JP2001215756A - Electrostatic charge image developing toner and method of forming image using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which has excellent fixing property and offset resistance for a wide range of the fixing rate, particularly even when development and fixing are carried out at a rate over 20 m/min, and the resultant fixed image has excellent wear resistance and peeling resistance. SOLUTION: The toner contains a polyester resin, coloring agent and releasing agent. The flow start temperature Tfb of the toner measured by a constant- load extrusion type tubular rheometer ranges from 70 deg.C to 150 deg.C, and the flow end temperature Tend ranges from 120 deg.C to 144 deg.C.

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 image used in an electrophotographic method, an electrostatic recording method, or an electrostatic printing method.

[0002]

2. Description of the Related Art As an electrophotographic method, US Pat.
No. 97,691, JP-B-42-23910 and JP-B-43-24748, various methods are described. Usually, various methods are described on an electrostatic latent image carrier such as a photoconductive photoreceptor. An electrostatic latent image is formed by charging and exposure, and then the electrostatic latent image is developed with a toner composition containing a colorant in a binder resin, and the obtained toner image is transferred to a support such as transfer paper. In general, a visible image is formed by fixing.

A copying machine or a printer is used as an apparatus using such an electrostatic image developing method. The processing speed varies depending on a maker and a type. Approximately 30 sheets / minute for printers, 60-100 for office copiers
Many machines have a processing speed of about one sheet / minute. In particular,
Due to the recent increase in speed of the developing device, the processing speed has been increased to 100 sheets / minute in A4 paper lengthwise conversion and to 140 sheets / minute in A4 paper width conversion.
Minutes and fixing speeds are shifting to high-speed machines corresponding to 30 m / min. Also, with the power saving, the amount of heat supplied to the toner is steadily decreasing, and the amount of heat given from the heat roll at the time of fixing is reduced. Properties and low-temperature fixability have become indispensable. Further, even in a high-speed machine, when a trouble occurs, there is a high possibility that the developed image is in contact with the heat roll for a long time and is exposed to an excessive amount of heat, so that sufficient hot offset resistance is required.

Therefore, the toner for developing an electrostatic image used here includes electrical properties such as triboelectric charging and electric resistance related to development and transfer performance, and thermal properties related to fixing performance and anti-offset performance. In mechanical properties as a powder such as properties, fluidity and hardness, an appropriate level is required according to the use conditions.

Conventionally, polyester, polystyrene, styrene (meth) acrylate copolymer, styrene butadiene copolymer, epoxy resin and the like have been researched and used as resin materials for powder toners. Various proposals have been made according to use conditions.

In particular, a number of design examples have been proposed for a resin for toner which is fixed by a heat roll with the aim of improving the fixing performance and the anti-offset performance. In order to improve the viscoelastic behavior during heating and melting, Alternatively, the molecular weight distribution is expanded in order to suppress the change in melt viscosity due to temperature change,
Various techniques such as providing a crosslinked structure and applying a rubber elastic material have been studied.

[0007] Recently, polyester resins have been attracting attention due to an increase in demand for low-temperature fixing performance due to energy saving during heat roll fixing or speeding up.

It has been widely known that polyester resins can be used as a heat roll fixing resin in previous studies. For example, Japanese Patent Publication No. 52-25420,
No. 17496, No. 55-49305, JP-A-55-3
No. 8524, No. 57-37353, No. 58-1195
There are various publications such as No. 2.

[0009] However, according to these conventionally proposed inventions, in order to improve the hot offset resistance, the softening point and the molecular weight of the resin must be increased.
Cold offset resistance and low-temperature fixability deteriorate. Conversely, when trying to improve the cold offset resistance and the low-temperature fixing property, the resin softening point or the glass transition point is lowered, and the hot offset resistance and the blocking resistance are deteriorated.

The toner is required to balance these contradictory properties in a well-balanced manner.
The performance such as fixing strength and chargeability greatly varies depending on the electrostatic image developing apparatus using the toner and the use environment. Therefore, a performance design according to the purpose is required.

[0011] As a means for easily measuring such properties as the thermal characteristics and viscosity of the resin, there is a constant load extrusion type capillary rheometer. The constant load extrusion type thin tube rheometer measures the viscous resistance of the melt as it passes through the thin tube, and specifically includes a flow tester “CFT-500” manufactured by Shimadzu Corporation.

FIG. 1 shows the structure of the cylinder section of the measuring apparatus. In the measurement by the temperature rise method using this device, the test is performed while raising the temperature at a constant rate over the course of the test time, so that the sample reaches the flow region from the solid region to the transition region, through the rubbery elastic region, The process can be measured continuously.
With this device, the shear rate at each temperature in the flow zone,
The viscosity can be easily measured.

FIG. 2 shows a flow curve obtained by the heating method. A
Region B (softening curve) shows the stage in which the sample is deformed under compression load and the internal voids are gradually reduced. Point B is the temperature at which the internal voids disappear and the transparent body or phase becomes uniform in appearance while having a non-uniform stress distribution, and indicates an inflection point from the solid region to the transition region. This temperature is defined as the softening temperature T
It is defined as s. The area of the BC (stop curve) shows the area where there is no apparent change in the position of the piston within a finite time and the sample begins to flow out of the die, including the rubbery elastic area of the sample. In the case of crystalline polymers, this region is short,
The softening temperature shows a value close to the outflow start temperature described in the next section. The point C indicates a temperature at which the sample starts flowing out of the die due to a decrease in the viscosity, and this temperature is defined as a flow start temperature Tfb. CD
An area E (outflow curve) indicates an area where the sample flows out of the die, and irreversible viscous flow is mainly performed.

The melting temperature T1 / 2 by the 1/2 method indicates a temperature at a half point of the piston stroke between Tfb and the outflow end temperature Tend in the outflow curve.

The softening temperature Ts, the outflow start temperature Tfb, the melting temperature T1 / 2 by the 1/2 method, and the outflow end temperature Tend specified here all affect the offset resistance and the low-temperature fixability at the time of fixing. If anything, the softening temperature T
s, the outflow start temperature Tfb greatly contributes to the low-temperature fixing property and the cold offset resistance, and the melting temperature T by the 1/2 method is large.
1/2, outflow end temperature Tend is hot offset resistance,
Large contribution to grindability.

As an invention based on the viscosity characteristics obtained by such a measuring method, for example, Japanese Patent Laid-Open No. 11-1
No. 90913. Although the toner described in this publication has excellent hot offset resistance, it is difficult to obtain sufficient fixing performance with the above-described high-speed machine, and the high-speed machine having a fixing speed exceeding 20 m / min or 30 m / min. However, a polyester toner having both an anti-offset property in a wide temperature range and a low-temperature fixing performance that can sufficiently cope with the above problem has not been obtained.

In the embodiment of the above publication, the image evaluation of the toner is performed using a high-speed copying machine (FT8200 manufactured by Ricoh Company). The processing speed of the copying machine is 80 sheets / min in A4 conversion. The fixing speed is about 16 m / min.

On the other hand, a technique of adding a release agent to the toner to impart releasability from a heat roll at the time of fixing and to prevent occurrence of offset has been studied in parallel. Until now, synthetic waxes such as polypropylene wax and polyethylene wax have been mainly studied.
No. 764, JP-A-5-119509 and the like disclose examples using natural waxes such as montan wax, carnauba wax and rice wax.

A variety of charge control agents have been studied so far, and a positive charge control agent and a negative charge control agent have been selected in accordance with the respective developing systems and the polarity of the photoreceptor. For example, a nigrosine dye, a quaternary ammonium salt compound, and the like are known as a charge control agent used in a positively chargeable toner used in a machine using a high-speed, high-durability selenium photoconductor. Examples of using these positively chargeable charge control agents alone or in combination are described in JP-A-1-259371, JP-A-3-79448,
And JP-A-10-246991.

However, in these reports, all the characteristics required in the developing system described above, that is,
Electrical properties such as triboelectric charging and electric resistance related to development and transfer performance during high-speed printing, and mechanical properties as powder such as thermal properties, fluidity and hardness related to fixing performance and anti-offset performance Are not disclosed.

In recent years, it has become necessary for environmental measures to minimize harmful substances generated in printers, copiers and the like and heavy metals contained in toner as much as possible. Hazardous substances generated from printers, copiers, etc. are those in which impurities contained in the toner volatilize during thermal fixing and come out to the environment. Or, it cannot be said that they are designed with due consideration given to their occurrence. Furthermore, heavy metals or harmful substances contained in the toner are liable to cause contamination of the non-image area and scattering of the toner during printing depending on the type and structure of the heavy metal or the harmful substance, and therefore, consideration should be given to the printing characteristics of the toner. . In particular, in a machine for high-speed printing, the amount of toner that is thermally fixed per unit time is large, so it is necessary to take measures against environmental pollution and printing quality more than in ordinary printers and copiers. However, there is no invention relating to a toner in which sufficient measures have been taken against such a point.

[0022]

SUMMARY OF THE INVENTION The present invention is directed to a wide range of fixing speeds, especially greater than 20 m / min, even 30 m / min.
In applications where development and fixing are performed at high speeds exceeding a minute, toner for electrostatic image development that has both offset resistance and fixing performance in a wide temperature range, and has excellent abrasion resistance and peeling resistance of the fixed image The purpose is to provide.

