JP3083023B2 - Electrostatic image developing toner and method of manufacturing the same - 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 image suitable for heat fixing used in electrophotography, electrostatic recording and magnetic recording, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Publication No. JP-A-Heisei, 43-24878 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. Forming and then developing the latent image with toner,
After transferring the toner image to a transfer material such as paper as necessary,
The toner is fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a copy, and the toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated.

Further, a general method of forming a full-color image will be described. A photosensitive member of a photosensitive drum is uniformly charged by a primary charger, and an image is formed by a laser beam modulated by a magenta image signal of a document. Exposure is performed to form an electrostatic latent image on the photosensitive drum, and the electrostatic latent image is developed by a magenta developing device having magenta toner to form a magenta toner image. Next, the developed magenta toner image is transferred onto the photosensitive drum by a transfer charger onto the transferred transfer material.

On the other hand, the photosensitive drum after the development of the electrostatic latent image is neutralized by a static eliminator, cleaned by a cleaning unit, and charged again by a primary charger. A cyan toner image is formed and the cyan toner image is transferred to a transfer material on which the magenta toner image has been transferred.
The same procedure is performed in the same manner as for the black color to transfer the four color toner images to the transfer material. A full-color image is formed by fixing the transfer material having the four color toner images by the action of heat and pressure by a fixing roller.

In recent years, such copying apparatuses have begun to be used not only as office work copying machines for simply copying original documents, but also as printers as personal computer outputs or personal copies for individuals. .

[0006] In addition to the field represented by such a laser beam printer, the development to a plain paper fax using a basic engine is also rapidly developing.

For this reason, smaller, lighter, faster, higher quality, and higher reliability have been strictly pursued, and machines have been constructed from simpler elements in various respects. . As a result, the performance required of the toner has become higher, and if the performance of the toner cannot be improved, a better machine cannot be realized.

In recent years, with the need for various copying,
The demand for color copying is also increasing rapidly, and further higher image quality, higher resolution, and the like are desired in order to copy original color images more faithfully.

From these viewpoints, the toner used in the color image forming method needs to have good meltability and color mixing when heat is applied thereto, and has a low softening point.
It is preferable to use a toner having a low melt viscosity and a high sharp melt property.

That is, by using such a sharp melt toner, the color reproduction range of a copy can be widened and a color copy faithful to the original image can be obtained.

However, such a color toner having a high sharp melt property generally has a high affinity with a fixing roller, and tends to be easily offset to the fixing roller during fixing.

Particularly, in the case of a fixing device in a color image forming apparatus, since a plurality of toner layers of magenta, cyan, yellow, and black are formed on a transfer material, offset tends to occur particularly due to an increase in toner layer thickness. It is in.

Conventionally, for the purpose of preventing toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material having excellent releasability to the toner, such as silicone rubber or a fluorine-based resin. In order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a highly releasable liquid such as silicone oil or fluorine oil. However, this method is extremely effective in preventing toner offset, but has a problem that a fixing device is complicated because a device for supplying an anti-offset liquid is required. Needless to say, this oil application causes delamination between the layers constituting the fixing roller, and consequently has a disadvantage that the life of the fixing roller is shortened. As a transfer material for fixing a toner image using these fixing devices, various papers, coated papers, plastic films and the like are generally used. In particular, the necessity of a transparency film (OHP) using an overhead projector for presentation has recently attracted attention. In particular, OHP, unlike paper, has a low oil-absorbing ability, so that the currently obtained copy OHP is inevitably sticky due to oil application, and there is still a large problem in the quality of the obtained image. . In addition, there is a great possibility that silicone oil and the like will evaporate due to heat and contaminate the inside of the machine, and there will be problems such as treatment of collected oil. Therefore, instead of using a silicone oil supply device, instead of supplying the anti-offset liquid during heating from the toner, low-molecular-weight polyethylene,
A method of adding a release agent such as low molecular weight polypropylene has been proposed. If a large amount of such an additive is added in order to obtain a sufficient effect, filming on a photoreceptor or contamination of the surface of a toner carrier such as a carrier or a sleeve will cause deterioration of an image and pose a practical problem. Therefore, a small amount of release agent is added to the toner to the extent that the image is not deteriorated, and a small amount of release oil is supplied or the offset toner is wound up using a device such as a web-type member or a cleaning pad. In addition, a cleaning device is used in combination.

However, in view of recent demands for miniaturization, weight reduction, and high reliability, it is necessary and preferable to remove even these auxiliary devices. Therefore, if there is no further performance improvement such as toner fixing and offset,
It is difficult to realize this without further improvement of the binder resin of the toner, the release agent and the like.

Further, especially in the full color field,
By using a release agent, when using OHP as a transfer material, the transparency and haze of the image after fixing is slightly reduced due to high crystallization of the release agent and a difference in refractive index from the resin. Problems arise.

It is known that a wax is contained in a toner as a release agent. For example, Japanese Patent Publication No. 52-330
No. 4, JP-B-52-3305, JP-A-57-305.
The technology is disclosed in, for example, Japanese Patent No. 52574.

Also, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-27
3554, JP-A-61-94092, JP-A-61-138259, and JP-A-60-25236
No. 1, Japanese Unexamined Patent Publication No. 60-252360, Japanese Unexamined Patent Publication No.
Japanese Patent Application Laid-Open No. 0-217366 discloses a technique for containing waxes.

Waxes are used to improve the anti-offset property of toner at low and high temperatures and to improve the fixability at low temperature. For example, when the temperature is increased, the developability exposed to heat deteriorates, and when the toner is left for a long period of time, the wax migrates to the toner surface to deteriorate the developability.

None of the conventional toners satisfies all of these aspects, causing some problems. For example, high-temperature offset and developability are excellent, but low-temperature fixability is just one step away, or low-temperature offset and low-temperature fixability are excellent, but blocking resistance is slightly inferior, and developability decreases when the temperature rises in the machine. Or the offset resistance at low and high temperatures cannot be compatible.
The transparency was extremely poor.

With respect to the transparency of OHP, in particular, Japanese Patent Application Laid-Open Nos. 4-149559 and 4-107467 disclose the addition of a crystallization nucleating agent or the like to the wax in order to reduce the crystallization of the wax itself. A proposal to use a material having a low degree of crystallinity (Japanese Patent Application Nos. 3-091108 and 3-242397) or a material having good compatibility with a binder and having a lower melt viscosity than the binder. JP-A-3-2126 proposes to improve the surface smoothness of the toner layer after fixing by adding it to the toner.
No. 52, for example.

One of the releasing agents having relatively good transparency and low-temperature fixing performance is montan wax, which is a mineral wax.

The following structural formula is used as the montan wax.

[0023]

[Outside 10] [Wherein, R represents a hydrocarbon group having 28 to 32 carbon atoms,
n represents an integer] It is possible to use a wax having a molecular weight of about 800 represented by JP-A-1-185660, JP-A-1-185661, JP-A-1-185662, JP-A-1-185661. JP-A-1-23
No. 8672 proposes a proposal.

However, these are all OHP
Is not fully satisfactory in terms of transparency and haze.

[0025]

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

It is another object of the present invention to provide a toner for developing an electrostatic image, which is excellent in low-temperature fixability to a transfer material and anti-offset property, and a method for producing the same.

Still another object of the present invention is to provide a toner for developing electrostatic images which can be fixed without using a large amount of oil or without applying any oil, and a method for producing the same. .

Still another object of the present invention is to provide a full-color toner capable of obtaining a high-quality full-color OHP excellent in transparency and a method for producing the same.

