the content of the wax and polyester resin contained in each toner particle becomes unstable.

When the toner particle size is reduced to obtain a high image quality, the polymerization method is superior to the pulverization method in terms of the yield of toner and the energy required for production, but it is high. It has become clear that it is difficult to stably obtain a toner charge amount suitable for image quality. Since the polymerized toner is granulated in an aqueous medium, a polar substance such as a charge control agent is unevenly distributed on the surface. However, due to this phenomenon, the charge may become excessive even when a small amount of the charge control agent is added. When the charge control agent is further reduced,
The rise of charging is delayed, which causes a problem. Even when a charge control agent having a weak charge imparting ability is used, the rise of charge tends to be a problem.

[0014]

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

That is, the present invention provides a toner for developing an electrostatic image, which has particularly good fluidity, and a method for producing the toner in order to obtain an image having a high image density and excellent reproducibility of fine lines and highlight gradation. The purpose is to do.

It is another object of the present invention to provide a toner for developing an electrostatic charge image and a method for producing the toner, in which the rise of charge is good and a stable image can be obtained immediately after use even if the content of the charge control agent is small. To do.

[0017]

Means and Actions for Solving the Problems The present invention achieves the above object by the following constitutions.

That is, the present invention provides a toner for developing an electrostatic charge image, which comprises toner particles obtained by polymerizing a polymerizable monomer composition containing at least a polymerizable monomer. i) 0.1 to 9.0% by weight of a modified polyester resin having a unit of at least one monomer selected from the group consisting of a styrene monomer, an acrylic monomer and a methacrylic monomer. ,
(Ii) 16 to 50% by weight of a wax having a melting point of 50 to 95 ° C. and (iii) 0.01 to 5.0% by weight of a charge control agent are contained;
A toner having a weight average molecular weight of 0 to 45,000; and the toner particles having a water absorption of 300 to 5,000 ppm.

The present invention further provides at least one monomer selected from the group consisting of at least a polymerizable monomer, (i) a styrene monomer, an acrylic monomer and a methacrylic monomer. Modified polyester resin having a unit of 0.1 to 9.0% by weight, (ii) melting point of 50 to 9
A method for producing a toner, comprising polymerizing a polymerizable monomer composition having 16 to 50% by weight of a wax at 5 ° C. and (iii) 0.01 to 5.0% by weight of a charge control agent to obtain toner particles, The toner particles obtained have a water absorption of 300 to 50.
The content of the resin component in the toner particles is 5 ppm.
And a weight average molecular weight of 5,000 to 45,000.

The present invention will be described in detail below.

As a result of intensive studies by the present inventors, a modified polyester resin having a unit of a specific monomer and a wax having a specific melting point are identified as polymerizable monomers in the polymerizable monomer composition. 0.1 to 9.
It has been found that a toner excellent in image quality and blocking resistance is obtained when the content is 0% by weight and 16 to 50% by weight. This is because the modified polyester resin has a specific monomer unit so that a binder component of the toner, that is, a modified polyester which is more hydrophilic than a polymerizable monomer and a wax which is hydrophobic in a monomer system. It is considered that the main cause is that the stable granulation in the presence of a large amount of wax and the encapsulation property of the toner could both be achieved by appropriately compatibilizing while maintaining the incompatibility.

That is, the toner of the present invention is stabilized in the state of oil droplets at the initial stage of suspension polymerization in a state in which the respective components in the monomer system are not separated, and becomes incompatible and encapsulated as the polymerization proceeds. For this reason, the prescription amount per toner particle becomes constant, and not only the particle size distribution becomes sharp, but also the toner charge amount distribution becomes sharp, so that the image quality is improved. Further, the improvement of the toner encapsulation almost eliminates the influence of the wax, which causes the deterioration of the blocking property.

Further, since the modified polyester is unevenly distributed on the surface due to the influence of the wax, the fluidity of the modified polyester itself is exhibited, and the fluidity of the polymerized toner is improved,
The image quality is improved.

The toner of the present invention contains the modified polyester resin in an amount of 0.1 to 9.0% by weight, preferably 0.1 to 9.0% by weight, based on the weight of the polymerizable monomer contained in the polymerizable monomer composition during the production of the toner. It is preferably contained in an amount of 1.0 to 8.0% by weight. The content of this modified polyester resin is 0.1% by weight.
When the amount is extremely small, it is insufficient to form the polyester layer on the toner surface layer, the fluidity is not sufficiently obtained, and the image quality is deteriorated. When the content of the modified polyester component exceeds 9.0% by weight, a large amount of fine powder containing a large amount of the polyester component is generated in the suspension, so that the particle size distribution becomes wide.

The polyester portion of the modified polyester resin in the present invention comprises terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, With acid monomers such as sebacic acid, camphoric acid, cyclohexanedicarboxylic acid, trimellitic acid;
Ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,
3-propylene glycol, 1,4-butanediol,
Alkylene glycols and polyalkylene glycols such as neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin , A polyhydric alcohol monomer such as trimethylolpropane and pentaerythritol.

As the modified polyester resin, the polyester resin obtained by the above condensation polymerization is a styrene-based monomer,
It has at least one monomer unit selected from the group consisting of acrylic monomers and methacrylic monomers as a modifying component.

The modified polyester resin is obtained by modifying the polyester resin with a styrene, acrylic or methacrylic monomer or polymer by radical polymerization or ionic bond modification.

That is, a graft copolymer in which a styrene-based, acrylic-based or methacrylic-based monomer unit is radically bonded to the polyester main chain or the above-mentioned monomer unit is a radical in the polyester main chain. Block copolymers incorporated by bonding or ionic bonding are mentioned. As the styrene-based monomer, the acrylic-based monomer and the methacrylic-based monomer used for modifying these polyester resins, any known one may be used, and as the styrene-based monomer, Examples thereof include styrene, o-methylene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; examples of acrylic monomers include acrylic acid, methyl acrylate, and acrylic acid. Acrylics such as ethyl, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acid esters; acrylonitrile, acrylamide, meta Examples of the ril monomer include methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate and methacrylic acid 2 -Ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate,
Methacrylic acid esters such as diethylaminoethyl methacrylate and methacrylonitrile may be mentioned.

