JP2010211016A - Electrostatic charge image developing toner, electrostatic charge image developer, toner cartridge, process cartridge, image forming method, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner for preventing offset of wax in pressure fixing at 10-50°C. <P>SOLUTION: The electrostatic charge image developing toner satisfies the following inequality (1) and includes a binding resin, a coloring agent, and wax. The wax satisfies fatty acid amide satisfying the following inequality (2), and/or the inequality (2), number average molecular weight Mn is 800 or below, and paraffin whose molecular weight distribution (Mw/Mn) is 1.25 or above is included. The inequality (1) is ΔT<SB>t</SB>=T<SB>t1</SB>-T<SB>t5</SB>≥20°C, and the inequality (2) is ΔT<SB>w</SB>=T<SB>w1</SB>-T<SB>w5</SB>≥20°C. In the inequalities (1) and (2), T<SB>t1</SB>and T<SB>w1</SB>denote temperatures, in which a melting viscosity is 10<SP>4</SP>Pa s, measured by a flow tester method in load 1 MPa respectively. T<SB>t5</SB>and T<SB>w5</SB>denote temperatures, in which a melting viscosity is 10<SP>4</SP>Pa s, measured by the flow tester method at load 5 MPa respectively. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrostatic latent image developing toner and an electrostatic charge image developer that can be used in an electrophotographic apparatus (image forming apparatus) using an electrophotographic process such as a copying machine, a printer, and a facsimile machine. The present invention also relates to a toner cartridge, a process cartridge, an image forming method, and an image forming apparatus.

A method of visualizing image information through an electrostatic charge image such as electrophotography is currently used in various fields. In electrophotography, an electrostatic charge image (electrostatic latent image) is formed on a photoreceptor (image carrier) by charging and exposure processes, the electrostatic latent image is developed with a developer containing toner, and a transfer and fixing process. It is visualized through. The developer used here includes a two-component developer composed of a toner and a carrier, and a one-component developer using a magnetic toner or a non-magnetic toner alone. The toner is usually produced by using a thermoplastic resin as a pigment. In addition, a kneading and pulverizing method is used in which the mixture is melt-kneaded with a release agent such as a charge control agent and wax, cooled, finely pulverized, and further classified. In these toners, if necessary, inorganic and organic particles for improving fluidity and cleaning properties may be added to the toner particle surfaces.
On the other hand, in the image forming method using the electrophotographic method, in order to reduce energy consumption, a technology capable of fixing at a lower temperature is desired. Especially in recent years, in order to thoroughly save energy, fixing is performed except during use. It is desirable to stop energizing the machine. Accordingly, the temperature of the fixing device needs to be energized and instantaneously raised to the use temperature, and therefore it has been required to lower the fixing temperature of the toner.

  Also, certain combinations using polymers that are hard at room temperature (high glass transition temperature (high Tg)) and soft (low Tg) polymers exhibit fluidity below the melting point of those polymers under pressure. Therefore, it is possible to perform pressure molding at a temperature below the melting point. A polymer material having such properties is called baroplastic. For example, Patent Document 1 discloses baroplastics, and pressure-formed bodies, elastomers, and pressure-sensitive adhesives are listed as application areas.

Further, the following are known.
Patent Document 2 discloses a latent image forming step of forming an electrostatic latent image on the surface of the latent image holding member, and the electrostatic latent image formed on the surface of the latent image holding member is used as an electrostatic charge image developing toner or the toner and carrier. A development process for developing a toner image by developing with an electrostatic charge image developer containing the toner, a process for transferring the toner image formed on the surface of the latent image holding body to the surface of the transfer body, and a transfer to the surface of the transfer body An image forming method including a fixing step for pressure-fixing a toner image, wherein the toner includes a block copolymer having a crystalline polyester block and an amorphous polyester block, and the maximum pressure during fixing is 1 MPa. An image forming method characterized in that it is 10 MPa or less is disclosed.
Patent Document 3 discloses an electrostatic charge image developing toner obtained by agglomerating resin particles having a core-shell structure, and the resin constituting the core and the shell is an amorphous resin, and the resin constituting the core The glass transition point of the resin and the glass transition point of the resin constituting the shell are different by 20 ° C. or more, and the resin constituting the shell contains an acidic or basic polar group or an alcoholic hydroxyl group. An electrostatic charge image developing toner is disclosed.
Patent Document 4 discloses a toner for developing an electrostatic charge image obtained by agglomerating resin particles having a core-shell structure, wherein the resin constituting the core and the shell contains a polycondensation resin, and the glass transition of the resin constituting the core Disclosed is a toner for developing an electrostatic charge image, wherein the difference between the point and the glass transition point of the resin constituting the shell is 20 ° C. or more.

US Pat. No. 6,632,883 JP 2007-114635 A JP 2007-310064 A JP 2007-322953 A

  An object of the present invention is to provide an electrostatic image developing toner capable of preventing wax offset at the time of pressure fixing at 10 to 50 ° C.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <3>, <4>, <5>, <6> or <8>. It is shown below together with <2>, <7> and <9> which are preferred embodiments.
<1> Satisfying the formula (1), including a binder resin, a colorant, and a wax, wherein the wax satisfies the following formula (2) and / or the following formula (2), and the number An electrostatic charge image developing toner comprising paraffin having an average molecular weight Mn of 800 or less and a molecular weight distribution (Mw / Mn) of 1.25 or more;
ΔT _t = T _t1 -T _t5 ≧ 20 ° C (1)
(In formula (1), T _t1 represents the temperature at which the melt viscosity of the toner measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _t5 represents the melting of the toner measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)
ΔT _w = T _w1 −T _w5 ≧ 20 ° C. (2)
(In formula (2), T _w1 represents the temperature at which the melt viscosity of the wax measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _w5 represents the melting of the wax measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)
<2> The electrostatic charge image developing toner according to <1>, wherein the wax contains paraffin having a number average molecular weight Mn of 800 or less and a molecular weight distribution (Mw / Mn) of 1.25 or more.
<3> An electrostatic charge image developer comprising the electrostatic charge image developing toner according to <1> or <2>, and a carrier,
<4> a toner cartridge containing at least the electrostatic charge image developing toner according to <1> or <2>;
<5> A process cartridge comprising a developer holder and containing the electrostatic charge image developing toner according to <1> or <2>, or the electrostatic charge image developer according to <3>,
<6> A latent image forming step for forming an electrostatic latent image on the surface of the image carrier, and a developing step for developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner to form a toner image. And a transfer step of transferring the toner image to the surface of the transfer member, and a fixing step of pressure-fixing the toner image transferred to the surface of the transfer member at 10 to 50 ° C. Or an image forming method using the electrostatic charge image developing toner according to <2>, or the electrostatic charge image developer according to <3>,
<7> The image forming method according to <6>, wherein the maximum pressure during fixing in the fixing step is 1 MPa or more and 5 MPa or less,
<8> Image carrier, charging unit for charging the image carrier, exposure unit for exposing the charged image carrier to form an electrostatic latent image on the surface of the image carrier, and development including toner Developing means for developing the electrostatic latent image with an agent to form a toner image, transfer means for transferring the toner image from the image holding member to the surface of the transfer target, and toner transferred to the surface of the transfer target A fixing unit that pressure-fixes the image at 10 to 50 ° C., and the electrostatic image developing toner according to <1> or <2> or the electrostatic image according to <3>. An image forming apparatus using a developer,
<9> The image forming apparatus according to <8>, wherein the fixing unit is a unit including a maximum pressure setting range of 1 MPa to 5 MPa in fixing.

According to the invention described in <1> above, it is possible to provide an electrostatic image developing toner capable of preventing wax offset during pressure fixing at 10 to 50 ° C.
According to the invention described in the above <2>, compared to the invention described in the above <1>, the electrostatic charge image development that can prevent the offset of the wax at the time of pressure fixing at 10 to 50 ° C. Toner can be provided.
According to the invention described in <3> above, it is possible to provide an electrostatic charge image developer capable of preventing wax offset during pressure fixing at 10 to 50 ° C.
According to the invention described in <4>, it is possible to provide a toner cartridge containing an electrostatic charge image developing toner capable of preventing wax offset during pressure fixing at 10 to 50 ° C.
According to the invention described in <5> above, a process cartridge containing an electrostatic charge image developing toner or an electrostatic charge image developer capable of preventing wax offset during pressure fixing at 10 to 50 ° C. is provided. can do.
According to the invention described in <6> above, it is possible to provide an image forming method capable of preventing wax offset during pressure fixing at 10 to 50 ° C.
According to the invention described in <7> above, an image forming method capable of further preventing the offset of wax at the time of pressure fixing at 10 to 50 ° C. as compared with the invention described in <6> above. Can be provided.
According to the invention described in <8> above, it is possible to provide an image forming apparatus capable of preventing defective melting of wax and offset during pressure fixing at 10 to 50 ° C.
According to the invention described in <9>, an image forming apparatus capable of further preventing the offset of wax at the time of pressure fixing at 10 to 50 ° C. as compared with the invention described in <8>. Can be provided.

This embodiment will be described in detail below.
In the present embodiment, the description “A to B” represents not only a range between A and B but also a range including A and B at both ends thereof. For example, if “A to B” is a numerical value range, “A or more and B or less” or “B or more and A or less” is represented.

(Electrostatic image developing toner)
The electrostatic image developing toner (hereinafter also referred to as “toner”) of the present embodiment satisfies the formula (1) and includes a binder resin, a colorant, and a wax, and the wax is represented by the following formula (2). And / or a paraffin having a number average molecular weight Mn of 800 or less and a molecular weight distribution (Mw / Mn) of 1.25 or more. .
ΔT _t = T _t1 -T _t5 ≧ 20 ° C (1)
(In formula (1), T _t1 represents the temperature at which the melt viscosity of the toner measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _t5 represents the melting of the toner measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)
ΔT _w = T _w1 −T _w5 ≧ 20 ° C. (2)
(In formula (2), T _w1 represents the temperature at which the melt viscosity of the wax measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _w5 represents the melting of the wax measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)

Conventionally, as a means for lowering the toner fixing temperature, it is known to use a polycondensation type crystalline resin exhibiting sharp melting behavior with respect to temperature as a binder resin constituting the toner. Toners that use a large amount of photosensitive resin are prone to yield deformation, and when they are actually used, troubles such as filming on the photoreceptor due to toner crushing or a decrease in transfer efficiency over time cannot be avoided. It was.
As described above, as the conventional image forming method, fixing is mainly promoted by heating rather than pressure. Therefore, energy reduction during fixing in the electrophotographic method does not greatly improve the improvement by changing the trend. There was no means to realize high-speed fixing with a simple fixing machine, which is important when responding to the printing market with electrophotography. As a resin for toner that promotes fixing by heating, a random monomer chain resin has been widely used also in addition polymerization and polycondensation.

Under these circumstances, as a toner fixing method, a fixing method by applying a pressure has been studied as a method instead of thermal fixing, and various methods using a low Tg binder resin, a solid core capsule structure, a liquid core capsule structure, and the like have been studied. Attempts have been made.
However, when these encapsulated toners are used in a normal electrophotographic process, it is difficult to obtain sufficient fixing performance, and particularly in full-color toners, the color is insufficient due to insufficient melting, It has been confirmed that bright colors are not developed.
In addition, a heatless pressure fixing method combined with toner microencapsulation, etc. is conceivable. However, since toner melting is difficult compared to heat fixing and the anchoring action is weak, paper selectivity, image quality, density when printing solid images, etc. Image quality defects such as unevenness, insufficient density and poor color development were likely to occur. For this reason, a fixing method using heat, which has excellent meltability and easily obtains high image quality, has been used.

By using the baroplastic resin, a color-fixed image can be obtained at room temperature. However, the toners described in Patent Documents 2 to 4 contain a baroplastic resin exhibiting pressure plasticity, while a wax. Does not show pressure plasticity.
Therefore, even when a color image such as a primary color, fine line, or character is printed, if a solid image of the secondary color is printed, there is a defect in the melting of the wax in the fixed image that is considered to be caused by the wax not melting due to pressure. Occurring and offsetting the wax to the fixing roll causes color loss and secondary color gloss unevenness.

In order to improve the melting failure and offset of the wax in the fixed image, it is necessary that not only the resin but also the wax exhibit pressure meltability when pressure is applied.
Conventionally, it has been thought that there is no such wax that exhibits pressure plasticity. However, as a result of detailed investigations by the present inventors, a wax that satisfies certain certain characteristics may exhibit pressure fluidity. confirmed.
In particular, paraffin-based and fatty acid amide (fatty acid amide) -based waxes having certain characteristics are subjected to pressure plasticity and fluidity due to the collapse of the crystal structure when a certain pressure or more is applied.
On the other hand, natural waxes such as carnauba wax and fatty acid ester waxes did not exhibit the above pressure fluidity.
By using the electrostatic charge image developing toner of this embodiment using a wax that satisfies the above formula (1) and exhibits pressure fluidity, defective melting of the wax in the fixed image occurs or the wax is offset to the fixing roll. This prevents the occurrence of gloss unevenness that occurs when a solid color secondary color solid image is printed.

In the pressure fixing toner, the toner particles are reversibly deformed with respect to the transfer pressure due to the viscoelastic property of the resin due to the transfer pressure when the photoconductor and the transfer body are in contact in the transfer process.
The toner particles for pressure fixing are more easily deformed reversibly depending on the presence or absence of the transfer pressure than the toner particles for heat fixing. Toner particles that are close to each other and charged to the same polarity are likely to generate so-called blur, in which toner is scattered during transfer due to electrostatic repulsion.
Since conventional waxes are not pressure plastic and do not have viscoelasticity, even when the wax is present in a compatible, semi-compatible or incompatible state with the resin, the wax is applied when pressure is applied. Therefore, the toner base particles whose resin is the main constituent material are easily deformed. As a result, blurring occurs.
However, the electrostatic charge image developing toner of the present embodiment using a wax exhibiting pressure fluidity does not cause melting of the wax with respect to the transfer pressure, but exhibits viscoelastic properties and the wax itself is reversible with respect to the pressure. Shrink to.
Due to the pressure shrinkage of the wax, the deformation amount of the toner base particles is suppressed as compared with the conventional wax, so that the occurrence of blur during transfer is prevented.
In the pressure fixing toner, the toner particles are reversibly changed with respect to the transfer pressure due to the viscoelastic property of the resin due to the transfer pressure when the photoconductor and the transfer body are in contact in the transfer process.
Since the pressure fixing toner particles are more likely to be plastically deformed with respect to the pressure than the heat fixing toner particles, the pressure fixing toner particles are more likely to be deformed with respect to the pressure applied during transfer. For this reason, toner particles come close to each other due to reversible deformation or crushing at the time of transfer, and toner particles charged to the same polarity generate so-called blur in which the toner is scattered at the time of transfer due to electrostatic repulsion. It becomes easy.
Since conventional waxes are not pressure plastic and do not have viscoelasticity, even when the wax is present in a compatible, semi-compatible or incompatible state with the resin, the wax is applied when pressure is applied. Therefore, the toner base particles whose resin is the main constituent material are easily deformed. As a result, blurring occurs.
However, the electrostatic charge image developing toner of the present embodiment using a wax exhibiting pressure fluidity does not cause melting of the wax with respect to the transfer pressure, but exhibits viscoelastic properties and the wax itself is reversible with respect to the pressure. Shrink to.
Due to the microscopic pressure shrinkage of the wax, the deformation amount of the toner base particles is suppressed as compared with the conventional wax, so that the occurrence of blur during transfer is prevented.