[0029]

The present invention provides a binder resin, a colorant, and a compound represented by the following formula [1], [2] or [3]:
And a polyfunctional polyester compound having a primary or secondary carbon and having two or more functional groups (excluding a polyfunctional polyester compound having a tertiary or quaternary carbon). The present invention relates to an image developing toner.

[0030]

[Outside 11] [Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms, and m and n are zero or 1
Indicating the above integers and not simultaneously being zero, X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. ]

[0031]

[Outside 12] [Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms, and m and n are zero or 1
Indicating the above integers and not simultaneously being zero, X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. ]

[0032]

[Outside 13] [Wherein, A represents an alicyclic group, R ₁ and R ₂ are the same or different and represent an organic group having ₁ to 35 carbon atoms, and Y ₁
And Y ₂ are the same or different groups, and represent a hydrogen atom,
A halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom, it may be different even in the same, Z ₁ And Z ₂ represent an oxygen atom or a sulfur atom;
They may be the same or different. ]

The present invention further relates to a binder resin, a colorant, and a polyfunctional compound having a primary or secondary carbon represented by the following formula [1], [2] or [3] and having two or more functional groups. A toner for developing an electrostatic image, wherein a mixture containing a polyester compound (excluding a polyfunctional polyester compound having a tertiary or quaternary carbon) is melt-kneaded, cooled, pulverized, and classified to form toner particles. And a method for producing the same.

[0034]

[Outside 14] [Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms, and m and n are zero or 1
Indicating the above integers and not simultaneously being zero, X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. ]

[0035]

[Outside 15] [Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms, and m and n are zero or 1
Indicating the above integers and not simultaneously being zero, X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. ]

[0036]

[Outside 16] [Wherein, A represents an alicyclic group, R ₁ and R ₂ are the same or different and represent an organic group having ₁ to 35 carbon atoms, and Y ₁
And Y ₂ are the same or different groups, and represent a hydrogen atom,
A halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom, it may be different even in the same, Z ₁ And Z ₂ represent an oxygen atom or a sulfur atom;
They may be the same or different. ]

Further, the present invention provides a polymerizable monomer, a colorant,
And 1 represented by the following formula [1], [2] or [3]
A toner particle is directly produced by polymerizing a mixture having a polyfunctional polyester compound having a tertiary or secondary carbon and having two or more functional groups (excluding a polyfunctional polyester compound having a tertiary or quaternary carbon). And a method for producing a toner for developing an electrostatic charge image.

[0038]

[Outside 17] [Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms, and m and n are zero or 1
Indicating the above integers and not simultaneously being zero, X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. ]

[0039]

[Outside 18] [Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms, and m and n are zero or 1
Indicating the above integers and not simultaneously being zero, X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different. ]

[0040]

[Outside 19] [Wherein, A represents an alicyclic group, R ₁ and R ₂ are the same or different and represent an organic group having ₁ to 35 carbon atoms, and Y ₁
And Y ₂ are the same or different groups, and represent a hydrogen atom,
A halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom, it may be different even in the same, Z ₁ And Z ₂ represent an oxygen atom or a sulfur atom;
They may be the same or different. ]

In the polyfunctional polyester compound represented by the formula [3], when Y ₁ is an organic group, for example,

[0042]

[Outside 20] Wherein R ₃ represents an organic group having 1 to 35 carbon atoms, X ₃ represents an oxygen atom or a sulfur atom, and Z ₃ represents an oxygen atom or a sulfur atom.
_{When 2} is an organic group, for example, the following formula

[0043]

[Outside 21] [Wherein, R ₄ represents an organic group having 1 to 35 carbon atoms, X ₄ represents an oxygen atom or a sulfur atom, and Z ₄ represents an oxygen atom or a sulfur atom].

More specifically, the following polyfunctional compounds can be mentioned.

[0045]

[Outside 22]

[0046]

[Outside 23]

The polyfunctional polyester compounds used in the present invention have an appropriate affinity for the binder resin in order to exhibit good low-temperature fixability, and have a high hydrophobicity and a low crystallinity having a low melting point. Compound.

Further, as a result of intensive studies, the present inventors have found that in order to further impart the function of transparency, the crystallinity of the release agent itself is impaired so that the structural symmetry of the release agent itself is broken. Turned out necessary.

More specifically, using the above-mentioned structural formula [3], the chain length of R1 and / or R2 is changed to Y ₁ and / or Y
It is preferred that the chain length be sufficiently longer than the chain length ₂ in order to achieve both low-temperature fixability and transparency characteristics.

In particular, a polyfunctional polyester compound in which R1 and R2 are organic groups having 10 to 35 carbon atoms and R3 and R4 are organic groups having 1 to 5 carbon atoms is particularly effective.

The polyfunctional polyester compound is preferably used in an amount of 1 to 40 parts by weight (preferably 2 to 30 parts by weight) based on 100 parts by weight of the binder resin of the toner.

In a dry toner production method in which a mixture containing a binder resin, a colorant and a polyfunctional polyester is melt-kneaded, cooled, pulverized and then classified to obtain toner particles, the amount of the polyfunctional polyester added is 100% by weight of the binder resin. It is preferred to use 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, per part by weight.

By polymerizing a mixture having a polymerizable monomer, a colorant and a polyfunctional polyester compound,
Polymerization method for directly obtaining toner particles In the toner production method, it is preferable to use 10 to 40 parts by weight, more preferably 15 to 30 parts by weight, per 100 parts by weight of the polymerizable monomer.

Polymerization method compared to dry toner production method In a toner production method, a generally used release agent is lower in polarity than a binder resin. Therefore, in a polymerization method in an aqueous medium, a large amount of a release agent is encapsulated in toner particles. In general, a large amount of a release agent can be used as compared with a dry toner production method, and the effect of preventing offset during fixing is particularly effective.

If the addition amount is less than the lower limit, the offset prevention effect tends to decrease, and if the addition amount exceeds the upper limit, the anti-blocking effect is reduced and the anti-offset effect is liable to be adversely affected. Further, in the case of a polymerization toner, a toner having a wide particle size distribution tends to be generated.

In order to obtain a sufficiently transparent OHP image with a low heat capacity of the fixing device, it is most important to lower the crystallinity of the release agent usually contained in the toner. However, in order to impart more sufficient transparency as a secondary effect, there are some undissolved toner grain boundaries that were not dissolved even after fixing, or the crystallinity of the release agent layer is caused by irregular reflection of light. In this case, the effective light transmittance is reduced, and as a result, haze is reduced. Further, even if the components mixed in the toner are sufficiently dissolved at the time of fixing, if the difference in the refractive index between the dissolved toner layer and the release agent layer formed between the fixing members is large, this is also the case of light. It is not preferable because it causes irregular reflection.

The increase in the irregular reflection of light leads to a decrease in the brightness of the projected image and a decrease in the sharpness of the color. In particular, when a transmission type overhead projector is used, this problem is further increased than when a reflection type overhead projector is used.

That is, in order to lower the crystallinity of the release agent, it is important to lower the crystallinity of the release agent alone. Further, in order to prevent unmelted toner grain boundaries from being present in the toner fixing layer, the glass transition temperature (T
A material having a small melting enthalpy (ΔH), which is the latent heat of the release agent, is particularly preferable in order to make g) and the melting point (mp) of the release agent as close as possible and to quickly dissolve it with a low energy amount. It is preferable that the difference in solubility parameter (SP) between the binder resin and the release agent is appropriately adjusted in order for the molten release layer to quickly move between the binder resin layer and the fixing member and form an anti-offset layer. .

Specific examples which are preferable for the present invention from such a viewpoint will be described in detail below.

