JP2984540B2 - 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 latent image and a method for producing the toner. Especially,
An electrostatic image developing toner 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 Electrophotography is described in U.S. Pat. No. 2,297,
As described in, for example, US Pat. No. 691 and the like, a number of methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means, and the latent image is formed. Is developed using a toner, a toner image is transferred to a recording material such as paper as needed, and then fixed by heating, pressure, solvent vapor, or the like to obtain a copy. Conventionally, various methods have been proposed as a method of developing using toner or a method of fixing a toner image, and a method suitable for each image forming process is adopted.

In recent years, there has been a demand for high-speed copying and high image quality in electrophotography.

In general, as a method for producing a toner, a colorant such as a dye or a pigment and an additive such as a charge control agent are melt-mixed in a thermoplastic resin, and the mixture is uniformly dispersed. There is known a method of producing a toner having a desired particle size by performing pulverization and classification by the method, that is, a pulverization method.

[0005] In the toners obtained by these pulverization methods, there is a restriction when a releasable substance such as wax is added.
In other words, it is necessary to maintain a certain degree of viscosity at the kneading temperature with the resin in order to obtain a sufficient level of dispersibility of the releasing material, and the content of the releasing material is reduced to about 5 parts by weight or less. And so on. Due to such restrictions, there is a limit to the fixability of the toner by the pulverization method.

On the other hand, a toner obtained by suspension polymerization, that is, a polymerization method (hereinafter referred to as a “polymerized toner”) has not only the above-mentioned restrictions but also can encapsulate a wax, and has good fixability and excellent resistance. Offset properties can be obtained.

However, conventionally, high-speed copying,
Investigation of fixability with a focus on higher image quality and full color has not been sufficiently conducted, and it cannot be said that the characteristics of the polymerized toner have been sufficiently derived.

In particular, in the case of a polymerized toner having a conventional constitution, when a large amount of wax is contained, the blocking resistance may be poor, and there is room for improvement. For example, in Japanese Patent Application Laid-Open No. 2-273758, the pseudo-encapsulation property is promoted, but it has become clear that there is still room for improvement when a large amount of wax is contained.

[0009] Further, in order to include such a low melting point wax, it 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, and while the blocking property is maintained to some extent, the fluidity of the toner becomes insufficient.

Regarding the fluidity and cohesion of the toner, Japanese Patent Application Laid-Open Nos.
JP-A-43-43 proposes a reactive polyester-containing polymerized toner, and JP-A-60-238846 proposes a saturated polyester-containing polymerized toner.

The toners obtained by these methods can solve the problem of fluidity to some extent. However, when a large amount of wax is contained, the fluidity of the toner is not sufficient, and further, the blocking property is deteriorated and the granulation property is deteriorated. The problem of a decrease in the temperature will occur.

This is because the granulation system becomes unstable due to poor compatibility between the polyester resin and the wax,
This is considered to be because a phenomenon occurs in which the contents of the wax and the polyester resin contained in the individual toner particles are not constant.

[0013] In order to improve the image quality by reducing the particle size of the toner, the polymerization method is superior to the pulverization method in terms of toner yield and energy required during production. 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, polar substances such as a charge control agent are unevenly distributed on the surface. However, due to this phenomenon, even when a small amount of a charge control agent is added, charging may be excessive. When the charge control agent is further reduced,
The rise of electrification becomes slow, causing a problem. Even when a charge control agent having a weak charge-imparting ability is used, rising of the charge tends to be a problem.

[0014]

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

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

It is a further object of the present invention to provide a toner for developing an electrostatic image capable of obtaining a stable charge immediately after use even if the charge control agent content is small, and a method for producing the toner. I do.

[0017]

The present invention attains the above object by the following constitutions.

The present invention relates to at least one monomer selected from the group consisting of at least (i) a polymerizable monomer, (ii) a styrene monomer, an acrylic monomer and a methacrylic monomer. Obtained by polymerizing in a water phase a polymerizable monomer composition having a modified polyester resin having monomer units, (iii) a wax having a melting point of 50 to 95 ° C, and (iv) a charge control agent. In a toner for developing an electrostatic image having particles, the toner particles comprise a resin prepared by polymerization of the polymerizable monomer, 0.1 to 9.0% by weight of the modified polyester resin,
6 to 50% by weight, and the charge control agent 0.01 to 5.
0% by weight, and the resin component of the toner particles is:
Having a weight average molecular weight of 5,000 to 45,000, and the toner particles have a weight average molecular weight of 300 to 5,000 pp
m, which has a water absorption of m.

