JP5446642B2 - Toner for developing electrostatic latent image and method for producing the same, developer using the toner, image forming apparatus, image forming method, and process cartridge - Google Patents

Description

  The present invention relates to a toner for developing an electrostatic latent image used for electrophotographic image formation such as copying machines, electrostatic printing, printers, facsimiles, electrostatic recording, and the like, a method for producing the same, and a developer using the toner The present invention relates to an image forming apparatus, an image forming method, and a process cartridge.

Conventionally, in an electrophotographic image forming apparatus, an electrostatic recording apparatus, or the like, an electric or magnetic latent image is visualized with an electrostatic latent image developing toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed using toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper and then fixed by a method such as heating.
The toner for developing an electrostatic latent image is generally colored particles containing a colorant, a charge control agent and the like in a binder resin, and the production methods are roughly classified into a pulverization method and a suspension polymerization method.

  In the pulverization method, a toner is produced by pulverizing and classifying a toner composition obtained by melt-mixing a colorant, a charge control agent, an offset preventing agent, and the like in a thermoplastic resin and uniformly dispersing them. According to this pulverization method, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of materials. For example, the toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable device. From this demand, the toner composition obtained by melt mixing must be made sufficiently brittle. However, when such a toner composition is pulverized, particles having a wide particle size distribution are likely to be formed. At this time, in order to obtain a copy image with good resolution and gradation, for example, fine powder having a particle size of 5 μm or less and coarse powder having a particle size of 20 μm or more must be removed by classification, yield. Is very low. In the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent and the like in the thermoplastic resin, and the obtained toner has an adverse effect on fluidity, developability, durability, image quality, and the like. There is a problem that arises.

Therefore, in Patent Documents 1 and 2, a resin solution in which a resin synthesized in advance by a polymerization reaction is dissolved is used as a dispersion (auxiliary) agent such as a surfactant or a water-soluble resin, and a dispersion stabilizer such as inorganic fine particles and resin fine particles. There has been proposed a dissolved resin suspension method in which a toner is obtained by dispersing in an aqueous medium in the presence of water and removing the solvent by heating, decompression or the like. According to this dissolved resin suspension method, a uniform toner can be obtained without classification.
In addition, in an electrophotographic image forming apparatus, in a fixing process by a contact heating method performed using a heating member such as a heat roller, releasability (hereinafter sometimes referred to as offset resistance) to the heating member is provided. Required. This offset resistance is solved by using a modified polyester resin in the dissolved resin suspension method (see Patent Document 3).

  By the way, most of the binder resin occupying 70% or more of the constituent components of the toner is made from petroleum resources. This is due to the problem of exhaustion of petroleum resources, large consumption of petroleum resources, and emission of carbon dioxide into the atmosphere. There are concerns about global warming. Therefore, if a plant-derived resin that grows by taking in carbon dioxide in the atmosphere is used as the binder resin, the resulting carbon dioxide will only circulate in the environment, which simultaneously raises the problem of global warming and the depletion of petroleum resources. Various toners using such plant-derived resins as binder resins have been proposed. For example, Patent Document 4 proposes using polylactic acid as a binder resin. However, when polylactic acid is used as it is as in this proposal, the concentration of the ester bond is higher than that of the polyester resin, so that the action as a thermoplastic resin is lowered during fixing. Further, since the toner becomes very hard, there is a problem that the grindability is poor and the productivity is inferior.

Patent Document 5 proposes an electrostatic latent image developing toner containing a polyester resin obtained by dehydration polycondensation of a composition containing lactic acid and a tri- or higher functional oxycarboxylic acid, and a colorant. ing. However, in this proposal, since the polyester resin is formed by dehydration polycondensation reaction between the hydroxyl group of lactic acid and the carboxyl group of oxycarboxylic acid, the molecular weight is increased, the sharp melt property is impaired, and the low-temperature fixing property is lacking. There's a problem.
Further, Patent Document 6 discloses an electrophotographic toner containing a polylactic acid-based biodegradable resin and a terpene phenol copolymer in order to improve thermal characteristics. However, low temperature fixability and hot offset property are disclosed. Cannot be satisfied at the same time.
Since all of the toners according to these prior art documents are obtained by a pulverization method, there is a problem of toner loss caused by classification and associated disposal. Further, since the amount of energy required for the pulverization method is relatively large, further reduction of the environmental load is required.

  Polylactic acid, which is widely available as a plant-derived resin, is synthesized by dehydration condensation of lactic acid or ring-opening polymerization of lactic acid cyclic lactide as described in Patent Documents 7 and 8. For this reason, when manufacturing a toner using polylactic acid, the dissolving resin suspension method like the said patent documents 1-3 can be used. However, since polylactic acid has high crystallinity only in the L-form or D-form, the solubility in an organic solvent is extremely low, and it is difficult to use the dissolved resin suspension method. On the other hand, Patent Document 9 discloses that the L-form and D-form of polylactic acid are mixed to lower the crystallinity and improve the solubility in an organic solvent.

On the other hand, polylactic acid is difficult to control the molecular weight and has ester bonds only through carbon atoms, so that it is difficult to achieve the physical properties necessary for the toner only with polylactic acid. On the other hand, it is conceivable to ensure the physical properties and thermal characteristics required for the toner by mixing polylactic acid and other resins as in the conventional methods. Is very difficult to produce a toner by such a method because the compatibility and dispersibility with respect to a polyester resin and a styrene-acrylic copolymer which are generally used for the toner are extremely poor.
In addition, since the crystallization speed of polylactic acid is slow, it is difficult to control the crystalline state of polylactic acid in a toner manufactured using the dissolved resin suspension method, and the crystallinity of polylactic acid is low and the crystallinity is low. May contain polylactic acid. Therefore, there is a problem that the charge amount and the image density change over time due to the crystal growth of the portion having polylactic acid with low crystallinity over time.

On the other hand, the thermal energy given to the toner at the time of fixing tends to decrease like low-temperature fixing and high-speed copying for the purpose of achieving energy saving. As a method for obtaining a toner compatible with low-temperature fixing, a method for achieving low-temperature fixing using a resin or wax having a low softening point has been proposed.
However, the low-temperature fixing toner obtained by such a method is vulnerable to heat, so there is a problem of causing solidification due to the heat of the machine used or heat during storage, and so-called blocking, and a sufficient fixing temperature range is secured. Difficult to do.

Therefore, for the purpose of improving low-temperature fixability, for example, a toner in which a specific crystalline resin having a glass melt temperature having a sharp melt property is contained in a binder resin has been proposed.
For example, Patent Document 10 includes a toner containing a crystalline resin and a specific polycarbonate resin, polyarylate resin, polyvinyl acetal resin, or the like, and Patent Document 11 includes a cycloolefin copolymer resin and a crystalline resin. Toner has been proposed.
However, with these methods, sufficient low-temperature fixability cannot be obtained, and even if a toner that contributes to low-temperature fixing of images can be obtained due to sharp melt properties, the glass transition temperature is lowered. If it is too high, the heat resistant storage stability may deteriorate. Further, if the molecular weight is decreased to reduce the softening temperature of the resin too much, there is a problem that the temperature at which hot offset occurs is lowered, and it is difficult to achieve both low-temperature fixing of the image and heat-resistant storage stability.

  As described above, a toner for developing an electrostatic latent image and related technology, which contains polylactic acid, has excellent fixability, image density, haze degree, and heat-resistant storage stability, and has little change in fixability with time, and the related technology is still available. However, the present situation is that further improvement and development are desired.

  Although the present invention contains a resin having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer such as polylactic acid, it can ensure hot offset resistance, has excellent low-temperature fixability, and has an image density and a haze degree. Of the electrostatic latent image developing toner having good heat resistance and storage stability and a method for producing the same, and a developer, an image forming apparatus, an image forming method, and a process cartridge using the toner. For the purpose of provision.

（上記式中、ｎ及びｍは繰返単位数を表し、ｐは１〜３の整数を表し、Ｒ^１及びＲ^２は互いに同一であっても異なっていてもよく、水素原子又は炭化水素基を表す。）
４） 前記樹脂（ｂ）のポリヒドロキシカルボン酸骨格が炭素数３〜６のヒドロキシカルボン酸が共重合した骨格であることを特徴とする１）〜３）のいずれかに記載の静電荷潜像現像用トナー。
５） 前記（ｂ１１）と（ｂ１２）の質量比が、３１：６９〜９０：１０であることを特徴とする４）に記載の静電荷潜像現像用トナー。
６） 前記樹脂（ａ）と樹脂（ｂ）の質量比が、１：９９〜３０：７０であることを特徴とする１）〜５）のいずれかに記載の静電荷潜像現像用トナー。
７） 有機溶媒中に少なくとも結着樹脂、着色剤、離型剤を溶解乃至分散させた溶液乃至分散液を水系媒体中で乳化乃至分散させて静電荷潜像現像用トナーを造粒することを特徴とする１）〜６）のいずれかに記載の静電荷潜像現像用トナーの製造方法。
８） １）〜６）のいずれかに記載の静電荷潜像現像用トナーを含むことを特徴とする現像剤。
９） 更にキャリアを含むことを特徴とする８）に記載の現像剤。
１０） 静電潜像担持体と、該静電潜像担持体表面を帯電させる帯電手段と、帯電された静電潜像担持体表面を露光して静電潜像を形成する露光手段と、前記静電潜像を現像剤を用いて現像して可視像を形成する現像手段と、前記可視像を記録媒体に転写する転写手段と、前記記録媒体に転写された転写像を定着させる定着手段とを少なくとも有する画像形成装置であって、前記現像剤が、８）又は９）に記載の現像剤であることを特徴とする画像形成装置。
１１） 静電潜像担持体表面を帯電させる帯電工程と、帯電された静電潜像担持体表面を露光して静電潜像を形成する露光工程と、前記静電潜像を現像剤を用いて現像して可視像を形成する現像工程と、前記可視像を記録媒体に転写する転写工程と、前記記録媒体に転写された転写像を定着させる定着工程とを少なくとも含む画像形成方法であって、前記現像剤が、８）又は９）に記載の現像剤であることを特徴とする画像形成方法。
１２） 静電潜像担持体と、該静電潜像担持体上に形成された静電潜像を現像剤を用いて現像し可視像を形成する現像手段とを少なくとも有し、画像形成装置本体に着脱可能なプロセスカートリッジであって、前記現像剤が、８）又は９）に記載の現像剤であることを特徴とするプロセスカートリッジ。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the above-mentioned problems are solved by the following inventions 1) to 12 ).
1) A toner for developing an electrostatic latent image containing at least a binder resin, a colorant, and a release agent,
The binder resin comprises a resin (a) having no polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and a resin (b) having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer,
The resin (a) is a polyester resin having crystallinity,
Polyhydroxycarboxylic acid skeleton of the resin (b) is a monomer component terms, the optical purity X (%) = | X ( L member) -X (D body) | is Ri der 80% or less,
[However, X (L isomer) represents the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) represents the D isomer ratio (mol%) in terms of optically active monomer). ]
The resin (b) is a straight chain obtained by reacting a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer and a polyester diol (b12) other than (b11) together with an extender. A toner for developing an electrostatic latent image, comprising a polyester resin (b1) .
2) The DSC endothermic peak temperature when the resin (a) is heated from −20 ° C. to 150 ° C. at a heating rate of 10 ° C./min is 50 to 150 ° C. Toner for developing electrostatic latent image.
3) The electrostatic latent image developing toner according to 1) or 2), wherein the resin (a) is represented by the following general formula (1).