The polyester resin, styrene-acrylic resin, epoxy resin or styrene-butadiene resin is often used as the binder resin for the toner, which functions as the polyfunctional polyester compound releasing agent used in the present invention. Therefore, those having a refractive index close to those of these resins are preferable.

As a method of measuring the refractive index, first, the vertical (2
0-30) x width (8) x thickness (3-10) to make a solid sample, then apply a small amount of bromonaphthalene to the prism surface to improve the adhesion to the prism surface.
A method of mounting a solid sample thereon and measuring the refractive index is exemplified. Further, as the measuring instrument, for example, an Appe refractometer 2T manufactured by Atago Co., Ltd. may be mentioned.

The difference in refractive index between the binder resin and the polyfunctional polyester compound at a temperature of 25 ° C. is 0.18 or less, more preferably 0.10 or less, is particularly effective. Introduction of a heteroester in which the ester group is replaced by a hetero element such as sulfur or phosphorus is also effective for adjusting the refractive index. If the refractive index difference exceeds 0.18, the transparency of the OHP image is likely to be reduced, and particularly, a halftone projected image is not preferable because the brightness becomes low.

The polyfunctional polyester compound used in the present invention preferably has a melting point of 30 to 120 ° C.
More preferably, 50 to 100 ° C is particularly preferable. When the melting point is lower than 30 ° C., the blocking resistance of the toner,
It is easy to reduce the contamination of the sleeve and the contamination of the photosensitive member when copying a large number of sheets. If the melting point exceeds 120 ° C., excessive energy is required for uniform mixing with the binder resin in the production of the toner by the pulverization method, and the use of a high-boiling solvent in the production of the toner by the polymerization method. And a pressure-resistant reaction vessel under high pressure is required, and the apparatus becomes extremely complicated, which is not preferable.

The solubility parameter (SP) value is determined by the method of Fedors using the additivity of atomic groups [Polym.
Eng. Sci. , 14 (2) 147 (1974)].

The SP value of the polyfunctional polyester compound used in the present invention is preferably in the range of 7.5 to 9.7. The polyfunctional polyester having an SP value of less than 7.5 has poor compatibility with the binder resin used, and as a result, it is difficult to obtain good dispersion in the binder resin,
At the time of copying a large number of sheets, the polyfunctional polyester compound easily adheres to the developing sleeve, and the charge amount of the toner tends to change. Further, the density fluctuates easily at the time of ground fog and toner supply.

When a polyfunctional polyester compound having an SP value of more than 9.7 is used, blocking between toners is likely to occur when the toner is stored for a long time. Further, since the compatibility with the binder resin is too good, it is difficult to form a sufficient releasable layer between the fixing member and the toner binder resin layer at the time of fixing, and the offset phenomenon is easily caused.

The melt viscosity of the polyfunctional polyester compound used in the present invention can be measured at 130 ° C. using a cone plate type rotor (PK-1) with VP-500 manufactured by HAAKE. The melt viscosity at 130 ° C. is preferably from 1 to 300 cps, more preferably a polyfunctional polyester compound having from 3 to 50 cps. When the melt viscosity is lower than 1 cps, when a thin layer of the toner layer is coated on the sleeve with a blade or the like in a non-magnetic one-component developing method, the sleeve is easily contaminated by mechanical shearing force. Further, in the two-component developing method, when a toner is developed using a carrier, damage due to a shear force between the toner and the carrier is apt to occur, and external additives are easily buried and the toner is crushed. When the toner has a melt viscosity of more than 300 cps, the viscosity of the dispersoid is too high when producing a toner using a polymerization method, and it is not easy to obtain a toner having a small particle size having a uniform particle size. The toner tends to have a wide distribution.

The hardness of the polyfunctional polyester compound is measured as follows.
For example, Shimadzu Dynamic Ultra-Micro Hardness Tester (DUH-20
0). The measurement conditions were as follows. After displacing 10 μm at a load speed of 9.67 mg / sec under a load of 0.5 g using a Vickers indenter, holding for 15 seconds, and analyzing the dents on the sample, the Vickers hardness was determined. . As the sample, a sample previously melted using a mold having a diameter of 20 mmφ is formed into a column having a thickness of 5 mm. The hardness of the release agent used in the present invention is 0.3 to 5.
A range of 0 is preferable, and a more preferable Vickers hardness is
0.5 to 3.0 is particularly effective.

A toner containing a polyfunctional polyester compound having a Vickers hardness lower than 0.3 is liable to be crushed at a cleaning portion of a copying machine in copying a large number of sheets, and is liable to cause toner fusion on a drum surface, resulting in an image. Black streaks are likely to occur on the top. Further, when multiple image samples are stored while being stacked, the toner is transferred to the surface and so-called show-through tends to occur, which is not preferable. A toner containing a polyfunctional polyester compound having a Vickers hardness of more than 5.0 requires an unnecessarily high pressure for a fixing device used at the time of heat fixing, and requires an unnecessarily high strength design for the fixing device. If a fixing device with a normal pressing force is used, the offset resistance tends to decrease, which is not preferable.

The degree of crystallinity of the polyfunctional polyester compound is preferably 10 to 50%, more preferably 20 to 35%.

When the crystallinity is less than 10%, the toner storability and fluidity tend to deteriorate, and when it exceeds 50%, the transparency of the OHP image tends to deteriorate.

The crystallinity in the present invention is measured by the following formula from the area ratio between the amorphous scattering peak and the crystal scattering peak without using a calibration curve.

[0073]

[Outside 24]

As a measuring device, for example, Rotorflex RU300 (Cu target, point focus, output 50 Kv / 250 mA) manufactured by Rigaku Corporation can be mentioned.

The transmission method-rotation method is used for the measurement, and the measurement angle is 2θ = 5 to 35 °.

The number average molecular weight of the polyfunctional polyester compound in the present invention is measured by a vapor pressure osmotic pressure (VPO) method.

The measurement conditions are as follows.

Apparatus: 115 type Hitachi molecular weight measuring apparatus Temperature: 61 ° C. Solvent: toluene (special grade reagent) Standard sample: benzyl (special grade reagent)

The number average molecular weight is calculated from the following equation.
The sample concentration is calculated from the charged amount, and the average molar concentration is read from the ΔR obtained by sample measurement using a ΔR-average molar concentration calibration curve prepared with benzyl.

[0080]

[Outside 25]

The number average molecular weight (Mn) of the polyfunctional polyester compound is preferably from 200 to 2,000. More preferably, Mn is from 500 to 1,000.

If the number average molecular weight is less than 200, the melting point tends to be too low and the blocking resistance tends to deteriorate.

When Mn exceeds 2,000, the releasing effect and OHP transparency tend to decrease.

As a method for producing the polyfunctional polyester compound used in the present invention, for example, a synthesis method by an oxidation reaction, a synthesis from a carboxylic acid or a derivative thereof, an ester group introduction reaction represented by a Michael addition reaction, and the like are used. A particularly preferred method for producing the polyfunctional polyester compound used in the present invention is a method utilizing a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound from the versatility of the raw materials and the ease of the reaction, or a method using an acid halide and an alcohol compound. Reactions are particularly preferred.

[0085]

[Outside 26]

In order to transfer the above ester equilibrium reaction to the production system, a large excess alcohol is used, or the reaction is carried out in an aromatic organic solvent capable of azeotropic distillation with water using a Dean-Stark water separator. . Further, a method of synthesizing an ester by using an acid halide compound and adding a base as an acceptor of an acid by-produced in an aromatic organic solvent can also be used.