  The electrostatic charge image developing toner according to the present embodiment uses a specific wax that satisfies the above-described formula (1) and exhibits pressure fluidity, thereby preventing defective melting and offset of the wax during normal temperature fixing. In addition, since the electrostatic charge image developing toner of the present embodiment prevents the melting failure and offset of the wax, for example, adhesion of the toner image, prevention of gloss unevenness when printing a color secondary solid image, and fine lines of the toner image Excellent reproducibility.

The electrostatic image developing toner of the present embodiment is a toner that satisfies the formula (1).
ΔT _t = T _t1 -T _t5 ≧ 20 ° C (1)
In the formula (1), T _t1 represents a temperature at which the melt viscosity of the toner measured by the flow tester method is 10,000 Pa · s at a load of 1 MPa (10 kgf / cm ² ), and T _t5 represents a load of 5 MPa (50 kgf / cm ^2). ) Represents the temperature at which the melt viscosity of the toner measured by the flow tester method reaches 10,000 Pa · s.
In order to satisfy the formula (1), the pressure fluidity of the whole toner is required, and the binder resin in the toner that greatly affects the pressure fluidity of the toner is a resin exhibiting pressure fluidity as described later. It is preferable.
[Delta] T _t in equation (1) is 20 ° C. or higher, preferably from 20 to 100 ° C., more preferably from 30 to 95 ° C., and more preferably a 30 to 90 ° C..

The method for measuring ΔT _t is not particularly limited as long as it is a measurement method by a flow tester method, but a method using a flow tester CFT-500A manufactured by Shimadzu Corporation is preferable.
Specifically, using a flow tester CFT-500A manufactured by Shimadzu Corporation, when each load of 5 MPa and 1 MPa was applied, the temperature was increased from 25 ° C. at a heating rate = 1 ° C./min. A method for measuring the temperature at 10,000 Pa · s under a pressure of 5 MPa and 1 MPa, respectively, is particularly preferred.
The toner used for measurement is molded by compression molding.
As a molded product, about 1.20 g of toner is weighed and molded so that the diameter Φ = 10 mm and the height = about 10 mm. The machine used for molding is not particularly limited, but it is preferable to use a molding jig with Φ = 10 mm.
In addition, it is also possible to use an extrusion plastometer defined by JIS K6760 as a test machine.
The diameter of the die (hole) used for the flow tester measurement is preferably 0.5 mmΦ to 1 mmΦ. Within the above range, the fluidity of the toner is moderate due to pressurization and heating, so that the measurement is easy and the measurement accuracy is excellent.
The measuring method includes an elevated flow tester and a lossy peak flow tester defined in JIS K7210. Although there are slight differences in the measuring method, in principle, the fluidity is measured by the amount of resin discharged.

<Wax>
The wax used in the present embodiment satisfies the formula (2) (hereinafter also referred to as “specific fatty acid amide”) and / or satisfies the formula (2), and the number average molecular weight Mn is 800 or less. And paraffin (hereinafter also referred to as “specific paraffin”) having a molecular weight distribution (Mw / Mn) of 1.25 or more.
ΔT _w = T _w1 −T _w5 ≧ 20 ° C. (2)
In formula (2), T _w1 represents the temperature at which the melt viscosity of the wax measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _w5 represents the melt viscosity of the wax measured by the flow tester method at a load of 5 MPa. Represents a temperature at which is 10,000 Pa · s.
ΔT _w in the formula (2) is 20 ° C. or higher, preferably 20 to 70 ° C., more preferably 25 to 65 ° C., and still more preferably 30 to 60 ° C.

The ΔT _w measurement method is not particularly limited as long as it is a measurement method based on the flow tester method, but a method using a flow tester CFT-500A manufactured by Shimadzu Corporation is preferable.
Specifically, using a flow tester CFT-500A manufactured by Shimadzu Corporation, when each load of 5 MPa and 1 MPa was applied, the temperature was increased from 25 ° C. at a heating rate = 1 ° C./min. A method for measuring the temperature at 10,000 Pa · s under a pressure of 5 MPa and 1 MPa, respectively, is particularly preferred.
Further, as a method for measuring the [Delta] T _w of the wax from the toner is not particularly limited, for example, may measure the [Delta] T _w to separate the wax from the toner, to identify the wax used in the toner, use ΔT _w may be measured for the same wax as the wax being applied.
The wax used for the measurement is molded by compression molding a powder obtained by a mortar or a simple pulverizer (ultracentrifugal pulverizer).
As a molded product, about 1.10 g of wax is weighed and molded so that the diameter Φ = 10 mm and the height = about 10 mm. The machine used for molding is not particularly limited, but it is preferable to use a molding jig with Φ = 10 mm.
The diameter of the die (hole) used for the flow tester measurement is preferably 0.5 mmΦ to 1 mmΦ. Within the above range, the fluidity of the toner is moderate due to pressurization and heating, so that the measurement is easy and the measurement accuracy is excellent.

The specific fatty acid amide (specific fatty acid amide) is not particularly limited as long as it is a fatty acid amide satisfying the formula (2), but is preferably a fatty acid amide that is solid at 25 ° C. The melting point of the characteristic fatty acid amide is preferably 90 ° C. or less, more preferably 25 ° C. or more and 85 ° C. or less, and further preferably 50 ° C. or more and 85 ° C. or less. Within the above range, the hardness of the wax at the fixing temperature is moderate, so it is excellent in releasability from the fixing roll, offset to the wax fixing roll is suppressed, and fixing defects such as image omission are suppressed, In addition, since the hardness of the wax at normal temperature is moderate, deformation and aggregation of the toner due to agitation stress in the developing machine is suppressed, the developability is excellent, and image quality such as a color point is deteriorated.
It is also fatty amides used in the present invention, monoamides (CONH _2), substituted amide (CONH), bisamide (CONH~NHCO), methylol amide (CONHCH ₂ OH), ester amide (CONH~COO~), A substituted urea compound (NHCONH) and the like are exemplified, and monoamide is preferable.
Fatty acid amides used in the present invention are particularly preferably fatty acid monoamides, such as stearic acid amide, oleic acid amide, erucic acid amide, behenic acid amide, N-oleyl palmitoamide, N-stearyl ergaamide, and the like. It is done.

The specific paraffin is not particularly limited as long as it satisfies the formula (2), the number average molecular weight Mn is 800 or less, and the molecular weight distribution (Mw / Mn) is 1.25 or more.
Paraffin is a general term for chain saturated hydrocarbons represented by the general formula C _n H _{2n + 2} , and may be linear or branched.
The specific paraffin has a number average molecular weight Mn of 800 or less and a molecular weight distribution (Mw (weight average molecular weight) / Mn (number average molecular weight)) of 1.25 or more. A variety of carbon chains are mixed. When pressure is applied (applying pressure), the crystal structure in which the molecules are arranged collapses, and the molecular chains mix and melt. But the phenomenon of flowing occurs.

The number average molecular weight Mn of the specific paraffin is 800 or less, preferably 200 to 800, more preferably 300 to 700, and still more preferably 400 to 600.
The molecular weight distribution (Mw / Mn) of the specific paraffin is 1.25 or more, preferably 1.25 to 3.0, more preferably 1.25 to 2.0, 1.25 More preferably, it is -1.8.
The specific paraffin is preferably a saturated hydrocarbon having 20 or more carbon atoms, more preferably a saturated hydrocarbon having 20 to 80 carbon atoms, and still more preferably a saturated hydrocarbon having 20 to 43 carbon atoms. .
The specific paraffin is preferably a solid paraffin at 25 ° C.
The melting point of the specific paraffin is preferably 90 ° C. or less, more preferably 25 ° C. or more and 85 ° C. or less, and further preferably 50 ° C. or more and 85 ° C. or less.
The specific paraffin is preferably a paraffin containing at least a long-chain saturated hydrocarbon (solid petroleum wax) and a short-chain saturated hydrocarbon (liquid paraffin).
The long-chain saturated hydrocarbon is preferably a saturated hydrocarbon having a molecular weight of 300 to 800, and more preferably a saturated hydrocarbon having a molecular weight of 350 to 700.
The short-chain saturated hydrocarbon is preferably a saturated hydrocarbon having a molecular weight of 200 to 500, and more preferably a saturated hydrocarbon having a molecular weight of 200 to 400.

In the electrostatic image developing toner of the present embodiment, the wax may be contained singly or in combination of two or more. In addition, the electrostatic charge image developing toner of the present embodiment may contain both the specific fatty acid amide and the specific paraffin, or may contain only one of them.
The wax content in the electrostatic image developing toner of this embodiment is preferably 1 to 20 parts by weight and more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the binder resin.

<Binder resin>
The electrostatic image developing toner of this embodiment contains a binder resin.
The binder resin used in the present embodiment is preferably a resin exhibiting pressure fluidity, that is, a baroplastic, a resin having a high glass transition temperature (hereinafter also referred to as “high Tg resin”) and a low. A resin composed of at least a glass transition temperature resin (hereinafter also referred to as “low Tg resin”) is preferable.
When a high Tg resin and a low Tg resin form a micro phase separation state, the resin exhibits a plastic behavior with respect to pressure, and exhibits fluidity even in a normal temperature region under a certain pressure or higher. Such resin is called baroplastic.

  As a resin constituted by combining at least a high Tg resin and a low Tg resin, (A) a block co-polymer having two types of blocks and having a difference in glass transition temperature between the two types of blocks of 20 ° C. or more. (B) a resin obtained by agglomerating at least resin particles having a core-shell structure in which the difference between the glass transition temperature of the resin constituting the core and the glass transition temperature of the resin constituting the shell is 20 ° C. or higher, and / or ( C) A resin mixture in which a sea-island structure is formed by two kinds of resins having a difference in glass transition temperature of 20 ° C. or more. (A) It has two kinds of blocks, and the two kinds of blocks The difference between the glass transition temperature of the block copolymer having a glass transition temperature difference of 20 ° C. and / or (B) the resin constituting the core and the glass transition temperature of the resin constituting the shell is 20 ° C. And more preferably a core-shell resin particles is above at least aggregated resin.

The Tg of the high Tg phase made of the high Tg resin is preferably 45 to 120 ° C, more preferably 50 to 110 ° C. When the Tg of the high Tg phase is 45 ° C. or more, the toner is excellent in storability, and it is difficult for filming to occur on the photoreceptor during caking or continuous printing during transportation or in a printer, It is preferable because image quality defects are less likely to occur. Further, it is preferable that the Tg of the high Tg phase is 120 ° C. or lower because the fixing temperature at the time of fixing (especially at the time of thick paper fixing) is moderate and damage to the recording medium such as curling is unlikely to occur.
Further, it is important that the Tg of the low Tg phase made of the low Tg resin is 20 ° C. or more lower than the Tg of the high Tg phase, and preferably 30 ° C. or less. When the Tg difference between the high Tg phase and the low Tg phase is within 20 ° C., the pressure plasticization behavior becomes difficult to be observed, the fixing temperature at the time of fixing (especially at the time of fixing to thick paper) becomes high, and curling to the recording medium such as curling. Damage is prevented.
In addition, in a resin in which resin particles having a core-shell structure are at least aggregated, it is preferable that the core is made of a low Tg resin and the shell layer is made of a high Tg resin. By using a low Tg resin as a core and a high Tg resin as a shell, the low Tg layer is not exposed to the resin particles so that each particle is formed. Since it is not exposed to the surface, the powder fluidity and storage property of the particles are secured.

[(A) a block copolymer having two types of blocks and having a glass transition temperature difference of 20 ° C. or more between the two types of blocks]
As the binder resin, (A) a block copolymer having two types of blocks and having a difference in glass transition temperature between the two types of blocks of 20 ° C. or more is preferable.
For the formation of each block of the block copolymer, an addition polymerization resin or a polycondensation resin may be used, and the former is exemplified by a homopolymer or a copolymer of an ethylenically unsaturated compound, Examples of the latter include polyester-based homopolymers or copolymers.
Polyester block copolymers include polyester block copolymers such as crystalline polyester blocks and non-crystalline polyester blocks.

The block copolymer is preferably a block copolymer having a block having a glass transition temperature of 60 ° C. or higher and a block having a glass transition temperature of 20 ° C. or lower.
Examples of the ethylenically unsaturated compound preferably used for producing a block having a glass transition temperature of 60 ° C. or higher include styrenes such as styrene, parachlorostyrene, and α-methylstyrene, and styrene is preferably used.
Moreover, as an ethylenically unsaturated compound preferably used for polymerization of a block having a glass transition temperature of 20 ° C. or lower, (meth) acrylic acid esters are preferable, acrylic acid esters are more preferable, and an alkyl group has 1 to 8 carbon atoms. More preferred are alkyl acrylates that are: methyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, and the like.
In preparation for block copolymerization of these ethylenically unsaturated compounds, various living polymerization methods such as anion polymerization, cation polymerization, radical polymerization, and coordination polymerization may be used. It is preferable to use a living radical polymerization method because of its ease.
The number average molecular weight Mn of the block copolymer is preferably 10,000 to 150,000, more preferably 20,000 to 100,000, and 30,000 to 60,000. Further preferred. The above range is preferable because sufficient pressure plasticizing flow behavior can be obtained.

The polyester block copolymer will be described.
The polyester-based block copolymer is produced by a polymer reaction or a polycondensation reaction. More specifically, for example, a method in which a mixture of a crystalline polyester resin and an amorphous polyester resin is bonded by a polymerization reaction, a crystalline polyester resin produced in advance is mixed with an amorphous polyester resin-forming monomer. For example, a polymerization method or the reverse method is used.

The polyester block copolymer preferably has a high Tg block glass transition temperature of 60 ° C. or higher, more preferably 70 to 110 ° C.
The high Tg block and the low Tg block preferably occupy 60% by weight or more of the block copolymer, more preferably 80 to 100% by weight, and the block copolymer is higher than the high Tg block and the low Tg block. More preferably, it is a diblock copolymer.
As a ratio of the high Tg block and the low Tg block, when the total amount of the high Tg block and the low Tg block is 100% by weight, the ratio of the high Tg block is preferably 25 to 75% by weight.

  Furthermore, the difference between the glass transition temperature of the high Tg resin forming the high Tg block and the glass transition temperature of the low Tg resin forming the low Tg block is 20 ° C. or higher, preferably 30 ° C. or higher, preferably 40 ° C. More preferably, it is more preferably 60 ° C. or higher.

Specific examples of the blocks forming the polyester block copolymer include a crystalline polyester block and an amorphous polyester block.
The crystalline polyester resin and non-crystalline polyester resin forming these blocks include, for example, aliphatic, alicyclic, aromatic polyvalent carboxylic acids or their alkyl esters, polyhydric alcohols or their ester compounds, hydroxy It is produced by using a polycondensable monomer such as carboxylic acid and performing polycondensation by direct esterification reaction or transesterification reaction in an aqueous medium.
“Crystallinity” as shown in the above “crystalline polyester resin” means that, in differential scanning calorimetry (DSC), it has a clear endothermic peak, not a stepwise endothermic change. Means that the half-value width of the endothermic peak when measured at a heating rate of 10 ° C./min is within 15 ° C.
On the other hand, a resin in which the half-value width of the endothermic peak exceeds 15 ° C. or a resin in which no clear endothermic peak is observed means that it is amorphous (amorphous).