(In the above formula, n and m represent the number of repeating units, p represents an integer of 1 to 3, R ¹ and R ² may be the same as or different from each other, and may be a hydrogen atom or a hydrocarbon group. Represents.)
4) The latent electrostatic latent image according to any one of 1) to 3), wherein the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by copolymerizing a hydroxycarboxylic acid having 3 to 6 carbon atoms. Development toner.
5 ) The toner for developing an electrostatic latent image according to 4 ), wherein a mass ratio of (b11) to (b12) is 31:69 to 90:10.
6 ) The toner for developing an electrostatic latent image according to any one of 1) to 5 ), wherein a mass ratio of the resin (a) to the resin (b) is 1:99 to 30:70.
7 ) To granulate toner for developing an electrostatic latent image by emulsifying or dispersing a solution or dispersion in which at least a binder resin, a colorant and a release agent are dissolved or dispersed in an organic solvent in an aqueous medium. The method for producing a toner for developing an electrostatic latent image according to any one of 1) to 6 ).
8 ) A developer comprising the electrostatic latent image developing toner according to any one of 1) to 6 ).
9 ) The developer according to 8 ), further comprising a carrier.
10 ) an electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, Developing means for developing the electrostatic latent image using a developer to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit, wherein the developer is the developer described in 8 ) or 9 ).
11 ) A charging step of charging the surface of the electrostatic latent image carrier, an exposure step of exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and developing the electrostatic latent image with a developer. An image forming method comprising at least a developing step for developing a visible image by using the developing method, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium An image forming method, wherein the developer is the developer described in 8 ) or 9 ).
12 ) At least an electrostatic latent image carrier and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a visible image. A process cartridge that can be attached to and detached from an apparatus main body, wherein the developer is the developer described in 8 ) or 9 ).

  According to the present invention, despite containing a resin having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer such as polylactic acid, it is possible to ensure hot offset resistance, excellent low-temperature fixability, image density, An electrostatic latent image developing toner capable of obtaining an image having a good haze degree and a good heat-resistant storage stability, a method for producing the same, a developer using the toner, an image forming apparatus, an image forming method, A process cartridge can be provided.

1 is a diagram illustrating an example of an image forming apparatus according to the present invention. It is a figure which shows an example of a process cartridge.

Hereinafter, the present invention will be described in detail.
The electrostatic latent image developing toner of the present invention (hereinafter sometimes simply referred to as toner) contains at least a binder resin, a colorant, and a release agent, and further contains other components as necessary.
As the binder resin, a resin (a) having no polyhydroxycarboxylic acid skeleton composed of an optically active monomer and a resin (b) having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer are used in combination.
The mass ratio of the resin (a) to the resin (b) is preferably 1:99 to 30:70. If the ratio of the resin (a) is 1:99 or more, the compatibility of the binder resin composition does not decrease or the low-temperature fixability does not deteriorate. There is no progress of plasticization of the resin composition and deterioration of storage stability.

As the resin (a), a crystalline polyester resin is used.
Such a resin (a) has a melting point, and at the same time undergoes a crystal transition at the melting point, and at the same time has a sharp melt property in which the melt viscosity rapidly decreases from the solid state. As a result, the heat-resistant storage stability is good due to crystallinity until just before the melting start temperature, and the toner starts fixing with a sharp viscosity drop at the melting start temperature. Can be produced. In addition, the mold release width (the difference between the low temperature fixing lower limit temperature and the hot offset occurrence temperature) is also excellent.
The resin (a) is one that is partially compatible with the resin (b). When at least a part of the resin (a) and the resin (b) are mutually compatible, the temperature at which the melt viscosity of the toner starts to decrease can be lowered. Further, even when the resin (a) having a higher melting point than the resin (b) is dispersed and the glass transition temperature of the toner is low, blocking resistance is ensured.

The resin (a) can be appropriately selected from polyester resins having crystallinity according to the purpose. For example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5 -Polyols such as pentanediol, 1,6-hexanediol, hexamethylene glycol, and tetramethylene glycol, and polybasic acids such as fumaric acid, maleic acid, itaconic acid, terephthalic acid, succinic acid, adipic acid, and sebacic acid. Polyesters obtained by condensation polymerization; polyethers such as polyethylene glycol and polypropylene glycol; linear alkyl esters such as behenyl acrylate, behenyl methacrylate, behenyl itaconate, stearyl itaconate; Examples include coalescence.
Specific examples include Nippon Synthetic Chemical; HP-320 and the like.

（上記式中、ｎ及びｍは、繰返単位数を表し、ｐは１〜３の整数を表し、Ｒ^１及びＲ^２は、互いに同一であっても異なっていてもよく、水素原子又は炭化水素基を表す。） Moreover, as said crystalline polyester resin, a C2-C6 diol compound, especially 1, 4- butanediol, 1, 6- hexanediol, and these derivatives are 80 mol% or more, Preferably it is 85-100. A resin represented by the following general formula (1) synthesized by using an alcohol component containing mol% and an acid component composed of fumaric acid, maleic acid, succinic acid, or a derivative thereof is preferable.

(In the above formula, n and m represent the number of repeating units, p represents an integer of 1 to 3, and R ¹ and R ² may be the same as or different from each other, and may be a hydrogen atom or carbonization. Represents a hydrogen group.)

In order to control the crystallinity and softening point of the resin (a), when synthesizing the resin (a), a trihydric or higher polyhydric alcohol such as glycerin is added as an alcohol component, or trimellitic anhydride as an acid component A non-linear polyester or the like that has been subjected to condensation polymerization by adding a trivalent or higher polyvalent carboxylic acid such as the above may be used. The molecular structure of the resin (a) can be confirmed by solid NMR.
The weight average molecular weight (Mw) of the resin (a) is a molecular weight distribution determined by gel permeation chromatography (GPC) of the orthodichlorobenzene-soluble component, preferably 1,000 to 30,000, and preferably 1,000 to 6,500. More preferred. When the weight average molecular weight (Mw) is 1,000 or more, the heat resistant storage stability is not deteriorated, and when it is 30,000 or less, the low temperature fixability is not deteriorated.
The number average molecular weight (Mn) of the resin (a) is preferably a molecular weight distribution by GPC of a soluble part of orthodichlorobenzene, preferably 500 to 6,000, more preferably 500 to 2,000.
Moreover, as (Mw / Mn), 1.7-8 are preferable and 2-5 are more preferable.
Furthermore, in the molecular weight distribution by GPC, the peak position of the molecular weight distribution diagram in which the horizontal axis represents log (M) and the vertical axis represents mass% is in the range of 3.5 to 4.0, and the peak half-value width is 1 It is preferable that it is 5 or less.

The measurement of the molecular weight distribution by GPC can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, orthodichlorobenzene was allowed to flow as a column solvent at a flow rate of 1 ml / min, and a resin orthodichlorobenzene solution adjusted to a sample concentration of 0.05 to 0.6% by mass was injected at 50 to 200 μl and measured with a detector. To do. The molecular weight of the sample is calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Alternatively, Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8. It is preferable to use 6 × 10 ⁵ , 2 × 10 ⁶ , and 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. As the detector, an RI (refractive index) detector can be used.

The melting temperature and F1 _{/ 2} temperature of the resin (a) are preferably low as long as the heat resistant storage stability is not deteriorated. For example, the endothermic peak temperature by the DSC method is preferably 50 to 150 ° C. If the melting temperature and the F1 _{/ 2} temperature are 50 ° C. or higher, heat resistant storage stability is not deteriorated, and blocking does not occur at the temperature inside the developing device. The lower limit temperature does not increase and the low temperature fixability does not deteriorate. The DSC method is a method defined in ASTM D3418-82.
Resin (a), at least one of 965 ± 10 cm ^-1 and 990 ± 10 cm ^-1 in the infrared absorption spectrum, having an absorption based on δCH olefin (out-of-plane deformation vibration) is preferred. When the absorption exists, the low-temperature fixability is improved.
In consideration of the affinity between the paper and the resin (a), the acid value of the resin (a) is preferably 8 mgKOH / g or more, more preferably 20 mgKOH / g or more in order to achieve low-temperature fixability. On the other hand, in order to improve hot offset property, 45 mgKOH / g or less is preferable.
The hydroxyl value of the resin (a) is preferably from 0 to 50 mgKOH / g, more preferably from 5 to 50 mgKOH / g, from the viewpoint of improving low-temperature fixability and charging characteristics.