Further, the present invention provides at least one kind selected from the group consisting of at least (i) a polymerizable monomer, (ii) a styrene monomer, an acrylic monomer and a methacrylic monomer. (Iii) 16 to 50% by weight of a wax having a melting point of 50 to 95 ° C, and (iv) a charge control agent of 0.01 to 5. A method for producing a toner in which toner particles are obtained by polymerizing a polymerizable monomer composition having 0% by weight, wherein the obtained toner particles have a water absorption of 3%.
The present invention relates to a method for producing a toner, wherein the toner component has a weight average molecular weight of 5,000 to 45,000.

Hereinafter, the present invention will be described in detail.

As a result of the inventor's intensive studies, the modified polyester resin having a specific monomer unit and the wax having a specific melting point have a polymerizable monomer in the polymerizable monomer composition. 0.1 to 9.
It has been found that when the content is 0% by weight and 16 to 50% by weight, a toner excellent in image quality and blocking resistance is obtained. This is because the modified polyester resin has a specific monomer unit, so that the binder component of the toner, that is, the modified polyester that is hydrophilic compared to the polymerizable monomer and the wax that is hydrophobic in the monomer system. It is considered that the main cause is that stable granulation with a large amount of wax contained and the encapsulation property of the toner can be achieved at the same time by maintaining the incompatibility and the appropriate compatibility.

That is, the toner of the present invention is stabilized in such a state that the components in the monomer system are not separated from the oil droplets at the initial stage of suspension polymerization, becomes incompatible with the progress of polymerization, and is encapsulated. For this reason, the prescribed 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 effect of the wax, which causes the deterioration of the blocking property due to the improved toner encapsulation, is almost eliminated.

Further, since the modified polyester is unevenly distributed on the surface under the influence of the wax, the fluidity of the modified polyester itself is exhibited, and the fluidity of the polymerized toner is improved.
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 at the time of manufacturing the toner. It is preferred to contain 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 a polyester layer on the surface layer of the toner, resulting in insufficient fluidity and poor image quality. 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 is widened.

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, Acidic monomers such as sebacic acid, succinic acid, cyclohexanedicarboxylic acid and 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 and 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, glycerin And polycondensation with a polyhydric alcohol monomer such as trimethylolpropane or pentaerythritol.

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

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

That is, a graft copolymer in which a styrene, acrylic or methacrylic monomer unit is radically bonded to the polyester main chain, or the above monomer unit has a radical in the polyester main chain. Block copolymers incorporated by bonding or ionic bonding. As the styrene monomer, acrylic monomer and methacrylic monomer used for modifying these polyester resins, any known one may be used, and as the styrene monomer, For example, styrene, o-methylene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene; and examples of the acrylic monomer 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 lylic 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 esters such as diethylaminoethyl methacrylate, and methacrylonitrile.

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

The amount of modification of the modified polyester resin is preferably 0.05 to 48% by weight, more preferably 0.1% by weight.
05 to 40% by weight, more preferably 0.1 to 20% by weight
, The image quality is further improved. Modification amount is 0.05% by weight
If less than the solubility of the polymerizable monomer and the polymerizable monomer composition having a wax will be slightly reduced,
An increase in fine powder and a decrease in fluidity are caused, and the image quality is apt to deteriorate.
If the modification amount exceeds 40% by weight, the ability to dissolve in the polymerizable monomer composition is too large, and the polyester component is hardly present on the toner surface. It tends to be inferior.

These resins are generally of high molecular weight and have a great effect on the fixability. However, the weight average molecular weight of the resin component of the obtained toner particles is 5,000 to 4,500.
0, preferably in the range of 12000 to 45000, not only keeps the excellent fixability of the polymerized toner,
The fixing area further expands.

This is presumably 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 adhesion 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.
When the average molecular weight of the resin component of the toner particles exceeds 45,000, the resin is too hard, so that not only low-temperature offset is easily caused but also the toner color mixing property tends to decrease.

In the present invention, it is preferable that the wax contains 16 to 50% by weight, preferably 16 to 40% by weight, based on the toner particles. 16 wax content
When the amount is less than% by weight, not only the fixing characteristics are reduced, but also the granulation properties, image quality and the like tend to be reduced. This is considered to be due to the fact that the amount of wax is small and the encapsulability of the surface polyester is weakened. Further, when the wax is contained in an amount of more than 50% by weight with respect to the toner, it is difficult to maintain the encapsulating property with the binder component, and the
The blocking resistance tends to decrease.

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

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

Of these, polyalkylene waxes are particularly preferred.