The polyvalent carboxylic acid used as the polycondensable monomer is a compound containing two or more carboxyl groups in one molecule. Among these, dicarboxylic acid is a compound containing two carboxyl groups in one molecule. For example, oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid Nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, Pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o -Phenylene diglycolic acid, diphenylacetic acid, Examples include phenyl-p, p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, cyclohexanedicarboxylic acid, and the like. The
Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid.
Moreover, you may use what derived the carboxyl group of these carboxylic acid into the acid anhydride, mixed acid anhydride, acid chloride or ester.

The polyol used as the polycondensable monomer is a compound containing two or more hydroxyl groups in one molecule. Among these, the diol is a compound containing two hydroxyl groups in one molecule, and examples thereof include ethylene glycol, propylene glycol, butanediol, diethylene glycol, hexanediol, cyclohexanediol, octanediol, decanediol, and dodecanediol. It is done.
Examples of polyols other than diols include glycerin, pentaerythritol, hexamethylol melamine, hexaethylol melamine, tetramethylol benzoguanamine, and tetraethylol benzoguanamine.
Since these polyols are hardly soluble or insoluble in the aqueous medium, the ester synthesis reaction proceeds in the monomer droplets in which the polyol is dispersed in the aqueous medium.

Moreover, hydroxycarboxylic acid is used as a polycondensable monomer.
Hydroxycarboxylic acid is a compound having both a hydroxyl group and a carboxyl group in the molecule. Examples of the hydroxycarboxylic acid include aromatic hydroxycarboxylic acids and aliphatic hydroxycarboxylic acids, but it is preferable to use aliphatic hydroxycarboxylic acids.
Examples of the hydroxycarboxylic acid used as the polycondensable monomer include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, tartaric acid, mucoic acid, malic acid, citric acid, and lactic acid.

By combining these polycondensable monomers, an amorphous polyester resin or a crystalline polyester resin can be easily obtained.
As the polyvalent carboxylic acid used to obtain the crystalline polyester resin, among the above carboxylic acids, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid Maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, isododecyl succinic acid, isododecenyl succinic acid, n-octyl succinic acid, n-octenyl succinic acid, These acid anhydrides or acid chlorides can be mentioned.

  Examples of the polyol used to obtain the crystalline polyester resin include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene diol glycol, 1,3-propylene glycol, 1,4-butane diol, 1, 4-butenediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, etc. It is done.

Further, a crystalline polyester resin obtained by ring-opening polymerization of a cyclic monomer such as caprolactone is preferable because the crystal melting point is in the vicinity of 60 ° C. and in a region suitable as a toner.
Examples of such crystalline polyester resins include polyester resins obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, or cyclohexanediol and adipic acid, 1,6-hexanediol and sebacic acid. A polyester resin obtained by reacting ethylene glycol and succinic acid, a polyester resin obtained by reacting ethylene glycol and sebacic acid, 1,4-butanediol and succinic acid The polyester resin obtained by reacting is mentioned. Among these, polyester resins obtained by reacting 1,9-nonanediol and 1,10-decanedicarboxylic acid, and 1,6-hexanediol and sebacic acid are more preferable.

The polyvalent carboxylic acid used to obtain the non-crystalline polyester resin includes phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid among the above polyvalent carboxylic acids. Acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid , Naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracene dicarboxylic acid, and cyclohexanedicarboxylic acid. Examples of the polyvalent carboxylic acid other than dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, and pyrenetetracarboxylic acid. Moreover, you may use what derived the carboxyl group of these carboxylic acid to the acid anhydride, the acid chloride, or ester.
Among these, it is preferable to use terephthalic acid or its lower ester, diphenylacetic acid, cyclohexanedicarboxylic acid, or the like. The lower ester refers to an ester of an aliphatic alcohol having 1 to 8 carbon atoms.

Moreover, as a polyol used in order to obtain an amorphous polyester resin, it is preferable to use especially polytetramethylene glycol, bisphenol A, bisphenol Z, hydrogenated bisphenol A, cyclohexane dimethanol, etc. among the above-mentioned polyols. .
Examples of the amorphous resin include a polycondensate of hydroxycarboxylic acid.
Specific examples include hydroxyheptanoic acid, hydroxyoctanoic acid, hydroxydecanoic acid, hydroxyundecanoic acid, and lactic acid. Of these, lactic acid is preferably used.

Moreover, an amorphous polyester resin or a crystalline polyester resin can be easily obtained by a combination of the above polycondensable monomers.
In order to produce one type of polycondensation resin, each of the polyvalent carboxylic acid and polyol may be used alone or in combination of two or more, each of which may be used alone or in combination of two or more. You may use each. Moreover, when using hydroxycarboxylic acid in order to produce 1 type of polycondensation resin, 1 type may be used individually, 2 or more types may be used, and polyvalent carboxylic acid and a polyol may be used together.

  When a crystalline polyester resin and an amorphous polyester resin are mixed and a block copolymer is obtained by a polymerization reaction, the crystalline polyester resin preferably has a crystalline melting point of 40 to 150 ° C. More preferably, it is 120 degreeC, and it is especially preferable that it is 50-90 degreeC.

  The melting point of the crystalline polyester resin is measured by, for example, “DSC-20” (manufactured by Seiko Instruments Inc.) according to differential scanning calorimetry (DSC). Specifically, about 10 mg of a sample is heated at a constant temperature. It is determined as the melting peak temperature of the input compensated differential scanning calorimetry shown in JIS K-7121: 87 when the measurement is performed at a rate of 10 ° C. per minute from room temperature to 150 ° C. at a rate (10 ° C./min). The crystalline resin may show a plurality of melting peaks, but in this embodiment, the maximum peak is regarded as the melting point.

  On the other hand, when a crystalline polyester resin and an amorphous polyester resin are mixed and a block copolymer is obtained by a polymerization reaction, the glass transition point Tg of the amorphous polyester resin is preferably 50 to 80 ° C., More preferably, it is 50-65 degreeC.

Here, the glass transition point of the non-crystalline resin refers to a value measured by a method (DSC method) defined in ASTM D3418-82.
Moreover, the measurement of the glass transition point in this embodiment is measured by, for example, “DSC-20” (manufactured by Seiko Instruments Inc.) according to the differential scanning calorimetry (DSC), specifically, About 10 mg of the sample is heated at a constant rate of temperature increase (10 ° C./min), and the glass transition point can be obtained from the intersection of the baseline and the endothermic peak slope.
Moreover, in this embodiment, it is preferable that the glass transition temperature of a block copolymer is 50-80 degreeC, and it is more preferable that it is 50-65 degreeC.
Moreover, it is preferable that it is 50-100 degreeC, and, as for melting | fusing point of a block copolymer, it is more preferable that it is 50-80 degreeC. It is preferable that the melting point of the block copolymer is in the above range since the cleaning property is improved.
In the block copolymer, the melting point and glass transition temperature may not be clearly observed.

When a crystalline polyester resin and an amorphous polyester resin are mixed and a block copolymer is obtained by a polymerization reaction, the weight average molecular weight Mw of the crystalline polyester resin to be mixed is 1,000 to 100,000. Is preferable, and it is more preferable that it is 1,500-10,000. Moreover, it is preferable that the weight average molecular weight Mw of the amorphous polyester resin to mix is 1,000-100,000, and it is more preferable that it is 2,000-10,000.
The weight average molecular weight Mw of the polyester-based block copolymer is preferably 5,000 to 500,000, and more preferably 5,000 to 50,000.
The polyester block copolymer may be partially branched or cross-linked by selecting the carboxylic acid valence or alcohol valence of the monomer, adding a cross-linking agent, or the like.

Note that the values of the weight average molecular weight Mw and the number average molecular weight Mn are determined by various known methods, and there are slight differences depending on the measurement method, but in the present embodiment, the values may be determined by the following measurement method. preferable. That is, the weight average molecular weight Mw and the number average molecular weight Mn are measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) is flowed at a flow rate of 1.2 ml per minute, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml is injected as a sample weight for measurement. When measuring the molecular weight of a sample, select the measurement conditions that fall within the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are linear, using several monodisperse polystyrene standard samples. .
The reliability of the measurement results was confirmed by the NBS706 polystyrene standard sample performed under the above-described measurement conditions having a weight average molecular weight Mw = 28.8 × 10 ⁴ and a number average molecular weight Mn = 13.7 × 10 ^4. Is done.
As the GPC column to be used, any column may be adopted as long as it satisfies the above conditions. Specifically, for example, TSK-GEL, GMH (manufactured by Tosoh Corporation) and the like are used.
In addition, a solvent and measurement temperature are not limited to the conditions described above, You may change to an appropriate condition.

Crystalline and non-crystalline polyester resins are produced by polycondensation reaction of polyol and polyvalent carboxylic acid according to a conventional method. This polycondensation reaction can be carried out by general polycondensation methods such as underwater polymerization such as bulk polymerization, emulsion polymerization and suspension polymerization, solution polymerization, and interfacial polymerization, but bulk polymerization is preferably used. Although the reaction is possible under atmospheric pressure, general conditions such as reduced pressure and nitrogen flow are used for the purpose of increasing the molecular weight of the resulting polyester molecule.
Specifically, the above polyhydric alcohol and polyvalent carboxylic acid, and if necessary, a catalyst are added, blended in a reaction vessel equipped with a thermometer, a stirrer, and a flow-down condenser, and an inert gas (nitrogen gas, etc.) By heating in the presence, continuously removing by-product low molecular weight compounds out of the reaction system, stopping the reaction when a predetermined acid value is reached, cooling, and obtaining the desired reactant Manufactured.

[(B) Resin obtained by aggregating at least resin particles having a core-shell structure in which the difference between the glass transition temperature of the resin constituting the core and the glass transition temperature of the resin constituting the shell is 20 ° C. or more]
As the binder resin, a resin obtained by aggregating at least resin particles having a core-shell structure in which the difference between the glass transition temperature of the resin constituting the core and the glass transition temperature of the resin constituting the shell is 20 ° C. or more is preferably used. Is done.
The core-shell particles are preferably such that the difference between the glass transition point of the resin constituting the core and the glass transition point of the resin constituting the shell is 20 ° C. or more. By setting the temperature difference of the glass transition point to 20 ° C. or more, plastic behavior with respect to pressure is expressed.

In the emulsion polymerization, when a method called stepwise feeding a monomer called a two-stage feed is used, core-shell particles made of Tg resins having different cores and shells can be obtained.
However, if the core-shell particles are mixed and processed at high temperature and high pressure as in the prior art, such as the kneading method, the precisely formed phase separation structure is destroyed and the desired characteristics are obtained. I can't.
Also for this purpose, a method for producing particles in a liquid using water or the like as a medium is suitable.
In order to use the obtained core-shell particles as a binder resin raw material by a dissolution suspension method or an emulsion polymerization aggregation method, for example, a conventionally known production method as described in the following literature is used. .
Core-Shell Polymer Nanoparticles for Baroplastic Processing, Macromolecules, 2005, 38, 8036-8044
Preparation and Characterization of Core-Shell Particles Containing Perfluoroalkyl Acrylate in the Shell, Macromolecules, 2002, 35, 6811-6818
Complex Phase Behavior of a Weakly Interacting Binary Polymer Blend, Macromolecules, 2004, 37, 5851-5855

Specific combinations of resins having different Tg of 20 ° C. or more include polystyrene and polybutyl acrylate, polystyrene and polybutyl methacrylate, polystyrene and poly (2-ethylhexyl acrylate), polystyrene and polyhexyl methacrylate, polyethyl methacrylate and poly A combination of ethyl acrylate, polyisoprene, and polybutylene is exemplified.
The core-shell particles by these combinations are observed to have pressure plastic behavior regardless of which becomes the shell or core. However, in order to make the toner into a toner and achieve both durability during transportation and storage, a high Tg phase is present on the shell side. It is preferable to come.

  Further, in order to use 50% or more of these core-shell particles as a composition in the toner, it is necessary to impart controllability when the toner is made into water to the core-shell particles, that is, controllability of particle size and particle size distribution. However, for this purpose, it is effective to contain an acidic or basic polar group or an alcoholic hydroxyl group in the resin in order to facilitate control by adding a flocculant. These are mainly realized by copolymerizing a monomer (monomer) having these polar groups in the shell component.

As said acidic polar group, a carboxyl group, a sulfonic acid group, an acid anhydride, etc. are illustrated preferably, and a carboxyl group is more preferable.
Examples of the monomer for forming an acidic polar group in the resin include an α, β-ethylenically unsaturated compound having a carboxyl group or a sulfone group.
Specific examples include acrylic acid, methacrylic acid, fumaric acid, maleic acid, itaconic acid, cinnamic acid, sulfonated styrene, and allylsulfosuccinic acid.
Preferred examples of the basic polar group include an amino group, an amide group, and a hydrazide group.
Examples of the monomer for forming a basic polar group in the resin include a monomer structural unit having the nitrogen atom (hereinafter also referred to as “nitrogen-containing monomer”).
Preferable compounds used as the monomer include (meth) acrylic acid amide compounds, (meth) acrylic acid hydrazide compounds, and (meth) acrylic acid aminoalkyl compounds.
Examples of the (meth) acrylic acid amide compound include acrylic acid amide, methacrylic acid amide, acrylic acid methylamide, methacrylic acid methylamide, acrylic acid dimethylamide, acrylic acid diethylamide, acrylic acid phenylamide, and acrylic acid benzylamide.
Examples of the (meth) acrylic acid hydrazide compound include acrylic acid hydrazide, methacrylic acid hydrazide, methyl acrylate hydrazide, methyl methacrylate hydrazide, acrylic acid dimethyl hydrazide, and acrylic acid phenyl hydrazide.
Examples of the (meth) acrylic acid aminoalkyl compound include (meth) acrylic acid (2-aminoethyl).
As a monomer (monomer) for forming an alcoholic hydroxyl group, hydroxy acrylates are preferable. Specifically, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate Etc.
The preferred use amount of the monomer having a polar group is preferably in the range of 0.01 to 20% by weight, more preferably in the range of 0.1 to 10% by weight based on the total weight of the polymerizable monomers used in the shell layer. preferable. It is excellent in the stability in the aqueous medium to a core-shell particle as it is the said range.

  These pressure plastic core-shell particles may be used alone as a raw material for the binder resin, or may be used by mixing resin particles obtained by conventional emulsion polymerization. In this case, the ratio of the resin obtained by aggregating the core-shell particles is preferably 30% by weight or more based on the total binder resin in order to achieve the object, and is preferably 50 to 100% by weight. More preferred.

The Tg of the high Tg phase is preferably 45 to 80 ° C, and more preferably 50 to 70 ° C.
The Tg of the low Tg phase is more preferably 30 ° C. or lower than the Tg of the high Tg phase.
The weight average molecular weight Mw of the resin used for the core is preferably 3,000 to 50,000, and more preferably 5,000 to 40,000.
The weight average molecular weight Mw of the resin used for the shell is preferably 3,000 to 50,000, and more preferably 5,000 to 40,000.
In the core-shell particles, the weight ratio of the resin constituting the core and the resin constituting the shell is preferably core: shell = 10: 90 to 90:10, and preferably 20:80 to 80:20. More preferred.