These monomers can be used alone or in combination to form a monomer unit for modifying the polyester resin.

The modified amount of the modified polyester resin is preferably 0.05 to 48% by weight, more preferably 0.1.
05-40% by weight, more preferably 0.1-20% by weight
If so, the image quality is further improved. Modified amount of 0.05% by weight
Since the solubility in the polymerizable monomer composition having a polymerizable monomer and a wax is slightly lower than that,
Image quality tends to deteriorate due to increased fine powder and reduced fluidity.
When the amount of modification exceeds 40% by weight, the ability to dissolve in the polymerizable monomer composition is too large, and the polyester component is less likely to be present on the toner surface. It tends to be inferior.

These resins generally have a high molecular weight and have a great influence on the fixability, but the weight average molecular weight of the resin component of the obtained toner particles is 5000 to 4500.
If the range is 0, preferably 12000 to 45000, not only the excellent fixability of the polymerized toner is retained, but also
The fixing area expands further.

It is considered that this is because the modified polyester not only contributes to the fixing property on the high temperature side as a polymer component, but also contributes to the adhesiveness to a transfer agent such as paper.

The average molecular weight of the resin component of the toner particles is 50.
If it is less than 00, the thermal solubility of the toner is too strong.
If the resin component of the toner particles has an average molecular weight of more than 45,000, it tends to be offset at high temperature, and since the resin is too hard, it tends to be offset at low temperature and the color mixing property of the toner tends to deteriorate.

In the present invention, the wax is contained in the toner particles in an amount of 16 to 50% by weight, preferably 16 to 40% by weight. Wax content is 16
If it is less than wt%, not only the fixing property is deteriorated, but also the granulation property, the image quality and the like tend to be deteriorated. It is considered that this is because the amount of wax is small and the capsule property of the surface layer polyester is weakened. Further, when the wax content is more than 50% by weight with respect to the toner, it becomes difficult to maintain the encapsulation property with the binder component, and the granulation property,
Blocking resistance tends to decrease.

The melting point of the wax is preferably 50 to 90 ° C., more preferably 55 to 80 ° C., in view of the solubility in the monomer during suspension polymerization. When the melting point of the wax is less than 50 ° C., the inside of the toner particles becomes a liquid core in a high temperature environment, so that the toner particles are easily broken,
Further, when the melting point of the wax is higher than 90 ° C., the temperature required for uniformly dispersing the wax in the monomer is close to the boiling point of the monomer, so that the production becomes difficult. It becomes more difficult to contain a large amount of.

The wax used in the present invention includes polyalkylene wax such as paraffin wax, polyolefin wax and Fischer-Tropish wax; amide wax: higher fatty acid: ester wax; and their derivatives or their graft / block compounds. Is available.

Among these, polyalkylene wax is particularly preferable.

Further, in the present invention, among the above waxes, it is preferable to use a wax having an SP value of 10 or less because it is necessary to maintain the compatibility with the polymerizable monomer and the hydrophobicity. The SP value is an index (solubility parameter) indicating the solubility of the substance.
r) is a value commonly displayed as Fed here.
It is shown as a calculated value by the method of Ors.

Further, the present inventors have found that the toner particles have a water absorption of 300 to 5000 ppm, preferably 320 to 2000.
When the amount of the charge control agent is 0.01 to 5% by weight, preferably 0.01 to 3% by weight, based on the toner, the charging rise of the toner of the present invention is It has been found that it becomes good and a stable image can be obtained immediately after use. It is considered that this is because the electric charge generated is easily moved by the water content in the toner particles, so that the charge rise is improved. Since the charge rise is good in this way, the amount of the charge control agent may be a small amount as described above, and in particular, the tint may change due to the color of the charge control agent remaining as in color toner. It becomes an effective means for dislike toner.

If the water absorption amount of the toner particles is less than 300 ppm, the image density becomes low especially in a low temperature and low humidity environment because the charge leak is too small. Further, if the water absorption amount of the toner particles exceeds 5000 ppm, there are too many charge leaks, and toner scattering and fog occur especially under high temperature and high humidity.

Further, when the amount of the charge control agent is less than 0.01% by weight based on the toner particles, the amount of the charge control agent in the entire toner is insufficient, so that sufficient toner charging characteristics cannot be obtained and the image density is low. Is low, toner scattering and fog are likely to occur, and pigment dispersion is also poor. Further, when the amount of the charge control agent exceeds 5.0% by weight with respect to the toner, the amount of the charge control agent present on the toner surface is too large, so that the insulating property of the toner is deteriorated, and especially at high temperature and high temperature. The image density is greatly affected under wet conditions. Furthermore, in order to further improve the charging characteristics of the toner of the present invention, it is preferable that the charge control agent has the following constitution.

That is, the toner particles in the present invention are
It is preferable that the toner particles and the charge control agent satisfy the following expression 2 ≦ X ₁ / X ≦ 100, and more preferably the following expression 5 ≦ X ₁ / X ≦ 50. (In the formula, X represents the charging rate of the charge control agent during the production of the toner particles (the ratio (% by weight) of the charge control agent to the weight of the polymerizable monomer in the polymerizable monomer composition), and X ₁ represents the content of the charge control agent present in the outermost surface layer of the toner particles (indicates the ratio (% by weight) of the charge control agent to the weight of the binder resin in the outermost surface layer of the toner particles).

The "outermost surface layer" of the toner particles means a range from the surface of the toner particles to a depth of 5 nm or less.