Furthermore, in the present invention, among the above waxes, it is preferable to use a wax having an SP value of 10 or less from the viewpoint of maintaining compatibility with the polymerizable monomer and maintaining hydrophobicity. Here, the SP value is an index (solubility parameter) indicating the solubility of the substance.
r) is a value commonly displayed as r), here Fed
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 ppm.
ppm, and 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 rise of the charge of the toner of the present invention is reduced. It turned out to be good and a stable image could be obtained immediately after use. This is considered to be due to the fact that the generated charges are easily moved by the moisture in the toner particles, so that the charging rise is good. And, in such a state that the rising of the charge is good, the amount of the charge control agent may be very small as described above, and particularly, the color changes due to the remaining color of the charge control agent such as a color toner. Disliked, it is an effective means for toner.

If the amount of water absorbed by the toner particles is less than 300 ppm, the charge leakage is too small, and the image density becomes low particularly in a low-temperature and low-humidity environment. Further, when the water absorption of the toner particles exceeds 5000 ppm, the charge leakage is too large, and the phenomenon of toner scattering and fogging particularly occurs under high temperature and high humidity.

When the amount of the charge controlling agent is less than 0.01% by weight based on the toner particles, the amount of the charge controlling agent in the entire toner is insufficient, so that sufficient toner charging characteristics cannot be obtained and the image density , Toner scattering and fogging are likely to occur, and the 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 existing on the toner surface is too large, so that the insulating property of the toner is reduced. It has a significant effect on image density under wet conditions. Further, in order to further improve the charging characteristics of the toner of the present invention, it is preferable that the charge controlling agent has the following structure.

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 formula: 2 ≦ X ₁ / X ≦ 100, and more preferably, the following formula: 5 ≦ X ₁ / X ≦ 50. (Where X represents the charge rate of the charge control agent during the production of the toner particles (the ratio of the charge control agent to the weight of the polymerizable monomer in the polymerizable monomer composition (% by weight)). Reference numeral ₁ indicates the content of the charge control agent present in the outermost surface layer of the toner particles (shows 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 refers to 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 rise of charging is delayed because the amount of the charge control agent present on the surface of the toner particles is insufficient, and the value of X ₁ / X is further reduced. Is more than 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 is easily peeled off, and sleeve contamination and drum contamination are likely to occur.
As a result, deterioration of the durability image is promoted.

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

In the suspension polymerization method, the viscosity of the polymerization reaction system increases as the polymerization proceeds, including the suspension polymerization toner, and the transfer of radicals and polymerizable monomers becomes difficult. In this case, a large amount of the polymerizable monomer component tends to remain. Particularly, in the case of a suspension polymerization method toner, components that may inhibit a polymerization reaction such as a dye, a pigment (particularly, carbon black), a charge controlling agent, and a magnetic substance are contained in a polymerizable monomer system. Since it is present in a large amount other than in the body, unreacted polymerizable monomers are more likely to remain.

If the toner particles contain not only the polymerizable monomer but also a large number of components that act as a solvent for the binder resin, the fluidity of the toner is reduced to deteriorate the image quality, and the anti-blocking property is reduced. Causes a decline. In addition to the performance directly related to the toner, especially when an organic semiconductor is used as the photoconductor, it also accompanies the deterioration phenomenon of the photoconductor such as memory ghost and blurred image other than the fusion phenomenon of the toner on the photoconductor drum. May cause problems. In addition to the matters relating to the performance of the product, there is a problem that the polymerizable monomer component volatilizes during fixing and emits an offensive odor.

As described above, also in the toner of the present invention, the effect of further improving the image quality can be seen by reducing the residual amount of the polymerizable monomer present in the toner particles. The residual amount of the polymerizable monomer is preferably 1000 ppm or less, more preferably 500 ppm or less.

When the amount of the polymerizable monomer remaining in the toner particles is 1
As a method for reducing the content to 000 ppm or less, a known polymerizable monomer consumption promoting means used when a binder resin is produced by a 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 dissolves the polymerizable monomer and / or the organic solvent component; A method of washing with an acid or an alkali; a solvent component that does not dissolve a foaming agent or a polymer is put in a polymer system, and the resulting toner is made porous, so that the volatilization area of the internal polymerizable monomer and / or organic solvent component is increased. And a method of volatilizing the main synthetic monomer and / or organic solvent component under reduced pressure. However, it is difficult to select a solvent such as elution of a toner constituent component due to a decrease in toner encapsulation property and persistence of the solvent. Therefore, a method of volatilizing the polymerizable monomer and / or the organic solvent component under reduced pressure is 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 particles have irregularities so as to suppress the rubbing of the toner external additive.

The polymerizable monomers which can be used for producing the toner by polymerization in the present invention include styrene-based monomers, acrylates and methacrylates which have already been used for modifying the polyester resins described above. And the like, ie, styrene monomers such as, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, pmethoxystyrene, 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, phenyl methacrylate Methacrylic esters such as dimethylaminoethyl and diethylaminoethyl methacrylate; and other monomers such as acrylonitrile, methacrylonitrile and acrylamide.