[(C) Resin mixture in which a sea-island structure is formed by two kinds of resins having a glass transition temperature difference of 20 ° C. or higher]
As the binder resin, (C) a resin mixture in which a sea-island structure is formed by two kinds of resins having a glass transition temperature difference of 20 ° C. or more is preferable.
The major axis of the island phase in the resin mixture in which the sea-island structure is formed is preferably 150 nm or less, and more preferably 1 to 150 nm.
The resin contained in the resin mixture having the sea-island structure may be a (co) polymer obtained from an ethylenically unsaturated compound or a (co) polymer obtained from a diol and a dicarboxylic acid. May be.
The resin mixture in which the sea-island structure is formed preferably forms an island phase with a low Tg resin as a small component and forms a continuous sea phase with the high Tg resin.
The resin mixture having the sea-island structure forms a sea-island structure, and the difference between the glass transition temperature of the resin that forms the sea phase and the glass transition temperature of the resin that forms the island phase is 30 ° C. or more. More preferably, the glass transition temperature of the resin is less than 55 ° C., and the major axis of the island phase is 150 nm or less.
The ratio of the weight of the resin forming the island phase to the weight of the resin forming the sea phase is preferably 0.25 or more.
The resin mixture in which the sea-island structure is formed includes a dispersion step of dispersing the high Tg resin particles and the low Tg resin particles in an aqueous medium, an aggregation step of aggregating the two dispersed resin particles to obtain aggregate particles, and Including a fusing step of fusing the agglomerated particles to form a sea-island structure, wherein the median diameter of the resin particles is 100 nm or less, and the major axis of the island phase contained in the sea-island structure is suitable for a production method of 150 nm or less Is obtained.

Moreover, it is preferable that the binder resin used for this embodiment is resin which satisfy | fills following formula (3).
ΔT _p = T _p1 −T _p5 ≧ 20 ° C. (3)
In formula (3), T _p1 represents the temperature at which the melt viscosity of the resin measured by the flow tester method at a load of 1 MPa (10 kgf / cm ² ) reaches 10,000 Pa · s, and T _t5 represents a load of 5 MPa (50 kgf / cm ^2). ) Represents the temperature at which the melt viscosity of the resin measured by the flow tester method reaches 10,000 Pa · s.
ΔT _p in formula (3) is 20 ° C. or higher, preferably 20 to 120 ° C., more preferably 30 to 110 ° C., and still more preferably 40 to 100 ° C.
The measuring method of ΔT _{p is the same as} the measuring method of ΔT _{w in} the wax.

  Further, the content of the binder resin in the electrostatic image developing toner of the present embodiment is preferably 10 to 90% by weight, more preferably 30 to 85% by weight, based on the total weight of the toner. More preferably, it is 50 to 80% by weight.

<Colorant>
The electrostatic image developing toner of this embodiment contains a colorant.
Examples of the colorant used in the toner of the exemplary embodiment include carbon black, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, Brilliantamine 3B, Brilliantamine 6B, Daypon Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Phthalocyanine Green, Malachite Various pigments such as green oxalate, titanium black, acridine, xanthene, azo, benzoquinone , Azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, thioindico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazine, thiazole, xanthene Various dyes such as those of the system are mentioned. Specific examples of the colorant include carbon black, nigrosine dye (C.I. No. 50415B), aniline blue (C.I.No. 50405), and calco oil blue (C.I.No. azoic). Blue 3), chrome yellow (C.I. No. 14090), ultramarine blue (C.I.No. 77103), DuPont oil red (C.I.No. 26105), quinoline yellow (C.I.No. 47005), methylene blue chloride (C.I.No. 52015), phthalocyanine blue (C.I.No. 74160), malachite green oxalate (C.I.No. 42000), lamp black (C.I.No. 77266), Rose Bengal (CI No. 45435), and mixtures thereof Preferably used.
The amount of the colorant used is preferably 0.1 to 20 parts by weight and particularly preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the toner.
Moreover, as a coloring agent, these pigments, dyes, etc. may be used individually by 1 type, or 2 or more types may be used together.
As these dispersion methods, any method, for example, a general dispersion method such as a rotary shear type homogenizer, a ball mill having a medium, a sand mill, or a dyno mill may be used, and the method is not limited at all. These colorant particles may be added to the mixed solvent at the same time as other particle components, or may be divided and added in multiple stages.

The electrostatic image developing toner of this embodiment may contain a magnetic material or a charge control agent as necessary.
As the magnetic substance, metals or alloys exhibiting ferromagnetism such as ferrite, magnetite, iron, cobalt, nickel, etc., compounds containing these elements, or containing no ferromagnetic elements, but subjected to appropriate heat treatment For example, alloys that exhibit ferromagnetism, such as manganese-copper-aluminum, manganese-copper-tin, and other types of alloys called Heusler alloys containing manganese and copper, chromium dioxide, and the like. For example, in the case of obtaining a black toner, magnetite that is black in itself and also functions as a colorant is particularly preferably used. In the case of obtaining a color toner, it is preferable to use a material with little blackness such as metallic iron. Some of these magnetic materials also function as a colorant, and in that case, they may also be used as a colorant. When the magnetic toner is used, the content of these magnetic materials is preferably 20 to 70 parts by weight, more preferably 40 to 70 parts by weight per 100 parts by weight of the toner.
As the charge control agent, conventionally known ones may be used. For example, nigrosine dyes, quaternary ammonium salt compounds, triphenylmethane compounds, imidazole compounds, polyamine resins, for example. Positively charged charge control agents such as chromium, metal-containing azo dyes such as chromium, cobalt, aluminum, iron, etc., metal salts and metals such as chromium, zinc, aluminum, etc. of hydroxycarboxylic acids such as salicylic acid, akilsalicylic acid and benzylic acid You may use well-known things, such as a negative charge control agent, such as a complex, an amide compound, a phenol compound, a naphthol compound, a phenolamide compound.

Furthermore, it is preferable that the toner of this embodiment is used by mixing inorganic particles such as a fluidity improver.
The inorganic particles preferably have a primary particle size of 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET (Brunauer, Emmett, Teller) method is 20-500 m < ² > / g. The proportion mixed with the toner is preferably 0.01 to 5% by weight, and more preferably 0.01 to 2.0% by weight.
Examples of such inorganic particles include silica powder, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. Chrome oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like, and silica powder is particularly preferable.

The silica powder here is a powder having a Si—O—Si bond, and includes any one produced by a dry method or a wet method. In addition to anhydrous silicon dioxide, any of aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, zinc silicate and the like may be used, but those containing SiO _{2 in an amount} of 85% by weight or more are preferable. Specific examples of these silica powders include various commercially available silicas, and those having a hydrophobic group on the surface are preferable. For example, AEROSIL R-972, R-974, R-805, R-812 (above, Aerosil) And Talux 500 (manufactured by Tarco). In addition, a silane coupling agent, a titanium coupling agent, silicon oil, silica powder treated with silicon oil having an amine in the side chain, or the like may be used.

In addition, the electrostatic image developing toner of the present embodiment may be used in combination with other release agents other than the specific fatty acid amide and the specific paraffin, if necessary. The aqueous dispersion may be added at the start of the production of the monomer emulsion, at the start of polymerization, or at the start of aggregation of the polymer particles.
Examples of other release agents include polyolefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and ethylene-propylene copolymers, paraffin waxes other than the specific paraffin, hydrogenated castor oil, carnauba wax, rice wax, and the like. Plant waxes, higher fatty acid ester waxes such as stearic acid esters, behenic acid esters, and montanic acid esters, higher alcohols such as higher fatty acid stearyl alcohols such as alkyl-modified silicone and stearic acid, and higher fatty acid amides other than the specific fatty acid amides. Well-known ones such as ketones having a long-chain alkyl group such as distearyl ketone are used.
Furthermore, the electrostatic charge image developing toner of this embodiment may use various known internal additives such as antioxidants and ultraviolet absorbers used for this type of toner, if necessary.

Cumulative volume-average particle diameter of the toner for developing an electrostatic image of the present embodiment (center diameter) D ₅₀ is more that is preferably 3.0～9.0Myuemu, in the range of 3.0~5.0μm preferable. When it is in the above range, the adhesive force is moderate, the developability is good, and the image resolution is excellent.

  Further, the volume average particle size distribution index GSDv of the electrostatic image developing toner of the present embodiment is preferably 1.30 or less, more preferably 1.24 or less, and further preferably 1.20 or less. . When GSDv is 1.30 or less, the resolution is excellent, and image defects such as toner scattering and fog (toner adhering to portions that are originally non-image portions) do not occur.

Here, the average particle size distribution index and the cumulative volume-average particle diameter D ₅₀ is, for example, Coulter Counter TA-II (Beckman - Coulter), Multisizer II - measured in (Beckman Coulter, Inc.) instrument For the particle size range (channel) divided based on the particle size distribution, the cumulative distribution is drawn from the smaller diameter side to the volume and number, and the particle size to be 16% is the volume D _16v , number D _16P , 50% cumulative _{Are defined} as a volume D _50v and a number D _50P , and a particle diameter at a cumulative 84% is defined as a volume D _84v and a number D _84P . Using these, the volume average particle size distribution index (GSDv) is calculated as (D _84v / D _16V ) ^1/2 and the number average particle size distribution index (GSDp) is calculated as (D _84P / D _16P ) ^1/2 .

The shape factor SF1 of the electrostatic image developing toner of the present embodiment is preferably from 100 to 140, more preferably from 110 to 135, from the viewpoint of image formability.
The shape factor SF1 is digitized mainly by analyzing a microscope image or a scanning electron microscope image with an image analyzer, and is obtained as follows, for example. For the measurement of the shape factor SF1, first, an optical microscope image of toner spread on a slide glass is taken into a Luzex image analyzer through a video camera, and SF1 of the following formula is calculated for 50 or more toners to obtain an average value. Can be obtained.

ここでＭＬはトナー粒子の絶対最大長、Ａはトナー粒子の投影面積である。

Here, ML is the absolute maximum length of the toner particles, and A is the projected area of the toner particles.

  The electrostatic charge image developing toner of the present embodiment is dried in the same manner as a normal toner for the purpose of imparting fluidity and improving cleaning properties, and then inorganic particles such as silica, alumina, titania, calcium carbonate, vinyl resins, and polyesters. Alternatively, resin particles such as silicone may be added to the toner particle surface while being sheared in a dry state.

  In addition, when adhering to the toner surface in an aqueous medium, examples of inorganic particles include silica, alumina, titania, calcium carbonate, magnesium carbonate, and tricalcium phosphate, which are all commonly used as external additives on the toner surface. May be dispersed in an ionic surfactant, a polymer acid, or a polymer base.

(Method for producing electrostatic image developing toner)
The method for producing an electrostatic charge image developing toner of the present embodiment includes at least a step of emulsifying and dispersing a resin in an aqueous medium to obtain a resin particle dispersion, a fatty acid amide that satisfies the above formula (2), and / or the above formula ( 2), a process of obtaining a release agent particle dispersion by dispersing paraffin having a number average molecular weight Mn of 800 or less and a molecular weight distribution (Mw / Mn) of 1.25 or more in an aqueous medium, In the dispersion containing the particle dispersion and the release agent particle dispersion, the resin particles and the fatty acid amide satisfying the formula (2) and / or the formula (2) are satisfied, and the number average molecular weight Mn is A step of aggregating paraffin having a molecular weight distribution (Mw / Mn) of 1.25 or more to obtain aggregated particles (hereinafter also referred to as “aggregation step”), and heating the aggregated particles. Fused That step (hereinafter, also referred to as "fusion process".) Preferably contains.

The method for producing an electrostatic charge image developing toner according to this embodiment includes, for example, mixing the prepared resin particle dispersion with a colorant particle dispersion and a release agent particle dispersion, and further adding a flocculant to generate heteroaggregation. Then, aggregated particles having a toner diameter are formed, and then heated to a temperature equal to or higher than the glass transition point or the melting point of the resin particles to fuse, coalesce, wash, and dry the aggregated particles. An electrostatic image developing toner is obtained. The toner shape is preferably from irregular to spherical. In addition to surfactants, inorganic salts and divalent or higher metal salts are preferably used as the flocculant. In particular, when a metal salt is used, it is preferable in terms of aggregation control and toner charging characteristics.
Further, in the agglomeration step, the resin particle dispersion and the colorant particle dispersion are agglomerated in advance, and after the formation of the first agglomerated particles, the resin particle dispersion or another resin particle dispersion is added to the first particle surface. It is also possible to form a second shell layer. In this illustration, the colorant dispersion is separately adjusted, but naturally, the colorant may be blended in advance with the resin particles in the resin particle dispersion.

  In the present embodiment, the formation method of the aggregated particles is not particularly limited, and a known aggregation method conventionally used in the emulsion polymerization aggregation method of electrostatic charge image developing toner, for example, temperature increase, pH change, A method of reducing the stability of the emulsion by adding salt or the like and stirring with a disperser or the like is used. Further, after the aggregation treatment, the particle surface may be cross-linked by heat treatment or the like for the purpose of suppressing the colorant exudation from the particle surface. In addition, you may remove the used surfactant etc. by water washing | cleaning, acid washing | cleaning, or alkali washing | cleaning as needed.

In addition, in the method for producing an electrostatic charge image developing toner of the present embodiment, a charge control agent used for this type of toner may be used as necessary. An aqueous dispersion may be used at the start of production of the particle emulsion, at the start of polymerization, or at the start of aggregation of the resin particles. The addition amount of the charge control agent is preferably 1 to 25 parts by weight, more preferably 5 to 15 parts by weight with respect to 100 parts by weight of the monomer or polymer.
As the charge control agent, those described above are preferably used.

The median diameter (center diameter) of the resin particles in the resin particle dispersion used in the method for producing an electrostatic charge image developing toner of this embodiment is preferably 0.1 μm or more and 2.0 μm or less.
When using an addition polymerization monomer to prepare an addition polymerization resin particle dispersion, an emulsion polymerization may be performed using an ionic surfactant or the like to prepare a resin particle dispersion. In the case of other resins, if they are oily and can be dissolved in a solvent having a relatively low solubility in water, the resin is dissolved in those solvents, and then dispersed with a disperser such as a homogenizer together with an ionic surfactant or polymer electrolyte. A resin particle dispersion is obtained by dispersing in an aqueous medium in the form of particles and then evaporating the solvent by heating or decompressing. Moreover, you may use a well-known polymerization initiator and a chain transfer agent at the time of superposition | polymerization of an addition polymerization type monomer.

  In the fusion process performed after the aggregation process, heating is performed after the progress of the aggregation is stopped by setting the pH of the suspension containing the aggregated particles formed through these processes to a desired range. To fuse the aggregated particles.

Adjustment of pH is performed by adding an acid and / or an alkali. The acid to be used is not particularly limited, but an aqueous solution containing an inorganic acid such as hydrochloric acid, nitric acid, sulfuric acid or the like in the range of 0.1 wt% to 50 wt% is preferable. The alkali to be used is not particularly limited, but an aqueous solution containing an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide in the range of 0.1 wt% to 50 wt% is preferable.
In the pH adjustment, if a local pH change occurs, the local aggregated particles themselves may be destroyed or locally excessively aggregated, and the shape distribution may be deteriorated. In particular, the larger the scale is, the more acid and / or alkali is added. In general, there is only one place where the acid and alkali are added, so that if the treatment is performed in the same time, the concentration of acid and alkali at the place where the scale is increased increases.

  After the pH adjustment described above, the aggregated particles are heated and fused (unified). The fusion may be performed by fusing the aggregated particles by heating at a temperature of 10 to 50 ° C. or higher (in other words, a temperature 10 to 50 ° C. higher than the glass transition temperature) from the glass transition temperature of the binder resin. preferable.

  After completing the coalesced particle fusion step, desired toner particles (toner base particles) are obtained through an arbitrary washing step, solid-liquid separation step, and drying step. In consideration of charging properties, the washing step is performed with ion-exchanged water. It is preferable to perform replacement washing. Moreover, although there is no restriction | limiting in particular in a solid-liquid separation process, From the point of productivity, suction filtration, pressure filtration, etc. are suitable. Further, the drying process is not particularly limited, but freeze drying, flash jet drying, fluidized drying, vibration fluidized drying and the like are preferably used from the viewpoint of productivity. In addition, the various external additives described above may be added to the dried toner particles (toner base particles) as necessary.