Another object of the present invention is to provide a high-speed printing when used as a toner for a two-component developer, especially at a high-speed printing such as exceeding 20 m / min, or even exceeding 30 m / min. An object of the present invention is to provide a highly durable and long-life toner for developing an electrostatic image, which exhibits stable development and transfer performance without fluctuation in triboelectric charging performance and electric resistance.

Another object of the present invention is to provide a high-speed printing when used as a toner for a two-component developer, especially at a high-speed printing such as exceeding 20 m / min, or even exceeding 30 m / min. For electrostatic charge image development, it shows good fluidity, mixes quickly with the carrier after toner replenishment, and quickly reaches a predetermined charge amount to obtain high quality and high quality printed images without background contamination To provide a toner.

Another object of the present invention is to minimize the content of heavy metals and the content of polycyclic aromatic hydrocarbons in the toner, and to perform high-speed printing, especially more than 20 m / min. It is an object of the present invention to provide a toner for developing an electrostatic charge image capable of minimizing the emission of harmful volatile components even at the time of high-speed printing exceeding 1 / min and obtaining a high-quality and high-quality printed image free from background contamination and toner scattering. .

[0026]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention.

That is, the present invention relates to a toner comprising a polyester resin, a colorant and a release agent, wherein the toner has an outflow starting temperature Tfb of 70 ° C. to 105 ° C. measured by a constant load extrusion type capillary rheometer. , Outflow end temperature Tend
Is 120 ° C. to 144 ° C. to provide an electrostatic image developing toner.

Softening temperature Ts and outflow starting temperature Tfb
If the temperature is too high, the low-temperature fixability deteriorates, and cold offset easily occurs. Further, if the temperature is too low, the storage stability decreases, and hot offset easily occurs.

Therefore, the softening temperature Ts of the toner for developing an electrostatic image of the present invention is preferably from 60 to 80 ° C., more preferably from 60 to 75 ° C., and the outflow starting temperature Tfb is from 70 to 105 ° C. Preferably, 8
The temperature is more preferably 5 to 100 ° C.

If both the melting temperature T1 / 2 according to the 1/2 method and the outflow end temperature Tend are too high, the pulverizability deteriorates and the productivity decreases. / 2 is preferably from 110 to 140 ° C, more preferably from 120 to 140 ° C, and the outflow end temperature Tend is preferably from 120 to 144, and from 125 to 140 ° C.
144 ° C. is more preferred.

Ts, Tfb, T1 / 2 and Tend measured by the constant load extrusion type capillary rheometer specified in the present invention are values obtained by measurement under the following conditions. <Measurement conditions of constant load extrusion type capillary rheometer> ・ Piston cross-sectional area 1cm ²・ Cylinder pressure 0.98MPa ・ Die length 1mm, Die hole diameter 1mm ・ Measurement start temperature 50 ° C ・ Temperature rising rate 6 ° C / min ・1.5g sample weight

Also, needless to say, the values of Ts, Tfb, T1 / 2, and Tend defined in the present invention vary depending on measurement conditions. According to the study of the present inventors,
For example, Japanese Unexamined Patent Application Publication No. 11-1
As set in No. 90913, when only the heating rate is set to 10 ° C./min in the above measurement conditions, 6 ° C./m
Ts, Tfb, T1 / 2, Ten for measured values in
It has been found that each value of d increases by 5 to 8 ° C.

The binder resin of the toner for developing an electrostatic image of the present invention is not particularly limited in molecular structure or composition as long as it exhibits the above-mentioned melting properties as a toner compound. A resin obtained by dehydrating and condensing a diol by an ordinary method can be used.

(1) Dicarboxylic acids Examples of dicarboxylic acids include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, and hexahydrophthalic anhydride. And dihydrocarboxylic acids such as tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid, and sebacic acid, and derivatives or esterified products thereof.

(2) Diols The diols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, bisphenol A, Polyoxyethylene- (2.0) -2,2-
Bis (4-hydroxyphenyl) propane and its derivatives, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -polyoxyethylene- ( 2.0)
-2,2-bis (4-hydroxyphenyl) propane,
Polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene-
(2.2) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxypropylene- (2.4) -2,2
-Bis (4-hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane and its derivatives, polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random copolymer Coalescent diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, polycaprolactone diol, and the like.

(3) Trivalent or higher polyvalent monomer In addition to the above dicarboxylic acids and diols, trifunctional or higher polyfunctional monomers such as trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride can be used. A polyvalent carboxylic acid or a derivative or esterified product thereof, or
Sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,
2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol,
2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-
Trimethylolbenzene, trifunctional or higher polyhydric alcohol, or cresol novolak type epoxy resin, phenol novolak type epoxy resin, polymer or copolymer of vinyl compound having epoxy group, epoxidized resorcinol-acetone condensation Products, partially epoxidized polybutadiene or other pentavalent epoxy compound,
Further, divalent to tetravalent bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, pentaerythritol tetraglycidyl ether, etc. Epoxy compounds and the like can be used as needed.

The polyester resin in the present invention can be obtained by performing a dehydration condensation reaction or a transesterification reaction using the above-mentioned raw material components in the presence of a catalyst.
The reaction temperature and reaction time at this time are not particularly limited, but are usually 150 to 300 ° C. and 2 to 24 hours.

As a catalyst for carrying out the above reaction, for example, zinc oxide, stannous oxide, tetrabutyl titanate, monobutyltin oxide, dibutyltin oxide, dibutyltin dilaurate, paratoluenesulfonic acid and the like can be used as appropriate. .

The binder resin for the toner in the present invention is not particularly limited in its molecular structure and the like as long as it satisfies the melting characteristics of the toner specified in the present invention by using the compounds and production methods exemplified so far. Although not a particular example, a particularly preferred embodiment includes the following method.

That is, the most preferred embodiment as the binder resin for the electrostatic image developing toner of the present invention is the first polyester resin (A) having a linear or crosslinked structure.
By using a mixed system of (hereinafter referred to as resin (A)) and a second polyester resin (B) (hereinafter referred to as resin (B)) having a crosslinked structure, each resin is assigned a function, and as a toner for a high-speed machine. This is a method to exhibit sufficient performance.

In the above method, the resin (A) mainly has cold offset resistance and low-temperature fixing property, and the resin (B) mainly has hot offset resistance and toughness.

The resin (A) and the resin (B) may have a THF-insoluble component in the structure as long as the above-mentioned performance is satisfied. The THF-insoluble matter referred to in the present invention refers to the residue on the filter paper after 1 g of the synthesized resin powder is taken on a special filter paper and refluxed for 8 hours in a Soxhlet reflux apparatus using THF as a solvent. In addition, the crosslinked structure referred to in the present invention includes both a branched structure in which the polyester main chain is branched and a structure in which the polyester main chain is connected in a network. Usually, the content of the THF-insoluble component defined in the present invention is 0% in the polyester having a branched structure, and the content of the THF-insoluble component increases as the network structure increases.

The linear polyester resin used for the resin (A) can be obtained by dehydrating and condensing the above-mentioned dicarboxylic acids (1) and diols (2). Further, the resin (A) or (B) having a branched or crosslinked structure can be obtained by appropriately using a trivalent or higher polyvalent monomer (3).

Considering each temperature characteristic by the constant load extrusion type capillary rheometer from the above viewpoint, the resin (A)
Softening temperature Ts (A), outflow start temperature Tfb (A),
Melting temperature T1 / 2 (A) by the 1/2 method, outflow starting temperature Tfb (B) of resin (B), melting temperature T1 by the 1/2 method
/ 2 (B), the outflow end temperature Tend (B) is particularly important.

Specifically, the softening temperature Ts of the resin (A)
(A) is preferably 50 to 80 ° C., and among them,
A range of 60 to 75C is more preferable.

Further, when the difference between the softening temperature Ts (A) and the outflow start temperature Tfb (A) is small, the pulverizability deteriorates due to the high crystallinity, and the crystallinity differs due to the heat history during cooling. Will affect the melting properties of the toner,
When the difference is large, the sharp melt property is lacking, and the low-temperature fixability deteriorates. Therefore, the temperature is preferably 5 to 20 ° C.

The melting temperature Tfb (A) by the 1/2 method is
It is preferably in the range of 70 to 130 ° C.,
More preferably, it is in the range of 20 ° C.

For the reasons described above, the outflow end temperature Tend
Regarding (A), since Tend (B) of resin (B) largely affects toner characteristics, Tend (A) of resin (A)
Is not particularly limited, but is preferably in the range of 80 to 140 ° C. in consideration of a mixed system of both, and 9
The temperature is more preferably in the range of 0 to 130 ° C.

Since the resin defined by these properties has a low softening temperature and a high crystallinity, in the fixing process using a heat roll, the heat energy given by lowering the temperature of the heat roll or increasing the process speed is reduced. Even when reduced, it melts sufficiently and exhibits excellent performance in cold offset resistance and fixing strength.

On the other hand, regarding the softening temperature Ts, mainly the resin
Since Ts (A) in (A) greatly affects the toner characteristics,
Ts (B) of the resin (B) is not particularly limited, but is preferably in the range of 60 to 100 ° C. in consideration of a mixed system of both, and more preferably in the range of 70 to 90 ° C. .