As the binder resin used in the toner of the present invention, the following binder resins can be used.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and their substituted products; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, Delpen resin, coumarone indene resin, petroleum resin and the like can be used. Preferred binders include styrene copolymers or polyester resins.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Double such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. A monocarboxylic acid having a bond or a substituted product thereof;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like;
Vinyl esters such as vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene, butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether and vinyl Vinyl monomers such as ethyl ether, vinyl isobutyl ether and the like; and vinyl monomers such as one or two or more are used.

The number average molecular weight of the THF-soluble component of the binder resin of the present invention is preferably from 3,000 to 1,000,000.

The styrene-based polymer or styrene-based copolymer may be crosslinked, or may be a resin mixture thereof.

As the crosslinking agent for the binder resin, a compound having two or more polymerizable double bonds may be mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; Carboxylic acid esters having two double bonds such as glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butadiol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and 3
Compound having at least two vinyl groups; used alone or as a mixture. The amount of the polymerizable monomer 10
0.001 to 10 parts by weight to 0 parts by weight is preferable.

The toner of the present invention may contain a charge control agent.

The following substances control the toner to be negatively charged.

For example, organic metal compounds and chelate compounds are effective, and examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

Further, urea derivatives, metal-containing salicyl oxygen compounds, quaternary ammonium salts, calixarenes, silicon compounds, styrene-acrylic acid copolymers, styrene-
Examples include methacrylic acid copolymer, styrene-acryl-sulfonic acid copolymer, and nonmetal carboxylic acid compounds.

The following substances control the toner to be positively charged.

Modified products such as nigrosine and fatty acid metal salts, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts such as phosphonium salts, which are analogs thereof, and lake pigments thereof, triphenylmethane dyes and these lake pigments. , Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids: diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide: dibutyltin borate, dioctyltin borate, dicyclohexyltin borate Diorganotin borates; these can be used alone or in combination of two or more. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

These charge control agents are used in an amount of 0.01 to 20 parts by weight (preferably 0.1 to 20 parts by weight) based on 100 parts by weight of the resin component.
5 to 10 parts by weight).

Examples of the colorant for the toner include black pigments such as carbon, black, alline black, and acetylene black.

Examples of magenta pigments include red lead graphite, molybdenum, orange, permanent orange GTR, pyrazolone orange, benzene orange G, cadmium red, permanent red 4R, watching red calcium salt, eosin lake, and brilliant carmine 3.
B, carmine 6B, manganese purple, fast violet B, methyl violet lake, rhodamine lake, alizarin lake, bengara, quinacridone, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 21, 22, 23, 30, 31, 32, 3,
7, 38, 39, 40, 41, 48, 49, 50, 5,
1, 52, 53, 54, 55, 57, 58, 60, 6
3, 64, 68, 81, 83, 87, 88, 89, 9
0, 112, 114, 122, 123, 163, 20
2,206,207,209; C.I. I. Pigment Violet 19, C.I. I. Butt Red 1, 2, 10, 1
3, 15, 23, 29, 35 and the like.

Examples of cyan pigments include C.I. I. Pigment Blue 2, 3, 15, 16, 17; I. Bat blue 6; I. Acid Blue 45, Indanthrene Blue, Navy Blue, Cobalt Blue, Alkaline Blue Lake, Vicryable Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Chrome Green, Chromium Oxide, Pigment Green B, Malachite Green Lake, Final Yellow green G
And the like.

Examples of the pigments for yellow include naphthol yellow, Hiza yellow, graphite, cadmium yellow, mithral fast yellow, navel yellow, permanent yellow NCG, tartrazine lake; I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10,
11, 12, 13, 14, 15, 16, 17, 23, 6
5, 73, 83, 97, 120, 127, 174, 17
6, 180, 181, 191; I. Bat Yellow 1, 3, 20 and the like.

These pigments are used in an amount necessary to maintain the optical density of the fixed image, and are used in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the resin. Is preferred.

Examples of the dye used as the coloring agent include the following.

Examples of magenta dyes include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 3
0, 49, 81, 82, 83, 84, 100, 109,
121; I. Disperse Red 9; I. Solvent Violet 8, 13, 14, 21, 27, C.I.
I. Disperse Violet 1; I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 1
8, 22, 23, 24, 27, 29, 32, 34, 3
5, 36, 37, 38, 39, 40; I. Basic violet 1, 3, 7, 10, 14, 15, 21,
C. 25, 26, 27, 28; I. Direct red 1.4; I. Acid Red 1, C.I. I. Modant Red 30 and the like.

Examples of cyan dyes include C.I. I. Direct Blue 1, C.I. 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.
Basic Green 6 and the like.

The amount of these dyes is preferably 0.1 to 20 parts by weight, more preferably 0.3 to 10 parts by weight, based on 100 parts by weight of the resin.

Further, the toner of the present invention can be used as a magnetic toner by further containing a magnetic material. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner includes iron oxide such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, magnesium, and tin of these metals. ,
Examples include alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

The ferromagnetic material preferably has an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount contained in the toner is preferably about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight, per 100 parts by weight of the resin component.

The magnetic properties at the application of 10K Oersted are as follows: the coercive force (Hc) is 20 to 300 Oersted, the saturation magnetization (σs) is 50 to 200 emu / g, and the residual magnetization (σr)
Those having 2 to 20 emu / g are preferred.

The additive for imparting various toner properties should have a particle diameter of not more than 1/5 of the volume average diameter of the toner particles from the viewpoint of durability when added to the toner or when added to the toner. Is preferred. The particle size of the additive means an average particle size obtained by observing the surface of the toner particles with an electron microscope. As additives for imparting these properties, for example, the following are used.

Examples of the fluidity-imparting agent include metal oxides (such as silicon oxide, aluminum oxide and titanium oxide), carbon black, and carbon fluoride. Those subjected to a hydrophobic treatment are more preferable. As an abrasive, metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.)
Nitride (such as silicon nitride) and carbide (such as silicon carbide)
Metal salts (eg, calcium sulfate, barium sulfate, calcium carbonate, etc.).

Examples of the lubricant include fluororesin powder (vinylidene fluoride, polytetrafluoroethylene, etc.) and fatty acid metal salts (zinc stearate, calcium stearate, etc.).

Examples of the charge control particles include metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide) and carbon black.

These additives are used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the toner particles.
0.1 to 5 parts by weight are used. These additives may be used alone or in combination of two or more.

The toner of the present invention can be used as a one-component or two-component developer in any developer.

For example, in the case of a magnetic toner in which a magnetic material is contained in a toner as a one-component developer, there is a method in which a magnet incorporated in a developing sleeve is used to convey and charge the magnetic toner. . When a non-magnetic toner containing no magnetic substance is used, there is a method in which the toner is conveyed by forcibly frictionally charging the developing sleeve with a blade and a fur brush and causing the toner to adhere to the sleeve.

On the other hand, when used as a generally used two-component developer, a carrier is used as a developer together with the toner of the present invention. The carrier used in the present invention is not particularly limited, but is mainly composed of a single ferrite and a composite ferrite composed of iron, copper, zinc, nickel, cobalt, manganese, and chromium. Carrier shape is also important from the viewpoint that saturation magnetization and electric resistance can be controlled in a wide range. For example, it is preferable to select a spherical shape, a flat shape, an irregular shape, and the like, and to further control a fine structure of a carrier surface state, for example, surface unevenness. . Generally, the above inorganic oxide is calcined,
By granulating, in advance, a method of coating the resin after generating the carrier core particles is used, but from the viewpoint of reducing the load on the toner of the carrier, kneading the inorganic oxide and the resin, pulverizing, A method of obtaining a low-density dispersed carrier by classifying, and further, a method of directly obtaining a polymerized carrier to obtain a spherically dispersed carrier by suspension-polymerizing a kneaded product of an inorganic oxide and a monomer in an aqueous medium is also used. It is possible.