When the value of X ₁ / X is less than 2, the amount of the charge control agent present on the surface of the toner particles is insufficient, so that the rise of charging is delayed, and the value of X ₁ / X is further increased. When the value exceeds 100, the amount of the charge control agent present on the toner surface is too large, so that the charge control agent on the surface easily peels off, and sleeve contamination or drum contamination easily occurs.
As a result, deterioration of durable images is promoted.

The charge control agent in the outermost surface layer is measured by XPS (X-ray Photo) of X-ray electron spectroscopy.
Electron Spectroscopy) was adopted. Then, the molar concentration of the constituent element is obtained as the measurement result obtained from this XPS, and this data, the composition formula of the known constituent element, and the molar ratio of the unknown constituent element are solved to solve the molar ratio. After obtaining and multiplying each by the molecular weight of the component, by normalizing,
The weight percent of the component is obtained.

The suspension polymerization method, including the suspension polymerization method toner, has a reaction form in which the viscosity of the polymerization reaction system increases as the polymerization progresses, and it becomes difficult for radicals and polymerizable monomers to move. A large amount of polymerizable monomer components tend to remain. In particular, in the case of a suspension polymerization method toner, a component such as a dye, a pigment (especially carbon black), a charge control agent and a magnetic substance which may inhibit the polymerization reaction is contained in the polymerizable monomer system. Since it is present in a large amount in addition to the body, the unreacted polymerizable monomer is more likely to remain.

If a large amount of a component that acts as a solvent for the binder resin, not limited to the polymerizable monomer, is present in these toner particles, the fluidity of the toner is deteriorated and the image quality is deteriorated. Cause decline. In addition to the ability to be directly involved as a toner, especially when an organic semiconductor is used as a photoconductor, in addition to the phenomenon of toner fusion to the photoconductor drum, it is accompanied by deterioration of the photoconductor such as memory ghost and image blur. May cause problems. In addition to such matters relating to the performance of the product, there is a problem that the polymerizable monomer component volatilizes during fixing to give off a bad odor.

As described above, in the toner of the present invention as well, the residual amount of the polymerizable monomer present in the toner particles is reduced to further improve the image quality. The residual amount of the polymerizable monomer is preferably 1000 ppm or less, more preferably 500 ppm or less.

The residual amount of the polymerizable monomer in the toner particles is 1
As the method for reducing the amount to 000 ppm or less, a known means for promoting the consumption of polymerizable monomers used when the binder resin is produced by the suspension polymerization method can be used. For example, as a method of removing the unreacted polymerizable monomer, a method of washing with a highly volatile organic solvent that does not dissolve the toner binder resin but does dissolve the polymerizable monomer and / or the organic solvent component; Method of washing with acid or alkali; by volatilizing the polymerizable monomer and / or organic solvent component inside by adding a solvent component that does not dissolve the foaming agent or polymer into the polymer system and making the resulting toner porous The main synthetic monomer and / or the organic solvent component is volatilized under reduced pressure. However, it is difficult to select the solvent such as the elution of the toner constituent component due to the deterioration of the toner capsule property and the residual solvent. Therefore, the method of volatilizing the polymerizable monomer and / or the organic solvent component under reduced pressure is the most preferable.

In order to further improve the durability of the toner of the present invention, it is preferable that the surface of the toner particle has an uneven shape so as to suppress the sliding friction of the toner external additive.

In the present invention, the polymerizable monomer that can be used for producing the toner by polymerization is a styrene-based monomer, an acrylic acid ester or a methacrylic acid ester, which is used for modifying the polyester resin described above. Styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene; for example, methyl acrylate, acrylic acid Acrylics such as ethyl, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acid esters;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylic acid esters such as dimethylaminoethyl and diethylaminoethyl methacrylate; and other monomers such as acrylonitrile, methacrylonitrile and acrylamide.

Among the above-mentioned monomers, the use of styrene or a styrene derivative alone, or a mixture thereof, or a mixture thereof with another monomer may improve the developing characteristics and durability of the toner. It is preferable from the point.

In the present invention, a charge control agent is added to the toner particles for the purpose of controlling the chargeability of the toner. However, since the surface material of the toner particles of the present invention is polyester, the toner particles have a negative chargeability and a negative charge control is performed. It is preferable to add an agent in order to obtain a negatively chargeable toner.

As the negative charge control agent, metal-containing salicylic acid compounds, metal-containing monoazo dye compounds, styrene-acrylic acid copolymers, imidazole derivatives, styrene-methacrylic acid copolymers (N, N'-diarylurea derivatives) ) Is mentioned.

Any suitable stabilizer can be used in the dispersion medium used in the present invention. For example,
As the inorganic compound, calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, Alumina etc. are mentioned. As an organic compound, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like can be used by dispersing in an aqueous phase. The stabilizer is preferably used in an amount of 0.2 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

For fine dispersion of these stabilizers, 0.001 to 0.1 part by weight of a surfactant may be used with respect to 100 parts by weight of the polymerizable monomer. This is for promoting the intended action of the above dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and sodium lariurate. , Potassium stearate, calcium oleate.

When calcium phosphate is used among these dispersion stabilizers, a preferable one is obtained in terms of particle size distribution, toner shape, and toner internal structure, and the effect of the present invention is further exerted.

Powdered calcium phosphate may be used as it is, but it is preferable to use calcium phosphate in water using a substance such as sodium phosphate and calcium chloride, and use the calcium phosphate. When this method is used, a very fine salt is obtained and a stable suspension state is obtained, so that the granulating property is good.

The polymerized toner used in the present invention is obtained by the following method.