When the difference between the softening temperature Ts (B) of the resin (B) and the outflow starting temperature Tfb (B) is too small,
The temperature is preferably 30 ° C. or more, and more preferably 40 ° C. or more, because the viscosity of the melted toner during the fixing process is reduced, and the internal cohesive force of the melted toner layer is also rapidly reduced and hot offset is likely to occur. More preferred.

Further, when the melting temperature Tfb (B) of the resin (B) according to the 法 method and the outflow end temperature Tend (B) are both too low, hot offset is liable to occur, and when it is too high. Since the crushability deteriorates and the productivity decreases, Tfb (B) is preferably 130 to 210 ° C., more preferably 140 ° C. to 200 ° C., and the outflow end temperature Tend (B) is 140 ° C-22
The temperature is preferably 0 ° C, more preferably 150 ° C to 210 ° C.

Since the resin defined by these properties has a strong rubber elasticity and a high melt viscosity, the internal cohesive force of the melted toner layer is maintained even during heating and melting in the fixing process, and hot offset occurs. It is hard to perform, and exhibits excellent friction resistance due to its toughness even after fixing.

With respect to the glass transition temperature Tg of the resin, if the Tg is too low, the heat-resistant storage stability and the blocking resistance decrease, and if the Tg is too high, the low-temperature fixability is affected. Resin used in the invention (A)
The glass transition temperature of the resin and the resin (B) is preferably 45 to 75 ° C. in both cases, even in the case of a resin in which both are mixed, or in the case of both of them alone. Those having a temperature of 50 to 75 ° C are particularly preferred.

By blending the resin (A) and the resin (B) in a well-balanced manner, it is possible to provide a toner which sufficiently satisfies the offset resistance and the fixing performance in a wide temperature range.

Weight ratio of resin (A) to resin (B) M (A) / M
If (B) is too small, it affects the fixability, and if it is too large, it affects the anti-offset property. Therefore, it is preferably 1/9 to 9/1, and 2/8 to 9/1.
It is more preferably 8/1, most preferably 3/7 to 7/3.

The melting temperatures of the resin (A) and the resin (B) according to the １ ／ method are T1 / 2 (A) and T1 / 2 (B), respectively.
In this case, T1 / 2 (A) <T1 / 2 (B) may be sufficient, but in particular, from the viewpoint of achieving a balance between low-temperature fixability and offset resistance, and from the difference in viscosity between resins. In order to facilitate uniform mixing when performing melt-kneading without causing cracking, the range of T1 / 2 (B) -T1 / 2 (A) is 20 to
The temperature is preferably 120 ° C, more preferably 30 to 110 ° C.

The weight average molecular weight (Mw) of the THF-soluble component of the resin (A) is preferably from 3,000 to 50,000, more preferably from 4,000 to 30,000. Mw / M
n is preferably 8 or less, and more preferably 4 or less. If Mw is less than 3000,
The toner is liable to cause a cohesion phenomenon, which is liable to cause trouble during storage or printing. When Mw exceeds 50,000, fixability deteriorates. As the resin (B), the Mw of the THF-soluble component is 60,000 to 400,000, and the Mw / Mn is 10
It is preferable that it is above. When Mw is 60000 or less, the toner tends to cause an offset phenomenon at the time of fixing,
When Mw exceeds 400,000, the fixing property is deteriorated.

Further, regarding the acid value, in the case of the resin (A) and the resin (B), the charge amount does not decrease due to the increase in hygroscopicity. , 20 or less, particularly preferably 10 or less.

As the coloring agent that can be used in the present invention, well-known coloring agents can be mentioned. Carbon blacks such as furnace black, channel black, acetylene black, thermal black, and lamp black classified according to the production method are used as black colorants, and phthalocyanine C.I. I. PigmentBl
ue 15-3, an indanthrone C.I. I. Pigm
ent Blue 60 and the like, and quinacridone C.I. I. Pigment Red 122,
Azo-based C.I. I. Pigment Red 22, C.I.
I. Pigment Red 48: 1, C.I. I. Pig
Ment Red 48: 3, C.I. I. Pigment
Red 57: 1, etc., and an azo-based C.I. I. Pigment Yellow 12, C.I. I.
Pigment Yellow 13, C.I. I. Pigm
ent Yellow 14, C.I. I. Pigment
Yellow 17, C.I. I. Pigment Yellow
ow 97, C.I. I. Pigment Yellow 1
55, isoindolinone-based C.I. I. Pigment
Yellow 110, a benzimidazolone C.I.
I. Pigment Yellow 151, C.I. I. P
pigment yellow 154, C.I. I. Pigm
ent Yellow 180, and the like. The colorant content is in the range from 1 part by weight to 20 parts by weight. These colorants can be used alone or in combination of two or more.

Among them, particularly when carbon black is used, the content of polycyclic aromatic hydrocarbons is 15
It is preferable to use carbon black of not more than ppm. More preferably, the polycyclic aromatic hydrocarbon content is 12
ppm or less of carbon black. Such carbon blacks include Regal 330, Rega
l 330R, Vulcan XC-72, Vulcan
XC-72R, Black Pearls L, Bla
ck Pearls 1300, Mogul L (or more,
Cabot Specialty Chemicals, Inc.), Raven 5750, Raven 5250, R
Aven 3500, Raven 780 (all manufactured by Columbia Carbon), Mitsubishi # 0025,
MITSUBISHI # 44 (Mitsubishi Chemical). Polycyclic aromatic hydrocarbons include benzpyrene, anthracene, benzopyrene, phenanthrene, pyrene and the like, which are carcinogenic substances. When carbon black containing these compounds in an amount of 15 ppm or more is used as a colorant for a toner, the charge amount is reduced, and stains in non-image areas and toner scattering are liable to occur.

The releasing agent used in the toner for developing an electrostatic image of the present invention includes known polypropylene wax, polyethylene wax, modified polyolefin wax, higher fatty acid ester, Fischer-Tropsch wax,
Graft polymerized waxes, higher aliphatic alcohols, amide waxes, natural waxes, etc. can be used. Among them, waxes mainly containing higher fatty acid ester compounds and / or aliphatic alcohol compounds and / or Fischer-Tropsch wax are the main components. The release agent is preferable because it has good dispersibility in the polyester resin, and has good release properties and slidability. When these waxes are added to the toner, better hot offset resistance and fixing strength can be obtained as compared with the same amount of polyolefin wax such as polypropylene wax and polyethylene wax.

Further, these waxes not only act as a release agent for preventing the offset phenomenon at the time of heat roll fixing, but also do not adhere to the carrier surface even when printing a large number of sheets for a long time, and are stable to the toner. This makes it possible to print high-quality and high-definition images without generating scattering toner.

The wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component is represented by carnauba wax, montan ester wax, rice wax, scale insect wax, lanolin wax or the following formulas 4 to 8: There are compounds. <General formula 4>

[0065]

Embedded image (R ₁ and R ₂ are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 5>

[0066]

Embedded image (R ₁ , R ₂ and R ₃ are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 6>

[0067]

Embedded image (R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 7>

[0068]

Embedded image (R ₁ is a hydrocarbon group having 12 to 40 carbon atoms. R ₂ is a hydrocarbon group having 1 carbon atom.
~ 40 hydrocarbon groups. Also, a + b = 4, and a is 1
And b represents an integer of 0 to 3. <General formula 8>

[0069]

Embedded image (R ₁ , R ₂ and R ₃ are a hydrocarbon group having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms, and a and c are integers of 0 to 2) And a
+ C = 2. b is an integer of 1 to 4, and d is 1 or 2. Furthermore, e = d-1. Specific examples of the wax represented by the above general formula include the following compounds. <Wax 1>: Specific example of general formula 4

[0070]

Embedded image <Wax 2>: Specific example of general formula 5

[0071]

Embedded image <Wax 3>: Specific example of general formula 6

[0072]

Embedded image <Wax 4>: Specific example of general formula 7

[0073]

Embedded image <Wax 5>: Specific example of general formula 8

[0074]

Embedded image <Wax 6>: Specific example of general formula 8

[0075]

Embedded image

As the carnauba wax, it is preferable to use a carnauba wax that has been freed from fatty acids and whose free fatty acids have been removed by purification. The acid value of the free fatty acid-type carnauba wax is preferably 8 or less, more preferably 5 or less. The free fatty acid type carnauba wax becomes finer crystals than the conventional carnauba wax, and the dispersibility in the polyester resin is improved. The montan-based ester wax is refined from a mineral, and becomes fine crystals like the carnauba wax by the purification, so that the dispersibility in the polyester resin is improved.

The montan ester wax preferably has an acid value of 30 or less. Rice wax is obtained by refining rice bran wax, and has an acid value of 13
The following is preferred.

The scale insect wax can be obtained by dissolving a waxy component secreted by the larva of the scale insect (also known as lobster) in, for example, boiling water, separating the upper layer, cooling and solidifying, or repeating the same. The scale insect wax purified by such a means is white in a solid state, has an extremely sharp melting point, and is suitable as a toner wax in the present invention. The acid value is reduced to 10 or less due to purification, and is preferably 5 or less for toner.