A system in which the surface of the carrier is coated with a resin or the like is particularly preferable. As the method, any conventionally known method such as a method of dissolving or suspending a coating material such as a resin in a solvent, coating and adhering to a carrier, and a method of simply mixing with a powder can be applied.

The substance to be fixed to the carrier surface varies depending on the toner material. Examples thereof include polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, metal compound of ditersharry butylsalicylic acid, and styrene-based compounds. Resins, acrylic resins, acrylic resins, polyacids, polyvinyl butyral, nigrosine, amino acrylate resins, basic dyes and lakes thereof, silica fine powder, alumina fine powder, etc. It is not necessarily limited to this.

The treatment amount of the above compound is generally preferably 0.1 to 30% by weight (preferably 0.5 to 20% by weight) based on the total amount of the carrier of the present invention.

The average particle size of these carriers is 10 to 100.
μ, preferably 20 to 50 μ.

In a particularly preferred embodiment, Cu—Zn—
Fe ternary ferrite whose surface is a combination of a resin such as a fluorine resin and a styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin: polytetrafluoroethylene and styrene-methyl methacrylate resin, A mixture of a fluorine-based copolymer and a styrene-based copolymer in a ratio of 90:10 to 20:80, preferably 70:30 to 30:70, and 0.01 to 5% by weight, preferably 0.1-1% by weight
Coated ferrite carriers having the above-mentioned average particle size, which are coated and have a 250 mesh pass, 400 mesh on carrier particles of 70% by weight or more, may be mentioned. As the fluorine-based copolymer, a vinylidene fluoride tetrafluoroethylene copolymer (10:90 to 90: 1)
0). Examples of the styrene copolymer include styrene-2-ethylhexyl acrylate (20:80 to 80:
20), styrene-2-ethylhexyne acrylate-methyl methacrylate (20-60: 5-30: 10-5)
0) is exemplified.

The coated ferrite carrier has a sharp particle size distribution, provides favorable triboelectricity to the toner of the present invention, and has the effect of improving electrophotographic properties.

When a two-component developer is prepared by mixing with the toner according to the present invention, the mixing ratio is from 2% by weight to 15% by weight, preferably from 4% by weight, based on the toner concentration in the developer.
Good results are usually obtained at 13% by weight. When the toner density is 2% or less, the image density is low and cannot be used practically.
If it is 5% or more, fog and scattering in the machine are increased, and the useful life of the developer is shortened.

Further, the following are preferred as the carrier magnetic characteristics.

The magnetization intensity (σ ₁₀₀₀ ) at 1000 Oe after magnetic saturation is 100 to 300.
It is required to be emu / cm ³ . In order to achieve higher image quality, preferably 100 to 250 e
It is preferably mu / cm ³ . 300 emu / cm ³
If it is larger, it becomes difficult to obtain a high quality toner image. If it is less than 100 emu / cm ³ , the magnetic binding force is reduced, and carrier adhesion is likely to occur.

The shape of the carrier is such that SF1 indicating the degree of roundness is 180 or less, and SF2 indicating the degree of unevenness is 2 degrees.
It is preferably 50 or less. Note that SF1, SF2
Is defined by the following formula, and is made by Nileco LVZEXII.
I was measured.

[0130]

[Outside 27]

The method for producing the pulverized toner in the present invention is as follows.
The binder resin, the polyfunctional ester compound of the present invention, a pigment or dye as a colorant, a dye, a magnetic substance, a charge control agent, if necessary, and other additives are sufficiently mixed with a mixer such as a Henschel mixer or a ball mill. Heating roll after mixing,
A metal compound, a pigment, a dye and a magnetic material are dispersed or dissolved in a resin kneaded by melt-kneading using a heat kneader such as a kneader or an extruder, and then crushed and classified after cooling and solidifying. The toner according to the present invention can be obtained.

Further, if necessary, desired additives are sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner for an electrostatic image developer according to the present invention.

The polymerized toner used in the present invention is obtained by the following method. That is, a monomer system obtained by adding a polyfunctional ester compound, a colorant, a charge control agent, a polymerization initiator, and other additives to a polymerizable monomer and uniformly dissolving or decomposing the homogenizer or an ultrasonic disperser. Is dispersed in a dispersion medium containing a dispersion stabilizer or an emulsifier by a stirrer, a homomixer, a homogenizer, or the like, and granulated. Thereafter, by the action of the dispersion stabilizer, stirring may be performed to such an extent that the monomer-based particle state is maintained and the sedimentation of the monomer-based particles is prevented. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, the temperature may be raised in the latter half of the polymerization reaction,
Further, in order to remove unreacted polymerizable monomers, by-products, and the like that cause odor at the time of fixing the toner, the aqueous medium may be partially distilled off in the latter half of the reaction or after the completion of the reaction. After the completion of the reaction, the generated toner particles are washed, collected by filtration, and dried. In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer system.

The particle size of the toner is 0.1 to 12 μm in a Coulter Counter Model TA-II (manufactured by Coulter Electronics Co., Ltd.), and the particle size distribution is such that the variation coefficient in the weight average size is 8 to 40%. Preferably, the shape is such that SF1 representing the degree of roundness is 10
0 <SF1 <150, SF2 representing the degree of unevenness is 10
It is preferable that 0 <SF2 <200.

When a toner is directly obtained by a polymerization method, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methylstyrene,
Styrene monomers such as methoxystyrene and p-ethylstyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-acrylate
-Propyl, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylates such as phenyl acrylate, methyl methacrylate,
Ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, Examples include methacrylic esters such as diethylaminoethyl methacrylate and the like, and monomers such as acrylonitrile, methacrylonitrile, and acrylamide. These monomers can be used alone or as a mixture.

Further, a polymer / copolymer having a polar group may be added as an additive to the monomer system of the polymerization method toner of the present invention for polymerization.

The polar polymers and copolymers that can be used in the present invention are exemplified below.

Polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, copolymers with styrene-unsaturated carboxylic acid esters and the like, nitrile monomers such as acrylonitrile, and vinyl chloride and the like Halogen-containing monomers, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic acids,
Examples thereof include polymers such as unsaturated dibasic acid anhydrides and nitro monomers or copolymers with styrene monomers, polyesters, epoxy resins and the like.

As the polymerization initiator, for example, 2,2'-
Azobis- (2,4-dimethylvaleronitrile), 2,
2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2 '
Azo or diazo polymerization initiators such as azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropylpyroxycarbonate, cumene hydroperoxide, t -Butyl hydroperoxide, di-t-butyl peroxide, dixyl peroxide, 2,4-dichlorobenzoyl peroxide, lautile peroxide, 2,2-bis'4,4-
Peroxide initiators such as t-butylperoxycyclohexyl) propane and tris (t-butylperoxy) triazine; polymer initiators having a peroxide in a side chain; and persulfates such as potassium persulfate and ammonium persulfate. , Hydrogen peroxide, and the like are used. The polymerization initiator is preferably added in an amount of 0.5 to 20 parts by weight of the polymerizable monomer.
Alternatively, they may be used in combination.

In the present invention, a known crosslinking agent or chain transfer agent may be added to control the molecular weight, and the preferable addition amount is 0.001 to 15 parts by weight.

In the present invention, emulsion polymerization, dispersion polymerization, suspension polymerization, seed polymerization, a polymerization method using salting out, or the like is used.
Any suitable stabilizer is used for the dispersion medium used in producing the polymerization toner. For example, as inorganic compounds, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium perhydrate,
Examples include aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. As organic compounds, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salts, starch polyacrylamide, polyethylene oxide, poly (hydroxystearic acid-g-methacrylic acid) For example, an acid-methyl-eu-methacrylic acid) copolymer or a nonionic or ionic surfactant is used.