Modified polyester resin having a unit of at least one monomer selected from the group consisting of styrene monomer, acrylic monomer and methacrylic monomer as a polymerizable monomer. 0.1 to 9.0% by weight, a wax having a melting point of 50 to 95 ° C. 16 to 50% by weight, and a charge control agent 0.01 to 5.0% by weight are added, and if necessary, a coloring agent or a polymerization initiator is added. , Other additives, a homogenizer, a polymerizable monomer composition which is uniformly dissolved or dispersed by a mixing means such as an ultrasonic disperser, is added to the aqueous phase containing the dispersion stabilizer, Disperse with a stirrer, homomixer or homogenizer. Preferably, granulation is carried out by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size, generally a particle size of 30 μm or less. After that, the action of the dispersion stabilizer is sufficient to maintain the particle state and perform stirring to the extent that the particles are prevented from settling and floating. After completion of the polymerization reaction, the dispersion stabilizer is removed, and the generated toner particles are washed,
Collect by filtration and dry. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

In the above step, the polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. At this time, as a method of controlling the polymerization temperature, a method of increasing the temperature by 5 to 30 ° C. during the progress of the polymerization is preferable.

In the present invention, as the polymerization initiator used in the polymerization at the time of producing the toner particles, for example, 2,
2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,
Azo- or diazo-type polymerization initiators such as 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl Examples thereof include peroxide type polymerization initiators such as peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are 0.5 to 2 of the polymerizable monomer.
An addition amount of 0% by weight is preferred.

Examples of the colorant used in the present invention include carbon black, iron black, C.I. I. Direct Red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I.
Mordant Red 30, C.I. I. Direct Blue 1,
C. I. Direct Blue 2, C.I. I. Acid Blue 9, 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, Yellow Lead, Cadmium Yellow, Mineral Fast Yellow, Navel Yellow, Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NC
G, tartrazine lake, molybdenum orange, permanent orange GTR, benzidine orange G, cadmium red, permanent red 4R, watching red calcium salt, brilliant carmine 3B, fast violet B, methyl violet lake, navy blue,
Pigments such as cobalt blue, alkali blue lake, Victoria blue lake, quinacridone, rhodamine lake, phthalocyanine blue, fast sky blue, pigment green B, malachite green lake, and final yellow green G are listed.

In the present invention, since the toner is obtained by using the polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant, and preferably, there is no surface modification such as polymerization inhibitory property. It is better to give a hydrophobic treatment with a substance. In particular, since many dyes and carbon black have a polymerization inhibitory property, caution is required when using them.
A preferred method of surface-treating a dye system is a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. Further, the carbon black may be subjected to a treatment similar to that of the above dye, or a graft treatment with a substance that reacts with the surface functional group of the carbon black, for example, polyorganosiloxane. In the present invention, a magnetic substance may be added, but it is also preferable to use a magnetic substance after surface treatment.

In addition to the hydrophobic inorganic oxide, for example, the following additives are used as additives for imparting various characteristics used in the present invention.

1) Fluidity imparting agent: carbon black, carbon fluoride 2) Abrasive: metal oxide (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide), nitride (silicon nitride), carbide (Silicon carbide), metal salt (calcium sulfate, barium sulfate, calcium carbonate) 3) Lubricant: Fluorine-based resin powder (vinylidene fluoride, polytetrafluoroethylene), fatty acid metal salt (zinc stearate, calcium stearate) 4) Charge Controllable Particles: Metal Oxides (Tin Oxide, Titanium Oxide, Zinc Oxide, Silicon Oxide, Aluminum Oxide), Carbon Black These additives are added in an amount of 0.
1 to 10 parts by weight is used, preferably 0.1 to 5 parts by weight. Even if these additives are used alone,
You may use together two or more.

Next, each measuring method used in the present invention will be described below.

(1) Measurement of particle size distribution A Coulter counter TA-II type (manufactured by Coulter) is used as a measuring device, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting number average distribution and volume average distribution and CX-
1 Connect a personal computer (made by Canon) and prepare a 1% NaCl aqueous solution using primary sodium chloride as an electrolyte.

As a measuring method, the electrolytic aqueous solution 100 to 1 is used.
To 50 ml, 0.1-5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 0.5-50 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes,
According to the Coulter Counter TA-II type, the aperture is 100 μm and the aperture is 2 to 40 μm.
The particle size distribution of the particles is measured to obtain a volume average distribution and a number average distribution.

A weight average particle diameter D ₄ is obtained from the thus obtained volume average distribution and number average distribution.

(2) Measurement of melting point of wax The melting point of wax was measured by using DSC-7 (manufactured by Perkin Elmer) at a heating rate of 10 ° C./minute, and a DSC curve during the first heating was used. The temperature at the top of the peak showing the maximum endotherm is the melting point of the wax.

(3) Measurement of residual amount of polymerizable monomer remaining in toner particles The polymerization conversion was obtained by adding a polymerization inhibitor to 1 g of a suspension and dissolving it in 4 ml of tetrahydrofuran (THF). The residual amount of the polymerizable monomer and the organic solvent remaining in the toner particles is quantified using 0.2 g of the toner and 4 ml of THF.
It was measured by an internal standard method under the following conditions by gas chromatography.

G. C. Conditions Measuring device: Shimadzu GC-15A (with capillary) Carrier: N ₂ , 2 kg / cm ² 50 ml / min split ratio 1:60, linear velocity 30 mm / sec Column: ULBON HR-1 50 m × 0.25 mm Sample volume: 2 μl Labeled substance: Toluene

(4) Measurement of Water Absorption of Toner Particles The water absorption of toner particles was measured by leaving 0.5 ± 0.1 g of a sample in an environment of 23 ° C./60% RH for 3 days or more to obtain a trace amount of water. Measuring device (AQ-6 Hiranuma Sangyo Co., Ltd.)
(Reagent for titration Hydranal Aquarite RS). The sample is heated by an automatic moisture vaporizer (SE-24 Hiranuma Sangyo Co., Ltd.) which is connected to AQ-6 through an interface (110 ° C. setting, N ₂ gas 0.25 liter / min).

(5) Measurement of Molecular Weight Distribution of Resin Component As a standard sample, the following commercially available standard polystyrene (manufactured by Tosoh Corporation) was used, and 15 standard polystyrenes were divided into 4 groups as follows.