The resin (b) has a polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and has an optical purity X (%) = | X (L form) -X (D form in terms of monomer components of the polyhydroxycarboxylic acid skeleton ) | Is 80% or less. Preferably it is 60% or less. Here, X (L form) represents the L form ratio (mol%) in terms of optically active monomer, and X (D form) represents the D form ratio (mol%) in terms of optically active monomer.
If the optical purity X is 80% or less, the solvent solubility and the transparency of the resin are improved, and the production method (I) described later, which is a preferred production method, can be easily applied.
Further, when the resin (b) is used, it is easy to uniformly disperse the pigment or wax in the resin, and since the transparency is high, the image density and the haze degree are low when used for the toner containing the pigment or wax. Become good.
The resin having a polyhydroxycarboxylic acid skeleton composed of the optically active monomer may be a copolymer of monomers having no optical activity, such as a linear polyester resin (b1) described later. .

The polyhydroxycarboxylic acid skeleton can be formed by a method of directly dehydrating condensation of a hydroxycarboxylic acid or a method of ring-opening polymerization of a corresponding cyclic ester. In order to increase the molecular weight of the polyhydroxycarboxylic acid, ring-opening polymerization of a cyclic ester is preferred.
Examples of the hydroxycarboxylic acid include aliphatic hydroxycarboxylic acids (such as glycolic acid, lactic acid, and hydroxybutyric acid), aromatic hydroxycarboxylic acids (such as salicylic acid, creosote acid, mandelic acid, burric acid, and syringic acid), or a mixture thereof. Examples of the corresponding cyclic ester include lactide such as glycolide, γ-butyrolactone, and 6-valerolactone.
Among these, from the viewpoint of the transparency and thermal characteristics of the binder resin, an aliphatic hydroxycarboxylic acid is preferable, more preferably an aliphatic hydroxycarboxylic acid having 2 to 6 carbon atoms, and particularly preferably glycolic acid, Lactic acid and their lactides, most preferably glycolic acid and lactic acid.
When a cyclic ester of hydroxycarboxylic acid is used, the hydroxycarboxylic acid skeleton of the resin obtained by polymerization is a skeleton obtained by polymerizing the hydroxycarboxylic acid constituting the cyclic ester. For example, the polyhydroxycarboxylic acid skeleton of a resin obtained by using lactide of lactic acid is a skeleton obtained by polymerizing lactic acid.

As the resin (b), a linear diol obtained by reacting a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer and a polyester diol (b12) other than (b11) together with an extender. containing polyester resin (b1).
Linear polyester has a simple structure, and it is easy to control molecular weight and physical properties (thermal characteristics, compatibility with other resins, etc.). The front Symbol (b11) and (b12) unit from the formed linear polyester resin (b1) is, the benefits made possible physical properties controlled by polyester type, molecular weight, structure used in the unit of (b12) Compared with the conventional composition containing lactic acid, it can be provided with a clear physical property control means.
In order to obtain the linear polyester resin (b1) composed of the units (b11) and (b12), it is necessary that each of (b11), (b12) and the extender is bifunctional. If any of them is trifunctional or more, a crosslinking reaction proceeds and a linear polyester cannot be obtained.

Polyester diol (b11) is obtained by adding diol (11) and copolymerizing when forming a polyhydroxycarboxylic acid skeleton. Preferred diols include alkylene oxide addition of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (Number of added moles 2 to 30) (hereinafter, alkylene oxide is abbreviated as “AO”) and the like. Examples of AO include ethylene oxide, propylene oxide, and butylene oxide.
The diol may be used alone or in combination of two or more, but preferably 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, An AO adduct of bisphenol A, particularly preferred is 1,3-propylene glycol.

As the polyester diol (b12) other than (b11), among the polyester resins described later, those similar to the reaction product of the diol (11) and the dicarboxylic acid (13) can be used. It can be obtained by adjusting the charging ratio of to make the hydroxyl group excessive. Dicarboxylic acid (13) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, dodecenyl succinic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.) Branched alkylene dicarboxylic acid having 8 or more carbon atoms [dimer acid, alkenyl succinic acid (dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, etc.), alkyl succinic acid (decyl succinic acid, dodecyl succinic acid, octadecyl) Succinic acid); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
Among them, preferred as (b12) are 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) The reaction product of one or more selected from AO adducts (number of added moles of 2 to 30) and one or more selected from terephthalic acid, isophthalic acid, adipic acid, and succinic acid.

The number average molecular weight (hereinafter abbreviated as Mn) of (b11) and (b12) is preferably 500 to 30000, more preferably 1000 to 20000, from the viewpoint of adjusting the physical properties of the linear polyester resin (b1). Most preferably, it is 2000-5000.
The mass ratio of (b11) and (b12) is preferably 31:69 to 90:10, and more preferably 40:60 to 80:20 from the viewpoint of the transparency and thermal characteristics of the binder resin. .

The extender is not particularly limited as long as it has two functional groups capable of reacting with the hydroxyl groups of (b11) and (b12), but dicarboxylic acid (13) and its anhydride described later. , Polyisocyanate (15), and polyepoxide (19) include bifunctional ones. Of these, from the viewpoint of compatibility with (b11) and (b12), diisocyanate compounds and dicarboxylic acid compounds are preferred, and diisocyanate compounds are more preferred.
Specifically, succinic acid, adipic acid, maleic acid (and anhydride), fumaric acid (and anhydride), phthalic acid, isophthalic acid, terephthalic acid, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane-4,4 '-Diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), bisphenol A diglycidyl ether, and the like, among which succinic acid, adipic acid, isophthalic acid, terephthalic acid, maleic acid (and anhydride) are preferred. , Fumaric acid (and anhydride), and HDI, IPDI, most Mashiino are maleic acid (and anhydride), fumaric acid (and anhydride), and IPDI.
The content of the extender in the linear polyester-based resin (b1) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass from the viewpoints of transparency and thermal characteristics.

The content of the linear polyester resin (b1) in the resin (b) may be appropriately adjusted within a preferable range depending on the use of the toner. From the viewpoint of the transparency and thermal characteristics of the binder resin, the resin (B) 40-100 mass% of the whole is preferable, More preferably, it is 60-90 mass%.
Even when the hydroxycarboxylic acid contained in the linear polyester resin (b1) is an optically active monomer such as lactic acid, the polyhydroxycarboxylic acid skeleton of the linear polyester resin (b1) in terms of monomer components When the optical purity Z (%) = | Z (L isomer) -Z (D isomer) | is 80% or less [wherein Z (L isomer) is the L isomer ratio (mol%) in terms of optically active monomer. ), Z (D-form) represents the D-form ratio (mol%) in terms of optically active monomer. From the viewpoint of solvent solubility, the same content as above is preferable. However, when the optical purity Z exceeds 80%, from the viewpoint of solvent solubility, the relationship between the content Y mol% of the linear polyester resin (b1) in the resin (b) and Z is Y It is preferable that ≦ −1.5Z + 220 is satisfied.

As the resin (b), in addition to the linear polyester-based resin (b1), a known resin that is preferable according to the intended use and purpose of the toner can be used in combination. The resin used in combination may be a resin (b2) obtained by reacting the precursor (b0) in the resin particle forming step, and the precursor (b0) is used from the viewpoint of easy particle formation. Thus, a method of containing a resin to be used in combination is preferable. As the reaction method for obtaining (b2) from the precursor (b0) and (b0), those described later can be used.
Preferred examples of the combination resin include vinyl resins, polyester resins, polyurethane resins, and epoxy resins. Among them, polyester resins and polyurethane resins are preferable, and polyester resins and polyurethanes having a constituent part composed of 1,2-propylene glycol are particularly preferable. Resins are preferred.
The content of the combined resin other than the linear polyester-based resin (b1) may be appropriately adjusted within a preferable range depending on the use. From the viewpoint of the transparency and thermal characteristics of the binder resin, the resin (b) 60 mass% or less of the whole is preferable, More preferably, it is 10-40 mass%.

Number average molecular weight of resin (b) (measured by GPC, details of measurement method will be described later. Hereinafter, abbreviated as Mn), melting point (measured by DSC), glass transition temperature (Tg), sp value (calculation of sp value) According to the method, Polymer Engineering and Science, February, 1974, Vol. 14, No. 2 P. 147 to 154) may be appropriately adjusted to a preferable range depending on the application.
For example, the Mn of the resin (b) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of the resin (b) is preferably 20 ° C to 300 ° C, more preferably 80 ° C to 250 ° C. The Tg of the resin (b) is preferably 20 ° C to 200 ° C, more preferably 40 ° C to 200 ° C. The sp value of the resin (b) is preferably 8 to 16, and more preferably 9 to 14.