Among the above-mentioned monomers, styrene or a styrene derivative may be used alone, as a mixture thereof, or as a mixture with other monomers, so that the developing characteristics and durability of the toner can be improved. Preferred 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 charge control agent is negatively charged. It is preferable to add an agent in order to obtain a negatively charged toner.

Examples of negative charge control agents include metal-containing salicylic acid compounds, metal-containing monoazo dye compounds, styrene-acrylic acid copolymers, imidazole derivatives, styrene-methacrylic acid copolymers (N, N'-diarylurea derivatives). ).

As the dispersion medium used in the present invention, any suitable stabilizer can be used. For example,
As inorganic compounds, 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 and the like can be mentioned. As the organic compound, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salts, starch and the like can be used by dispersing them in an aqueous phase. This stabilizer is preferably used in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer.

In order to finely disperse these stabilizers, a surfactant may be used in an amount of 0.001 to 0.1 part by weight based on 100 parts by weight of the polymerizable monomer. This is to promote the intended action of the above-mentioned dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and sodium raliurate. , Potassium stearate and calcium oleate.

When calcium phosphate is used among these dispersion stabilizers, those having favorable particle size distribution, toner shape and toner internal structure can be obtained, and the effects of the present invention can be further exerted.

The calcium phosphate may be used in the form of a powder as it is. However, a method in which calcium phosphate is formed in water using a substance such as sodium phosphate and calcium chloride, and the resultant is preferably used. When this method is used, a very fine salt is obtained and a stable suspension state is obtained, so that the granulation property is good.

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

A modified polyester resin having at least one monomer unit selected from the group consisting of a styrene monomer, an acrylic monomer and a methacrylic monomer as a polymerizable monomer. 0.1 to 9.0% by weight, 16 to 50% by weight of a wax having a melting point of 50 to 95 ° C. and 0.01 to 5.0% by weight of a charge control agent, and if necessary, a colorant or a polymerization initiator. Add other additives, homogenizer, polymerizable monomer composition uniformly dissolved or dispersed by mixing means such as an ultrasonic disperser, added to the aqueous phase containing a dispersion stabilizer, the usual Disperse with a stirrer, homomixer or homogenizer. Preferably, the agitation speed and time are adjusted so that the monomer droplets have a desired toner particle size, generally a particle size of 30 μm or less, and granulation is performed. Thereafter, by the action of the dispersion stabilizer, the particles may be stirred to such an extent that the particle state is maintained and the particles are prevented from settling or floating. After the 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 generally 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 steps, 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 raising 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'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,
Azo or diazo polymerization initiators such as 1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl Examples include peroxide polymerization initiators such as peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide. These polymerization initiators may be used in an amount of 0.5 to 2 of the polymerizable monomer.
An addition amount of 0% by weight is preferred.

The coloring agent used in the present invention includes, for example, carbon black, iron black and 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.
Modant 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. Modant Blue 7, C.I. I. Direct Green 6, C.I.
I. Basic Green 4, C.I. I. Dyes such as Basic Green 6, graphite, 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.

In the present invention, in order to obtain a toner by using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant. It is better to carry out a hydrophobic treatment with a substance. In particular, attention must be paid to the use of dyes and carbon black since many of them have polymerization inhibitory properties.
As a preferable method for surface-treating the dye system, there is a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system. Further, regarding carbon black, in addition to the same treatment as the above-described dye, a graft treatment with a substance that reacts with the surface functional group of carbon black, for example, a polyorganosiloxane may be performed. In the present invention, a magnetic material may be added, but it is also preferable to use the material after performing a surface treatment.

In the present invention, for example, the following additives other than the hydrophobic inorganic oxide are used as additives for imparting various properties.

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: fluororesin 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 100 parts by weight of the toner particles.
1 to 10 parts by weight are used, preferably 0.1 to 5 parts by weight. Even if these additives are used alone,
You may use two or more together.

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

(1) Measurement of Particle Size Distribution Coulter Counter TA-II type (manufactured by Coulter) was used as a measuring device, and an interface (manufactured by Nikkaki) for outputting a number average distribution and a volume average distribution and CX-
1 A personal computer (manufactured by Canon Inc.) is connected, and a 1% aqueous NaCl solution is prepared using primary grade sodium chloride as an electrolyte.

The measuring method is as follows.
In 50 ml, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 0.5 to 50 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser,
With the Coulter Counter TA-II, 2 to 40 μm using a 100 μm aperture as the aperture
Is measured to obtain a volume average distribution and a number average distribution.