<Electrostatic image developer>
The electrostatic image developing toner of this embodiment may be used as an electrostatic image developer. The developer is not particularly limited except that it contains the electrostatic image developing toner, and any suitable component composition may be used depending on the purpose. When the electrostatic image developing toner is used alone, it is prepared as a one-component electrostatic image developer, and when used in combination with a carrier, it is prepared as a two-component electrostatic image developer.
The carrier used in the present embodiment is not particularly limited, but magnetic particles such as iron powder, ferrite, iron oxide powder, and nickel; the magnetic particles are used as a core material and the surface thereof is a styrene resin, vinyl resin, ethylene Resin-coated carrier formed by coating a resin such as a resin, a rosin resin, a polyester resin, a melamine resin, or a wax such as stearic acid to form a resin coating layer; dispersing magnetic particles in a binder resin And a magnetic material dispersed carrier. Among them, the resin-coated carrier is particularly preferable because the chargeability of the toner and the resistance of the entire carrier can be controlled by the configuration of the resin coating layer. The mixing ratio of the toner and the carrier of this embodiment in the two-component electrostatic image developer is preferably 2 to 10 parts by weight of the toner with respect to 100 parts by weight of the carrier. Moreover, the preparation method of a developing agent is not specifically limited, For example, the method of mixing with a V blender etc. is mentioned.

The carrier used in the present embodiment is preferably a magnetic material dispersed carrier (a carrier in which the core is composed of magnetic material dispersed particles) in which a magnetic material such as magnetite is dispersed in a resin as the core of the carrier.
The core of the magnetic material dispersed carrier is magnetic powder dispersed particles in which magnetic particles are dispersed in a resin.

1) Core Examples of the magnetic material dispersed in the core include magnetic metals such as iron, steel, nickel, and cobalt, and alloys of these with manganese, chromium, rare earth elements, and the like (for example, nickel-iron alloys, cobalt) -Iron alloys, aluminum-iron alloys, etc.) and magnetic oxides such as ferrite and magnetite may be applied, and among these, iron oxide is preferred. When the magnetic particles are iron oxide particles, it is advantageous in that the characteristics are stable and the toxicity is low.
These magnetic materials may be used alone or in combination of two or more.

The particle size of the magnetic substance to be dispersed is preferably 0.01 to 1 μm, more preferably 0.03 μm to 0.5 μm, and still more preferably 0.05 μm to 0.35 μm. Within the above range, saturation magnetization is sufficient, the viscosity of the composition (monomer mixture) is moderate, and a carrier having a uniform particle diameter can be easily obtained.
The content of the magnetic substance in the magnetic powder dispersed particles is preferably 30 to 99% by weight, more preferably 45 to 97% by weight, and still more preferably 60 to 95% by weight. Within the above range, scattering of the magnetic material dispersed carrier is suppressed, and cracking of the magnetic material dispersed carrier is suppressed.

Examples of the resin component in the magnetic powder-dispersed particles include cross-linked styrene resins, acrylic resins, styrene-acrylic copolymer resins, and phenol resins.
In addition to the matrix and the magnetic powder, the magnetic powder dispersed particles may further contain other components depending on the purpose. Examples of the other components include a charge control agent and fluorine-containing particles.
The volume average particle diameter of the core in the carrier of the first aspect is preferably in the range of 10 to 500 μm, more preferably in the range of 30 to 150 μm, and still more preferably in the range of 30 to 100 μm. Within the above range, the carrier is suppressed from moving to the photoconductor, is excellent in manufacturability, has carrier-derived streaks called brush marks on the image, and has a rough image. It is prevented.
The volume average particle diameter of the core refers to a value measured using a laser diffraction / scattering particle size distribution analyzer (LS Particle Size Analyzer: LS13 320, manufactured by Beckman Coulter, Inc.). For the particle size range (channel) obtained by dividing the obtained particle size distribution, the volume cumulative distribution is subtracted from the small particle size side, and the particle size that becomes 50% cumulative is _defined as the volume average particle size D _50v .

The method for producing the magnetic powder-dispersed particles is, for example, a melt-kneading method in which a magnetic powder and a binder resin such as a styrene acrylic resin are melt-kneaded using a Banbury mixer, a kneader, etc., cooled, ground, and classified ( Japanese Patent Publication No. 59-24416, Japanese Patent Publication No. 8-3679, etc.), a monomer unit of a binder resin and magnetic powder are dispersed in a solvent to prepare a suspension, and this suspension is polymerized. Known are suspension polymerization methods (JP-A-5-1000049, etc.), and spray-drying methods in which a magnetic powder is mixed and dispersed in a resin solution and then spray-dried.
In each of the melt-kneading method, the suspension polymerization method, and the spray-drying method, a magnetic powder is prepared in advance by some means, the magnetic powder and a resin solution are mixed, and the resin solution is mixed. Preferably, the method includes a step of dispersing the magnetic powder.

2) Coating layer The magnetic powder-dispersed carrier preferably has the core (magnetic powder-dispersed particles) and a coating layer on the surface thereof. The coating layer is preferably a coating resin layer formed of a matrix resin.
The coverage of the core by the coating layer is preferably 95% or more, and more preferably 97% or more. Within the above range, there are few portions where the core is exposed, and carrier cracking and pulverization are sufficiently suppressed.
In this embodiment, the coverage of the core is expressed by the following formula by measuring the constituent element ratios of the surfaces of the core (without coating) and the carrier (with coating) by X-ray photoelectron analysis (XPS). Value.
Coverage (%) = {1− (peak area due to iron in carrier) / (peak area due to iron in core)} × 100

  The coating layer has an average film thickness of preferably 0.1 μm to 10 μm, more preferably 0.1 μm to 3.0 μm, and still more preferably 0.1 μm to 1.0 μm. Within the above range, resistance reduction due to peeling of the coating layer during use for a long time is suppressed, carrier pulverization is sufficiently suppressed, and the time until the carrier reaches the saturation charge amount is short.

As the matrix resin contained in the coating resin layer, a general matrix resin may be used.
For example, polyolefin resins such as polyethylene and polypropylene; polystyrene and acrylic resins, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polyvinyl ketone and other polyvinyl and polyvinylidene resins; Vinyl-vinyl acetate copolymer; Styrene-acrylic acid copolymer; Straight silicone resin composed of organosiloxane bonds or modified products thereof; Fluorine such as polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene, etc. Polyester; Polyurethane; Polycarbonate; Phenol resin; Urea-formaldehyde resin, melamine resin, benzoguanamine resin, resin A resin, amino resins such as polyamide resins; silicone resins; epoxy resins.
These may be used individually by 1 type and may use 2 or more types together.
In particular, for contamination of the toner component, it is preferable to use a low surface energy resin such as a fluororesin or a silicone resin as a coating resin, and it is more preferable to coat with a fluororesin.
Examples of the fluororesin include a fluorinated polyolefin, a fluoroalkyl (meth) acrylate polymer and / or copolymer, a vinylidene fluoride polymer and / or copolymer, and a mixture thereof to form a fluororesin. Examples of fluorine-containing monomers include fluorine-containing fluoroalkyl methacrylate monomers such as tetrafluoropropyl methacrylate, pentafluoropropyl methacrylate, octafluoropentyl methacrylate, perfluorooctylethyl methacrylate, and trifluoroethyl methacrylate. Is preferred. However, it is not limited to these.
As a compounding quantity of the monomer containing a fluorine, it is preferable to mix | blend in the range of 0.1-50.0 weight% with respect to all the monomers which comprise coating resin, and 0.5-40. More preferably, it is blended in the range of 0% by weight, and even more preferably in the range of 1.0-30.0% by weight. When it is in the above range, the contamination resistance is sufficiently ensured, the adhesion of the coating resin to the core is excellent, and the carrier charging property is excellent.

The coating layer may contain resin particles dispersed in the layer.
Examples of the resin particles include thermoplastic resin particles and thermosetting resin particles. Among these, thermosetting resins that are relatively easy to increase the hardness are suitable, and in order to impart negative chargeability to the toner, it is preferable to use resin particles containing nitrogen atoms. In addition, these resin particles may be used individually by 1 type, and may use 2 or more types together.
The resin particles contained in the coating layer are preferably uniformly dispersed in the matrix resin in the thickness direction of the coating resin layer and in the tangential direction to the carrier surface. It is preferable that the resin of the resin particles and the matrix resin have high compatibility since the uniformity of dispersion of the resin particles in the coating resin layer is improved.
Examples of the thermoplastic resin include polyolefin resins such as polyethylene and polypropylene; polyvinyl such as polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, and polyvinyl ketone; Polyvinylidene resin; vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; straight silicone resin composed of organosiloxane bond or modified product thereof; polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychloro Fluorine resin such as trifluoroethylene; polyester; polyurethane; polycarbonate and the like.
Examples of the thermosetting resin used for the resin particles contained in the coating layer include phenol resins; urea-formaldehyde resins, melamine resins, silicone resins, benzoguanamine resins, urea resins, polyamide resins, and other amino resins; epoxy resins; Is mentioned.
The resin of the resin particles contained in the coating layer and the matrix resin may be the same material or different materials. Particularly preferably, the resin of the resin particles contained in the coating layer and the matrix resin are made of different materials.
It is preferable to use thermosetting resin particles as the resin of the resin particles contained in the coating layer because the mechanical strength of the carrier is improved. A resin having a crosslinked structure is particularly preferable. Further, in order to improve the function of the resin particle as a charging site, it is preferable to use a resin with a fast rise in toner charging. Examples of such resin particles include nylon resin, amino resin, and melamine resin. The nitrogen-containing resin particles are preferred.

The resin particles to be included in the coating layer are a method of producing granulated resin particles using polymerization such as emulsion polymerization or suspension polymerization, or a monomer or oligomer is dispersed in a solvent and a crosslinking reaction proceeds. The resin particles are made by granulating the resin particles, the low molecular components and the crosslinking agent are mixed and reacted by melt kneading and the like, and then pulverized to a predetermined particle size by wind force, mechanical force, etc. It is manufactured by the method of manufacturing.
The volume average particle size of the resin particles contained in the coating layer is preferably 0.1 to 2.0 μm, and more preferably 0.2 to 1.0 μm. Within the above range, it is sufficiently dispersed in the coating layer, falling off from the coating layer is suppressed, and stable chargeability is obtained.
The method for measuring the volume average particle diameter of the resin particles contained in the coating layer is the same as that for the volume average particle diameter of the core.
The resin fine particles are preferably contained in the coating layer at 1 to 50% by volume, more preferably 1 to 30% by volume, and even more preferably 1 to 20% by volume. When it is in the above range, the effect of the resin particles is sufficiently exhibited, the falling off from the coating layer is suppressed, and stable chargeability is obtained.

The coating layer may further contain conductive powder dispersed therein.
Examples of the conductive powder include metals such as gold, silver, and copper; carbon black; and titanium oxide, magnesium oxide, zinc oxide, aluminum oxide, calcium carbonate, aluminum borate, potassium titanate, and calcium titanate powder. Metal oxides such as titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate powder, etc. The surface of the powder is covered with tin oxide, carbon black, or metal.
These may be used alone or in combination of two or more.
When a metal oxide is used as the conductive fine powder, the environmental dependency of the charging property is further reduced, and titanium oxide is particularly preferable.

Furthermore, it is preferable to treat the conductive powder made of the material with a coupling agent. Of these, metal oxides treated with a coupling agent are preferred, and titanium oxide treated with a coupling agent is particularly preferred.
The conductive fine powder treated with the coupling agent can be obtained by dispersing the untreated conductive powder in a solvent such as toluene, mixing the coupling agent, treating, and then drying under reduced pressure.
Furthermore, in order to remove aggregates from the conductive powder treated with the obtained coupling agent, it may be crushed by a crusher, if necessary. As the crusher, a known crusher such as a pin mill, a disk mill, a hammer mill, a centrifugal classification mill, a roller mill, or a jet mill may be used, and it is particularly preferable to use a jet mill. As the coupling agent to be used, known ones such as a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent may be used.
Among these, use of a silane coupling agent, particularly conductive powder treated with methyltrimethoxysilane, is particularly effective for the environmental stability of charging.
The volume average particle size of the conductive powder is preferably 0.5 μm or less, more preferably 0.05 μm or more and 0.45 μm or less, and further preferably 0.05 μm or more and 0.35 μm or less. When it is in the above range, falling off from the coating layer is suppressed, and stable chargeability is obtained.
The method for measuring the volume average particle diameter of the conductive powder is in accordance with the method for measuring the volume average particle diameter of the core.

The conductive fine powder preferably has a volume electrical resistance of 10 ¹ Ω · cm to 10 ¹¹ Ω · cm, and preferably has a volume electrical resistance of 10 ³ Ω · cm to 10 ⁹ Ω · cm. More preferably. In addition, in this specification, the volume electrical resistance of electroconductive powder means the value measured with the following method.
Under normal temperature and normal humidity, the conductive powder is filled into a container having a cross-sectional area of 2 × 10 ⁻⁴ m ^{2 so} as to have a thickness of about 1 mm, and then on the filled conductive powder by a metal member, applying a 1 load × 10 ⁴ kg / m ^2. A voltage that generates an electric field of 10 ⁶ V / m is applied between the metal member and the bottom electrode of the container, and a value calculated from the current value at that time is defined as a volume electric resistance value.
The conductive powder is preferably contained in the coating resin layer in an amount of 1 to 80% by volume, more preferably 2 to 20% by volume, and still more preferably 3 to 10% by volume.

As a method of forming the coating layer on the surface of the core of the carrier, a coating layer forming solution containing the resin, conductive powder and solvent is prepared, and a core particle is immersed in the solution, or a coating layer is formed. A spray method in which the solution for spraying is sprayed on the surface of the core particles, a fluidized bed method in which the coating solution for forming the coating layer is sprayed in a state where the core particles are suspended by flowing air, or the core particle and the coating layer forming solution in a kneader coater. A kneader coater method of mixing and removing the solvent may be used.
The solvent used for preparing the coating layer forming solution is not particularly limited as long as it dissolves the resin. For example, aromatic hydrocarbons such as toluene and xylene, ketones such as acetone and methyl ethyl ketone, and the like. Ethers such as tetrahydrofuran, dioxane and the like may be used.
In order to make the coating layer have the above-described coverage, it is preferable to use a fluidized bed apparatus in which the core particles are dispersed and fluidized in an air stream and the coating layer is sprayed to coat.