Said Tg is a value calculated | required from DSC measurement or a flow tester measurement (when it cannot measure by DSC).
DSC measurement can be performed by a method (DSC method) defined in ASTM D3418-82 using DSC20 and SSC / 580 manufactured by Seiko Denshi Kogyo.
For the flow tester measurement, an elevated flow tester CFT500 type manufactured by Shimadzu Corporation is used. The measurement conditions are as follows, and the same applies to the examples described later.
(Flow tester measurement conditions)
・ Load: 30 kg / cm ²
・ Raising rate: 3.0 ° C / min
・ Die diameter: 0.50mm
・ Die length: 10.0mm

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) of a resin other than a polyurethane resin such as a polyester resin are measured by GPC under the following conditions for a tetrahydrofuran (THF) soluble content.
・ Apparatus (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSKgelGMHXL (2)
: TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
・ Flow rate: 1 ml / min ・ Measurement temperature: 40 ° C.
-Detection device: Refractive index detector-Reference material: Tosoh standard polystyrene (TSKstandardPOLYS)
TYRENE) 12 points
(Molecular weight 500 1050 2800 5970 9100
18100 37900 96400 190000
355,000 1090000 2890000)

Further, Mn and Mw of the polyurethane resin are measured by GPC under the following conditions.
・ Device (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn αTSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection volume: 100 μl
・ Flow rate: 1ml / min ・ Temperature: 40 ℃
-Detection device: Refractive index detector-Reference material: Tosoh standard polystyrene (TSKstandardPOLYS)
TYRENE) 12 points
(Molecular weight 500 1050 2800 5970 9100
18100 37900 96400 190000
355,000 1090000 2890000)

  As the precursor (b0), a combination of a prepolymer (α) having a reactive group and a curing agent (β) can also be used. Here, “reactive group” means a group capable of reacting with the curing agent (β). In this case, as a method for forming toner particles containing the resin (b2) obtained by reacting the precursor (b0) in the toner particle forming step, a reactive group-containing prepolymer (α), a curing agent (β ) And, if necessary, an oil phase containing an organic solvent (u) is dispersed in an aqueous dispersion of the toner material solution, and the reactive group-containing prepolymer (α) and the curing agent (β) are reacted by heating to form a resin ( a method of forming toner particles containing b2); a reactive group-containing prepolymer (α) or an organic solvent solution or dispersion thereof is dispersed in an aqueous dispersion of a toner material solution, and a water-soluble curing agent ( β) is added and reacted to form toner particles containing the resin (b2); when the reactive group-containing prepolymer (α) is cured by reacting with water, the reactive group-containing prepolymer Polymer (α) or its organic Examples thereof include a method in which a solvent solution or a dispersion is dispersed in an aqueous dispersion (W) of a toner material solution and reacted with water to form toner particles containing the resin (b2).

Examples of the combination of the reactive group contained in the reactive group-containing prepolymer (α) and the curing agent (β) include the following [1] and [2]. From the viewpoint of the reaction rate in water, 1] is preferable.
[1] A combination in which the reactive group of the reactive group-containing prepolymer (α) is a functional group (α1) capable of reacting with an active hydrogen compound, and the curing agent (β) is an active hydrogen group-containing compound (β1) .
[2] A combination in which the reactive group of the reactive group-containing prepolymer (α) is an active hydrogen-containing group (α2), and the curing agent (β) is a compound (β2) that can react with the active hydrogen-containing group.

  As the functional group (α1) capable of reacting with the active hydrogen compound in the combination [1], an isocyanate group (α1a), a blocked isocyanate group (α1b), an epoxy group (α1c), an acid anhydride group (α1d), an acid And a halide group (α1e). Of these, (α1a), (α1b), and (α1c) are preferable, and (α1a) and (α1b) are particularly preferable. The blocked isocyanate group (α1b) refers to an isocyanate group blocked with a blocking agent. Examples of the blocking agent include oximes [acetooxime, methyl isobutyl ketoxime, diethyl ketoxime, cyclopentanone oxime, cyclohexanone oxime, methyl ethyl ketoxime, etc.]; lactams [γ-butyrolactam, ε-caprolactam, γ-valerolactam Etc.]: C1-C20 aliphatic alcohols [ethanol, methanol, octanol, etc.]; phenols [phenol, cresol, xylenol, nonylphenol, etc.]; active methylene compounds [acetylacetone, ethyl malonate, ethyl acetoacetate, etc.] A basic nitrogen-containing compound [N, N-diethylhydroxylamine, 2-hydroxypyridine, pyridine-N-oxide, 2-mercaptopyridine and the like]: and a mixture of two or more thereof.Of these, oximes are preferred, and methyl ethyl ketoxime is particularly preferred.

Examples of the skeleton of the reactive group-containing prepolymer (α) include polyether (αw), polyester (αx), epoxy resin (αy), and polyurethane (αz). Of these, (αx), (αy), and (αz) are preferable, and (αx) and (αz) are particularly preferable.
Examples of the polyether (αw) include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, and the like.
Examples of polyester (αx) include polycondensates of diol (11) and dicarboxylic acid (13), polylactones (ring-opening polymerization products of ε-caprolactone), and the like.
Examples of the epoxy resin (αy) include addition condensation products of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S) and epichlorohydrin.
Examples of polyurethane (αz) include polyaddition product of diol (11) and polyisocyanate (15), polyaddition product of polyester (αx) and polyisocyanate (15), and the like.

Examples of the method for adding a reactive group to polyester (αx), epoxy resin (αy), polyurethane (αz), and the like include the following methods [1] and [2].
[1] A method of leaving a functional group of a constituent at the terminal by using one of two or more constituents in excess.
[2] A compound containing a functional group and a reactive group capable of reacting with the remaining functional group by leaving the functional group of the structural component at the terminal by excessively using one of two or more structural components How to react.

In the above method [1], a hydroxyl group-containing polyester prepolymer, a carboxyl group-containing polyester prepolymer, an acid halide group-containing polyester prepolymer, a hydroxyl group-containing epoxy resin prepolymer, an epoxy group-containing epoxy resin prepolymer, a hydroxyl group-containing polyurethane prepolymer, an isocyanate A group-containing polyurethane prepolymer or the like is obtained.
For example, in the case of a hydroxyl group-containing polyester prepolymer, the ratio of the constituent components is such that the ratio of polyol (1) to polycarboxylic acid (2) is equivalent ratio [OH] / [COOH] of hydroxyl group [OH] and carboxyl group [COOH]. ] Is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1. In the case of other skeleton and end group prepolymers, the ratios are the same except that the constituent components are changed.

In the above method [2], an isocyanate group-containing prepolymer is obtained by reacting the preprimer obtained in the above method [1] with a polyisocyanate, and a blocked polyisocyanate is reacted to cause a blocked isocyanate group-containing prepolymer. A polymer is obtained, an epoxy group-containing prepolymer is obtained by reacting polyepoxide, and an acid anhydride group-containing prepolymer is obtained by reacting polyanhydride.
The amount of the compound containing a functional group and a reactive group is, for example, when the isocyanate group-containing polyester prepolymer is obtained by reacting a hydroxyl group-containing polyester with a polyisocyanate, and the ratio of the polyisocyanate is an isocyanate group [NCO]. The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the hydroxyl group-containing polyester is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, particularly preferably 2.5 /. 1 to 1.5 / 1. In the case of prepolymers having other skeletons and terminal groups, the ratio is the same except that the constituent components are changed.

The number of reactive groups per molecule in the reactive group-containing prepolymer (α) is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. is there. By setting it as the above range, the molecular weight of the cured product obtained by reacting with the curing agent (β) increases.
The Mn of the reactive group-containing prepolymer (α) is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 2,000 to 10,000.
The weight average molecular weight of the reactive group-containing prepolymer (α) is 1,000 to 50,000, preferably 2,000 to 40,000, and more preferably 4,000 to 20,000.
The viscosity of the reactive group-containing prepolymer (α) is preferably 2,000 poise or less, more preferably 1,000 poise or less at 100 ° C. By setting it to 2,000 poise or less, it is preferable in that a binder resin having a sharp particle size distribution can be obtained with a small amount of organic solvent.

  Examples of the active hydrogen group-containing compound (βl) include polyamine (β1a), polyol (β1b), polymercaptan (β1c), water (β1d) and the like which may be blocked with a detachable compound. Of these, (β1a), (β1b), and (β1d) are preferable, and (β1a) and (β1d) are more preferable. Particularly preferable are blocked polyamines and (β1d). ).

Examples of (β1a) include aliphatic polyamines (C2 to C18): aliphatic polyamines {C2 to C6 alkylenediamine (ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.), polyalkylene (C2-C6) polyamine [diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.}}; these alkyls (C1 to C4) or hydroxyalkyl (C2 -C4) Substituent [dialkyl (C1-C3) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, Riminobispropylamine, etc.]; alicyclic or heterocyclic-containing aliphatic polyamines [3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, etc.]; Aromatic ring-containing aliphatic amines (C8 to C15) (xylylenediamine, tetrachloro-p-xylylenediamine, etc.), alicyclic polyamines (C4 to C15): 1,3-diaminocyclohexane, isophoronediamine, mensendiamine , 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc., heterocyclic polyamines (C4-C15): piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis Aromatic polyamines (C6-C20) such as (2-amino-2-methylpropyl) piperazine: Substituted aromatic polyamines [1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4′-diphenylmethanediamine, 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylene Polyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthy Range amines and the like; aromatic polyamines having a nucleus-substituted alkyl group (C1-C4 alkyl group such as methyl, ethyl, n-propyl, i-propyl, butyl, etc.), such as 2,4-tolylenediamine, 2,6-triene Rangeamine, Crude Torrille Diamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, diaminoditolylsulfone, 1,3-dimethyl-2,4 -Diaminobenzene, 1,3-diethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diethyl-2,5-diaminobenzene, 1,4-diisopropyl-2 , 5-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,4-diaminomesitylene, 1,3,5-triethyl-2,4-diaminobenzene, 1,3,5-triisopropyl- 2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 1-methyl-3,5-diethyl-2,6- Aminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl-1,5-diaminonaphthalene, 2,6-diisopropyl-1,5-diaminonaphthalene, 2,6-dibutyl-1, 5-diaminonaphthalene, 3,3 ', 5,5'-tetramethylbenzidine, 3,3', 5,5'-tetraisopropylbenzidine, 3,3 ', 5,5'-tetramethyl-4,4' -Diaminodiphenylmethane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetrabutyl-4,4'-diaminodiphenylmethane, 3,5-diethyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,5-dii Sopropyl-3'-methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminobenzophenone, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminobenzophenone, 3,3', 5,5'-tetraethyl-4, 4'-diaminodiphenyl ether, 3,3 ', 5,5'-tetraisopropyl-4,4'-diaminodiphenylsulfone, etc.), and mixtures of these isomers in various proportions; nuclear substituted electron withdrawing groups (Cl, Aromatic polyamines [methylene bis-o-chloro] such as halogens such as Br, I and F; alkoxy groups such as methoxy and ethoxy; Niline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1, 4-phenylenediamine, 5-nitro-1,3-phenylenediamine, 3-dimethoxy-4-aminoaniline; 4,4'-diamino-3,3'-dimethyl-5,5'-dibromodiphenylmethane, 3,3 '-Dichlorobenzidine, 3,3'-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis (4-aminophenyl) sulfide, bis (4-aminophenyl) Nyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4'-methylenebis (2-iodoaniline), 4,4'-methylenebis (2-bromoaniline) ), 4,4′-methylenebis (2-fluoroaniline), 4-aminophenyl-2-chloroaniline, etc.]; aromatic polyamine having a secondary amino group [part or all of —NH ₂ of the above aromatic polyamine] Is replaced by —NH—R ′ (R ′ is an alkyl group such as a lower alkyl group such as methyl or ethyl)] [4,4′-di (methylamino) diphenylmethane, 1-methyl-2-methyl Amino-4-aminobenzene, etc.], polyamide polyamine: dicarboxylic acid (such as dimer acid) and excess (more than 2 moles per mole of acid). Amines (above alkylenediamine, polyalkylene polyamine and the like) and low molecular weight polyamide polyamines obtained by condensation of polyether polyamines such as hydrides of cyanoethylation products of polyether polyols (polyalkylene glycol and the like).