Lanolin wax is obtained by purifying and dehydrating a waxy substance adhering to wool's wool, and preferably has an acid value of 8 or less, more preferably 5 or less.

Examples of the release agent mainly containing an aliphatic alcohol compound include those mainly containing a higher alcohol obtained by an oxidation reaction of paraffin, olefin or the like. Examples of the release agent containing an aliphatic alcohol as a main component include “Unilin 425”, “Unilin 550” (both by Petrolite), “NPS-9210”,
“PARACOL 5070” (Nippon Seiro Co., Ltd.) and the like. Sasol wax (SasolChem. Ltd.) as the Fischer-Tropsch wax
Is suitable.

Sasol wax is characterized by being hard and crystalline wax and having low viscosity relative to the melting point, and is characterized by the fact that Sasol wax H1, H2, H8, C1, C2,
C3, C4, C2N3, fine particle type H1-N6, S
There are PRAY30, SPRAY40, oxidation type sasol waxes A1, A2, A3, A6, A7, A14 and the like, and among them, sasol waxes C1, C
C series such as 2, C3, C4, C2N3, etc. are most suitable and preferred in the present invention.

Of the above specific examples, carnauba wax having an acid value of 8 or less, <i> Wax 4 </ i> which is a tetrabehenyl ester of pentaerythritol is the most preferred wax which can be used in the present invention.

The wax of the present invention has a melting point of 65.
Those in the range of ゜ C to 130 ° C. have a large contribution to the offset resistance and are particularly preferable.

The release agent may be used alone or in combination, and good fixing offset performance can be obtained by adding 0.3 to 15 parts by weight, preferably 1 to 5 parts by weight, to the binder resin. Can be If the amount is less than 0.3 part by weight, the offset resistance is impaired. If the amount is more than 15 parts by weight, the fluidity of the toner is deteriorated. Will be given.

Incidentally, synthetic waxes such as polyamide wax, graft polymerization wax, modified polyolefin wax, polypropylene wax and polyethylene wax can be used in combination with the wax in the present invention.

In the present invention, an optional charge control agent can be used if necessary. The positively chargeable charge control agent used in the present invention is not particularly limited as long as it is a compound that imparts positive chargeability to the toner, but is preferably a triphenylmethane dye, a nigrosine dye, a quaternary ammonium salt, or a quaternary ammonium salt. A resin containing an ammonium group and / or an amino group is preferable. In addition to these compounds being used alone, 2
More than one kind of charge control agent can be used in combination. Examples of the positive charge control agent include the following products, but are not limited to the examples.

Examples of triphenylmethane dyes include “OIL BLUE” (Orient Chemical Co., Ltd.),
"Copy Blue PR" (Clariant Co., Ltd.)
And the like.

Examples of the nigrosine dye include “NIGRO”.
SINE BASE EX ”,“ OIL BLACK ”
BS "," BONTORON N-01 "," BONT
ORON N-04 "," BONTORON N-0 "
7 "," BONTORON N-21 "(all Orient Chemical Co., Ltd.) and the like.

As the quaternary ammonium salt compound, “B
ONTORON P-51 "(Orient Chemical Co., Ltd.)," TP-302 "," TP-610 "," T
P-415 "(above, Hodogaya Chemical Co., Ltd.) and the like. Examples of the resin containing a quaternary ammonium group and / or an amino group include “FCA-201-PS” (Fujikura Kasei Co., Ltd.).

The quaternary ammonium salt compound is particularly preferably at least one selected from the following formulas 1, 2 and 3. The compound of the general formula 1 includes Bontron P-51; (manufactured by Orient Chemical), and the compound of the general formula 2 includes TP-302, TP-415, and TP.
-610; (made by Hodogaya Chemical). <General formula 1>

[0091]

Embedded image [Wherein, R _{1 to} R ₃ represent a CnH2n + 1 group. Where n
Represents an integer of 1 to 10. Further, R _{1 to} R ₃ may be the same or different. <General formula 2>

[0092]

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 22 carbon atoms, an unsubstituted or substituted aromatic group having 1 to 20 carbon atoms, Represents an aralkyl group having 7 to 20 carbon atoms, A ^- is a molybdate anion or a tungstate anion,
Represents a heteropolyacid anion containing molybdenum or tungsten atoms. ] <General formula 3>

[0093]

Embedded image Wherein m represents 1, 2 or 3, and n represents 0, 1
Or 2, and M is a hydrogen atom or a monovalent metal ion. X and Z each represent 1 or 2, and Y represents 0 or 1. Further, when X = 1, Y = 1 and Z = 1, and when X = 2, Y = 0 and Z = 2. R _{5 to} R ₁₂ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, an alkoxylene group having 1 to 4 carbon atoms, or a general formula (-C 2-5 alkylene-O ) N-R
(Where R is hydrogen or an alkyl group or acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), wherein R ₁ , R ₂ ,
R ₃ and R ₄ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, or a general formula (—CH ₂ —CH ₂ —O) n—R (however, R is hydrogen or an alkyl group or an acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), an oxyethyl group represented by the formula: and a mononuclear or polynuclear alicyclic group having 5 to 12 carbon atoms. Residue, mononuclear or polynuclear aromatic residue or araliphatic residue. More specifically, there are the following compounds. (1-1)

[0094]

Embedded image (2-1)

[0095]

Embedded image (2-2)

[0096]

Embedded image (2-3)

[0097]

Embedded image (2-4)

[0098]

Embedded image (2-5)

[0099]

Embedded image (2-6)

[0100]

Embedded image (2-7)

[0101]

Embedded image (2-8)

[0102]

Embedded image (2-9)

[0103]

Embedded image (2-10)

[0104]

Embedded image (2-11)

[0105]

Embedded image (3-1)

[0106]

Embedded image (3-2)

[0107]

Embedded image The charge control agents exemplified above may be used in combination of two or more. For example, when a nigrosine dye and a quaternary ammonium salt compound are used in combination, the use ratio is preferably 1/9 to 9/1, and more preferably 2/8 to 8/2. Nigrosine dyes have a high positive charge imparting ability,
The quaternary ammonium salt compound is excellent in charging uniformity and stability. By using both of them, a clear printed image without fog can be stably obtained during continuous printing. The volatile amine content remaining in the toner of the present invention is 150 ppm
The following is preferred. The volatile amine content is not limited to 0 ppm as much as possible in order to maximize the technical effect of the present invention, but is usually set to more than 0 and 150 ppm or less. More preferably, it is more than 0 and 100 ppm or less. If the amount is more than 150 ppm, background staining (toner adhesion to a white background) during continuous copying is likely to occur.
In addition, volatile chemical substances generated at the time of copying and using a printer need to be controlled and managed from the viewpoint of toxicity, odor problem, etc., and remain in the toner due to such environmental considerations. 150 pp volatile amine content
m or less is preferable.

Although there are various causes of the generation of the volatile amine component, a positively chargeable charge controlling agent having a quaternary ammonium salt structure which originally contains a volatile amine or generates a volatile amine by thermal decomposition is mainly used. Source. Therefore, as a means for keeping the content of the volatile amine remaining in the toner within the above range, a content of the volatile amine component is small, or a quaternary ammonium salt structure which does not generate a volatile amine due to thermal decomposition or the like. It is effective to use a positively-chargeable charge control agent having the above or the following forced degassing treatment.

As an example of the forced deaeration treatment, removal of a volatile amine component at the time of melt-kneading the toner may be mentioned. In particular, prior to mixing and melt-kneading the raw materials of the toner, a charge control agent is blended in the binder resin so as to have a high concentration, and the mixture is dispersed and preliminarily kneaded (generally referred to as master batch processing). Performing forced degassing at the time of the above step) is extremely effective in reducing volatile amine components.

In the present invention, as the quaternary ammonium salt compound, (1-1) and (2-
The compounds of 1), (3-1) and (3-2) can be suitably used. However, when the compound of (1-1) is used, tributylamine may be generated by thermal decomposition. It is necessary to minimize the content by forced deaeration.

In the present invention, a nigrosine-based charge control agent can be suitably used, but in this case, it is also preferable to use a volatile amine having a lower content or not containing the same component. The volatile amine in the nigrosine-based charge control agent includes aniline. When aniline is contained, forcible deaeration is effective as a method for reducing the amount of volatile amine in the quaternary ammonium salt compound as described above. The aniline content in the toner of the present invention is 10 p.
pm or less. If it is more than this, an odor will be felt, and fog and toner scattering will easily occur.

Further, it has already been described that the compound (2-1) is an example of a quaternary ammonium salt which can be suitably used in the present invention. When the compound is used, the content in the toner is reduced. It is desirable that the content be 5000 mg / kg or less in terms of molybdenum atoms.
More preferably, it is not more than 00 mg / kg. 5000
At mg / kg or more, fogging and toner scattering tend to occur, and it is not desirable that molybdenum is contained in a large amount in toner because it is a heavy metal.

The negatively chargeable charge control agent used in the present invention is not particularly limited as long as it is a compound that imparts negative chargeability to the toner. Examples of the azo metal complex (salt) and salicylic acid metal complex ( Salts), benzyl acid metal complexes (salts), tetraphenyl metal complexes (salts), calixarene-type phenol condensates, cyclic polysaccharides, and resin-based charge control agents.