8.42 × 10 ⁶ 7.06 × 10 ⁵
3.79 × 10 ⁴ 2.98 × 10 ³ 4.48 × 10 ⁶ 3.35 × 10 ⁵ 1.96 × 1
0 ⁴ 8.7 × 10 ³ 2.89 × 10 ⁶ 1.9 × 10 ⁵ 9.1 × 10 ³
5.0 x 10 ² 1.09 x 10 ⁶ 9.64 x 10 ⁴ 5.57 x 1
0 ³ Approximately 3 mg of the sample in the group in a 30 ml sample bottle
(1 cup for microspatels), take 15 ml of TH
Add F and leave at room temperature for 4 hours. Then, it is filtered using a membrane filter (0.50 μm: manufactured by Tosoh Corporation) to obtain a standard sample.

(Unknown sample) A 60 mg sample is weighed in a sample bottle, and 15 ml of THF is further added. The extraction conditions are such that the initial 3 hours are shaken every 30 minutes and left at room temperature for 24 hours. Insoluble matter is centrifuged (5000 rpm / 20
After sedimentation by (min), the supernatant is filtered using a membrane filter (0.50 μm: manufactured by Tosoh Corporation) to obtain a sample.

As a (GPC) device, Waters Corporation, 1
It measured using 50C ALC / GPC on the following conditions.

1. Solvent THF (Kishida Chemical's special grade) 2. Column Shortex A-801, A-802,
A-803, A-804, A-805, A-806, A
-807 7 connections (Showa Denko) 3. Temperature 40 ° C 4. Flow rate 1.0 ml / min 5. Injection volume 1.0 ml 6. Detector RI

The weight average molecular weight of the resin component of the toner particles in the present invention is a value calculated from the GPC chromatogram obtained by the above method by removing the peaks or shoulders caused by components other than the resin such as the wax component. .

[0081]

EXAMPLES The present invention will be specifically described below based on examples. The parts in the following formulations are parts by weight unless otherwise specified.

Modified Polyester Resin Production Example 1 15 parts by weight of 2 ethylhexyl acrylate and 15 parts by weight of 2 ethylhexyl acrylate in a polyester solution prepared by dissolving 300 parts by weight of a vinyl group-containing polyester resin in 1 liter of benzene.
% Cobalt naphthenate-styrene solution was added, and the mixture was vigorously stirred at room temperature for 1 hour, then stirred at 50 ° C. for 5 hours to polymerize, and then benzene and 2 ethylhexyl acrylate were distilled off to obtain modified polyester resin A. Got
The modified polyester resin A thus obtained had a modification amount of 3% by weight in view of the increase in weight of the polyester resin.

Modified Polyester Resin Production Example 2 100 parts by weight of styrene, 150 parts by weight of methyl methacrylate, 5 parts by weight of benzoyl peroxide and 2 parts by weight of α-methylstyrene dimer were stirred at 80 ° C. for 1 hour,
A polyester solution in which 200 parts by weight of a vinyl group-containing polyester resin was dissolved in 1 liter of benzene was gradually added dropwise to this reaction solution, and the mixture was polymerized by stirring for 6 hours while maintaining the temperature at 80 ° C. Only the styrene-methyl methacrylate polyester copolymer was separated to obtain a modified polyester resin B. The modified polyester resin B obtained had a modification amount of 45% by weight in view of the increase in weight of the polyester resin.

Modified Polyester Resin Production Example 3 20 parts by weight of styrene and 1 part by weight of a 15% cobalt naphthenate-styrene solution were added to a polyester solution in which 300 g of a polyester resin containing a vinyl group was dissolved in 1 liter of benzene. Then, while stirring vigorously for 5 hours at room temperature to polymerize, benzene and styrene were distilled off to obtain a modified polyester resin C. The modified polyester resin C thus obtained had a modification amount of 3% by weight in view of the increase in weight of the polyester resin.

Modified Polyester Resin Production Example 4 Styrene and 1 used in Modified Polyester Resin Production Example 1
The amount of the 5% cobalt naphthenate-styrene solution used was changed to 60 parts by weight of styrene and 2 parts by weight of the 15% cobalt naphthenate-styrene solution, and the polymerization conditions were changed to 70 ° C.
A modified polyester resin D was obtained in the same manner as in Modified Polyester Resin Production Example 1 except that the time was changed.
The modified polyester resin D thus obtained had a modified amount of 35% by weight in view of the increase in weight of the polyester resin.

Example 1 A 0.1 M Na ₃ PO ₄ aqueous solution and a 1 M CaCl ₂ aqueous solution are prepared. TK type homomixer (made by Tokushu Kika Kogyo)
In a 2 liter flask containing 0.1 M Na ₃ PO ₄
22g and 850g of ion-exchanged water are charged, and 12000r
Stirred at pm. 4M g of 1M CaCl ₂ aqueous solution
Was gradually added under stirring with the homomixer heated to 60 ° C. to obtain a dispersion medium containing Ca ₃ (PO ₄ ) ₂ .

Styrene: 180 g n-Butyl acrylate: 20 g Paraffin wax (mp 70 ° C.): 60 g C.I. I. Pigment Blue 15: 3 ... 10 g Modified polyester resin A ... 10 g Di-tert-butylsalicylic acid metal compound ... 1 g Among the above formulations, modified polyester resin A, C.I. I. Pigment Blue 15: 3, chromium di-tert-butylsalicylate compound and 100 g of styrene were predispersed using an Attritor (Mitsui Miike) to prepare a colorant dispersion.