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

(2) Measurement of Melting Point of Wax The melting point of the wax was measured at a heating rate of 10 ° C./min using DSC-7 (manufactured by PerkinElmer). The temperature at the peak of the peak showing the maximum endotherm is defined as the melting point of the wax.

(3) Measurement of Residual Amount of Polymerizable Monomer Remaining in Toner Particles The polymerization conversion was determined by adding a polymerization inhibitor to 1 g of a suspension and dissolving the same in 4 ml of tetrahydrofuran (THF). The amount of the polymerizable monomer and the organic solvent remaining in the toner particles is determined by using 0.2 g of the toner in 4 ml of THF.
Were dissolved in the above, and each 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 measurement of water absorption of toner particles was performed by leaving a 0.5 ± 0.1 g sample in an environment of 23 ° C./60% RH for 3 days or more, Measuring device (AQ-6 Hiranuma Sangyo Co., Ltd.)
(Titration reagent Hydranal Aqualite RS). The sample is heated by an automatic moisture vaporizer (SE-24 Hiranuma Sangyo Co., Ltd.) connected to AQ-6 via 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) is used, and 15 standard polystyrenes are divided into four 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 × 10 ² 1.09 × 10 ⁶ 9.64 × 10 ⁴ 5.57 × 1
0 ³ Approximately 3mg of the sample in the group in a 30ml sample bottle
(1 cup in microspatula), take 15ml of TH
Add F and leave at room temperature for 4 hours. Next, the solution is filtered using a membrane filter (0.50 μm: manufactured by Tosoh Corporation) to obtain a standard sample.

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

(GPC) Waters Company, 1
It measured using 50C ALC / GPC under the following conditions.

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

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

[0081]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below based on embodiments. The parts in the following formulations are parts by weight unless otherwise specified.

Production Example 1 of Modified Polyester Resin 15 parts by weight of 2-ethylhexyl acrylate and 15 parts by weight of 15 parts by weight of a polyester solution in which 300 parts by weight of a vinyl group-containing polyester resin are dissolved in 1 liter of benzene.
1% by weight of a 1% by weight cobalt-naphthenate-styrene solution, vigorously stirred at room temperature for 1 hour, and then stirred at 50 ° C. for 5 hours to polymerize. Then, benzene and 2-ethylhexyl acrylate were distilled off, and the modified polyester resin A I got
The modified polyester resin A thus obtained had a modified amount of 3% by weight in view of the weight increase of the polyester resin.

Preparation Example 2 of Modified Polyester Resin 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 is dissolved in 1 liter of benzene is gradually dropped into the reaction solution, and the mixture is stirred and polymerized 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 amount of modification of the resulting modified polyester resin B was 45% by weight in view of the weight increase of the polyester resin.

Production Example 3 of Modified Polyester Resin 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 vinyl group-containing polyester resin was dissolved in 1 liter of benzene. After stirring at room temperature for 5 hours with vigorous stirring to polymerize, benzene and styrene were distilled off to obtain a modified polyester resin C. The amount of modification of the obtained modified polyester resin C was 3% by weight in view of the weight increase 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 was changed to 60 parts by weight of styrene and 2 parts by weight of the 15% cobalt naphthenate-styrene solution.
A modified polyester resin D was obtained in the same manner as the modified polyester resin production example 1 except that the time was changed.
The resulting modified polyester resin D had a modified amount of 35% by weight when viewed from the weight increase of the polyester resin.

Example 1 A 0.1 M aqueous solution of Na ₃ PO ₄ and a 1 M aqueous solution of CaCl ₂ are prepared. TK homomixer (made by Tokushu Kika Kogyo)
0.1M Na ₃ PO ₄ in a 2 liter flask
22g and 850g of ion-exchanged water are charged and 12000r
Stirred at pm. 48.4 g of 1 M CaCl ₂ aqueous solution
Was gradually added with stirring to the above-mentioned 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 I. Pigment Blue 15: 3 ... 10 g Modified polyester resin A ... 10 g Metal compound of di-tert-butylsalicylate ... 1 g Of the above-mentioned formulations, modified polyester resins A, C.I. I. Pigment Blue 15: 3, only a chromium di-tert-butylsalicylate compound and 100 g of styrene were pre-dispersed using an attritor (manufactured by Mitsui Miike) to prepare a colorant dispersion.