3) Physical properties of the carrier The saturation magnetization of the carrier is preferably 40 emu / g or more, and more preferably 50 emu / g or more.
As a device for measuring the magnetic properties, a vibration sample type magnetic measuring device VSMP10-15 (manufactured by Toei Industry Co., Ltd.) is used. The measurement sample is packed in a cell having an inner diameter of 7 mm and a height of 5 mm and set in the apparatus. The measurement is performed by applying an applied magnetic field and sweeping up to 1,000 oersted. Next, the applied magnetic field is decreased to create a hysteresis curve on the recording paper. Saturation magnetization, residual magnetization, and coercive force are obtained from the curve data. In the present embodiment, the saturation magnetization indicates the magnetization measured in a 1,000 oersted magnetic field.
The volume electric resistance of the carrier is preferably controlled in the range of 1 × 10 ⁷ to 1 × 10 ¹⁵ Ωcm, more preferably in the range of 1 × 10 ⁸ to 1 × 10 ¹⁴ Ωcm. More preferably, it is in the range of 10 ⁸ to 1 × 10 ¹³ Ωcm. If it is in the above range, the resistance value is moderate, it acts sufficiently as a developing electrode at the time of development, is excellent in solid reproducibility, and when the toner concentration in the developer is lowered, charge is injected from the developing roll to the carrier. And the development of the carrier itself is suppressed.
The volume electric resistance (Ω · cm) of the carrier is measured as follows. The measurement environment is a temperature of 20 ° C. and a humidity of 50% RH.
The carrier to be measured is placed flat on the surface of a circular jig having a 20 cm ² electrode plate so as to have a thickness of about 1 to 3 mm to form a carrier layer. A 20 cm ² electrode plate similar to the above is placed on this and the carrier layer is sandwiched. In order to eliminate the gap between the carriers, the thickness (cm) of the carrier layer is measured after a load of 4 kg is applied on the electrode plate placed on the carrier layer. Both electrodes above and below the carrier layer are connected to an electrometer and a high-voltage power generator. A high voltage is applied to both electrodes so that the electric field is 10 ^3.8 V / cm, and the current value (A) flowing at this time is read to calculate the volume electric resistance (Ω · cm) of the carrier. The calculation formula of the volume electric resistance (Ω · cm) of the carrier is as shown in the following formula.
R = E × 20 / (I−I ₀ ) / L
(Where R is the volume electrical resistance of the carrier (Ω · cm), E is the applied voltage (V), I is the current value (A), I ₀ is the current value (A) at an applied voltage of 0 V, and L is the carrier layer. (The coefficient of 20 represents the area (cm ² ) of the electrode plate.)

<Production of developer>
The two-component developer of this embodiment is produced by mixing the electrostatic image developing toner of this embodiment and a carrier. The mixing ratio (weight ratio) of the toner and the carrier in the developer is preferably in the range of toner: carrier = 1: 99 to 20:80, preferably in the range of 3:97 to 12:88. It is more preferable.

(Image forming method)
The electrostatic image developer (electrostatic image developing toner) may be used in an image forming method of a normal electrostatic image developing system (electrophotographic system).
The image forming method of the present embodiment includes a latent image forming step of forming an electrostatic latent image on the surface of the image carrier, and developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner. A development step for forming an image, a transfer step for transferring the toner image to the surface of the transfer target, and a fixing step for pressure-fixing the toner image transferred to the surface of the transfer target at 10 to 50 ° C. An image forming method using the electrostatic image developing toner of the present embodiment or the electrostatic image developer of the present embodiment as an agent is preferable. Moreover, the cleaning process may be included as needed.
Each of the above steps is a general step per se, and is described in, for example, JP-A-56-40868 and JP-A-49-91231. Note that the image forming method of this embodiment may use a known image forming apparatus such as a copying machine or a facsimile machine.
The latent image forming step is a step of forming an electrostatic latent image on the surface of the image carrier.
The developing step is a step of developing the electrostatic latent image with a developer layer on a developer carrier to form a toner image. The developer layer is not particularly limited as long as it contains the electrostatic image developer of this embodiment containing the electrostatic image developer of the present embodiment.
The transfer step is a step of transferring the toner image onto a transfer target.

The fixing step is a step of forming a copy image by pressure-fixing a toner image transferred onto a recording medium such as recording paper by a pressure fixing device or the like.
In the present embodiment, the fixing step is performed by applying pressure.
The fixing temperature is preferably 10 to 50 ° C, more preferably 15 to 45 ° C, and still more preferably 15 to 40 ° C. When the fixing temperature is within the above range, good fixability can be obtained.
The fixing pressure is preferably 1 MPa or more and 10 MPa or less, and more preferably 1 MPa or more and 5 MPa or less. When the pressure during fixing (fixing pressure) is 1 MPa or more, sufficient fixability can be obtained. Further, when the pressure is 10 MPa or less, there are few occurrences of image contamination, fixing roll contamination and paper wrapping due to the occurrence of offset and the like, and the problem that the paper after fixing is bent (referred to as paper curl) is difficult to occur.
Here, the fixing pressure means the following maximum fixing pressure.

As the fixing roll, a conventionally known fixing roll may be appropriately selected and used as long as the fixing pressure can be applied.
For example, a fluorine-based resin (eg, Teflon (registered trademark)), a silicon-based resin, a copolymer of tetrafluoroethylene (C ₂ F ₄ ) and perfluoroalkoxyethylene (PFA) or the like is formed on a cylindrical metal core. A coated fixing roll is exemplified, and in order to obtain a high fixing pressure, a fixing roll made of stainless steel (SUS) may be used. The fixing step is generally performed by passing a transfer medium between two rolls, but the two rolls may be formed of the same material or different materials. For example, combinations such as SUS / SUS, SUS / silicone resin, SUS / PFA, and PFA / PFA can be used.

  The pressure distribution between the fixing roll and the pressure roll may be measured by a commercially available pressure distribution measurement sensor, and specifically, may be measured by a pressure measurement system between rollers manufactured by Iwata Industry Co., Ltd. In the present embodiment, the maximum pressure at the time of pressure fixing represents the maximum value in the change in pressure from the fixing nip entrance to the exit in the paper traveling direction.

The cleaning step is a step of removing the electrostatic charge image developer remaining on the latent image holding member. In the image forming method of the present embodiment, an aspect that further includes a recycling step is preferable.
The recycling step is a step of transferring the electrostatic charge image developing toner collected in the cleaning step to a developer layer. The image forming method including the recycling step may be performed using an image forming apparatus such as a toner recycling system type copying machine or facsimile machine. Further, the present invention may be applied to a recycling system in which the cleaning process is omitted and toner is collected simultaneously with development.
Through such a series of processing steps, a desired duplicate product (printed matter or the like) is obtained.

(Image forming device)
The image forming apparatus of the present embodiment includes an image carrier, a charging unit that charges the image carrier, and an exposure unit that exposes the charged image carrier to form an electrostatic latent image on the surface of the image carrier. Developing means for developing the electrostatic latent image with a developer containing toner to form a toner image; transfer means for transferring the toner image from the image holding member to the surface of the transferred body; and the transferred body Fixing means for pressure-fixing the toner image transferred to the surface at 10 to 50 ° C., and the electrostatic image developing toner of the present embodiment or the electrostatic image developer of the present embodiment is used as the developer. An image forming apparatus is preferable. In the transfer unit, the transfer may be performed twice or more using an intermediate transfer member.

It is preferable that the image carrier and each unit described above have the configurations described in the respective steps of the image forming method.
Any of the above-described means may be a known means in the image forming apparatus. Further, the image forming apparatus used in the present embodiment may include means and devices other than the above-described configuration. Further, the image forming apparatus used in the present embodiment may simultaneously perform a plurality of the above-described means.
The fixing temperature that can be fixed by the fixing unit preferably includes 10 to 50 ° C, more preferably includes 15 to 45 ° C, and further preferably includes 15 to 40 ° C. When the fixing temperature is within the above range, good fixability can be obtained.
The fixing pressure that can be applied by the fixing unit is preferably 1 MPa or more and 10 MPa or less, and more preferably 1 MPa or more and 5 MPa or less. When the pressure during fixing (fixing pressure) is 1 MPa or more, sufficient fixability can be obtained. Further, when the pressure is 10 MPa or less, there are few occurrences of image contamination, fixing roll contamination and paper wrapping due to the occurrence of offset and the like, and the problem that the paper after fixing is bent (referred to as paper curl) is difficult to occur.

(Toner cartridge and process cartridge)
The toner cartridge of this embodiment is a toner cartridge that contains at least the electrostatic charge image developing toner of this embodiment.
The toner cartridge of this embodiment may contain the electrostatic image developing toner of this embodiment as an electrostatic image developer.
The process cartridge of the present embodiment is a process cartridge that includes a developer holder and contains at least the electrostatic charge image developing toner of the present embodiment or the electrostatic charge image developer of the present embodiment.

The toner cartridge of this embodiment is preferably detachable from the image forming apparatus. That is, in the image forming apparatus having a configuration in which the toner cartridge can be attached and detached, the toner cartridge of the present embodiment in which the toner of the present embodiment is stored is preferably used.
Further, the toner cartridge may be a cartridge that stores toner and a carrier, or a cartridge that stores toner alone and a cartridge that stores a carrier independently.

It is preferable that the process cartridge of the present embodiment is attached to and detached from the image forming apparatus.
In addition, the process cartridge according to the present embodiment may include other members such as a static elimination unit as necessary.
As the toner cartridge and the process cartridge, known configurations may be adopted, and for example, Japanese Patent Application Laid-Open No. 2008-209489 and Japanese Patent Application Laid-Open No. 2008-233736 may be referred to.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited at all.
In the following description, “parts” means “parts by weight” unless otherwise specified.

[Measurement method for wax / toner resin and resin dispersion / toner characteristics]
<Measurement of resin particle in resin dispersion or molecular weight of resin>
For the measurement of the resin particle molecular weight contained in the resin or resin dispersion used for the toner, the weight average molecular weight Mw and the number average molecular weight Mn were measured by gel permeation chromatography (GPC) under the conditions described below. At a temperature of 40 ° C., a solvent (tetrahydrofuran) is flowed at a flow rate of 1.2 ml per minute, and 3 mg of a tetrahydrofuran sample solution having a concentration of 0.2 g / 20 ml is injected as a sample weight for measurement. When measuring the molecular weight of a sample, select the measurement conditions that fall within the range in which the logarithm of the molecular weight of the prepared calibration curve and the count number are linear, using several monodisperse polystyrene standard samples. .
In addition, the reliability of the measurement results is that the NBS706 polystyrene standard sample performed under the above measurement conditions is
Weight average molecular weight Mw = 28.8 × 10 ⁴
Number average molecular weight Mn = 13.7 × 10 ⁴
This is confirmed.
Further, as the GPC column, TSK-GEL, GMH (manufactured by Tosoh Corporation), etc. satisfying the above conditions were used.

<Measurement of resin particle in resin dispersion or glass transition point of resin>
A differential scanning calorimeter (Shimadzu Corporation, DSC50) was used to measure the glass transition temperature Tg of the polyester.

<Measuring method of ΔT _t of toner>
The method for measuring ΔT _t of the toner is not particularly limited as long as it is a measurement method using a flow tester method, but in the present invention, measurement was performed using a flow tester CFT-500A manufactured by Shimadzu Corporation.
In addition, you may measure using the Koka type | mold flow tester method with which the outline is described in JISK7210.
In the present invention, a load of 1 MPa or 5 MPa is applied by a plunger while heating a 1 cm ³ sample (weight 1.20 g) obtained by compression molding a toner to a diameter of 10 mm × 10 mm at a heating rate of 1 ° C./min. While extruding the melt from a die having a hole with a diameter of 0.5 mm, the respective temperatures at which the melt viscosity when applying a load of 1 MPa or 5 MPa is 10,000 Pa · s are measured, and the difference is expressed by the following formula (1). It is required by taking.
ΔT _t = T _t1 -T _t5 ≧ 20 ° C (1)
(In formula (1), T _t1 represents the temperature at which the melt viscosity of the toner measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _t5 represents the melting of the toner measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)

<Measurement method of ΔT _w of wax>
Method of measuring the [Delta] T _w of wax, if measurement method by a flow tester method is not particularly limited, in the present invention was measured using a Shimadzu Corp. Flow Tester CFT-500A type.
In addition, you may measure using the Koka type | mold flow tester method with which the outline is described in JISK7210.
In the present invention, a 1 cm ³ sample (weight 1.20 g) obtained by compression-molding wax into a 10 mm diameter × 10 mm height is heated at a heating rate of 1 ° C./min, and a load of 1 MPa or 5 MPa is applied by a plunger. While extruding the melt from a die having a hole with a diameter of 0.5 mm, each temperature at which the melt viscosity becomes 10,000 Pa · s when a load of 1 MPa or 5 MPa is applied is measured, and the difference is expressed by the following equation (2). It is required by taking.
ΔT _w = T _w1 −T _w5 ≧ 20 ° C. (2)
(In formula (2), T _w1 represents the temperature at which the melt viscosity of the wax measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _w5 represents the melting of the wax measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)

<Preparation of release agent particle dispersion (W1)>
Paraffin wax (Mn = 536, manufactured by Nippon Seiwa Co., Ltd., HNP3, melting point 64 ° C.): 50 parts by weight Anionic surfactant (Rohdia Dowfax): 5 parts by weight Part The above components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then dispersed with a pressure discharge homogenizer (manufactured by Gorin, Gorin homogenizer) to disperse the release agent particles. A liquid (W1) was prepared.
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 140 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of release agent particle dispersion (W2)>
Paraffin wax (Mn = 560, manufactured by Nippon Seiwa Co., Ltd., FNP0090, melting point 75 ° C.): 50 parts by weight Anionic surfactant (Dowfax manufactured by Rhodia): 5 parts by weight Part The above components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then dispersed with a pressure discharge homogenizer (manufactured by Gorin, Gorin homogenizer) to disperse the release agent particles. A liquid (W2) was prepared.
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 155 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of release agent particle dispersion (W3)>
・ Oleic acid amide (Mn = 253, manufactured by Nippon Seika Co., Ltd., Neutron, melting point 102 ° C.): 50 parts by weight ・ Anionic surfactant (Dowfax manufactured by Rhodia): 5 parts by weight ・ Ion exchange water: 200 parts by weight The above components are sufficiently dispersed while being heated to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then dispersed with a pressure discharge homogenizer (manufactured by Gorin, Gorin homogenizer) to release the agent A particle dispersion (W3) was prepared.
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 175 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of release agent particle dispersion (W4)>
Erucic acid amide (Mn = 309, manufactured by Nippon Seika Co., Ltd., Neutron S, melting point 106 ° C.): 50 parts by weight Anionic surfactant (Dowfax, Rhodia): 5 parts by weight : 200 parts by weight The above components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Turrax T50), then dispersed with a pressure discharge type homogenizer (manufactured by Gorin, Gorin homogenizer), and released. An agent particle dispersion (W4) was prepared.
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 190 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of release agent particle dispersion (W5)>
Polyethylene wax (Polywax PW725, manufactured by Toyo Petrolite Co., Ltd., Mn = 725, melting point = 104 ° C., Mw / Mn = 1.08): 50 parts by weight Anionic surfactant (Dowfax, Rhodia) : 5 parts by weight / ion-exchanged water: 200 parts by weight The above components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (manufactured by IKA, Ultra Tarrax T50), and then a pressure discharge homogenizer (manufactured by Gorin, Gorin homogenizer). ) To prepare a release agent particle dispersion (W5).
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 160 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of release agent particle dispersion (W6)>
Carnauba wax (manufactured by Toagosei Co., Ltd., Mn = 460, melting point = 82 ° C.): 50 parts by weight Anionic surfactant (Dowfax, Rhodia): 5 parts by weight Ion exchange water: 200 parts by weight The components were sufficiently dispersed while being heated to 95 ° C. with a homogenizer (IKA, Ultra Turrax T50), then dispersed with a pressure discharge type homogenizer (Gorin, Gorin homogenizer), and a release agent particle dispersion ( W6) was prepared.
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 195 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of release agent particle dispersion (W7)>
-Mn = 1,060-Mw / Mn = 1.30 paraffin wax: 50 parts by weight-Anionic surfactant (Dowfax manufactured by Rhodia): 5 parts by weight-Ion exchange water: 200 parts by weight The above ingredients are homogenizers (IKA, Ultra Turrax T50) was sufficiently dispersed while being heated to 95 ° C., and then dispersed with a pressure discharge type homogenizer (Gorin, Gorin homogenizer) to obtain a release agent particle dispersion (W7). Prepared.
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 205 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

<Preparation of release agent particle dispersion (W8)>
-Mn = 760-Mw / Mn = 1.21 paraffin wax: 50 parts by weight-Anionic surfactant (Dowfax manufactured by Rhodia): 5 parts by weight-Ion-exchanged water: 200 parts by weight The above components were homogenizer (IKA) After being sufficiently dispersed while being heated to 95 ° C. by Ultra Turrax T50), a dispersion agent (W8) was prepared by dispersing with a pressure discharge homogenizer (Gorin homogenizer, manufactured by Gorin). .
The number average particle diameter D _50n of the release agent particles in the obtained dispersion was 220 nm.
Thereafter, ion exchange water was added to adjust the solid concentration of the dispersion to 30%.