Examples of the azo metal complex (salt) include “BON
TORON S-34 "," BONTORON S-4 "
4 "(all Orient Chemical Co., Ltd.) and the like.
As salicylic acid-based metal complexes, "BONTORON"
E-81 "," BONTORON E-84 "," BO
NTORON E-88 "(orient Chemical Co., Ltd.) and the like. Examples of the benzyl acid metal complex include “LR-147” and “LR-297” (Nippon Carlit Co., Ltd.). Examples of the tetraphenyl-based metal complex include “COPY CHARGE NX” (Clariant Co., Ltd.). Examples of calixarene-type compounds include “BONTORON E-89” and “B
ONTORON F-21 "(orient Orient Chemical Co., Ltd.). Examples of the cyclic polysaccharide include "COPY CHARGE NCA" (Clariant Co., Ltd.). As a resin-based charge control agent,
“FCA-1001-NS” (Fujikura Kasei Co., Ltd.), “C
OPY LEVEL NCS ”(Clariant Co., Ltd.)
And the like. Further, although the structure is not clear, "TN-105" manufactured by Hodogaya Chemical can also be suitably used as a colorless negative charge control agent.

The content of the charge control agent is determined by the binder resin 10
It is preferably used in an amount of 0.3 to 10 parts by weight, more preferably 1 to 5 parts by weight, per 0 parts by weight.

The toner for developing an electrostatic image according to the present invention comprises:
A binder resin comprising a polyester resin as described above,
Although a coloring agent, a release agent, and a charge control agent are constituted as essential components, other additives may be included.

For example, lubricants such as metal soap and zinc stearate can be used, and cerium oxide, silicon carbide and the like can be used as abrasives. When a part or all of the colorant is replaced with magnetic powder, it can be used as a magnetic one-component developing toner. As the magnetic powder, a ferromagnetic metal such as iron, cobalt, and nickel, or a powder of an alloy or a compound such as magnetite, hematite, or ferrite is used. As these magnetic powders, those subjected to a hydrophobic treatment with an organic silicon or a titanium compound or the like, if necessary, are preferably used. The content of the magnetic powder is preferably 15 to 70% by weight based on the weight of the toner.

The toner of the present invention can be obtained by an extremely general manufacturing method regardless of a specific manufacturing method.
For example, it can be obtained by melt-kneading a resin, a colorant, and a charge control agent at a temperature equal to or higher than the melting point (softening point) of the resin, and then pulverizing and classifying.

Specifically, for example, the above resins, colorants,
Prior to melt-kneading, the mixture is uniformly mixed in advance with a Henschel mixer or the like before using a release agent and a charge control agent as essential components. The conditions for the mixing are not particularly limited, but the mixing may be performed in several stages so as to obtain a desired uniformity. The coloring agent and / or the charge control agent used here may be previously subjected to a flushing treatment so as to be uniformly dispersed in the resin, or a master batch melt-kneaded with the resin at a high concentration.

The above mixture is mixed by a kneading means such as a two-roll, three-roll, pressure kneader or a twin-screw extruder. At this time, the colorant and the like may be uniformly dispersed in the resin, and the conditions for the melt-kneading are not particularly limited, but are usually 80 to 180 ° C. for 30 seconds to 2 hours. The kneaded material is usually cooled by a cooling belt, a roller, or the like, but since the dispersion state of the release agent changes depending on the cooling conditions, the cooling conditions can be set so as to obtain a desired dispersion state.

If necessary, coarse pulverization is performed for the purpose of reducing the load in the fine pulverization step and improving the pulverization efficiency. The apparatus and conditions used for the coarse pulverization are not particularly limited, but the coarse pulverization is generally performed using a rotoplex, a pulperizer, or the like to a particle size of 3 mm mesh pass or less.

Next, fine pulverization is performed by a mechanical pulverizer such as a turbo mill or a kryptron, or an air pulverizer such as a spiral jet mill, a counter jet mill, or an impingement plate jet mill, and the resulting mixture is classified by an air classifier or the like. No. Fine grinding and classification equipment, conditions are the desired particle size,
What is necessary is just to select and set it so that it may become a particle size distribution and a particle shape.

The volume average particle diameter of the particles constituting the toner is:
Although not particularly limited, it is usually adjusted to be 5 to 15 μm.

Usually, an external additive is mixed with the thus obtained toner using a mixer such as a Henschel mixer.

In the present invention, various additives (referred to as external additives) can be used for modifying the surface of the toner such as improving the fluidity of the toner and improving the charging characteristics. As the external additive that can be used in the present invention, for example, inorganic fine powders such as silicon dioxide, titanium oxide, and alumina and those obtained by surface-treating them with a hydrophobizing agent such as silicone oil, resin fine powders, and the like are used. .

Among these, hydrophobic silica obtained by surface-treating silicon dioxide with various polyorganosiloxanes, silane coupling agents and the like is preferably used as an external additive.

[0127] Specifically, there is one commercially available under the following trade names. AEROSIL; R972, R974, R202, R8
05, R812, RX200, RY200, R80
9, RX50, RA200HS, RA200H [Nippon Aerosil Co., Ltd.] WORKER; HDK H2000, H2050, H3
050, HVK2150 [Wacker Chemicals Co., Ltd.], Nipsil; SS-10, SS-15, SS-20,
SS-50, SS-60, SS-100, SS-50
B, SS-50F, SS-10F, SS-40, SS-
70, SS-72F, [Nippon Silica Industry Co., Ltd.], CABOSIL; TS-500, TS-530, TS-
610, TS-720, TG-308F, TG-709
F, TG-810G, TG-811F, TG820F
[Cabot Specialty Chemicals, Inc.].

The titanium oxide may be a hydrophilic grade or a hydrophobic grade surface-treated with octylsilane or the like. For example, there is one that is commercially available under the following trade names. Titanium oxide T
805 (Degussa Co., Ltd.), titanium oxide P25 (Nippon Aerosil Co., Ltd.) and the like.

Examples of the alumina include aluminum oxide C (Degussa Co., Ltd.).

Among the above examples, the bulk density is 100 g /
Liter or less, BET surface area is 100-250m
^It is preferable to use hydrophobic silica having a bulk density of not more than 80 g / liter and a BET surface area of 12 / g.
Hydrophobic silica of 0 to 230 m ² / g is more preferred. Further, hydrophobic silica surface-treated with hexamethyldisilazane, aminosilane and / or cyclic silazane is most preferred.

Hydrophobic silica having a bulk density of 100 g / l or more or a BET surface area of 100 m ² / g or less is
When used as the toner for a two-component developer intended in the present invention, it does not show good fluidity during high-speed printing, particularly at high speeds of more than 20 m / min, and even more than 30 m / min. Therefore, at the time of toner replenishment, the toner does not quickly mix with the carrier, cannot reach a predetermined charge amount quickly, and causes background contamination and toner scattering. In addition, the print image becomes a blurred and unclear print image around the image.

In order to prevent this, it is necessary to externally add a large amount of silica. If this is done, the fluidity is certainly improved, and high-quality and high-quality images can be obtained even in high-speed printing. By externally adding a large amount, silica easily adheres to the photoreceptor, and in the worst case, the silica adhering to the photoreceptor agglomerates into a film to cause image defects.

Further, since a large amount of silica is adhered to the toner surface to cover the toner surface, it is difficult to fuse the toner particles at the time of heat roll fixing, thereby deteriorating the fixability.

In the present invention, the bulk density is 100 g / liter, and the BET surface area is 100 to 250 m ² / g.
By using the hydrophobic silica, a sufficient fluidity can be imparted to the toner with a small amount of addition, so that filming on the photoreceptor does not occur and fixability is not impaired.

In the present invention, as apparent from the above description, by using the hydrophobic silica having the above-mentioned physical properties, the toner can maintain sufficient fluidity even at high speed printing, and a good rise of charge can be obtained even when replenishing the toner. And a high-quality and high-quality print image without fog or toner scattering can be obtained.

The above characteristics are most remarkably exhibited in hydrophobic silica using hexamethyldisilazane, aminosilane and / or cyclic silazane as a surface treating agent. Examples of such hydrophobic silica include RA-200HS (Nippon Aerosil Co., Ltd.) and TG-820F (Cabot.
Specialty Chemicals, Inc.).

The particle diameter of these external additives is preferably 1/3 or less of the diameter of the toner, particularly preferably 1/1.
0 or less. Further, these external additives may be used in combination of two or more kinds having different average particle diameters. The use ratio of silica is usually 0.05 to 5% by weight, and preferably 0.1 to 3% by weight, based on the toner.

When the electrostatic image developing toner of the present invention is used in a two-component developing system, the following carriers can be used. The core material of the carrier can be iron powder, magnetite, ferrite, etc. used in a normal two-component developing method, but among others, the true specific gravity is low, and the resistance is high.
Ferrite or magnetite which is excellent in environmental stability and easy to form into a sphere and has good fluidity is preferably used. The shape of the core agent can be used without any particular problem, such as spherical or amorphous. The average particle size is generally 10 to 500 μm, but is preferably 30 to 80 μm for printing a high-resolution image.