When the emulsion polymerization method is used, an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant are used. These stabilizers, based on 100 polymerized parts of the polymerizable monomer,
It is preferred to use from 0.2 to 30 parts by weight.

When an inorganic compound is used among these stabilizers, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be formed in a dispersion medium.

In order to finely disperse these stabilizers,
A surfactant of 0.001 to 0.1 polymerization part may be used. This is to promote the intended action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and lauryl acid. Sodium, potassium stearate, calcium oleate and the like.

In the present invention, it is necessary to pay attention to the polymerization inhibitory property and the water phase migration property of the colorant used in the polymerization method toner. It is better to perform a hydrophobic treatment without inhibition. In particular, many dyes and carbon blacks have polymerization inhibitory properties, so care must be taken when using them. As a preferable method for surface-treating the dye system, a method in which a polymerizable monomer is previously polymerized in the presence of these dyes is mentioned, and the obtained colored polymer is added to the monomer system. The carbon black may be treated with a substance that reacts with the surface functional group of the carbon black, for example, a polyorganosiloxane, in addition to the same treatment as the above dye.

In the present invention, fixing property, offset resistance,
The evaluation method of the mixed color region and the transparency is as follows.

1) Fixing Property, Offset Resistance, and Color Mixing Area First, an appropriate amount of the above external additive is externally added to a toner containing the polyfunctional polyester compound of the present invention to obtain a developer. An unfixed image of the obtained developer is prepared by a commercially available copying machine.

When the toner is a black toner, the fixing property and the anti-offset property are evaluated by a heat roller external fixing device having no oil application function.

Further, in the case of a mono-color toner or a full-color toner, in addition to a heat roller external fixing device having no oil application function, a commercially available full-color copying machine CLK
-500 (manufactured by Canon Inc.), a small amount of oil is uniformly applied to the fixing roller (for example, 0.02 g / A4
Size), and evaluate the fixability, the anti-offset property, and the color mixture area, and obtain a fixed image for evaluating the transparency.

In this case, as the roller material, a fluorine-based material is used for both the upper and lower parts. The fixing conditions are as follows: when the transfer material is SK paper (manufactured by Nippon Paper Co., Ltd.), the nip is 6.0 mm, and the process speed is 85 mm / sec.
When the transfer material is an OHP sheet (Pictorico Trapen for copiers / manufactured by Asahi Glass Co., Ltd.), the nip is 6.0 mm, the process speed is 18 mm / sec, and the temperature is 80 ° C. to 23 ° C.
The temperature control is performed every 5 ° C. within a temperature range of 0 ° C.

The fixing property was determined by applying a load of 50 g / cm ² to a fixed image (including a low-temperature offset image) and applying a load to silbon paper [Lenz Cleaning Paper “daspe”.
r (R) ”(Ozu Paper Co. Ltd)], and the temperature at which the density reduction rate before and after the rubbing is less than 10% is defined as the fixing start point.

The offset resistance is determined by setting the temperature at which the offset disappears visually as the low-temperature offset starting point, and raising the temperature.
The highest temperature without offset is defined as the hot offset end point.

Further, in the mixed color area, the image in the non-offset area is converted to a handy gloss meter gloss checker IG-310.
(Manufactured by Horiba, Ltd.), and the gloss value was 7
The area is determined by defining the area as the maximum value.

2) Regarding Transparency The transmittance and haze (haze) of the obtained fixed image with respect to each toner amount per unit area were measured, and the numerical value at a toner weight of 0.75 mg / cm ² per unit area was determined. And the transparency was evaluated. The method for measuring the transmittance and haze is described below.

The transmittance was measured using a Shimadzu self-recording spectrophotometer UV.
Using 2200 (manufactured by Shimadzu Corporation), the transmittance of the OHP film alone was set to 100%, and the transmittance at the maximum absorption wavelength at magenta toner: 650 nm for cyan toner: 500 nm for yellow toner: 600 nm was measured. I do.

The haze was measured using a haze meter NDH.
It measured using -300A (made by Nippon Shikara Kogyo Co., Ltd.). The test results are shown in Tables 1 and 2.

Tables 1 and 2 show the fixing start temperature, low temperature offset start point, high temperature offset end point, non-offset area,
The values of the low temperature start point, the high temperature end point, the color mixing area, the transmittance, and the haze are described.

In the DSC measurement in the present invention, since the exchange of heat of the polyfunctional polyester compound is measured and its behavior is observed, it is necessary to measure with a high-precision internal heating input compensation type differential scanning calorimeter from the measurement principle. There is. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is as described in ASTM, D3418-82.
Perform according to. As the DSC curve used in the present invention, a DSC curve measured when the temperature is raised once, a pre-history is taken, and then the temperature is decreased and raised at a temperature rate of 10 ° C./min.

For the FT-IR measurement, for example, the KBr method is adopted, and FTS60A manufactured by Bio-Rad is used.

The NMR measurement is performed by using, for example, EX400 manufactured by JEOL Ltd. at 400 MHz.

The present invention will be described in detail with reference to a method for synthesizing a polyfunctional polyester compound, toner examples and comparative examples.

Synthesis Method of Polyfunctional Polyester Compound-1 In a 4-liter four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator, 2 l of benzene, 220 g of trifluoroacetic acid, 1770 g of behenic acid, 200 g of glycerol, and p -Toluenesulfonic acid was added, and the mixture was sufficiently stirred and dissolved. After refluxing for 7 hours, the valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the residue was sufficiently washed with sodium hydrogen carbonate, dried, and the solvent was distilled off. The obtained compound was recrystallized, washed and purified. Thus, a polyfunctional polyester compound No. 1 was obtained. The physical properties are shown below.

DSC (peak value) 61 ° C. (ΔH) 112 J / g Refractive index 1.48 SP value 8.8 Hardness 2.8 Crystallinity 20 Viscosity 12 cps Number average molecular weight 840

Synthesis method of polyfunctional polyester compound-2 In a 4-liter four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator, 2 l of benzene, 110 g of acetic acid, 1200 g of behenic acid, 1,2,6-hexane Triol (200 g) and p-toluenesulfonic acid were further added, sufficiently stirred and dissolved, and then refluxed for 6 hours. Other procedures were performed in the same manner as in Synthesis method-1.

Thus, polyfunctional polyester compound No. 2 was synthesized.

The physical properties are shown below.

DSC (peak value) 55 ° C. (ΔH) 108 J / g Refractive index 1.49 SP value 8.9 Hardness 1.9 Crystallinity 25 Viscosity 12 cps Number average molecular weight 850

Synthetic method of polyfunctional polyester compound-3 In a 4-liter four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator, 2 l of benzene, 1750 g of montanic acid, 1,4 cyclohexanediol 20
After addition of 0 g and p-toluenesulfonic acid, the mixture was sufficiently stirred and dissolved, and then refluxed for 7 hours. Other procedures were performed in the same manner as in Synthesis method-1.

Thus, polyfunctional polyester compound No. 3 was synthesized. The physical properties are shown below.

DSC (peak value) 64 ° C. (ΔH) 125 J / g Refractive index 1.47 SP value 8.7 Hardness 3.4 Crystallinity 28 Viscosity 15 cps Number average molecular weight 950

Synthesis of Polyfunctional Polyester Compound-4 A 4- liter four-necked flask equipped with a Dimroth condenser and a Dean-Stark water separator was charged with 2 l of benzene, 1750 g of montanic acid, 1,2-cyclohexanediol 20
After addition of 0 g and p-toluenesulfonic acid, the mixture was sufficiently stirred and dissolved, and then refluxed for 7 hours. Other procedures were performed in the same manner as in Synthesis method-1.