Of these, preferred as (β1a) are 4,4′-diaminodiphenylmethane, xylylenediamine, isophoronediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, and mixtures thereof.
Examples of the case where (β1a) is a polyamine blocked with a detachable compound include ketimine compounds obtained from the polyamines and ketones having 3 to 8 carbon atoms (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And aldimine compounds, enamine compounds and oxazolidine compounds obtained from aldehyde compounds having 2 to 8 carbon atoms (formaldehyde, acetaldehyde).

Examples of the polyol (β1b) are the same as those of the diol (11) and polyol (12). Diol (11) alone or a mixture of diol (11) and a small amount of polyol (12) is preferred.
Examples of the polymercaptan (β1c) include ethylenedithiol, 1,4-butanedithiol, 1,6-hexanedithiol, and the like.

  If necessary, a reaction terminator (βs) can be used together with the active hydrogen group-containing compound (β1). The resin (b2) can be adjusted to a predetermined molecular weight by using a reaction terminator in combination with (βl) at a certain ratio. As the reaction terminator (βs), monoamine (diethylamine, dibutylamine, butylamine, laurylamine, monoethanolamine, diethanolamine, etc.); monoamine blocked (ketimine compound, etc.): monool (methanol, ethanol, isopropanol, butanol) , Phenol, etc.); monomercaptan (such as butyl mercaptan, lauryl mercaptan); monoisocyanate (such as lauryl isocyanate phenyl isocyanate): monoepoxide (such as butyl glycidyl ether).

  As the active hydrogen-containing group (α2) of the reactive group-containing prepolymer (α) in the combination [2], an amino group (α2a), a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group) (α2b), a mercapto group ( α2c), a carboxyl group (α2d), and an organic group (α2e) blocked with a compound from which they can be removed. Of these, (α2a), (α2b) and an organic group (α2e) blocked with a compound capable of removing an amino group are preferred, and (α2b) is particularly preferred. Examples of the organic group blocked with the compound from which the amino group can be removed include the same groups as in the case of (β1a).

Examples of the compound (β2) capable of reacting with the active hydrogen-containing group include polyisocyanate (β2a), polyepoxide (β2b), polycarboxylic acid (β2c), polycarboxylic acid anhydride (β2d), polyacid halide (β2e), and the like. Can be mentioned. Of these, (β2a) and (β2b) are preferable, and (β2a) is more preferable.
Examples of the polyisocyanate (β2a) include those similar to the polyisocyanate (15) described above, and preferred ones are also the same. Examples of the polyepoxide (β2b) include those similar to the polyepoxide (19) described above.

Examples of the polycarboxylic acid (β2c) include a dicarboxylic acid (β2c-1), a trivalent or higher polycarboxylic acid (β2c-2), (β2c-1) alone, and (β2c-1) and a small amount of ( A mixture of β2c-2) is preferred. Examples of the dicarboxylic acid (β2c-1) include those similar to the dicarboxylic acid (13) described above. Examples of the trivalent or higher polycarboxylic acid (β2c-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms. Examples include acids (trimellitic acid, pyromellitic acid, etc.), and preferable ones are also the same. In addition, as dicarboxylic acid (13) or trivalent or higher polycarboxylic acid (β2c-2), acid anhydrides, acid halides or lower alkyl esters (methyl esters, ethyl esters, isopropyl esters, etc.) described above are used. Also good.
Examples of the polycarboxylic acid anhydride (β2d) include pyromellitic acid anhydride.
Examples of the polyacid halides (β2e) include the acid halides (acid chloride, acid bromide, acid iodide) of the above (β2c).
Furthermore, a reaction terminator (βs) can be used together with (β2) if necessary.

  The ratio of the curing agent (β) is the ratio of the equivalent [α] of the reactive group in the reactive group-containing prepolymer (α) to the equivalent of the active hydrogen-containing group [β] in the curing agent (β) [α. ] / [Β] is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and particularly preferably 1.2 / 1 to 1 / 1.2. When the curing agent (β) is water (β1d), water is handled as a divalent active hydrogen compound.

The resin (b2) obtained by reacting the reactive group-containing prepolymer (α) and the precursor (b0) containing the curing agent (β) in an aqueous medium becomes a component of the resin particles (B) and the binder resin. .
The weight average molecular weight of the resin (b2) obtained by reacting the reactive group-containing prepolymer (α) and the curing agent (β) is preferably 3000 or more, more preferably 3,000 to 10,000,000, particularly preferably 5,000 to 100. It is ten thousand.
Further, during the reaction of the reactive group-containing prepolymer (α) and the curing agent (β) in an aqueous medium, the reactive group-containing prepolymer (α) and the curing agent such as a linear polyester resin (b1) By including in the system a polymer that does not react with (β) [so-called dead polymer], the resin (b) reacts the reactive group-containing prepolymer (α) with the curing agent (β) in an aqueous medium. A mixture of the obtained resin (b2) and an unreacted resin such as the linear polyester resin (b1) is obtained.

(Coloring agent)
As the colorant of the toner of the present invention, known pigments and dyes capable of obtaining toners of yellow, magenta, cyan and black colors can be used.
Examples of yellow pigments include cadmium yellow, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG and Tartrazine Lake. Can be mentioned.
Examples of the orange pigment include molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, indanthrene brilliant orange RK, benzidine orange G, and indanthrene brilliant orange GK.
Examples of red pigments include Bengala, Cadmium Red, Permanent Red 4R, Resol Red, Pyrazolone Red, Watching Red Calcium Salt, Lake Red D, Brilliant Carmine 6B, Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B.
Examples of purple pigments include fast violet B and methyl violet lake.
Examples of blue pigments include cobalt blue, alkali blue, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, and indanthrene blue BC.
Examples of the green pigment include chrome green, chromium oxide, pigment green B, and malachite green lake.
Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and composite metal oxides.
These may be used individually by 1 type and may use 2 or more types together.

  The content of the colorant in the toner is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass. When the content is less than 1% by mass, the coloring power of the toner may be reduced. When the content exceeds 15% by mass, poor dispersion of the pigment in the toner occurs, resulting in a reduction in coloring power and a decrease in toner electrical characteristics. Sometimes.

  The colorant may be used as a master batch combined with a resin. Examples of such resins include polyesters, styrene or substituted polymers thereof, styrene copolymers, polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, and epoxy resins. , Epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax Etc. These may be used individually by 1 type and may use 2 or more types together. Among these, styrene or a substituted polymer thereof is particularly preferable.

  Examples of the polymer of styrene or a substituted product thereof include polystyrene, poly (p-chlorostyrene), and polyvinyl toluene. Examples of the styrene copolymer include styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer. Copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-methacrylic copolymer Acid butyl copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene- Acrylonitrile-indene copolymer, steel Down - maleic acid copolymer, styrene - maleic acid ester copolymers and the like.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

(Release agent)
As the release agent for the toner of the present invention, known ones can be used, and in particular, a free fatty acid type carnauba wax, a polyethylene wax, a montan wax and an oxidized rice wax can be used alone or in combination. The carnauba wax is preferably a microcrystalline one, having an acid value of 5 or less and a particle size of 1 μm or less when dispersed in a toner binder. The montan wax generally refers to a montan wax refined from minerals, and like a carnauba wax, it is microcrystalline and preferably has an acid value of 5 to 14. The oxidized rice wax is obtained by air-oxidizing rice bran wax, and the acid value is preferably 10-30. The reason is that these waxes are moderately finely dispersed in the toner binder resin of the present invention, and as described later, it is easy to obtain a toner excellent in offset prevention, transferability and durability. is there. These waxes may be used alone or in combination of two or more.

As other mold release agents, various conventionally known mold release agents such as solid silicone wax, higher fatty acid higher alcohol, montan ester wax, polyethylene wax, polypropylene wax and the like can be mixed and used.
The melting point of the release agent used in the toner of the present invention is preferably 70 to 90 ° C. If it is 70 ° C. or higher, the heat resistant storage stability of the toner will not be deteriorated. It does not occur.
The amount of these release agents used is preferably about 1 to 20% by weight, more preferably 3 to 10% by weight, based on the toner resin component. If it is 1% by mass or more, a sufficient offset prevention effect is obtained, and if it is 20% by mass or less, transferability and durability are not deteriorated.