Examples of the coating resin for covering these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, and vinyl chloride. / Vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin comprising organosiloxane bond or its modified product, fluororesin, (meth) acrylic resin, polyester, polyurethane, polycarbonate, phenolic resin, amino resin, melamine resin , Benzoguanamine resin, urea resin, amide resin, epoxy resin, acrylic polyol resin and the like can be used. Among these,
In particular, silicone resins, fluororesins, and (meth) acrylic resins are excellent in charge stability, coating strength, and the like, and can be more preferably used. That is, the resin-coated carrier used in the present invention is:
It is preferable that the magnetic carrier is a resin-coated magnetic carrier that uses ferrite or magnetite as a core agent and is coated with at least one resin selected from silicone resins, fluororesins, and (meth) acrylic resins.

The toner for developing an electrostatic image of the present invention is 20 m
/ Min or more, more preferably 30 m / min or more in a high-speed machine for forming an image with a heat roll fixing speed of 30 m / min or more. Even so, sufficient low-temperature fixability and hot offset resistance can be obtained.

[0141]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. In the following, numerical values in the composition table represent "parts by weight".

The measurement with a constant load extrusion type capillary rheometer was performed using a piston cross-sectional area of 1 cm 2 and a cylinder pressure of 0.98.
MPa, die length 1 mm, die hole diameter 1 mm, measurement start temperature 50 ° C., heating rate 6 ° C./min, sample weight 1.5 g
Was performed under the following conditions.

An example of the synthesis of the binder resin used in preparing the toner first is shown below. Note that the polyester resin obtained in each of the synthesis examples was replaced with tetrahydrofuran (T
HF), and the molecular weight of the THF-soluble component obtained by filtration was measured. For the analysis, the molecular weight was calculated from a calibration curve prepared with standard polystyrene using a gel permeation chromatography (GPC) method.

(Synthesis of linear polyester A-1) Terephthalic acid: 664 parts by weight Ethylene glycol: 150 parts by weight Polyoxyethylene- (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 632 parts by weight

The above materials were placed in a two-liter four-necked flask equipped with a stirrer, a condenser and a thermometer. Under a nitrogen gas stream, 4 parts by weight of tetrabutyl titanate was added, and water produced by dehydration condensation was removed. While 240
The reaction was carried out at normal pressure for 15 hours at ゜ C. Thereafter, the pressure was sequentially reduced, and the reaction was continued at 5 mmHg. Reaction is ASTM E28
The reaction was followed by a softening point according to -517, and the reaction was terminated when the softening point reached 85 ° C. As for the molecular weight of the obtained polyester, the weight average molecular weight was Mw, and the number average molecular weight was Mn.
Mw: 4500, Mw / Mn: 2.1, Ts: 62 ° C., Tfb: 69 ° C., T1 / 2: 8
3 ° C, Tend: 88 ° C, acid value 4, and Tg by DSC measurement were 47 ° C.

(Synthesis of linear polyester A-2) Terephthalic acid: 664 parts by weight Polyoxypropylene- (2.2) -2.2-bis (4-hydroxyphenyl) propane: 688 parts by weight Ethylene Glycol: 150 parts by weight

Using the above materials, a linear polyester A-
As a result of performing synthesis in the same manner as in Example 1, the molecular weight was Mw: 860.
0, Mw / Mn: 2.8, Ts: 73 ° C, Tfb: 8
3 ° C, T1 / 2: 95 ° C, Tend: 102 ° C,
A polyester resin having an acid value of 9.8 and a Tg of 59 ° C. was obtained.

(Synthesis of Crosslinked Polyester A-3) Terephthalic acid: 332 parts by weight Isophthalic acid: 332 parts by weight Polyoxypropylene- (2.2) -2.2-bis (4-hydroxyphenyl) propane: 460 parts by weight polyoxyethylene- (2.2) -2.2-bis (4
-Hydroxyphenyl) propane: 210 parts by weight-Ethylene glycol: 130 parts by weight-Glycerin: 30 parts by weight

Using the above materials, a linear polyester A
As a result of synthesizing in the same manner as -1, the molecular weight was Mw: 15
000, Mw / Mn: 3.8, Ts: 79 ° C, Tf
b: 95 ° C, T1 / 2: 119 ° C, Tend: 12
A polyester resin having a temperature of 9 ° C, an acid value of 3.5 and a Tg of 65.0 was obtained.

(Synthesis of Crosslinked Polyester B-1) Terephthalic acid: 664 parts by weight Ethylene glycol: 150 parts by weight Neopentyl glycol: 166 parts by weight Trimethylolpropane: 80 parts by weight

The above materials were placed in a two-liter four-necked flask equipped with a stirrer, a condenser, and a thermometer, and 4 parts by weight of tetrabutyl titanate was added under a stream of nitrogen gas to remove water generated by dehydration condensation. While 240
The reaction was performed at normal pressure for 10 hours at ゜ C. Thereafter, the pressure was sequentially reduced, and the reaction was continued at 5 mmHg. Reaction is ASTM E28
Tracking was performed using a softening point according to −517, and the softening point was 145.
When the temperature reached ゜ C, the reaction was terminated. The crosslinked polyester thus obtained has a THF-insoluble content of 0.3%, a molecular weight of a THF-soluble content of Mw: 155000, Mw / Mn: 30.3, Ts: 74 ° C., Tfb: 106 ° C., T1 / 2:
141 ° C., Tend: 152 ° C., acid value 3.3, D
Tg by SC measurement was 61 ° C. For the THF-insoluble matter, take 1 g of the synthesized resin powder on a special filter paper, and add THF
Was refluxed for 8 hours in a Soxhlet type reflux apparatus as a solvent.

(Synthesis of Crosslinked Polyester B-2) Terephthalic acid: 498 parts by weight Isophthalic acid: 166 parts by weight Polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane: 550 parts by weight ・ Ethylene glycol: 150 parts by weight ・ Trimethylolpropane: 80 parts by weight

Using the above materials, a crosslinked polyester B-
As a result of performing synthesis in the same manner as in Example 1, the THF insoluble content was 0.7
%, The molecular weight of the THF-soluble component is Mw: 222000, M
w / Mn: 38.8, Ts: 83 ° C., Tfb:
117 ° C, T1 / 2: 160 ° C, Tend: 175
A polyester resin having a ΔC of 4.9, an acid value of 4.9, and a Tg by DSC measurement of 64 ° C. was obtained.

(Synthesis of Crosslinked Polyester B-3) Terephthalic acid: 332 parts by weight Isophthalic acid: 266 parts by weight Trimellitic acid: 115 parts by weight Polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane: 688 parts by weight ・ Ethylene glycol: 150 parts by weight

Using the above materials, a crosslinked polyester B-
As a result of performing synthesis in the same manner as in Example 1, the unnecessary portion of THF was 9.8.
%, The molecular weight of the THF-soluble component is Mw: 114000, M
w / Mn: 40, Ts: 81 ° C., Tfb: 12
A polyester resin having 0 ° C, T1 / 2: 165 ° C, Tend: 178 ° C, acid value 10.8, and Tg: 63 ° C was obtained.

(Synthesis of Crosslinked Polyester B-4) Terephthalic acid: 332 parts by weight Isophthalic acid: 232 parts by weight Trimellitic acid: 154 parts by weight Polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane: 688 parts by weight ・ Ethylene glycol: 150 parts by weight

Using the above materials, a crosslinked polyester B-
As a result of performing synthesis in the same manner as in Example 1, the THF insoluble content was 37%,
The molecular weight of the THF-soluble component is Mw: 82,500, Mw / M
n: 19.1, Ts: 87 ° C., Tfb: 138
{C, T1 / 2: 198 ° C, Tend: 217 ° C,
A polyester resin having an acid value of 14.1 and a Tg by DSC measurement of 59 ° C was obtained.

(Synthesis of Crosslinked Polyester B-5) Terephthalic acid: 332 parts by weight Isophthalic acid: 332 parts by weight Polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane: 550 parts by weight ・ Ethylene glycol: 185 parts by weight ・ Trimethylolpropane: 65 parts by weight

Using the above materials, a crosslinked polyester B-
As a result of performing synthesis in the same manner as in Example 1, the THF insoluble content was 0.3
%, The molecular weight of the THF-soluble component is Mw: 85900, Mw
/ Mn: 27.4, Ts: 70 ° C, Tfb: 1
01 ° C, T1 / 2: 128 ° C, Tend: 136 ° C, acid value: 6.4, Tg by DSC measurement: 59.8
A polyester resin of ΔC was obtained.

(Synthesis of Crosslinked Polyester B-6) Terephthalic acid: 664 parts by weight Polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane: 660 parts by weight Ethylene glycol: 125 parts by weight Trimethylolpropane: 80 parts by weight

Using the above materials, a crosslinked polyester B-
As a result of performing synthesis in the same manner as in Example 1, the THF insoluble content was 0.3
%, The molecular weight of the THF-soluble component is Mw: 172000, M
w / Mn: 31.4, Ts: 78 ° C., Tfb:
136 ° C, T1 / 2: 157 ° C, Tend: 168
ΔC, acid value: 5.2, Tg by DSC measurement: 65.
A polyester resin at 0 ° C. was obtained.