Next, the rest of the above formulation is added to the colorant dispersion, heated to 70 ° C., dissolved and dispersed to form a polymerizable monomer mixture. 10 g of 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 above polymerizable monomer composition was charged into a dispersion medium prepared in a 2-liter flask of the homomixer. Using a TK homomixer in a nitrogen atmosphere at 70 ° C., the mixture was stirred at 10,000 rpm for 20 minutes to granulate the polymerizable monomer composition. Thereafter, 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 , filtered, washed with water and dried to obtain a powder having a sharp particle size distribution and a weight average diameter of 8.2 μm. Polymerized toner particles were obtained. The toner particles are heated at 45 ° C.
Degassing was performed for 12 hours under reduced pressure of mHg. At this time, the amount of the polymerizable monomer remaining in the toner particles, that is, the content of the toner particles was 150 ppm.

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

Next, 0.7 part of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method was externally added to 100 parts of the obtained toner particles. This externally added toner is 55
Excellent performance was also exhibited in a blocking test at 7 ° C. for 7 days. To 7 parts of this externally added toner, 93 parts of a ferrite carrier coated with an acrylic resin were mixed to prepare a developer.

Using this developer, a commercial color copier (CLC-500, manufactured by Canon) was modified and a durability test of 20,000 sheets was performed. Developing conditions are 23 ° C / 65% RH
The development contrast was set to 220 V under the environment described above. As a result, an image having an image density of 1.3 or more, no fog, an extremely high resolution, and an excellent fixing property was stably obtained.

Further, a similar test was conducted in an environment of 15 ° C./10% RH, and similar results were obtained.

Comparative Example 1 In the formulation of Example 1, the amount of the modified polyester A was changed to 3
In the same manner as in Example 1 except that the amount was set to 0 g, toner particles having a weight average particle size of 9.1 μm were obtained. However, since a large amount of fine powder was generated, the particle size distribution was widened.

Using the toner particles obtained, a developer was prepared in the same manner as in Example 1, and when an image was formed, the image density was 1.4 or more, but a large amount of fog occurred. ,
Further, the fixing temperature range was narrowed.

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

Comparative Example 3 Toner particles having a weight average particle diameter of 6.1 μm were prepared in the same manner as in Example 1 except that the amount of the metal di-tert-butylsalicylate was changed to 15 g. I got In the obtained toner particles, a large amount of fine powder was generated. Using the obtained toner particles, a developer was prepared in the same manner as in Example 1, and an image was formed. As a result, fogging occurred in the obtained image. Furthermore, the image density decreased as the durability increased.

Comparative Example 4 In the formulation of Example 1, 5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) as an initiator was used.
In the same manner as in Example 1, toner particles having a weight average particle size 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 performed. 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 resulting image was narrow.

Comparative Example 5 In the formulation of Example 1, the modified polyester was used in an amount of 0.1
In the same manner as in Example 1, except that the amount was changed to g, toner particles having a weight average particle size of 9.7 μm were obtained. Using the obtained toner particles, a developer was prepared in the same manner as in Example 1, and an image was formed. As a result, the obtained toner had low blocking characteristics. It was low and the image quality was low.

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

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

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

A running test was performed on the above developer under the same conditions as in Example 1. As a result, the image was slightly inferior in resolution to Example 1, but was excellent in fixability.

Example 3 Example 1 was repeated except that the formulation of Example 1 was changed as follows.
In the same manner as in the above, magnetic toner particles having a weight average particle size 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-butylsalicylate Zn compound 1 g

The weight average particle size 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. When a running test was similarly performed on the obtained magnetic toner using NP2020 (manufactured by Canon),
An image having an image density of 1.4 or more, 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. Pigment Blue 15: 3 was prepared in the same manner as in Example 1, except that the pigment blue 15: 3 was subjected to a hydrophobic treatment with a titanium coupling agent, to thereby obtain toner particles and prepare a developer. The water absorption of the obtained toner particles was 150 ppm.

When a running test was performed on the above developer under the same conditions as in Example 1, the same results as in Example 1 were obtained in an environment of 23 ° C./60% RH.
In an environment of / 10% RH, fog was slightly observed and the image quality was reduced, but was at a level causing no practical problem, and the image density was 1.1 or more. Table 1 shows the results.

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. And a developer were prepared. The water absorption of the obtained toner particles is 800 pp
m.

When a running test was performed on the above developer under the same conditions as in Example 1, similar results were obtained.