Next, the rest of the above formulation was added to the colorant dispersion, heated to 70 ° C., dissolved and dispersed into a polymerizable monomer mixture, and the mixture was maintained at 70 ° C. while starting. 10 g of the agent 2,2′-azobis (2,4-dimethylvaleronitrile) and 1 g of dimethyl 2,2′-azobisisobutyrate were added and dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition was added to the dispersion medium prepared in the 2 liter flask of the homomixer. The polymerizable monomer composition was granulated by stirring at 70 rpm for 20 minutes at 10,000 rpm using a TK homomixer in a nitrogen atmosphere. Then, the mixture was reacted at 70 ° C. for 6 hours while stirring with a paddle stirring blade, and then polymerized at 90 ° C. for 10 hours.

After completion of the reaction, the suspension was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) _2, and the mixture was filtered, washed with water and dried to obtain a sharp particle size distribution. Weight average diameter = 8.2 μm Polymerized toner particles were obtained. The toner particles are heated to 45 ° C. and 50 m
A degassing treatment was performed for 12 hours under a reduced pressure of mHg. At this point, the amount of the polymerizable monomer remaining in the toner particles, that is, the content of the toner particles was 150 ppm.

When the molecular weight distribution of the resin component of the toner particles and the water absorption amount of the toner particles were measured, the weight average molecular weight was 25,000 and the water absorption amount was 630 ppm.

Next, to 100 parts of the obtained toner particles, 0.7 part of hydrophobic silica having a specific surface area according to the BET method of 200 m ² / g was externally added. This externally added toner is 55
It also showed excellent performance in a blocking test at 7 ° C for 7 days. A developer was prepared by mixing 93 parts of a ferrite carrier coated with an acrylic resin with 7 parts of the externally added toner.

Using this developer, a durability test of 20,000 sheets was carried out by using a commercially available color copying machine (CLC-500 made by Canon) remodeling machine. Development conditions are 23 ° C / 65% RH
Under the environment, the development contrast was set to 220V. As a result, an image having an image density of 1.3 or more, no fog, a very high resolution and an excellent fixing property was stably obtained.

Further, when the same test was conducted under the environment of 15 ° C./10% RH, the same result was obtained.

Comparative Example 1 In the formulation of Example 1, the amount of modified polyester A used was 3
Toner particles having a weight average particle diameter of 9.1 μm were obtained in the same manner as in Example 1 except that the amount was 0 g, but a large amount of fine powder was generated, so that the particle size distribution was widened.

Using the obtained toner particles, a developer was prepared in the same manner as in Example 1 and an image was formed. The image density was 1.4 or more, but a large amount of fog was generated. ,
Furthermore, the fixing temperature range has become narrower.

Comparative Example 2 In the formulation of Example 1, the amount of paraffin wax used was 1
Toner particles having a weight average particle diameter of 7.2 μm were obtained in the same manner as in Example 1 except that the amount was 0 g. The toner particles obtained had a sharp particle size distribution and had good developing characteristics after being used as a developer, but their fixing temperature range was narrow.

Comparative Example 3 Toner particles having a weight average particle diameter of 6.1 μm were obtained in the same manner as in Example 1 except that the amount of the metal compound of di-tert-butylsalicylic acid used in Example 1 was changed to 15 g. Got A large amount of fine powder was generated in the obtained toner particles. Using the obtained toner particles, a developer was prepared in the same manner as in Example 1 and an image was formed. Fogging occurred in the obtained image. In addition, the image density decreased as the durability increased.

Comparative Example 4 In the formulation of Example 1, 5 g of the initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was used.
In the same manner as in Example 1 except for the above, toner particles having a weight average particle diameter of 8.1 μm were obtained. Using the obtained toner particles, a developer was prepared in the same manner as in Example 1 and image formation was carried out. As a result, the weight average molecular weight of the resin component of the obtained toner particles was as large as 67,000. The fixing area of the captured image becomes narrow.

Comparative Example 5 In the formulation of Example 1, the amount of modified polyester used was 0.1.
Toner particles having a weight average particle diameter of 9.7 μm were obtained in the same manner as in Example 1 except that the amount was changed to g. Using the obtained toner particles, a developer was prepared in the same manner as in Example 1 and an image was formed. The obtained toner had a low blocking property, and the image after durability had a density of It was low and the image quality was also poor.

Example 2 A developer was prepared in the same manner as in Example 1 except that only the colorant component and modified polyester A in the formulation of Example 1 were changed as follows.

Carbon black: 8 g Modified polyester resin B: 10 g

The weight average particle diameter of the toner particles is 8.1 μm.
m, and the externally added toner had excellent fluidity even in the blocking test.

A running test was conducted on the above developer under the same conditions as in Example 1. As a result, the image was excellent in fixing property, although it was slightly inferior in resolution as compared with Example 1.

Example 3 Example 1 except that the formulation of Example 1 was changed as follows.
In the same manner as described above, magnetic toner particles having a weight average particle diameter of 9.3 μm were obtained.

Styrene 180 g 2 Ethylhexyl acrylate 20 g Titanium coupling agent treated magnetite 100 g Paraffin wax (mp 75 ° C.) 35 g Modified polyester resin C 16 g Di-tert-butylsalicylic acid Zn compound 1 g

The weight average particle diameter of the obtained toner particles before external addition was 9.3 μm, and the amount of the charge control agent on the toner surface was 8.
%Met. The obtained magnetic toner was subjected to a running test in the same manner using NP2020 (manufactured by Canon Inc.).
The image density was 1.4 or more and there was no fog, and an image having a very high resolution was stably obtained.

Example 4 The modified polyester resin A used in Example 1 was replaced with the modified polyester resin D, and C.I. I. Toner particles were obtained and a developer was prepared in the same manner as in Example 1 except that Pigment Blue 15: 3 was replaced with a hydrophobized titanium coupling agent. The water absorption of the obtained toner particles was 150 ppm.

A running test was conducted on the above developer under the same conditions as in Example 1. Under the environment of 23 ° C./60% RH, the same result as in Example 1 was obtained, but at 15 ° C.
Under the environment of / 10% RH, some fog was observed and the image quality was deteriorated, but there was no problem in practical use, and the image density was 1.1 or more. The results are shown in Table 1.