(Example 1) <Production of toner> Linear polyester A-1: 18 parts by weight Crosslinked polyester B-1: 72 parts by weight Carbon black Black Pearls 460 (manufactured by Cabot Specialty Chemicals, Inc.) ): 5 parts by weight * Polycyclic aromatic hydrocarbon content: 12 ppm or less -Charge control agent (positive charge control agent) Bontron N-04 (Orient Chemical Industry Co., Ltd.)
2 parts by weight Wax Purified carnauba wax No. 1 (acid value 5, Seralica NO
DA Co.): 3 parts by weight The above materials are mixed with a Henschel mixer and kneaded with a twin-screw kneader. The kneaded material thus obtained was pulverized and classified to obtain a toner base having a volume average particle diameter of 10.1 μm. 100 parts by weight of the obtained toner base material and silica HDK3050E
After mixing 1 part by weight of P (Waker Chemicals Co., Ltd.) with a Henschel mixer, the mixture was sieved to obtain a toner a.

In the same manner, toners a (Example 1) to m (Example 13) and y (Comparative Example 1) to bb (Comparative Example 4) were obtained by blending Tables 1-1 and 1-2. Was.

<Forcible deaeration treatment charge control agent (treatment CCA)
Production> Mix the formulations in Table 2 with a Henschel mixer,
The mixture was subjected to a mixing treatment at a resin temperature of about 200 ° C. for one hour while forcible deaeration was carried out in a 3 L capacity heating kneader open system. Thereafter, the temperature was lowered to a resin temperature of about 120 ° C., the mixture was further mixed for 30 minutes, and then taken out. After cooling, the mixture was crushed with a rotoplex to a particle diameter of about 2 mm or less. 1)) to (Processed CCA (4)) were obtained.

Using this, in the same manner as in Example 1, the toners n (Example 14) to x
(Example 24) and cc (Comparative Example 5) were produced. Except for Examples 21 and 24, the coloring agent used was Black Pearls 460; 5 parts by weight. In Example 21, 5 parts by weight of carbon black having a polycyclic aromatic hydrocarbon content of 15 ppm was used. Further, in Example 24, a magnetic powder (B
L-200; manufactured by Titanium Industry Co., Ltd.).

<Adjustment of developer> Table 1-1 and Table 1-
As shown in FIG. 2, 3 parts by weight of the toner and 97 parts by weight of a carrier (silicone resin-coated ferrite carrier) were mixed and stirred to prepare developers (a + x) to (cc + x).
The toner of Example 24 was used as a magnetic one-component developer without mixing with the carrier.

[0167]

[Table 1]

[Table 2]

[Table 3]

In Tables 1-1, 1-2, and 2, carnauba wax; purified carnauba wax No. 1 (acid value 5, manufactured by Celarica NODA Co., Ltd.) NPS-9210; higher aliphatic alcohol ( Nippon Seiro Co., Ltd.
・ Viscol 550P; polypropylene wax (manufactured by Sanyo Chemical Co., Ltd.) ・ Sasol H-1; Fischer-Tropsch wax (manufactured by Sasol) ・ Wax 4; the above chemical formula <wax 4> ・ N-04; Bontron N- 04 (Orient Chemical Industry Co., Ltd.)
E-84; Bontron E-84 (a metal complex of salicylic acid manufactured by Orient Chemical Co., Ltd.) P-51; Bontron P-51 (a quaternary ammonium salt manufactured by Orient Chemical Co., Ltd. (of chemical formula (1-1)) Compound)) ・ TP-415; quaternary ammonium salt (compound of chemical formula (2-1)) manufactured by Hodogaya Chemical Industry Co., Ltd. ・ HDK3050EP; hydrophobic silica manufactured by Wacker Chemicals Co., Ltd. Surface treatment agent: amino silicon oil, bulk density 115 g / l, BET surface area of ^{130m 2 / g · RA-200HS} ; manufactured by Nippon Aerosil Co., Ltd. hydrophobic silica surface treating agent: hexamethyldisilazane and aminosilane, bulk density 40 g / l, BET surface area of 140 m ² / g · TG-820F; hydrophobic silica manufactured by Cabot Specialty Chemicals, Inc. Surface treatment agent: cyclic silazane, bulk density 40 g / l, BET surface area 210 m ² / g, carrier x; silicone resin-coated ferrite Light carrier ・ Carrier y; Acrylic polyol resin-coated ferrite carrier ・ * 1: Carbon black having a polycyclic aromatic hydrocarbon content of 15 PPM or more.

With respect to the toners obtained in the above Examples and Comparative Examples, the viscosity characteristics were measured by a constant load extrusion type capillary rheometer, and the glass transition point was measured by a DSC measurement method.
Further, the apparent density was measured as an index of the fluidity of the toner. The higher the apparent density, the better the fluidity of the toner. The apparent density was measured by the following procedure using a Kasa specific gravity measuring device manufactured by Kuramochi Scientific Instruments.

The toner having passed through a sieve having an opening of 0.5 mm was passed through a funnel having an angle of 40 ° C., and had an inner diameter of 22 mm.
It is gently dropped into a container having a depth of 80 mm and a volume of 30 cm ³ . When the toner overflows from the container, the container is allowed to stand for 30 seconds. In the meantime, when the toner sinks into the container and the upper surface of the toner becomes lower than the upper end of the container, the toner is further poured by the above method. When the toner overflows again from the container, the portion raised from the upper surface of the container is scraped off so as to be flush with the upper surface of the container. Finally, the toner remaining in the container was weighed and determined by dividing by the volume of the container. Table 3 shows the measurement results.

Table 3 also shows the measured values and calculated values of the contents of aniline, tributylamine, molybdenum, and polycyclic aromatic hydrocarbon in each toner. The content of aniline and tributylamine in the toner is determined by gas chromatography
ad Space Analysis method (150 ° C., 60
Min). The molybdenum and polycyclic aromatic hydrocarbon contents are calculated values from the amount of the molybdenum-containing charge control agent and the polycyclic aromatic hydrocarbon content in carbon black, respectively.

[0172]

[Table 4] Measurement conditions of the constant load extrusion type capillary rheometer: ・ Piston cross-sectional area 1cm2 ・ Cylinder pressure 0.98MPa ・ Die length 1mm, die hole diameter 1mm ・ Measurement start temperature 50 ° C ・ Heating rate 6 ° C / min, () Inside is a heating rate of 10 ° C /
Measured value in min. The measurement was performed under the condition of a sample weight of 1.5 g. TBA; tributylamine Mo; molybdenum

(Offset generation temperature) Except for Examples 6 and 24, a commercial laser beam printer (with a selenium photoreceptor) was used to modify A4 paper with a width of 2 cm and a length of 2
A 0 cm strip-shaped unfixed image sample was prepared, and the presence or absence of the hot offset phenomenon was confirmed using a heat roll fixing unit having the following specifications. In Example 6, a similar unfixed image sample was prepared using a commercially available laser beam printer (OPC photoconductor) remodeling machine and evaluated. Example 2
4 using a commercially available magnetic one-component printer modified machine,
A similar unfixed image sample was prepared and evaluated.

[0174]

[Table 5]

The offset start temperature was a temperature at which the offset phenomenon was visually observed by observing the fixed image sample.

(Peel-Fixing Strength) An unfixed image similar to that in the anti-offset test was obtained with the above-mentioned modified commercial copying machine. This was fixed under the condition 2 in Table 4 while changing the fixing temperature. Mending tape (Sumitomo 3M, 81
0) was adhered at a constant pressure, and then peeled at a constant speed from a constant direction. The peel fixing strength was determined based on the image density remaining ratio calculated by the following equation. The image density was measured by Macbeth image densitometer RD-918. Peeling fixation test residual ratio = image density after peeling test / image density before peeling test The peeling fixing strength was set to a level at which the residual ratio was 80% or more and had no practical problem, and the lowest temperature was the peeling fixing starting temperature.

(Rubbing Fixing Strength) Using a fixed image fixed in the same manner as in the peel fixing strength test, a Gakushin type friction fastness tester (friction element: Whatman filter paper No. 42, load: 500)
g, rubbing operation: 20 strokes). The rub fixing strength was determined by an image density remaining ratio calculated by the following equation. The image density was measured by Macbeth image densitometer RD-918. Rub-fixing strength test residual ratio = image density after rubbing test / image density before rubbing test The rubbing-fixing strength was set to a level at which there was no practical problem at a residual ratio of 80% or more, and the lowest temperature was the rub-fixing start temperature. Table 5 shows the above evaluation results.

[0178]

[Table 6]

(Printing Test) The printing quality of continuous printing was evaluated using a commercially available laser beam printer (with a selenium photosensitive member), and the charge amount of the developer was measured. In Example 6, the same evaluation was performed using a commercially available printer (OPC photoconductor).

The charge amount was measured by a blow-off charge amount measuring device. The image density was measured with a Macbeth densitometer RD-918, and the background stain was determined by subtracting the white paper density before printing from the white background density. Replenishment of toner during continuous printing was performed automatically during continuous printing by filling the toner after silica addition into a replenishing toner hopper of the machine.

The toner of Example 24 was tested by modifying a commercially available magnetic one-component developing printer. Regarding the charge amount, a toner is collected from the inside of the developing device for each number of printed sheets, a developer is prepared with toner / carrier (silicone resin-coated ferrite carrier) = 5/95 (weight ratio), and another two-component developer is prepared. It measured similarly to.