Incidentally, when measuring the [Delta] T _w of the wax in the resulting release agent particle dispersion (W1) ~ (W8), it was as follows.
ΔT _{w of} HNP9 used in the release agent particle dispersion (W1) = 41 ° C.
ΔT _{w of} FNP0090 used in the release agent particle dispersion (W2) = 30 ° C.
Neutron ΔT _w used for the release agent particle dispersion (W3) = 34 ° C.
ΔT _{w of} Neutron S used in the release agent particle dispersion (W4) = 30 ° C.
ΔT _{w of} polywax PW725 used in the release agent particle dispersion (W5) = 4 ° C.
Carnauba ΔT _w used in the release agent particle dispersion (W6) = 4 ° C.
ΔT _{w of} the wax used in the release agent particle dispersion (W7) = 5 ° C.
ΔT _{w of} the wax used in the release agent particle dispersion (W8) = 5 ° C.
It became.

[Preparation of Toner Resin / Resin Particle Dispersion]
<Preparation of resin particle dispersion (A1) (styrene-butyl acrylate type, acidic polar group type)>
In a round glass flask, 300 parts by weight of ion-exchanged water and 1.5 parts by weight of TTAB (tetradecyltrimethylammonium bromide, manufactured by Sigma) were placed, nitrogen bubbling was performed for 20 minutes, and 65 ° C. with stirring. The temperature was raised to. 40 parts by weight of n-butyl acrylate monomer was added, and the mixture was further stirred for 20 minutes. After dissolving 0.5 parts by weight of initiator V-50 (2,2′-azobis (2-methylpropionamidine) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.) in 10 parts by weight of ion-exchanged water, Charged into flask. Holding at 65 ° C. for 4 hours, 55 parts by weight of styrene monomer, 15 parts by weight of n-butyl acrylate monomer, 2.5 parts by weight of acrylic acid and 0.5 parts by weight of dodecanethiol are added to 0.5 parts by weight of tetradecyl. An emulsified liquid emulsified in 100 parts by weight of ion-exchanged water in which trimethylammonium bromide (TTAB, manufactured by Sigma) was dissolved was continuously charged into the flask using a metering pump over 2 hours. The temperature was raised to 70 ° C. and held for an additional 3 hours to complete the polymerization.
A core-shell type resin particle dispersion (A1) having a weight average molecular weight Mw of 56,000, an average particle diameter D _50n of 160 nm, and a solid content of 25% by weight was obtained.
After the resin was air-dried at 40 ° C., when Tg behavior was analyzed from −150 ° C. with a differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation, a glass transition due to polybutyl acrylate was observed around −50 ° C., and 56 A glass transition due to a copolymer considered to be composed of a styrene-butyl acrylate-acrylic acid copolymer was observed in the vicinity of 0 ° C. (glass transition temperature difference: 106 ° C.).

<Preparation of Resin Particle Dispersion (A2) (Preparation of Polyester Block Copolymer)>
A three-necked flask is equipped with a thermometer, a condenser, and a stirrer. To this, 15 parts by weight of toluene is added 5 parts by weight of a polyester monomer 1,5-dioxepan-2-one as a raw material for a low Tg block. As follows: 0.15 parts by weight of dioctyltin and 0.025 parts by weight of ethanol were added, and a polymerization reaction was carried out at 110 ° C. for 24 hours in a nitrogen atmosphere. The reaction was stopped when the molecular weight reached 22,000. After leaving to cool, 21 parts by weight of L-lactide was added as a raw material for the high Tg block, and the reaction was similarly carried out at 80 ° C. for 72 hours in a nitrogen atmosphere, resulting in a low Tg (−40 ° C.) component / high Tg (65 ° C.). ) To obtain a block copolymer having a weight average molecular weight of 21,000. This block copolymer was washed with methanol, dried and taken out.

To 100 parts by weight of this resin, 0.5 part by weight of soft sodium dodecylbenzenesulfonate is added as a surfactant, 300 parts by weight of ion-exchanged water is further added, and heated at 80 ° C. in a round glass flask. The mixture was sufficiently mixed and dispersed using IKA's Ultra Turrax T50).
A resin particle dispersion (A2) having a resin particle center diameter of 200 nm and a solid content of 25% was obtained.

<Preparation of resin particle dispersion (A3)>
1. Polymerization of crystalline polyester block resin, 1,824 parts by weight of succinic acid, 1,176 parts by weight of propanediol, and 3,000 parts by weight of the above in a flask equipped with a stirrer, a nitrogen inlet tube, a temperature sensor, and a rectifying tower The temperature was raised from room temperature to 90 ° C. over 1 hour, and after confirming that the reaction system was uniformly stirred, the catalyst Ti (OBu) ₄ (tetrabutoxy titanium, relative to the amount of polycarboxylic acid) , 0.003% by weight (5.47 parts by weight).
Further, while distilling off the generated water, the temperature was increased to 240 ° C. in 6 hours from the same temperature, and after dehydration polycondensation reaction was further performed at 240 ° C. for 24 hours, 292 parts by weight of succinic acid was added, Polymerization was performed for 8 hours to prepare a crystalline polyester block (1).
The weight average molecular weight of the obtained crystalline polyester block resin (1) was 11,300, Tg = −39 ° C. measured by DSC.

2. Polymerization of Amorphous Polyester Block Resin (1) • 984 parts by weight of terephthalic acid • 2,016 parts by weight of adduct of bisphenol A ethylene oxide 2,016 parts by weight In the same manner as in the above crystalline polyester (1), the above was 3,000 weights in a flask. After charging partly and raising the temperature from room temperature to 90 ° C. over 1 hour and confirming that the inside of the reaction system was uniformly stirred, the catalyst Ti (OBu) ₄ (0. 003 wt% = 3.0 parts by weight).
Further, while distilling off the water to be purified, the temperature was increased to 240 ° C. in 6 hours from the same temperature, and after the dehydration polycondensation reaction was further performed at 240 ° C. for 24 hours, the remaining 2-mole bisphenol A ethylene oxide adduct 323 parts by weight was added, and polymerization was further performed for 8 hours to produce an amorphous polyester block resin (1).
The obtained amorphous polyester block resin (1) had a weight average molecular weight of 16,600 and Tg = 69 ° C. measured by DSC.

3. Synthesis of polyester block copolymer The crystalline polyester block resin (1) and the non-crystalline polyester block resin (1) obtained above were charged in 1,000 parts by weight, respectively, and the temperature was raised to 150 ° C. Then, 0.5 part by weight of dodecylbenzenesulfonic acid was added, and the reaction at the same temperature was continued under reduced pressure of 0.5 kPa to obtain a polyester block copolymer. The molecular weight of the obtained polyester block resin was 26,800.

4). Preparation of resin particle dispersion liquid To 100 parts by weight of this resin, 0.5 part by weight of soft sodium dodecylbenzenesulfonate is added as a surfactant, and further 300 parts by weight of ion-exchanged water is added. The mixture was thoroughly mixed and dispersed in a flask made with a homogenizer (IKA, Ultra Turrax T50).
A resin particle dispersion (A3) having a resin particle central diameter of 220 nm and a solid content of 25% was obtained.

<Preparation of Resin Particle Dispersion (A4) (Styrene-Butyl Methacrylate (nBMA) System, Alcohol Hydroxyl System, Comparative Example Resin)>
In a round glass flask, 300 parts by weight of ion-exchanged water and 1.5 parts by weight of TTAB (tetradecyltrimethylammonium bromide, manufactured by Sigma) were placed, nitrogen bubbling was performed for 20 minutes, and 65 ° C. with stirring. The temperature was raised to. 40 parts by weight of n-butyl methacrylate monomer was added, and the mixture was further stirred for 20 minutes. After dissolving 0.5 parts by weight of initiator V-50 (2,2′-azobis (2-methylpropionamidine) dihydrochloride, manufactured by Wako Pure Chemical Industries, Ltd.) in 10 parts by weight of ion-exchanged water, Charged into flask. Holding at 65 ° C. for 3 hours, 0.5 part by weight of 50 parts by weight of styrene monomer, 30 parts by weight of n-butyl acrylate monomer, 2 parts by weight of 2-hydroxyethyl methacrylate and 0.8 part by weight of dodecanethiol The emulsified liquid emulsified in 100 parts by weight of ion-exchanged water in which was dissolved was continuously charged into the flask using a metering pump over 2 hours. The temperature was raised to 70 ° C. and held for another 2 hours to complete the polymerization. A core-shell resin particle dispersion (A4) having a weight average molecular weight Mw of 25,000, an average particle diameter of 280 nm, and a solid content of 25% by weight was obtained.
After the resin was air-dried at 40 ° C., when Tg behavior was analyzed from −150 ° C. using a differential scanning calorimeter (DSC) manufactured by Shimadzu Corporation, a glass transition due to polybutyl methacrylate was observed around 25 ° C., and around 40 ° C. The glass transition by the copolymer considered to consist of a styrene-butyl acrylate-acrylic acid copolymer was observed (glass transition temperature difference: 15 ° C.).

<Preparation of Colorant Particle Dispersion (P1)>
Cyan pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., copper phthalocyanine CI Pigment Blue 15: 3) 50 parts by weight Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) 5 parts by weight Ion exchange 200 parts by weight of water The above components are mixed and dissolved, and dispersed for 5 minutes by a homogenizer (IKA, Ultra Tarrax) for 10 minutes by an ultrasonic bath, and a cyan colorant particle dispersion having a center diameter of 190 nm and a solid content of 21.5% (P1) was obtained.

<Preparation of colorant particle dispersion (P2) (for secondary color image formation)>
・ Yellow pigment (Clariant Japan, CI Pigment Yellow 74) 20 parts by weight ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts by weight ・ Ion-exchanged water 78 parts by weight Components were prepared in the same manner as the colorant particle dispersion (P1) to obtain a colorant particle dispersion (P2). The number average particle diameter D _50n of the pigment in the dispersion was 118 nm. Thereafter, ion exchange water was added to adjust the solid content concentration of the dispersion to 15%.

(Toner Example 1)
<Preparation of cyan toner particles>
Resin particle dispersion (A1) 168 parts by weight (resin 42 parts by weight)
Colorant particle dispersion (P1) 40 parts by weight (8.6 parts by weight of pigment)
Release agent particle dispersion (W1) 40 parts by weight (release agent 8.6 parts by weight)
-Polyaluminum chloride 0.15 parts by weight-Ion-exchanged water 300 parts by weight According to the above composition, the above ingredients were thoroughly mixed and dispersed in a round stainless steel flask with a homogenizer (IKA, Ultra Turrax T50). The flask was heated to 42 ° C. while stirring the flask in a heating oil bath, and maintained at 42 ° C. for 60 minutes, and then 84 parts by weight (21 parts by weight of the resin particle dispersion (1)) was added and gently stirred.
Thereafter, the pH in the system was adjusted to 6.0 with a 0.5 mol / liter aqueous sodium hydroxide solution, and then heated to 95 ° C. while stirring was continued. During the period up to 95 ° C., an aqueous sodium hydroxide solution was added dropwise so that the pH did not become 5.0 or less. Hold at 95 ° C. for 3 hours.
After completion of the reaction, the mixture was cooled, filtered, sufficiently washed with ion exchange water, and then solid-liquid separated by Nutsche suction filtration. And it re-dispersed in 3,000 weight part of ion-exchange water of 40 degreeC, and it stirred and wash | cleaned at 300 rpm for 15 minutes. This washing operation was repeated 5 times, followed by solid-liquid separation by Nutsche suction filtration, and then vacuum drying for 12 hours to obtain toner particles.
Thus, when the particle size of the toner particles was measured with a Coulter Counter TA-II (manufactured by Beckman Coulter, Inc.), the cumulative volume average particle size D ₅₀ was 5.50 μm, and the volume average particle size distribution index GSDv was 1.20. there were. The shape factor SF1 of the toner particles obtained from the shape observation by the Luzex image analyzer was 121 potato shapes.
To 50 parts by weight of the toner particles, 1.5 parts by weight of hydrophobic silica (manufactured by Cabot, TS720) was added and mixed with a sample mill to obtain a cyan externally added toner.

(Cyan Toner Example 2)
Using the resin particle dispersion (A2), the release agent particle dispersion (W2), and the colorant particle dispersion (P1), the aluminum chloride is replaced with aluminum sulfate, and the pH when raising the temperature to 95 ° C. is 7 A toner was prepared and evaluated in the same manner as in Toner Example 1 except that the value was changed to 0.0.

(Cyan Toner Example 3)
Using the resin particle dispersion (A2), the release agent particle dispersion (W3), and the colorant particle dispersion (P1), a toner was produced in the same manner as in Toner Example 1.

(Cyan Toner Example 4)
Using the resin particle dispersion (A3), the release agent particle dispersion (W4), and the colorant particle dispersion (P1), a toner was prepared in the same manner as in Toner Example 1.

(Cyan toner comparative example 1)
A toner was prepared in the same manner as in Toner Example 1 except that the release agent particle dispersion (W5) was used. Evaluation was performed in the same manner.

(Cyan toner comparative example 2)
A toner was prepared in the same manner as in Toner Example 1 except that the release agent particle dispersion (W6) was used.

(Cyan toner comparative example 3)
A toner was prepared in the same manner as in Toner Example 1 except that the resin particle dispersion was changed from (A1) to (A4) and the release agent particle dispersion was changed from (W1) to (W4).

(Cyan toner comparative example 4)
A toner was prepared in the same manner as in Toner Example 1 except that the release agent particle dispersion (W7) was used. Evaluation was performed in the same manner.

(Cyan toner comparative example 5)
A toner was prepared in the same manner as in Toner Example 1 except that the release agent particle dispersion (W8) was used. Evaluation was performed in the same manner.

(Yellow Toner Examples 1 to 4 and Comparative Examples 1 to 5)
In yellow toner examples 1 to 4 and comparative examples 1 to 5, except that the colorant particle dispersion was changed from (P1) to (P2), cyan toner examples 1 to 4 and comparative examples 1 to 5, respectively. Similarly, each yellow toner was produced.