Example 5 Toner particles were obtained in the same manner as in Example 1 except that an ester wax (mp 75 ° C.) was used instead of the paraffin wax used in Example 1. , A developer was prepared. The water absorption of the obtained toner particles is 800 pp.
It was m.

A running test was conducted on the above developer under the same conditions as in Example 1, and similar results were obtained.

The characteristics and evaluation results of the toners described in Examples 1 to 5 and Comparative Examples 1 to 5 are shown in Tables 1 and 2 below.

[0113]

[Table 1]

[0114]

[Table 2]

[0115]

The toner for developing an electrostatic charge image of the present invention has toner particles produced by polymerizing a polymerizable monomer composition containing at least a polymerizable monomer. , A modified polyester resin having a unit of a specific monomer, a wax having a melting point of 50 to 95 ° C. and a charge control agent are contained in specific amounts, and the resin component of the toner particles has a weight average of 5,000 to 45,000. The toner has a molecular weight of 300 to 5,000.
Since it has a water absorption of ppm, the modified polyester and the wax are appropriately compatibilized in the monomer system while maintaining their incompatibility, so that stable granulation property and toner in the presence of a large amount of wax can be obtained. Since the capsule properties of both are compatible, the fixability is excellent, the chargeability is stable, the image quality and blocking resistance are improved, and the toner particles have excellent fluidity, so the image density is high, An image excellent in fine line reproducibility and highlight gradation can be obtained, and even if the content of the charge control agent is small, the rise of charging is good, and a stable image can be obtained immediately after use.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical display location G03G 9/08 365 381 384 (72) Inventor Koji Inaba 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Makoto Kamibayashi 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Kazuyuki Miyano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Stock In the company

Claims (32)