(Toner Scattering Amount) After printing 50KP (50,000 sheets) and after printing 100KP (100,000 sheets), the inside of the machine was observed. , A case where slight dirt occurred, and a case x when severe dirt occurred. (Photoreceptor filming) The surface of the photoreceptor after printing at 100 KP (100,000 sheets) was observed, and the case where no filming of silica was recognized on the surface of the photoreceptor was evaluated as ○, and the case where slight adhesion occurred was evaluated as △. . Table 6-1 and Table 6-
It is shown in FIG.

[0183]

[Table 7]

[0184]

[Table 8]

The description of each item in Table 6-1 and Table 6-2 is as follows. * Comparative Example 1 was canceled because a hot offset occurred from the beginning. * “Charge amount”; μC / g * “Evaluation of background contamination” ○: less than 0.01, Δ: 0.01 to less than 0.03,
×: 0.03 or more * “Toner scattering”; after printing 50 KP (50,000 sheets) and 10
Visual observation after printing 0KP (100,000 sheets) ○: Almost no scattering △: Slight scattering caused dirt ×: Vigorous scattering occurred

As is clear from Table 3, Table 5, Table 6-1 and Table 6-2, the outflow starting temperature is 70 to 105 ° C.
A toner having an outflow end temperature of 120 to 144 ° C. has both low-temperature fixing property and hot offset resistance, and exhibits excellent fixing strength, particularly in a high-speed electrostatic image developing apparatus having a fixing speed exceeding 20 m / min. I do. In Comparative Example 1, the outflow end temperature was lower than the range specified in the present invention. Although this toner is excellent in fixing strength and cold offset resistance, hot offset resistance is greatly reduced.

On the other hand, in Comparative Example 3, the outflow starting temperature was higher than the range specified in the present invention. Although this toner is excellent in hot offset resistance and toughness, cold offset resistance and fixing strength are reduced. In particular, when fixing is performed at high speed, a high fixing temperature is required.

As the release agent, a conventionally known release agent can provide sufficient performance. Among them, a toner using a release agent containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component is particularly fast. In the apparatus in which fixing is performed, the image and paper after fixing are excellent in releasability from the sharp melt property, and the contribution to hot offset resistance is large. In addition, when these release agents are used, the friction coefficient of the fixed image surface is reduced and the abrasion resistance is improved, so that even when the paper is conveyed at a high speed, the color transfer to the member and the abrasion of the image are prevented. Less, and good print quality can be maintained. Similar effects were obtained when using Fischer-Tropsch wax.

[0189] Observation with a microscope shows that these release agents have good dispersibility in the polyester resin, and the scattering of toner due to poor dispersion is reduced.

[0190]

As described in detail above, the toner for developing an electrostatic image of the present invention has good fixing characteristics in a wider temperature range, particularly in applications where development and fixing are performed at high speeds. It has offset resistance and is excellent in abrasion resistance and peeling resistance of a fixed image. In addition, it has a sufficient mechanical strength to withstand friction with the carrier in the developing device, and does not generate spent carrier and toner scattering, and can stably obtain a high-density and high-quality printed image without fog. Can

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing a structure of a cylinder portion of a constant load extrusion type thin tube rheometer.

FIG. 2 is an example of a flow curve obtained by a heating method.

[Description of Signs] 1 Piston 2 Cylinder 3 Heater 4 Die 5 Die presser 6 Sample

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) G03G 9/113 G03G 9/08 361 15/20 101 9/10 351 352 354 (72) Inventor Shinji Amagaya Saitama 1-4-1 Minamiurawa, Urawa-shi, Prefecture F-term (reference) 2H005 AA01 AA02 AA06 AA08 BA06 CA08 CA11 CA12 CA14 CA17 CA22 CA28 CB18 DA01 DA03 EA03 EA06 FA01 2H033 AA20 BA11 BA58 CA36

Claims (19)

[Claims] 1. A toner comprising a polyester resin, a colorant and a release agent, wherein the toner has an outflow starting temperature Tfb of 7 by a constant load extrusion type capillary rheometer.
0 ° C to 105 ° C, end flow temperature Tend is 120 ° C to 14 ° C
A toner for developing electrostatic images, wherein the temperature is 4 ° C. 2. The method according to claim 1, wherein the polyester resin is (A) T1 / 2 by a constant load extrusion type capillary rheometer.
Is 70 ° C. to 130 ° C., and the glass transition point Tg is 45 ° C.
First resin having a linear or cross-linked structure at -75 ° C. (B) T1 / 2 by constant load extrusion type capillary rheometer
Is 130 ° C. to 210 ° C., and the glass transition point Tg is 45.
2. The electrostatic image developing toner according to claim 1, wherein the toner is a mixture of a second resin having a crosslinked structure at a temperature of from 75 to 75 [deg.] C. 3. The weight ratio of the first resin (A) to the second resin (B) is (A) / (B) = 1/9 to 9/1. 3. The toner for developing an electrostatic image according to 2. 4. Melting temperatures of the first resin (A) and the second resin (B) measured by a constant load extrusion type capillary rheometer by T1 / 2 (A) and T1 / 2, respectively. The toner according to claim 2, wherein, when (B) is satisfied, 20 ° C. ≦ T1 / 2 (B) −T1 / 2 (A) ≦ 120 ° C. 5. 5. The weight average molecular weight Mw of the first resin (A) in GPC is from 3,000 to 50,000, and Mw / Mn.
Is not more than 8, Mw of the second resin (B) is 100,000 to 400,000, and Mw / Mn is 10
The toner for developing an electrostatic image according to claim 2, 3 or 4, wherein: 6. The electrostatic image developing toner according to claim 1, wherein the release agent is a wax containing a higher fatty acid ester compound, an aliphatic alcohol compound and / or Fischer-Tropsch wax as a main component. 7. The colorant is carbon black,
2. The electrostatic image developing toner according to claim 1, wherein the content of the polycyclic aromatic hydrocarbon in the carbon black is 15 ppm or less. 8. The toner according to claim 1, further comprising a charge controlling agent. 9. The toner for developing an electrostatic charge image according to claim 8, wherein a nigrosine dye and / or a quaternary ammonium salt compound is contained as the charge control agent. 10. The quaternary ammonium salt compound is at least one selected from compounds represented by the following general formula 1, 2 or 3.
The toner for developing an electrostatic image according to the above. <General formula 1> [Wherein, R _{1 to} R ₃ represent a CnH2n + 1 group. Where n
Represents an integer of 1 to 10. Further, R _{1 to} R ₃ may be the same or different. <General formula 2> Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 22 carbon atoms, an unsubstituted or substituted aromatic group having 1 to 20 carbon atoms, Represents an aralkyl group having 7 to 20 carbon atoms, A ^- is a molybdate anion or a tungstate anion,
Represents a heteropolyacid anion containing molybdenum or tungsten atoms. <General formula 3> Wherein m represents 1, 2 or 3, and n represents 0, 1
Or 2, and M is a hydrogen atom or a monovalent metal ion. X and Z each represent 1 or 2, and Y represents 0 or 1. Further, when X = 1, Y = 1 and Z = 1, and when X = 2, Y = 0 and Z = 2. R _{5 to} R ₁₂ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, an alkoxylene group having 1 to 4 carbon atoms, or a general formula (-C 2-5 alkylene-O ) N-R
(Where R is hydrogen or an alkyl group or acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), wherein R ₁ , R ₂ ,
R ₃ and R ₄ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, or a general formula (—CH ₂ —CH ₂ —O) n—R (however, R is hydrogen or an alkyl group or an acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), an oxyethyl group represented by the formula: and a mononuclear or polynuclear alicyclic group having 5 to 12 carbon atoms. Residue, mononuclear or polynuclear aromatic residue or araliphatic residue. ] 11. The toner according to claim 1, wherein the content of the volatile amine compound in the toner is 150 ppm or less. 12. The method according to claim 11, wherein the volatile amine compound is aniline and / or tributylamine, the aniline content in the toner is 10 ppm or less, and the tributylamine content is 150 ppm or less. For developing electrostatic images. 13. The method according to claim 13, wherein the content of molybdenum in the toner is 5 or less.
2. The amount is not more than 000 mg / kg.
The toner for developing an electrostatic image according to the above. 14. The electrostatic image according to claim 1, wherein hydrophobic silica having a bulk density of 100 g / l or less and a BET surface area of 100 to 250 m ² / g is adhered to the toner surface. Development toner. 15. The method according to claim 1, wherein the hydrophobic silica is a silica surface-treated with hexamethyldisilazane, aminosilane and / or cyclic silazane.
4. The toner for developing an electrostatic image according to item 4. 16. The toner according to claim 1, further comprising a magnetic powder as a coloring agent. 17. A carrier selected from the group consisting of silicone resin, fluororesin, and (meth) acrylic resin.
2. The toner according to claim 1, wherein a resin-coated magnetic carrier coated with at least one kind of resin is used. 18. An image forming method using the toner for developing an electrostatic image according to claim 1, wherein the fixing speed is 20 m / min or more. 19. An image forming method using the electrostatic image developing toner according to claim 1, wherein the fixing speed is 30 m / min or more.