(Charge control agent: CCA)
The toner of the present invention can contain a charge control agent as required.
Examples thereof include nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627), basic dyes such as C.I. I. Basic Yellow 2 (C.I. 41000), C.I. I. Basic Yellow 3, C.I. I. Basic Red 1 (C.I. 45160), C.I. I. Basic Red 9 (C.I. 42500), C.I. I. Basic Violet 1 (C.I. 42535), C.I. I. Basic Violet 3 (C.I. 42555), C.I. I. Basic Violet 10 (C.I. 45170), C.I. I. Basic Violet 14 (C.I. 42510), C.I. I. Basic Blue 1 (C.I. 42025), C.I. I. Basic Blue 3 (C.I. 51005), C.I. I. Basic Blue 5 (C.I. 42140), C.I. I. Basic Blue 7 (C.I. 42595), C.I. I. Basic Blue 9 (C.I. 52015), C.I. I. Basic Blue 24 (C.I. 52030), C.I. I. Basic Blue 25 (C.I. 52025), C.I. I. Basic Blue 26 (C.I. 44045), C.I. I. Basic Green 1 (C.I. 42040), C.I. I. Basic Green 4 (C.I. 42000) and the like and lake pigments of these basic dyes, I. Solvent Black 8 (C.I. 26150), quaternary ammonium salts such as benzoylmethyl hexadecyl ammonium chloride, decyl trimethyl chloride, or dialkyl tin compounds such as dibutyl or dioctyl, dialkyl tin borate compounds, guanidine derivatives, containing amino groups Polyamine resins such as vinyl polymers, condensation polymers containing amino groups, Japanese Patent Publication No. 41-20153, Japanese Patent Publication No. 43-27596, Japanese Patent Publication No. 44-6397, Japanese Patent Publication No. 45-26478 Metal complex salts of monoazo dyes described, Japanese Patent Publication No. 55-42752, Japanese Patent Publication No. 59-7385, salicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid Zn, Al, Co, Cr , Fe, etc. Metal complex, a copper phthalocyanine pigment obtained by sulfonation, organic boron salts, fluorine-containing quaternary ammonium salts, calixarene compounds, and the like.
Naturally, color toners other than black should avoid the use of charge control agents that impair the desired color, and white metal salts of salicylic acid derivatives are preferably used.

  The content of the charge control agent is preferably 0.01 to 2 parts by mass and more preferably 0.02 to 1 part by mass with respect to 100 parts by mass of the binder resin. If the content is 0.01 parts by mass or more, sufficient charge controllability is obtained. If the content is 2 parts by mass or less, the chargeability of the toner does not become too large, and the effect of the main charge control agent is reduced. In other words, the electrostatic attraction force with the developing roller is not increased and the fluidity of the toner and the image density are not lowered.

  The toner of the present invention preferably contains a layered inorganic mineral (hereinafter abbreviated as a modified layered inorganic mineral) in which at least a part of ions between layers of the layered inorganic mineral is modified with organic ions. As such a modified layered inorganic mineral, a material having a smectite basic crystal structure modified with an organic cation is desirable. Moreover, a metal anion can be introduce | transduced by substituting a part of bivalent metal of a layered inorganic mineral for a trivalent metal. However, since a hydrophilic property is increased when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal anion is modified with an organic anion is desirable.

Examples of the organic cation modifier for the modified layered inorganic mineral include quaternary alkyl ammonium salts, phosphonium salts, imidazolium salts, and the like, and quaternary alkyl ammonium salts are desirable. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
As the organic anion modifier for the modified layered inorganic mineral, branched, unbranched or cyclic alkyl (C1-C44), alkenyl (C1-C22), alkoxy (C8-C32), hydroxyalkyl (C2-C22), ethylene Examples thereof include sulfates, sulfonates, carboxylates, and phosphates having oxide, propylene oxide, and the like. A carboxylic acid having an ethylene oxide skeleton is desirable.

The modified layered inorganic mineral has moderate hydrophobicity, the oil phase containing the toner composition has non-Nutnian viscosity, and can deform the toner.
The content of the modified layered inorganic mineral is preferably 0.05 to 10% by mass, and more preferably 0.05 to 5% by mass.
The layered inorganic mineral can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and a mixture thereof. Among these, organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.

Commercially available layered inorganic minerals partially modified with an organic cation include Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Kraton XL Quartium 18 bentonite, such as (manufactured by Southern Clay), and stearalkonium bentonite, such as Bentone 27 (manufactured by Leox), Thixogel LG (manufactured by United catalyst), Clayton AF, Clayton APA (manufactured by Southern Clay) Quaternium 18 / benzalkonium bentonite such as Clayton HT and Clayton PS (manufactured by Southern Clay). Particularly preferred are Clayton AF and Clayton APA.
Further, as a commercial product of a layered inorganic mineral partially modified with an organic anion, a product obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula is particularly preferable. Specific examples thereof include Haitenol 330T (Daiichi Kogyo Seiyaku Co., Ltd.).
R1 (OR2) nOSO ₃ M
[Wherein R 1 represents an alkyl group having 13 carbon atoms, and R 2 represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element. ]

  The toner of the present invention preferably has a volume average particle diameter (Dv) of 3 to 8 μm, and a ratio of Dv to the number average particle diameter (Dn) (Dv / Dn) is 1.00 to 1.25. Is preferred. Thereby, it is excellent in all of heat resistant storage stability, low-temperature fixability and hot offset resistance, and particularly when used in a full-color copying machine or the like, it is excellent in image glossiness. In addition, when used in a two-component developer, the toner particle size will not fluctuate even if the toner balance (toner consumption and toner replenishment to compensate for the consumed toner) is performed over a long period of time. Less. As a result, good and stable developability can be obtained even with long-term stirring in the developing device. Conventionally, for example, a toner having a larger particle size is consumed more rapidly, and as a result, a phenomenon in which the content of a toner having a smaller particle size increases after a long run may occur. In addition, even when used as a one-component developer, even if the balance of the toner is performed, fluctuations in the particle size of the toner are reduced, toner filming on the developing roller, and toner thinning Toner adhesion to a member such as a blade can be suppressed. As a result, good and stable developability and images can be obtained even in the long-term use (stirring) of the developing device.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is for obtaining a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning property. When a toner having toner base particles having a volume average particle diameter (Dv) of less than 3 μm is used as a two-component developer, the toner is fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier is increased. May decrease. Further, when used as a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may easily occur.
On the other hand, when the volume average particle diameter (Dv) of the toner exceeds 8 μm and Dv / Dn exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and in the developer. In many cases, when the toner balance is increased, fluctuations in the particle size of the toner increase.

The volume average particle diameter (Dv) and the number average particle diameter (Dn) are measured with an aperture diameter of 100 μm using, for example, a particle size measuring device (Multisizer III, manufactured by Beckman Coulter, Inc.), and the analysis software Beckman Coulter Multisizer 3 Analysis can be performed with Version 3.51.
Specifically, 0.5 ml of a 10% by weight aqueous solution of alkylbenzene sulfonate (Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and 0.5 g of toner base particles are added to a glass 100 ml beaker. After stirring with a spatula, 80 ml of ion exchange water is added. The obtained dispersion is subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser W-113MK-II (manufactured by Honda Electronics Co., Ltd.). Further, the sample dispersion subjected to the dispersion treatment is measured using Multisizer III and a measurement solution Isoton III (manufactured by Beckman Coulter, Inc.). In the measurement, the sample dispersion is dropped so that the concentration indicated by Multisizer III is 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of measurement reproducibility of the particle diameter.

(Toner production method)
The method for producing the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a pulverization method, a monomer composition containing a specific crystalline polymer and a polymerizable monomer. A composition containing a specific crystalline polymer and an isocyanate group-containing prepolymer directly in the aqueous phase with an amine in a polymerization method (suspension polymerization method, emulsion polymerization method) for directly polymerizing the product in the aqueous phase For example, a polyaddition reaction method of extending / crosslinking, a polyaddition reaction method using an isocyanate group-containing prepolymer, a method of dissolving with a solvent, desolvating and pulverizing, and a melt spraying method.

The pulverization method is, for example, a method in which toner base particles are obtained by melting or kneading a toner material such as a binder resin, a colorant, a release agent, and a resin for dispersing the release agent, and pulverizing and classifying the toner material. is there. In the case of the pulverization method, the shape may be controlled by applying a mechanical impact force to the obtained toner base particles for the purpose of increasing the average circularity of the toner. In this case, the mechanical impact force can be applied to the toner base particles using a device such as a hybridizer or mechanofusion.
A mixture obtained by mixing the above toner materials is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. For example, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay, PCM type twin screw extruder manufactured by Ikegai Co., Ltd. It is done. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt kneading temperature is performed with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

In the pulverization, the kneaded product obtained by kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At that time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a rotor and a stator that rotate mechanically is preferably used. .
In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. Classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like to produce a toner having a predetermined particle size.

The suspension polymerization method includes an oil-soluble polymerization initiator, a colorant, a release agent, a resin for dispersing the release agent dispersed in a polymerizable monomer, a surfactant, and other solid dispersants. In an aqueous medium to be emulsified and dispersed by an emulsification method to be described later. Thereafter, a polymerization reaction may be performed to form particles, and then wet processing may be performed in which inorganic fine particles are adhered to the toner particle surfaces in the present invention. At that time, it is preferable to wash the excess surfactant and the like, and to treat the removed toner particles.
Examples of the polymerizable monomer include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; acrylamide, Methacrylamide, diacetone acrylamide, or their methylol compounds; vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate and other (meth) acrylates with amino groups are used on the toner particle surface. Functional groups can be introduced.
Further, by selecting a dispersant having an acid group or a basic group as the dispersant to be used, the dispersant can be adsorbed and left on the particle surface to introduce a functional group.

  As the emulsion polymerization method, a water-soluble polymerization initiator and a polymerizable monomer are emulsified in water using a surfactant, and a latex is synthesized by a usual emulsion polymerization method. Separately, a dispersion in which a colorant, a release agent, a resin for dispersing the release agent and the like are dispersed in an aqueous medium is prepared, and after mixing, the toner is aggregated to a toner size and heat-fused to obtain a toner. Thereafter, wet processing of inorganic fine particles described later may be performed. A functional group can be introduced on the surface of the toner particles by using a latex similar to the monomer used in the suspension polymerization method.