Thus, polyfunctional polyester compound No. 4 was synthesized. The physical properties are shown below.

DSC (peak value) 58 ° C. (ΔH) 101 J / g Refractive index 1.50 SP value 8.7 Hardness 1.8 Crystallinity 36 Viscosity 33 cps Number average molecular weight 950

[0175]

EXAMPLES Example 1 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1000 parts by weight Magnetic iron oxide (average particle size = 0.25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Polyfunctional polyester compound No. 140 parts by weight After the above materials were preliminarily mixed, melt kneading was performed by a biaxial kneading extruder set at 130 ° C. After cooling, the kneaded product was coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier to obtain a toner having a weight average particle size of 8.0 μm. 100 parts by weight of this toner and 0.7 parts by weight of hydrophobic colloidal silica fine powder were mixed (externally added) to obtain a magnetic toner having colloidal silica fine powder on the surface of toner particles.

Using this magnetic toner, an unfixed image was obtained using a commercially available electrophotographic copying machine NP-8582 (manufactured by Canon Inc.), and the fixability and offset resistance were evaluated by the above-described evaluation methods.

Table 1 shows the results and measured values.

Example 2 Styrene-butyl acrylate-divinylbenzene copolymer (copolymerization weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Polyfunctional polyester compound No. After premixing the above materials, a magnetic toner was obtained in the same manner as in Example 1, and a fixing test was performed. The weight average particle diameter of the obtained magnetic toner was 8.2 μm.

Table 1 shows the results.

Example 3 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1,000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Polyfunctional polyester compound No. 340 parts by weight After premixing the above materials, a magnetic toner was obtained and a fixing test was performed in the same manner as in Example 1. The weight average particle diameter of the obtained magnetic toner was 8.1 μm.

The results are shown in Table 1.

Example 4 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 Oe) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Polyfunctional polyester compound No. 440 parts by weight After premixing the above materials, a magnetic toner was obtained and a fixing test was performed in the same manner as in Example 1. The weight average particle diameter of the obtained magnetic toner was 8.0 μm.

The results are shown in Table 1.

Example 5 Polyester resin (condensate of bisphenol A-based diol-terephthalic acid-trimellitic acid) (monomer mixture weight ratio = 50: 45: 5) (weight average molecular weight = about 5000)
0) 1000 parts by weight Copper phthalocyanine pigment 40 parts by weight Monoazo metal compound 20 parts by weight Polyfunctional polyester compound No. After premixing the above materials, a color toner having a weight average particle diameter of 7.9 μm was obtained in the same manner as in Example 1. Hydrophobic titanium oxide fine powder 1.2 with respect to 100 parts by weight of the toner
By weight, a cyan color toner having titanium oxide fine powder on the surface of the toner particles was obtained.

A developer was prepared by mixing 94 parts by weight of a ferrite carrier coated with an acrylic resin with 6 parts by weight of the externally added toner.

The results are shown in Table 1.

Example 6 0.1 M Na ₃ PO ₄ was added to 708 parts by weight of ion-exchanged water.
An aqueous solution (452 parts by weight) was charged and heated to 60 ° C.
Using a K-type homomixer (manufactured by Tokushu Kika Kogyo), 120
The mixture was stirred at 00 rpm. 1.0M-CaCl ₂
69 parts by weight of an aqueous solution was gradually added, and Ca ₃ (PO ₄ ) ₂
Was obtained. On the other hand, styrene 165 parts by weight n-butyl acrylate 35 parts by weight Magnetic iron oxide (average particle size = 0.25 μm) (saturation magnetization = 60 emu / g residual magnetization = 10 K under 10 K Oersted)
emu / g coercive force = 120 oersted) 95 parts by weight styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57)
000) 9 parts by weight Divinylbenzene 2 parts by weight Di-t-butylsalicylic acid metal compound 2 parts by weight Polyfunctional ester compound No. 140 parts by weight The above material was heated to 60 ° C., and was uniformly dissolved and dispersed at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). Into this, 10 parts by weight of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. The polymerizable monomer composition was charged into the aqueous medium, and the mixture was subjected to 10,000 rpm with a TK homomixer at 60 ° C. in an N ₂ atmosphere.
Then, the mixture was stirred at m for 20 minutes to granulate the polymerizable monomer composition.
Thereafter, the temperature was raised to 80 ° C. while stirring with a paddle stirring blade.
The reaction was performed for 0 hours.

After the completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then filtered, washed with water and dried to obtain polymer particles.

To 100 parts by weight of the obtained magnetic toner particles, 0.8 part by weight of hydrophobic silica having a specific surface area of 200 m ² / g by the BET method was externally added to obtain a suspension polymerization toner. The weight average particle diameter of the obtained magnetic toner was 8.1 μm.

Using this magnetic toner, a fixing test was performed in the same manner as in Example 1.

Table 1 shows the results.

Example 7 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Polyfunctional ester compound No. Using 140 parts by weight of the polymerizable composition, in the same manner as in Example 6,
A cyan color toner having a weight average particle size of 8.2 μm was obtained.
1.2 parts by weight of hydrophobic titanium oxide fine powder was externally added to 100 parts by weight of the cyan color toner to obtain a cyan color toner having fine particles of titanium oxide on the surface of toner particles. 94 parts by weight of a ferrite carrier coated with an acrylic resin was mixed with 6 parts by weight of the externally added toner to obtain a two-component developer.

Table 1 shows the results.

Example 8 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Polyfunctional ester compound No. 120 parts by weight Using the above polymerizable composition, a developer was obtained in the same manner as in Example 7, and the fixability, the offset resistance, the color mixing region, the OHP transmittance, and the haze were measured. In addition,
The resulting cyan color toner has a weight average particle size of 8.0.
μm.

The results are shown in Table 1.

Example 9 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Quinacridone pigment 16 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57)
000) 9 parts by weight Monoazo metal compound 2 parts by weight Polyfunctional ester compound No. After obtaining a polymerizable composition such as 120 parts by weight, a developer was obtained in the same manner as in Example 7, and the fixability, offset resistance, color mixture area, OHP transmittance, and haze were measured. Incidentally, the weight average particle size of the obtained magenta color toner,
It was 8.0 μm.

The results are shown in Table 1.

[Example 10] Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Disazo yellow pigment 13 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = approx. 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Polyfunctional ester compound No. 120 parts by weight Using the above polymerizable composition, a developer was obtained in the same manner as in Example 7, and the fixability, the offset resistance, the color mixing region, the OHP transmittance, and the haze were measured. In addition,
The weight average particle size of the obtained yellow color toner is 8.
It was 1 μm.

The results are shown in Table 1.

Comparative Example 1 Styrene-butyl acrylate-divinylbenzene copolymer (copolymer weight ratio = 80: 16: 4) (weight average molecular weight = about 50,000) 1000 parts by weight Magnetic iron oxide (average particle size = 0) .25 μm) (saturation magnetization = 60 emu / g under 10K Oersted residual magnetization = 10
emu / g coercive force = 120 oersted) 800 parts by weight Di-t-butylsalicylic acid metal compound 20 parts by weight Low molecular weight polypropylene (Viscose 660P; manufactured by Sanyo Chemical Co., Ltd.) 40 parts by weight In the same manner as described above, a magnetic toner was obtained, and a fixing test was performed. The weight average particle diameter of the obtained magnetic toner was 8.1 μm.

The results are shown in Table 2.