[Claims] 1. An electrostatic charge image developing toner having toner particles obtained by polymerizing a polymerizable monomer composition having at least a polymerizable monomer, wherein the toner particles are (i) a styrene-based toner. 0.1 to 9.0% by weight of modified polyester resin having a unit of at least one monomer selected from the group consisting of monomers, acrylic monomers and methacrylic monomers, (ii) 16 to 50% by weight of wax having a melting point of 50 to 95 ° C., and
(Iii) 0.01 to 5.0% by weight of a charge control agent is contained; the resin component of the toner particles is 5,000 to 4
An electrostatic charge image developing toner having a weight average molecular weight of 5,000; and the toner particles having a water absorption of 300 to 5,000 ppm. 2. The toner particles comprise (i) 1.0 to 8.0% by weight of the modified polyester resin, (ii) 16 to 40% by weight of the wax, and (iii) 0.0 of the charge control agent.
The toner for developing an electrostatic charge image according to claim 1, wherein the toner is contained in an amount of 1 to 3.0% by weight. 3. The wax is selected from the group consisting of paraffin wax, polyolefin wax, Fischer-Tropish wax, amide wax, higher fatty acid wax and ester wax, derivatives thereof, graft compounds thereof and block compounds thereof. The toner for developing an electrostatic charge image according to claim 1, wherein the toner has the following properties. 4. The toner particles have a particle size of 320 to 2000 p.
The toner for developing an electrostatic image according to claim 1, having a water absorption amount of pm. 5. The toner particles include a toner particle and a charge control agent represented by the following formula: 2 ≦ X ₁ / X ≦ 100 (wherein, X is a charge control agent charging rate (polymerizable monomer Shows the ratio (% by weight) of the charge control agent to the weight of the polymerizable monomer in the monomer composition, and X ₁ represents the content of the charge control agent present in the outermost surface layer of the toner particles (toner particles 2. The toner for developing an electrostatic charge image according to claim 1, wherein the ratio (% by weight) of the charge control agent to the weight of the binder resin on the outermost surface is satisfied. 6. The toner particles, wherein the toner particles and the charge control agent are represented by the following formula: 5 ≦ X ₁ / X ≦ 50 (wherein, X is a charge control agent charging rate at the time of manufacturing the toner particles (polymerizable monomer). The ratio (% by weight) of the charge control agent to the weight of the polymerizable monomer in the composition and the composition, and X ₁ represents the content rate of the charge control agent present in the outermost surface layer of the toner particles (toner The ratio of the charge control agent to the weight of the binder resin in the outermost surface layer of the particles (% by weight is shown). 7. A toner for developing an electrostatic charge image, wherein the residual amount of the polymerizable monomer remaining in the toner particles is 1000 ppm or less. 8. A toner for developing an electrostatic charge image, wherein the residual amount of the polymerizable monomer remaining in the toner particles is 500 ppm or less. 9. The polymerizable monomer is a styrene-based monomer,
The toner for developing an electrostatic image according to claim 1, comprising at least one monomer selected from the group consisting of acrylic monomers and methacrylic monomers. 10. The polymerizable monomer is styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, acrylic acid. n-butyl, isobutyl acrylate, n-propyl acrylate,
N-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylic acid
Propyl, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylic acid. The toner for developing an electrostatic charge image according to claim 1, which has one or more kinds of monomers selected from the group consisting of ronitrile and acrylamide. 11. The styrene monomer as the polymerizable monomer;
Styrene derivative monomer; mixture of styrene monomer and styrene derivative monomer; mixture of styrene monomer and other monomer; or mixture of styrene derivative monomer and other monomer The toner for developing an electrostatic charge image according to claim 1, characterized in that it has. 12. The modified polyester resin is 0.05
The toner for developing an electrostatic charge image according to claim 1, which has a modification amount of 40 to 40% by weight. 13. The toner according to claim 1, wherein the modified polyester resin has a modification amount of 0.1 to 20% by weight. 14. The modified polyester resin is styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, n-acrylic acid n-. Butyl, isobutyl acrylate, acrylic acid n-
Propyl, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-methacrylate. Butyl, isobutyl methacrylate, n-octyl methacrylate, methacrylsanddecyl, 2-ethylhexyl methacrylate,
It is characterized by having a unit of at least one monomer selected from the group consisting of stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile and acrylamide. The toner for developing an electrostatic charge image according to claim 1. 15. The modified polyester resin is a graft copolymer in which a unit of a styrene-based, acrylic-based or methacrylic-based monomer is radically bonded to the main chain of (i) the polyester resin or (ii). The toner for developing an electrostatic charge image according to claim 1, which is a block copolymer incorporated into a main chain of a polyester resin by a radical bond or an ionic bond. 16. A unit of at least one monomer selected from the group consisting of at least a polymerizable monomer, (i) a styrene monomer, an acrylic monomer and a methacrylic monomer. Modified polyester resin having 0.1 to 9.0% by weight, (ii) 16 to 50% by weight of wax having a melting point of 50 to 95 ° C., and (iii) 0.01 charge control agent
To 5.0 wt% of a polymerizable monomer composition to obtain toner particles, wherein the toner particles have a water absorption of 300 to 5000 ppm. The resin component of the particles is 5000 to 45
And a weight average molecular weight of 000. 17. The toner particles comprise (i) 1.0 to 8.0 wt% of the modified polyester resin, (ii) 16 to 40 wt% of the wax, and (iii) 0.0 of the charge control agent.
17. The method for producing a toner according to claim 16, wherein the content is 1 to 3.0% by weight. 18. The paraffin wax,
Characterized by having one selected from the group consisting of polyolefin wax, Fischer-Tropish wax, amide wax, higher fatty acid wax, and ester wax, derivatives thereof, graft compounds thereof and block compounds thereof, The method of manufacturing a toner according to claim 16. 19. The toner comprises 320 to 2000 pp.
The method for producing a toner according to claim 16, wherein the toner has a water absorption amount of m. 20. In the toner particles, the toner particles and the charge control agent are represented by the following formula 2 ≦ X ₁ / X ≦ 100 (wherein, X is a charge control agent charging rate (polymerizable monomer Shows the ratio (% by weight) of the charge control agent to the weight of the polymerizable monomer in the monomer composition, and X ₁ represents the content of the charge control agent present in the outermost surface layer of the toner particles (toner particles 17. The method for producing a toner according to claim 16, wherein the ratio (% by weight) of the charge control agent to the weight of the binder resin on the outermost surface is satisfied. 21. In the toner particles, the toner particles and the charge control agent are represented by the following formula: 5 ≦ X ₁ / X ≦ 50 (where X is a charge control agent charging rate (polymerizable monomer) at the time of manufacturing the toner particles. Shows the ratio (% by weight) of the charge control agent to the weight of the polymerizable monomer in the monomer composition, and X ₁ represents the content of the charge control agent present in the outermost surface layer of the toner particles (toner particles 17. The method for producing a toner according to claim 16, wherein the ratio (% by weight) of the charge control agent to the weight of the binder resin in the outermost surface layer is satisfied. 22. The residual amount of the polymerizable monomer remaining in the obtained toner particles is reduced to 1000 ppm or less by removing the unreacted polymerizable monomer in the toner particles. The method for producing a toner according to claim 16, wherein: 23. The residual amount of the polymerizable monomer remaining in the obtained toner particles is reduced to 500 ppm or less by removing the unreacted polymerizable monomer in the toner particles. The method for producing a toner according to claim 16, wherein: 24. A method of removing an unreacted polymerizable monomer in the toner particles is a highly volatile method in which a toner binder resin is not dissolved but a polymerizable monomer and / or an organic solvent component is dissolved. A method of washing with an organic solvent; a method of washing with an acid or an alkali; a solvent component that does not dissolve a foaming agent or a polymer is added to a polymer system; 24. A method selected from the group consisting of a method of increasing a volatilization area of an organic solvent component; and a method of volatilizing a polymerizable monomer and / or an organic solvent component under a reduced pressure. Manufacturing method of toner. 25. The polymerizable monomer has at least one monomer selected from the group consisting of styrene-based monomers, acrylic-based monomers and methacrylic-based monomers. The method for producing a toner according to claim 16, wherein: 26. The polymerizable monomer is styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, acrylic acid. n-butyl, isobutyl acrylate, n-propyl acrylate,
N-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-methacrylic acid
Propyl, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, The method for producing a toner according to claim 16, further comprising one or more kinds of monomers selected from the group consisting of methacrylonitrile and acrylamide. 27. The polymerizable monomer is a styrene monomer;
Styrene derivative monomer Mixture of styrene monomer and styrene derivative monomer; Mixture of styrene monomer and other monomer; or Mixture of styrene derivative monomer and other monomer It is characterized by having. The method for producing a toner according to claim 16. 28. The modified polyester resin is 0.05
17. The method for producing a toner according to claim 16, wherein the toner has a modified amount of 40 to 40% by weight. 29. The method for producing a toner according to claim 16, wherein the modified polyester resin has a modification amount of 0.1 to 20% by weight. 30. The modified polyester resin is styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, n-acrylic acid. Butyl, isobutyl acrylate, acrylic acid n-
Propyl, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-methacrylate. Butyl, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile and acrylamide. 17. The method for producing a toner according to claim 16, further comprising at least one monomer unit selected from the group. 31. The modified polyester resin is a graft copolymer or (ii) in which a unit of styrene-based, acrylic-based or methacrylic-based monomer is radically bonded to the main chain of (i) the polyester resin. The method for producing a toner according to claim 16, which is a block copolymer incorporated into the main chain of a polyester resin by a radical bond or an ionic bond. 32. The toner particles are obtained by suspension polymerization in which the polymerizable monomer composition is added to an aqueous phase and dispersed to carry out a polymerization reaction. 16. The method for producing a toner according to item 16.