In the production of each cyan toner, the following cyan toners were obtained.
In Toner Example 1, a potato-shaped toner having D ₅₀ = 4.65, GSDv = 1.20, GSDp = 1.20, and shape factor SF1 = 125 was obtained.
In Toner Example 2, a potato-shaped toner having D ₅₀ = 4.76, GSDv = 1.20, GSDp = 1.19, and shape factor SF1 = 129 was obtained.
In Toner Example 3, a potato-shaped toner having D ₅₀ = 4.66, GSDv = 1.20, GSDp = 1.21 and shape factor SF1 = 122 was obtained.
In Toner Example 4, a potato-shaped toner having D ₅₀ = 4.71, GSDv = 1.20, GSDp = 1.21 and shape factor SF1 = 124 was obtained.
In Toner Comparative Example 1, a potato-shaped toner having D ₅₀ = 4.51, GSDv = 1.21, GSDp = 1.21, and shape factor SF1 = 124 was obtained.
In Toner Comparative Example 2, a potato-shaped toner having D ₅₀ = 4.59, GSDv = 1.21, GSDp = 1.21, and shape factor SF1 = 120 was obtained.
In Toner Comparative Example 3, a potato-shaped toner having D ₅₀ = 4.80, GSDv = 1.20, GSDp = 1.21 and shape factor SF1 = 120 was obtained.
In Toner Comparative Example 4, a potato-shaped toner having D ₅₀ = 4.88, GSDv = 1.20, GSDp = 1.21, and shape factor SF1 = 129 was obtained.
In Toner Comparative Example 5, a potato-shaped toner having D ₅₀ = 4.79, GSDv = 1.20, GSDp = 1.21, and shape factor SF1 = 130 was obtained.

In the production of each yellow toner, the following yellow toners were obtained.
In Toner Example 1, a potato-shaped toner having D ₅₀ = 4.70, GSDv = 1.20, GSDp = 1.20, and shape factor SF1 = 120 was obtained.
In Toner Example 2, a potato-shaped toner having D ₅₀ = 4.71, GSDv = 1.20, GSDp = 1.19, and shape factor SF1 = 119 was obtained.
In Toner Example 3, a potato-shaped toner having D ₅₀ = 4.63, GSDv = 1.20, GSDp = 1.21, and shape factor SF1 = 122 was obtained.
In Toner Example 4, a potato-shaped toner having D ₅₀ = 4.51, GSDv = 1.20, GSDp = 1.21 and shape factor SF1 = 131 was obtained.
In Toner Comparative Example 1, a potato-shaped toner having D ₅₀ = 4.69, GSDv = 1.20, GSDp = 1.21, and shape factor SF1 = 124 was obtained.
In Toner Comparative Example 2, a potato-shaped toner having D ₅₀ = 4.84, GSDv = 1.22, GSDp = 1.21, and shape factor SF1 = 120 was obtained.
In Toner Comparative Example 3, a potato-shaped toner having D ₅₀ = 4.73, GSDv = 1.21, GSDp = 1.22, and shape factor SF1 = 129 was obtained.
In Toner Comparative Example 4, a potato-shaped toner having D ₅₀ = 4.81, GSDv = 1.20, GSDp = 1.21, and shape factor SF1 = 129 was obtained.
In Toner Comparative Example 5, a potato-shaped toner having D ₅₀ = 4.75, GSDv = 1.20, GSDp = 1.21, and shape factor SF1 = 126 was obtained.

<Measurement of melt viscosity of toner>
Using a flow tester CFT-500A manufactured by Shimadzu Corporation, the temperature rises from 25 ° C. at a rate of temperature increase of 1 ° C./min when a load of 5 MPa and 1 MPa is applied, and under a pressure of 5 MPa and 1 MPa. The temperature at 10,000 Pa · s was measured.

<Creation of carrier>
(Preparation of core particle 1)
・ Phenol 40 parts by weight ・ Formalin 60 parts by weight ・ Magnetite 400 parts by weight (average particle size 0.20 μm, spherical, 1% by weight KBM403 treated product)
・ Add 12 parts by weight of ammonia water ・ 60 parts by weight of ion-exchanged water, gradually raise the temperature to 85 ° C. while mixing and stirring, react for 4 hours, cure, cool, filter, wash, dry, particle size 37.3 μm spherical core particles 1 were obtained.

(Preparation of carrier 1)
Core particle 1 100 parts by weight <Coating layer forming solution 1>
-Toluene 120 parts by weight-Styrene-methyl methacrylate (St-MMA) copolymer (weight ratio 60:40, weight average molecular weight 80,000) 3.5 parts by weight-Carbon black (Regal 330; manufactured by Cabot Corporation) 0.4 weight Part The above components excluding the core particles 1 were stirred / dispersed with a stirrer for 60 minutes to prepare a coating layer forming solution 1.
Furthermore, then the coating layer forming solution 1 and core particles C1 and a fluidized bed (Powrex Co., Ltd., trade name: MP-01SFP) put, the blade rotation speed 1,000 rpm, air flow rate 1.2 m ³ / min, the solution The carrier 1 was produced by coating at a projection speed of 10 g / min at 70 ° C. and passing through a mesh having an opening of 75 μm.
The coating resin coverage of carrier 1 was 96%.

<Production of developer>
After weighing so that the weight ratio of the toner and the carrier 1 is 8:92, both are stirred and mixed in a ball mill for 20 minutes to prepare each developer. Developers of Comparative Examples 1 to 5 were prepared.

<Evaluation of fixed image quality>
For the evaluation of the image quality of the fixed image, the above-mentioned developer is used, and in a modified machine of Docu Center Color f450 manufactured by Fuji Xerox Co., Ltd., a two-roll type so that the maximum fixing pressure is 5 MPa (50 kgf / cm ² ). The fusing machine was remodeled, J-coated paper manufactured by Fuji Xerox Co., Ltd. was used as the transfer paper, the fixing roll temperature was adjusted to 30 ° C, and the process speed was adjusted to 60 mm / sec to evaluate the image quality of the toner fixed image. It was.

<Image adhesion evaluation: Cellophane tape peeling>
Except for changing the colorant particle dispersion (P1) to the colorant particle dispersion (P2), the yellow toner was prepared in the same manner as the cyan toners prepared in Examples 1 to 4 and Comparative Examples 1 to 5. Each was produced. In addition, a yellow developer was prepared using the obtained yellow toner.
Using the modified machine described above, a single-color secondary image (area coverage 100%) composed of cyan and yellow was printed on A4.
After obtaining the above-mentioned fixed image, a cellophane tape (Cellotape (registered trademark) manufactured by Nichiban Co., Ltd.) was attached to the image and allowed to stand for 1 minute, and then the cellophane tape was peeled off. The image density was measured.
Based on the result of the absolute value (ΔID) of the difference in density before and after peeling the cellophane tape, a three-step evaluation was performed according to the following criteria.
○: ΔID value before and after tape peeling ≦ 0.05
Δ: ΔID value before and after tape peeling = 0.05 to 0.10
×: ΔID value before and after tape peeling ≧ 0.10

In Toner Examples 1 to 3, even if the tape was peeled off after the tape was applied to the image, no tape set-off was confirmed.
Further, when the image density was measured, no difference was visually observed before and after the tape was peeled off, but the density was reduced by about 0.02 to 0.03 (the value of the density difference is shown in Table 1). 1).
In Toner Examples 4 and 5, when the tape was peeled off after the tape was attached to the image, no set-off was confirmed. Further, when the image density was measured, there was no difference in the image before and after the tape was peeled off visually, but the density was reduced by about 0.06 (values of density difference are shown in Table 1). .
In toner comparative examples 1 and 2, even if the tape was peeled off after the tape was attached to the image, no tape set-off was confirmed.
Further, when the image density was measured, no difference was visually observed between before and after the tape was peeled off, but the density was reduced by about 0.04 (values of density difference are shown in Table 1). ).
In Toner Comparative Example 3, it was confirmed that a large amount of images were transferred to the tape when the tape was peeled off because the pressure fixing property of the toner and the adhesion to paper were poor.
Moreover, when the image after peeling off a tape was seen, it was confirmed that the resin component has almost disappeared.
In Toner Comparative Examples 4 and 5, when the tape was peeled off after the tape was attached to the image, almost no set-off was confirmed, but a very light green color was observed.
Further, when the image density was measured, there was almost no difference in the image before and after the tape was peeled off visually, but the image after the tape peeling was slightly thinner (the value of the density difference is Shown in Table 1.).

<Evaluation of secondary color gloss unevenness (ΔGloss)>
5 × 5 cm unfixed solid image formed with a secondary color of the obtained cyan toner and yellow toner was formed, and after fixing by the above fixing method, the central portion of the solid image forming portion; Gloss measurement at 60 degrees was performed on five points including the periphery thereof, and the determination was made as follows based on the difference value (ΔGloss) between the maximum value and the minimum value of the five points.
○: ΔGloss = (Gloss maximum value) − (Gloss minimum value) ≦ 1.5
Δ: 1.5 <ΔGloss <2
×: 2 ≦ ΔGloss

In Toner Examples 1 to 4, no gloss unevenness was visually confirmed.
The value of ΔGloss is shown in Table 1.
In toner comparative examples 1 and 2, it was confirmed that there was uneven gloss even visually. The value of ΔGloss is shown in Table 1.
In Toner Comparative Example 3, since the pressure fixability of the image was poor, the value of Gloss was originally low, so there was no Gloss unevenness and ΔGloss was 1.5 or less.
In Toner Comparative Examples 4 and 5, when the image was tilted slightly in a lighted room and the image was viewed, it was confirmed that there was uneven gloss even visually.
The density difference values are shown in Table 1.

<Evaluation of offset property of wax>
Evaluation of the presence or absence of wax offset was performed as follows.
After fixing the secondary color solid image consisting of cyan and yellow (printing so that the image density is the highest) using the cyan and yellow developers prepared above, if there is any deposit on the surface of the fixing roll, a scraper or After scraping off 0.2 mg or more of the roll surface deposit with a spatula or the like, infrared spectroscopy (IR) measurement was performed.
If no offset occurs, no infrared spectroscopic measurement is performed because nothing is scraped off even if the roll surface is scraped off with a scraper.
Moreover, when there was very little deposit | attachment, not only 1 sheet but 2 sheets or more of solid images were printed, and the deposit | attachment was scraped off each time and the amount of 0.2 mg or more was scraped up.
Infrared spectroscopy can be measured using, for example, FT / IR-410 (manufactured by JASCO Corporation). When measuring using this apparatus, the measurement sample was mixed with about 0.2 mg (0.5% concentration) of KBr powder in 40 mg, sufficiently pulverized and mixed in a mortar, and then subjected to pressure molding. We will analyze later.
The determination of wax offset is
(1): Prior to this measurement, IR measurement is performed on the wax used in the present invention in advance, and the detected peak of the deposit is a peak derived from the wax by comparing with the IR measurement result of the deposit on the roll surface. Judged whether or not.
(2): General paraffins, the carbon in the IR spectrum - the strong absorption in the vicinity of 2960～2850Cm ^-1 with hydrogen stretching vibration, carbon - has an absorption by carbon stretching vibration in the vicinity of 1300～800Cm ^-1, and a carbon - hydrogen When the number of carbon atoms is 4 or more, the bending vibration shows weak absorption in the vicinity of 725 cm ⁻¹ , and thus it was judged by the presence or absence of these peaks.

In Toner Examples 1 to 4 and Comparative Example 3, no sample was collected because there was no deposit on the fixing roll.
In toner comparative examples 1, 2, 4, and 5, since there was an adhering matter to the fixing roll, the adhering matter was scraped from the roll each time one image was printed, and this was repeated 20 times to collect a sample.
As a result, IR analysis is performed for each of the toner before fixing, the fixed image, and the collected matter on the roll, and the difference spectrum of the IR chart between the toner before fixing and the fixed image is taken. It was confirmed that the peak where the peak disappeared or the intensity was weakened in the fixed image overlapped with the peak position of the roll deposit.

<Evaluation of fine line reproducibility (Evaluation of blur)>
Using the cyan and yellow developers prepared above, a thin line image was formed on the image carrier so as to have a line width of 30 μm, and this was transferred and fixed to a transfer material.
J-coated paper manufactured by Fuji Xerox Co., Ltd. was used as the transfer material.
The fine line image of the fixed image is observed at a magnification of 175 times using a VH-6200 micro high scope (manufactured by Keyence Corporation). Specific evaluation criteria are as follows.
A: The amount of toner scattered around the fine line is within 5 particles / mm per 1 cm of the line.
(Triangle | delta): The amount of toner scattering to the circumference | surroundings of a thin wire | line is within 6-10 pieces / mm per 1cm line.
X: The amount of toner scattered around the fine line is 11 / mm or more per 1 cm of the line.

In Toner Examples 1 and 2, the amount of toner scattering was 1 per 1 cm line.
In Toner Examples 3 and 4, the amount of scattered toner was 7 per 1 cm of line.
In Toner Comparative Examples 1 and 2, the amount of toner scattering was 13 per 1 cm line.
In toner comparative examples 3 to 5, the amount of toner scattering was 3 to 4 per 1 cm of the line.

  The evaluation results in Toner Examples 1 to 4 and Comparative Examples 1 to 5 are summarized in Table 1 below.

Claims (9)

Satisfies formula (1),
Including a binder resin, a colorant, and a wax;
The wax satisfies the following formula (2) and / or the following formula (2), the number average molecular weight Mn is 800 or less, and the molecular weight distribution (Mw / Mn) is 1.25 or more. An electrostatic image developing toner comprising a certain paraffin.
ΔT _t = T _t1 -T _t5 ≧ 20 ° C (1)
(In formula (1), T _t1 represents the temperature at which the melt viscosity of the toner measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _t5 represents the melting of the toner measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)
ΔT _w = T _w1 −T _w5 ≧ 20 ° C. (2)
(In formula (2), T _w1 represents the temperature at which the melt viscosity of the wax measured by the flow tester method at a load of 1 MPa becomes 10,000 Pa · s, and T _w5 represents the melting of the wax measured by the flow tester method at a load of 5 MPa. (This represents the temperature at which the viscosity reaches 10,000 Pa · s.)   The electrostatic image developing toner according to claim 1, wherein the wax includes paraffin having a number average molecular weight Mn of 800 or less and a molecular weight distribution (Mw / Mn) of 1.25 or more.   An electrostatic image developer comprising the electrostatic image developing toner according to claim 1 and a carrier.   A toner cartridge containing at least the electrostatic image developing toner according to claim 1. A developer holder,
A process cartridge containing the electrostatic charge image developing toner according to claim 1 or 2, or the electrostatic charge image developer according to claim 3. A latent image forming step for forming an electrostatic latent image on the surface of the image carrier;
A developing step of forming a toner image by developing the electrostatic latent image formed on the surface of the image carrier with a developer containing toner;
A transfer step of transferring the toner image onto the surface of the transfer target; and
A fixing step of pressure-fixing the toner image transferred to the surface of the transfer medium at 10 to 50 ° C .;
An image forming method using the electrostatic charge image developing toner according to claim 1 or 2 or the electrostatic charge image developer according to claim 3 as the developer.   The image forming method according to claim 6, wherein a maximum pressure during fixing in the fixing step is 1 MPa or more and 5 MPa or less. An image carrier,
Charging means for charging the image carrier;
Exposure means for exposing the charged image carrier to form an electrostatic latent image on the surface of the image carrier;
Developing means for developing the electrostatic latent image with a developer containing toner to form a toner image;
Transfer means for transferring the toner image from the image carrier to the surface of the transfer target;
Fixing means for pressure-fixing the toner image transferred onto the surface of the transfer medium at 10 to 50 ° C .;
An image forming apparatus using the electrostatic charge image developing toner according to claim 1 or the electrostatic charge image developer according to claim 3 as the developer.   The image forming apparatus according to claim 8, wherein the fixing unit is a unit including a maximum pressure setting range of 1 MPa to 5 MPa in fixing.