Comparative Example 2 Polyester resin (condensate of bisphenol A-based diol-terephthalic acid-trimellitic acid) (monomer mixture weight ratio = 50: 40: 10) (weight average molecular weight = about 5500)
0) 1000 parts by weight magnetic iron oxide (average particle size = 0.25 μm) (saturation magnetization = 60 emu / g under 10 K Oersted residual magnetization = 10)
emu / g coercive force = 120 Oersted) 750 parts by weight Monoazo metal compound 20 parts by weight Montan ester wax E (Hoechst) 40 parts by weight After premixing the above materials, a magnetic toner was obtained in the same manner as in Example 1. Then, a fixing test was performed. The weight average particle diameter of the obtained magnetic toner was 8.2 μm.

The results are shown in Table-2.

Comparative Example 3 Polyester resin (condensate of bisphenol A-based diol-terephthalic acid-trimellitic acid) (monomer mixture weight ratio = 50: 45: 5) (weight average molecular weight = about 5000)
0) 1000 parts by weight Copper phthalocyanine pigment 40 parts by weight Monoazo metal compound 20 parts by weight Montan ester wax KP (Hoechst) 40
Parts by weight After the above materials were premixed, a toner was obtained and a developer was prepared in the same manner as in Example 5, and the fixability, the offset resistance, the color mixing area, the OHP transmittance, and the haze were measured. Incidentally, the weight average particle size of the obtained color toner,
It was 7.9 μm.

The results are shown in Table 2.

Comparative Example 4 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Magnetic iron oxide (average particle size = 0.25 μm) (Saturation magnetization = 60 emu / g residual magnetization = 10 under 10 K Oersted)
emu / g coercive force = 120 oersted) 95 parts by weight styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57)
000) 9 parts by weight Divinylbenzene 2 parts by weight Monoazo metal compound 2 parts by weight Montan ester wax KP (Hoechst) 40
Using parts by weight of the polymerizable composition, in the same manner as in Example 6,
A magnetic toner was obtained and a fixing test was performed. The weight average particle size of the obtained magnetic toner was 8.2 μm.

Table 2 shows the results.

Comparative Example 5 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57
000) 9 parts by weight Di-t-butylsalicylic acid metal compound 2 parts by weight Using the above polymerizable monomer composition, a toner was obtained in the same manner as in Example 7, a developer was prepared, and fixing properties and anti-offset properties were obtained. The properties, the color mixing area, the OHP transmittance, and the haze were measured. The weight average particle size of the obtained color toner was 7.9 μm.

The results are shown in Table-2.

Comparative Example 6 Styrene 165 parts by weight n-butyl acrylate 35 parts by weight Copper phthalocyanine pigment 14 parts by weight Styrene-methacrylic acid-methyl methacrylate (monomer weight ratio = 85: 5: 10) (weight average molecular weight = about 57
000) 9 parts by weight Monoazo metal compound 2 parts by weight Montan ester wax E (Hoechst) 40 parts by weight Using the above polymerizable monomer composition, a toner is obtained in the same manner as in Example 7, and a developer is prepared. Then, the fixability, the offset resistance, the color mixing area, the OHP transmittance, and the haze were measured. The obtained color toner had a weight average particle size of 8.0 μm.

The results are shown in Table 2.

[0212]

[Table 1]

[0213]

[Table 2]

[0214]

By using the polyfunctional polyester compound of the present invention, it is possible to obtain a toner excellent in low-temperature fixability to a transfer material and offset resistance without applying a small amount of oil or at all. Can be.

Also, high quality full color OH with excellent transparency
P can be generated.

Continuation of the front page (72) Inventor Tatehiko Chiba 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (56) References JP-A-50-81342 (JP, A) JP-A-58-11953 ( JP, A) JP-A-60-252365 (JP, A) JP-A-59-125750 (JP, A) JP-A-1-185557 (JP, A) JP-A-1-185558 (JP, A) 57-96354 (JP, A) JP-A-58-203456 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (6)

(57) [Claims] 1. A binder resin, a colorant, and a polyfunctional polyester compound having a primary or secondary carbon and represented by the following formula [1] , [2] or [3] and having two or more functional groups. (Excluding a polyfunctional polyester compound having a tertiary or quaternary carbon). [Outside 1] [ Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms , and m and n are zero or 1
Indicating the above integers and not simultaneously being zero , X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different . ] [Outside 2] [ Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms , and m and n are zero or 1
Indicating the above integers and not simultaneously being zero , X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different . ] [Outside 3] [Wherein, A represents an alicyclic group, R ₁ and R ₂ are the same or different and represent an organic group having ₁ to 35 carbon atoms, and Y ₁
And Y ₂ are the same or different groups, and represent a hydrogen atom,
A halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom, it may be different even in the same, Z ₁ And Z ₂ represent an oxygen atom or a sulfur atom;
They may be the same or different . ] 2. The method according to claim 1, wherein 100 parts by weight of the binder resin is 1 to 4 parts.
0 parts by weight of polyfunctional polyester compound
The toner for developing an electrostatic image according to claim 1, wherein
- 3. A binder resin, a colorant, and a polyfunctional polyester compound having a primary or secondary carbon and represented by the following formula [1] , [2] or [3] and having two or more functional groups. Wherein a mixture having a tertiary or quaternary carbon-containing polyfunctional polyester compound) is melt-kneaded, cooled, pulverized, and classified to produce toner particles. . [Outside 4] [ Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms , and m and n are zero or 1
Indicating the above integers and not simultaneously being zero , X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different . ] [Outside 5] [ Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms , and m and n are zero or 1
Indicating the above integers and not simultaneously being zero , X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different . ] [Outside 6] [Wherein, A represents an alicyclic group, R ₁ and R ₂ are the same or different and represent an organic group having ₁ to 35 carbon atoms, and Y ₁
And Y ₂ are the same or different groups, and represent a hydrogen atom,
A halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom, it may be different even in the same, Z ₁ And Z ₂ represent an oxygen atom or a sulfur atom;
They may be the same or different . ] 4. An amount of 1 to 4 with respect to 100 parts by weight of the binder resin.
The use of 0 parts by weight of a polyfunctional polyester compound is
4. The production of the toner for developing an electrostatic image according to claim 3.
Method. 5. A polyfunctional polyester having a polymerizable monomer, a colorant and a primary or secondary carbon represented by the following formula [1] , [2] or [3] and having at least two functional groups. A method for producing a toner for developing an electrostatic image, characterized by directly producing toner particles by polymerizing a mixture containing a compound (excluding a polyfunctional polyester compound having a tertiary or quaternary carbon). [Outside 7] [ Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms , and m and n are zero or 1
Indicating the above integers and not simultaneously being zero , X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different . ] [Outside 8] [ Wherein, R ₁ and R ₂ are the same or different and represent an organic group having 1 to 35 carbon atoms , and m and n are zero or 1
Indicating the above integers and not simultaneously being zero , X ₁
And X ₂ represent an oxygen atom or a sulfur atom, which may be the same or different, and Z ₁ and Z ₂ represent an oxygen atom or a sulfur atom, which may be the same or different . ] [Outside 9] [Wherein, A represents an alicyclic group, R ₁ and R ₂ are the same or different and represent an organic group having ₁ to 35 carbon atoms, and Y ₁
And Y ₂ are the same or different groups, and represent a hydrogen atom,
A halogen atom or an organic group, m and n represents zero or an integer of 1 or more, X ₁ and X ₂ represents an oxygen atom or a sulfur atom, it may be different even in the same, Z ₁ And Z ₂ represent an oxygen atom or a sulfur atom;
They may be the same or different . ] 6. One hundred parts by weight of the polymerizable monomer,
Use of 0 to 40 parts by weight of a polyfunctional polyester compound
The toner for developing an electrostatic image according to claim 5, wherein
Manufacturing method.