  Among these, since the selectivity of the resin is high, the low-temperature fixability is high, the granulation property is excellent, and the particle size, particle size distribution, and shape can be easily controlled. And a toner material containing a resin for dispersing the release agent is dissolved or dispersed in an organic solvent to prepare a toner solution, and then the toner solution is emulsified or dispersed in an aqueous medium to prepare a dispersion to prepare a toner. A method of granulating is preferred. Further, as the binder resin, a resin containing a polyester resin having a functional group capable of reacting with an active hydrogen group such as an isocyanate group is used. In the aqueous medium, the active hydrogen group-containing compound and the active hydrogen group-containing compound are used. It is more preferable to obtain a binder resin in the form of particles by reacting a polyester resin capable of reacting with a compound and removing the organic solvent. Specifically, it is preferable to include the following steps (1) to (6).

(1) Preparation of toner material liquid A toner material liquid is prepared by dissolving or dispersing a toner material in an organic solvent.
Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. These may be used individually by 1 type and may use 2 or more types together. Among these, an ester solvent is preferable because of excellent solubility of the polyester resin, and ethyl acetate is particularly preferable because it can be easily removed.
The amount of the organic solvent used can be appropriately selected according to the purpose. For example, 40 to 300 parts by weight, preferably 60 to 140 parts by weight, and more preferably 80 to 120 parts by weight with respect to 100 parts by weight of the toner material. Part by mass is more preferable.

(2) Preparation of aqueous medium The aqueous medium can be prepared, for example, by dispersing resin fine particles in an aqueous solvent. Although the addition amount of the resin fine particles in the aqueous solvent can be appropriately selected according to the purpose, it is preferably 0.5 to 10% by mass.
Examples of the aqueous solvent include water, a water-miscible solvent, and the like. Two or more types may be used in combination, and water is preferred. Examples of the water-miscible solvent include alcohol (eg, methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves, lower ketones (eg, acetone, methyl ethyl ketone, etc.) and the like.

The material of the resin fine particles is not particularly limited as long as it is a resin that can be dispersed in an aqueous solvent. For example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, Examples thereof include thermoplastic resins or thermosetting resins such as phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. These may be used individually by 1 type and may use 2 or more types together. Among these, a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) acrylic acid- An acrylic ester copolymer, a styrene-acrylonitrile copolymer, a styrene-maleic anhydride copolymer, a styrene- (meth) acrylic acid copolymer, and the like can be given.
Also, resin fine particles can be formed using a monomer having two or more unsaturated groups. Examples of the monomer having two or more unsaturated groups include sodium salt of sulfate ester of methacrylic acid ethylene oxide adduct, divinylbenzene, 1,6-hexanediol diacrylate, and the like.

The resin fine particles can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).
(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, and a dispersion polymerization method.
(B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent and curing.
(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method of preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.
(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, The resin solution dissolved by heating is cooled to precipitate resin fine particles, and the solvent is removed to form resin fine particles. Then, the resin fine particles are dispersed in water in the presence of an appropriate dispersant, and the resin fine particles are aqueous. A method for preparing a dispersion.
(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

In addition, the aqueous medium contains a dispersant as necessary from the viewpoint of stabilizing the oil droplets and obtaining a desired shape while sharpening the particle size distribution when emulsifying or dispersing the toner material liquid. It is preferable.
Examples of the dispersant include a surfactant, a poorly water-soluble inorganic compound dispersant, and a polymer protective colloid. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants such as anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants are particularly preferable.

Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters and the like, and those having a fluoroalkyl group are preferable. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonyl glutamate, 3- [ω-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [ω-fluoroalkanoyl (carbon number 6-8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (Carbon number 11-20) carboxylic acid or its metal salt, perfluoroalkyl carboxylic acid (carbon number 7-13) or its metal salt, perfluoroalkyl (carbon number 4-12) sulfonic acid or its metal salt, perfluoro Octanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) par -Fluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate and the like.
Moreover, as a commercial item of the anionic surfactant which has a fluoroalkyl group, for example, Surflon S-111, S-112, S-113 (above, Asahi Glass Co., Ltd.); Fluorad FC-93, FC-95, FC-98, FC-129 (above, manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191 F-812, F-833 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (Tochem Products) Product); tergent F-100, F150 (manufactured by Neos) and the like.

Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type surfactants. Examples of amine salt type surfactants include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type surfactant include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, and benzethonium chloride. Among them, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salt, benzalkonium salts, Benzethonium chloride, pyridinium salts, imidazolinium salts and the like are preferable.
Commercially available cationic surfactants include, for example, Surflon S-121 (Asahi Glass Co., Ltd.); Florard FC-135 (Sumitomo 3M Co.); Unidyne DS-202 (Daikin Kogyo Co., Ltd.), MegaFuck F- 150, F-824 (manufactured by Dainippon Ink & Chemicals, Inc.); Xtop EF-132 (manufactured by Tochem Products); and Ftergent F-300 (manufactured by Neos).
Examples of the amphoteric surfactant include alanine, dodecylbis (aminoethyl) glycine, bis (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.
Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.

Examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acid monomers, (meth) acrylic monomers having a hydroxyl group, ethers of vinyl alcohol, esters of compounds having a vinyl alcohol and a carboxyl group, monomers having an amide bond, monomers having an amide bond Homopolymers or copolymers such as methylolates, acid chloride monomers, monomers having nitrogen atoms or heterocycles containing nitrogen atoms, polyoxyethylene resins, celluloses and the like.

Examples of the acid monomer include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and the like.
Examples of the (meth) acrylic monomer having a hydroxyl group include acrylic acid-β-hydroxyethyl, methacrylic acid-β-hydroxyethyl, acrylic acid-β-hydroxypropyl, methacrylic acid-β-hydroxypropyl, and acrylic acid- γ-hydroxypropyl, methacrylic acid-γ-hydroxypropyl, acrylic acid-3-chloro-2-hydroxypropyl, methacrylic acid-3-chloro-2-hydroxypropyl, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin Examples include monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide, and the like.

Examples of the vinyl alcohol ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like.
Examples of the ester of the compound having a vinyl alcohol and a carboxyl group include vinyl acetate, vinyl propionate, vinyl butyrate and the like.
Examples of the monomer having an amide bond include acrylamide, methacrylamide, diacetone acrylamide acid and the like.
Examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride.
Examples of the monomer having a nitrogen atom or a heterocyclic ring containing a nitrogen atom include vinylpyridine, vinylpyrrolidone, vinylimidazole, and ethyleneimine.
Examples of the polyoxyethylene resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Examples include polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester.
Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

When preparing an aqueous dispersion of resin fine particles, a dispersion stabilizer can be used as necessary. Examples of the dispersion stabilizer include acids such as calcium phosphate salts and alkali-soluble compounds.
When the binder resin contains a polyester prepolymer, the aqueous medium can also contain a catalyst for urea reaction such as dibutyltin laurate and dioctyltin laurate, and urethane reaction.

(3) Preparation of Emulsified Slurry The emulsified slurry is prepared by emulsifying or dispersing the toner material liquid in an aqueous medium, but it is preferable to emulsify or disperse while stirring. As an apparatus for emulsifying or dispersing, for example, a homogenizer (manufactured by IKA), a polytron (manufactured by Kinematica), a batch emulsifier such as a TK auto homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), Ebara Minder (manufactured by Ebara Seisakusho) ), TK Philmix, TK Pipeline Homomixer (above, manufactured by Special Machinery Corporation), Colloid Mill (made by Shinko Pantech Co., Ltd.), Thrasher, Trigonal Wet Fine Crusher (above, manufactured by Mitsui Miike Chemical Co., Ltd.), Captron High pressures such as continuous emulsifiers (Eurotech), fine flow mill (Pacific Kiko), microfluidizer (Mizuho Kogyo), nanomizer (Nanomizer), APV Gaurin (Gaulin) Vibration type milk such as emulsifier, membrane emulsifier (made by Chilling Industries Co., Ltd.) Machine, ultrasonic emulsifier such as an ultrasonic homogenizer (manufactured by Branson Co., Ltd.). Among these, APV Gaurin, homogenizer, TK auto homomixer, Ebara milder, TK fillmix, and TK pipeline homomixer are preferable from the viewpoint of uniform particle size.

(4) Removal of organic solvent When removing the organic solvent from the emulsified slurry, a method of evaporating and removing the organic solvent in the emulsified dispersion by gradually raising the temperature of the entire reaction system, and the emulsified dispersion in a dry atmosphere Examples thereof include a method of spraying in to remove the organic solvent and evaporate and remove the aqueous solvent.

(5) Washing, drying, classification, etc. When the organic solvent is removed from the emulsified slurry, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified as desired. For example, classification may be performed by removing fine particle components by cyclone, decanter, centrifugation, or the like in an aqueous medium, or toner base particles after drying may be classified.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble compound is used as the dispersion stabilizer, the dispersion stabilizer is dissolved with an acid such as hydrochloric acid and then washed with water, etc. The dispersion stabilizer can be removed.

(6) External addition of inorganic fine particles, etc. The toner base particles are mixed with inorganic fine particles such as silica and titanium oxide as necessary, and further a mechanical impact force is applied, so that inorganic particles from the surface of the toner base particles can be applied. Desorption of fine particles and the like can be suppressed. As a method of applying a mechanical impact force, for example, using a blade rotating at high speed, a method of applying an impact force to particles, a particle is introduced into a high-speed air stream and accelerated, and particles or composite particles are mixed. For example, a method of applying an impact force by colliding with an appropriate collision plate may be used. As a device for applying a mechanical impact force, for example, an ong mill (manufactured by Hosokawa Micron Co.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, a hybridization system (Nara) Machine mill), kryptron system (manufactured by Kawasaki Heavy Industries), automatic mortar and the like.