The properties 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 image of the present invention comprises at least (i) a polymerizable monomer, (ii) a styrene monomer, an acrylic monomer and a methacrylic monomer. Modified polyester resin having at least one or more monomer units selected, (iii) melting point 50
(Iv) a toner for developing an electrostatic image having toner particles obtained by polymerizing a polymerizable monomer composition having a wax at a temperature of from about 95 ° C. and (iv) a charge control agent in an aqueous phase. A resin prepared by polymerization of the polymerizable monomer, 0.1 to 9.0% by weight of the modified polyester resin, 16 to 50% by weight of the wax, and 0.01 to 5.0% by weight of the charge control agent. %, And the resin component of the toner particles is 5,000 to 45,000.
And the toner particles have a weight average molecular weight of
Since it has a water absorption of 300 to 5,000 ppm, the modified polyester and the wax are appropriately compatible with each other while maintaining incompatibility in the monomer system, so that stable production under a large amount of wax is contained. Since both the graininess and the encapsulation property of the toner can be compatible, the fixing property is excellent, the charging property is stable, the image quality and the blocking resistance are improved, and the toner particles have excellent fluidity, so that the image quality is improved. An image having a high density and excellent in fine line reproducibility and highlight gradation can be obtained, and even with a small charge control agent content, the rising of charging is good and a stable image can be obtained immediately after use.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03G 9/08 (72) Inventor Koji Inaba 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Invention Person Makoto Kambayashi Canon Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo Inventor Kazuyuki Miyano Canon Inc. 3- 30-2 Shimomaruko 3-chome, Ota-ku, Tokyo (56) References JP 56-116043 (JP, A) JP-A-60-238846 (JP, A) JP-A-3-89360 (JP, A) JP-A-1-292357 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03G 9/08

Claims (32)

(57) [Claims] (1) at least (i) a polymerizable monomer , (i)
i) Styrene-based monomer, acrylic-based monomer and methacrylic
At least one selected from the group consisting of
A modified polyester resin having the above monomer unit,
(Iii) a wax having a melting point of 50 to 95 ° C, and (i)
v) In the toner for developing electrostatic images having toner particles obtained by the polymerizable monomer composition having a charge control agent <br/> polymerization in the aqueous phase, the toner particles are polymerizable Prepared by polymerization of monomers
Resin, the modified polyester resin 0.1 to 9.0 wt%, the wax 16 to 50% by weight, and which contain the charge control agent 0.01 to 5.0 wt%, the resin of said toner particles Wherein the component has a weight average molecular weight of 5,000 to 45,000 , and the toner particles have 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.
2. The electrostatic image developing toner 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-Tropsch 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 image according to claim 1, wherein the toner comprises: 4. The toner particles have a particle size of 320 to 2000 p.
The electrostatic image developing toner according to claim 1, wherein the toner has a water absorption of pm. 5. The toner particles, wherein the toner particles and the charge control agent are represented by the following formula: 2 ≦ X ₁ / X ≦ 100 (where X is the charge rate of the charge control agent during the production of the toner particles (polymerizable monomer). X1 is the ratio of the charge control agent to the weight of the polymerizable monomer in the monomer composition (% by weight), and X ₁ is the content of the charge control agent present in the outermost surface layer of the toner particles (toner particles). Of charge control agent to the weight of binder resin on the outermost surface of the resin (% by weight)
Is shown. 2. The electrostatic image developing toner according to claim 1, wherein 6. The toner particles, wherein the toner particles and the charge control agent are represented by the following formula: 5 ≦ X ₁ / X ≦ 50 (where X is a charge rate of the charge control agent during the production of the toner particles (polymerizable monomer). X1 is the ratio of the charge control agent to the weight of the polymerizable monomer in the composition (% by weight)), and X ₁ is the content of the charge control agent present in the outermost surface layer of the toner particles (toner 2. The toner according to claim 1, wherein the ratio of the charge control agent to the weight of the binder resin in the outermost layer of the particles (% by weight) is satisfied. 7. A toner for developing an electrostatic image, wherein the amount of the polymerizable monomer remaining in the toner particles is 1000 ppm or less. 8. A toner for developing an electrostatic image, wherein the amount of the polymerizable monomer remaining in the toner particles is 500 ppm or less. 9. The polymerizable monomer is a styrene monomer,
2. The toner for developing an electrostatic image according to claim 1, wherein the toner has at least one monomer selected from the group consisting of an acrylic monomer and a methacrylic monomer. 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 2. The toner for developing an electrostatic image according to claim 1, comprising one or more monomers selected from the group consisting of lonitrile and acrylamide. 11. The polymerizable monomer is a styrene monomer;
A styrene derivative monomer; a mixture of a styrene monomer and a styrene derivative monomer; a mixture of a styrene monomer and another monomer; or a mixture of a styrene derivative monomer and another monomer. The toner for developing an electrostatic image according to claim 1, further comprising: 12. The modified polyester resin has a content of 0.05
2. The electrostatic image developing toner according to claim 1, wherein the toner has a modified amount of from about 40% by weight to about 40% by weight. 13. The electrostatic image developing 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 includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, and n-acrylate. Butyl, isobutyl acrylate, n-acrylate
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, methacrylsand decyl, 2-ethylhexyl methacrylate,
It is characterized by having at least one or more monomer units selected from the group consisting of stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile and acrylamide. The toner for developing an electrostatic image according to claim 1. 15. The modified polyester resin is a graft copolymer in which a unit of a styrene, acrylic or methacrylic monomer is radically bonded to (i) a main chain of the polyester resin, or (ii) 2. The electrostatic image developing toner according to claim 1, wherein the toner is a block copolymer incorporated into the main chain of the polyester resin by a radical bond or an ionic bond. 16. At least (i) a polymerizable monomer, ( i
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. , ( Iii ) melting point 50-95
A polymerizable monomer composition having 16 to 50% by weight of a wax at 16 ° C. and ( iv ) 0.01 to 5.0% by weight of a charge control agent, the method comprising the steps of: The obtained toner particles have a water absorption of 300 to 500.
0 ppm, and the resin component of the toner particles is 50 ppm.
A method for producing a toner, having a weight average molecular weight of from 00 to 45000. 17. 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.
17. The method for producing a toner according to claim 16, wherein the content is 1 to 3.0% by weight. 18. The wax may be paraffin wax,
A polyolefin wax, a Fischer-Tropsch wax, an amide wax, a higher fatty acid wax, an ester wax, a derivative thereof, a graft compound thereof, and a block compound thereof. The method for producing a toner according to claim 16, wherein 19. The toner according to claim 19, wherein the toner is 320 to 2000 pp
17. The method for producing a toner according to claim 16, having a water absorption of m. 20. The toner particles, wherein the toner particles and the charge control agent are represented by the following formula: 2 ≦ X ₁ / X ≦ 100 (where X is a charge rate of the charge control agent during the production of the toner particles (polymerizable monomer). X1 is the ratio of the charge control agent to the weight of the polymerizable monomer in the monomer composition (% by weight), and X ₁ is the content of the charge control agent present in the outermost surface layer of the toner particles (toner particles). 17. The method 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 is satisfied. 21. The toner particles, wherein the toner particles and the charge control agent are represented by the following formula: 5 ≦ X ₁ / X ≦ 50 (where X is the charge rate of the charge control agent during the production of the toner particles (polymerizable monomer). X1 is the ratio of the charge control agent to the weight of the polymerizable monomer in the monomer composition (% by weight), and X ₁ is the content of the charge control agent present in the outermost surface layer of the toner particles (toner particles). 17. The method 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 amount of polymerizable monomer remaining in the obtained toner particles is reduced to 1000 ppm or less by removing unreacted polymerizable monomers in the toner particles. 17. The method for producing a toner according to claim 16, wherein: 23. An unreacted polymerizable monomer in the toner particles is removed to reduce the amount of the polymerizable monomer remaining in the obtained toner particles to 500 ppm or less. 17. The method for producing a toner according to claim 16, wherein: 24. A method for removing unreacted polymerizable monomers in the toner particles, wherein the polymerizable monomer and / or the organic solvent component is dissolved while the toner binder resin is not 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 put into a polymer system; the method increasing the volatilization area of the organic solvent component; and the polymerizable monomer and / some have under reduced pressure or claim 22 characterized in that it is a method selected from the group consisting of a method of volatilizing the organic solvent component 24. The method for producing a toner according to 23. 25. The polymerizable monomer has at least one monomer selected from the group consisting of a styrene monomer, an acrylic monomer and a methacrylic monomer. 17. 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, methacrylic acid 17. The method for producing a toner according to claim 16, comprising at least one monomer selected from the group consisting of lonitrile 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. A method for producing a toner according to claim 16. 28. The modified polyester resin has a composition of 0.05
17. The method for producing a toner according to claim 16, wherein the toner has a modification amount of from about 40% by weight to about 40% by weight. 29. The method 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 comprises styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, methyl acrylate, ethyl acrylate, n-acrylate. Butyl, isobutyl acrylate, n-acrylate
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, comprising isobutyl methacrylate, n- octyl, 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, comprising at least one unit of a monomer selected from the group. 31. The modified polyester resin, wherein the styrene, acrylic or methacrylic monomer unit is (i) a graft copolymer having a radical bond to the main chain of the polyester resin, or (ii) 17. The method according to claim 16, wherein the polyester resin is a block copolymer incorporated by a radical bond or an ionic bond into a main chain of the polyester resin. 32. The toner particles, wherein the polymerizable monomer composition is obtained by suspension polymerization in which a polymerization reaction is performed by adding and dispersing the polymerizable monomer composition in an aqueous phase. 17. The method for producing a toner according to item 16.