(Developer)
The developer contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, In view of this, a two-component developer is preferable.

(Career)
There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used individually by 1 type and may use 2 or more types together.
The core material has a weight average particle diameter (D50) of preferably 10 to 200 μm, more preferably 40 to 100 μm. If the weight average particle size (D50) is less than 10 μm, the fine particle system is increased in the distribution of carrier particles, and the magnetization per particle may be lowered to cause carrier scattering, and if it exceeds 200 μm, the specific surface area decreases. Toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. Examples thereof include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, and polyesters. Resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and Examples include copolymers with vinyl fluoride, fluoroterpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers (triple fluoride (multiple) copolymers), and silicone resins. . These may be used individually by 1 type and may use 2 or more types together. Among these, silicone resins are particularly preferable.

There is no restriction | limiting in particular as said silicone resin, According to the objective from the silicone resin generally known, it can select suitably according to the objective, for example, straight silicone resin which consists only of organosiloxane bonds; alkyd resin, polyester Examples thereof include silicone resins modified with resins, epoxy resins, acrylic resins, urethane resins, and the like.
Examples of commercially available silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone. As modified silicone resins, KR206 (alkyd modified), KR5208 (acrylic modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy modified) manufactured by Toray Dow Corning Silicone Co., Ltd. ), SR2110 (alkyd modified), and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in an organic solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core by a known coating method, drying, and baking. Can be formed. Examples of the application method include an immersion method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

The baking method is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace Etc., a method using a microwave, and the like.
The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount of the resin layer is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thicker. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. A preferable mixing ratio of the toner and the carrier is generally 1 to 10.0 parts by mass of the toner with respect to 100 parts by mass of the carrier.

(Image forming device)
An outline of the image forming apparatus of the present invention will be described.
The image forming apparatus of the present invention comprises an electrostatic latent image carrier (photosensitive member), a charging unit for charging the surface of the electrostatic latent image carrier, and the electrostatic latent image carrier surface exposed to electrostatic charge. An exposure unit that forms a latent image; a developing unit that develops the electrostatic latent image using toner to form a visible image; a transfer unit that transfers the visible image to a recording medium; and It has at least fixing means for fixing the transferred image, and the developer of the present invention is used as the developer.
FIG. 1 shows an internal configuration of a tandem indirect transfer type electrophotographic copying apparatus which is an example of the image forming apparatus of the present invention, but the image forming apparatus of the present invention is not limited to this example.

In the figure, reference numeral 100 is a copying apparatus main body, 200 is a paper feed table on which the copying apparatus main body 100 is placed, 300 is a scanner (reading optical system) mounted on the copying apparatus main body 100, and 400 is an automatic document feeder (400) further mounted thereon ADF). An intermediate endless belt-shaped intermediate transfer member 10 extending in the lateral direction is provided at the center position of the copying apparatus main body 100, and the intermediate transfer member is wound around three support rollers 14, 15, 16 and rotated clockwise in the figure. It can be transported. On the left side of the second support roller 15, an intermediate transfer body cleaning device 17 that removes residual toner remaining on the intermediate transfer body 10 after image transfer is provided. On the intermediate transfer member 10 stretched between the first support roller 14 and the second support roller 15, four image forming units 18 of black, yellow, magenta, and cyan are arranged along the conveyance direction. The tandem image forming unit 20 is arranged side by side. An exposure device 21 is further provided immediately above the tandem image forming unit 20.
On the other hand, a secondary transfer device 22 is provided on the opposite side of the intermediate transfer body 10 from the tandem image forming unit 20. The secondary transfer device 22 is configured by spanning a secondary transfer belt 24, which is an endless belt, between two rollers 23, and is pressed against the third support roller 16 via the intermediate transfer member 10, The image on the intermediate transfer member 10 is transferred to a sheet. A fixing device 25 for fixing the transfer image on the sheet is provided beside the secondary transfer device 22. The fixing device 25 is configured by pressing a pressure roller 27 against a fixing belt 26 that is an endless belt. The secondary transfer device 22 also has a sheet transport function for transporting the image-transferred sheet to the fixing device 25. A sheet reversing device 28 for reversing the sheet so as to record images on both sides of the sheet is provided below the secondary transfer device 22 and the fixing device 25 in parallel with the tandem image forming unit 20.

  When making a copy using the color electrophotographic apparatus shown in FIG. 1, a document is set on the document table 30 of the automatic document feeder 400. Alternatively, the automatic document feeder 400 is opened, a document is set on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed and pressed by it. Next, when a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is placed on the contact glass 32. Immediately after the setting, the scanner 300 is driven to cause the first traveling body 33 and the second traveling body 34 to travel. Then, the first traveling body 33 emits light from the light source, further reflects the reflected light from the document surface, sends it to the second traveling body 34, and reflects the light reflected by the mirror of the second traveling body 34 to the imaging lens. The document content is sent to the reading sensor 36 through 35. When a start switch (not shown) is pressed, one of the support rollers 14, 15 and 16 is rotationally driven by a drive motor (not shown) and the other two support rollers are driven to rotate. Rotate and transport. At the same time, the photoconductors 40 are rotated by the individual image forming means 18 to form black, yellow, magenta, and cyan monochrome images on the photoconductors 40, respectively. Then, along with the conveyance of the intermediate transfer member 10, the single color images are sequentially transferred to form a composite color image on the intermediate transfer member 10.

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers 42 of the paper feed table 200 is selectively rotated, the sheet is fed out from one of the paper feed cassettes 44 provided in the paper bank 43 in multiple stages, and the separation roller The sheet is separated one by one at 45 and put into the sheet feeding path 46, conveyed by the conveying roller 47, guided to the sheet feeding path 48 in the copying machine main body 100, abutted against the registration roller 49 and stopped. Then, the registration roller 49 is rotated in synchronization with the composite color image on the intermediate transfer member 10, the sheet is fed between the intermediate transfer member 10 and the secondary transfer device 22, and transferred by the secondary transfer device 22. A color image is recorded on the sheet. The image-transferred sheet is conveyed by the secondary transfer device 22 and sent to the fixing device 25. The fixing device 25 applies heat and pressure to fix the transferred image. Are discharged and stacked on the discharge tray 57. Alternatively, it is switched by the switching claw 55 and put into the sheet reversing device 28, where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then discharged onto the discharge tray 57 by the discharge roller 56. On the other hand, the intermediate transfer body 10 after the image transfer is removed by the intermediate transfer body cleaning device 17 to remove residual toner remaining on the intermediate transfer body 10 after the image transfer, so that the tandem image forming unit 20 can prepare for another image formation.
In the tandem image forming unit 20, each image forming unit 18 includes a charging device (not shown), a developing device (not shown), a primary transfer device 62, and a photoconductor around a drum-shaped photoconductor 40. A cleaning device (not shown), a static eliminator (not shown), and the like are provided. The photoreceptor cleaning device has at least a blade cleaning member.

(Image forming method)
The image forming method of the present invention comprises a charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic A development process for developing a latent image using a developer to form a visible image, a transfer process for transferring the visible image to a recording medium, and a fixing process for fixing the transferred image transferred to the recording medium. A developer containing at least the toner of the present invention is used as the developer.

The toner of the present invention can be used by being housed in a process cartridge that includes at least the electrostatic latent image carrier and the developing unit and is detachable from the main body of the image forming apparatus.
FIG. 2 shows a schematic configuration of an image forming apparatus including a process cartridge having the toner of the present invention. In FIG. 2, 1 indicates the entire process cartridge, 2 indicates a photosensitive member, 3 indicates a charging unit, 4 indicates a developing unit, and 5 indicates a cleaning unit.
A plurality of components such as the photosensitive member 2, the charging unit 3, the developing unit 4, and the cleaning unit 5 are integrally combined as a process cartridge, and the process cartridge is formed in an image forming device such as a copying machine or a printer. It is configured to be detachable from the apparatus main body.

The operation of the image forming apparatus in FIG. 2 is as follows.
When the photosensitive member 2 is rotationally driven at a predetermined peripheral speed, the photosensitive member 2 is uniformly charged with a predetermined positive or negative potential on the peripheral surface thereof by the charging unit 3 during the rotation process. Further, upon receiving image exposure light from image exposure means such as slit exposure or laser beam scanning exposure, electrostatic latent images are sequentially formed on the peripheral surface of the photoreceptor 2. The formed electrostatic latent image is developed with toner by the developing unit 4, and the developed toner image is fed from the paper feeding unit between the photoconductor and the transfer unit in synchronization with the rotation of the photoconductor. Then, the images are sequentially transferred by the transfer means. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing toner remaining after transfer by a cleaning unit, and after being further neutralized, it is repeatedly used for image formation.

EXAMPLES Hereinafter, although an Example , a reference example, and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. In addition, "part" in description shows a mass part.

[Production Examples 1 to 3] -Production of resin (a)-
The raw materials shown in Table 1 were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, reacted at 160 ° C for 5 hours, then heated to 200 ° C. Resins 1 to 3 were synthesized by reacting for 1 hour and further reacting at 8.3 kPa for 1 hour.

About the obtained resins 1 to 3, the endothermic peak temperature of DSC when heated from −20 ° C. to 150 ° C. at a heating rate of 10 ° C./min, the weight average molecular weight in the molecular weight distribution by GPC of the soluble part of orthodichlorobenzene Absorption based on (Mw), number average molecular weight (Mn), Mw / Mn, and δCH (out-of-plane variable angular vibration) of olefin in infrared absorption spectrum was measured. The results are shown in Table 2.

[Production Examples 4 to 6] -Production of resin (b)-
Into an autoclave reaction vessel equipped with a thermometer, a stirrer, and a nitrogen insertion tube, the raw materials shown in the column of polyester diol (b11) in Table 3 and 2 parts of tin 2-ethylhexylate were placed, and the pressure was increased at 160 ° C. under normal pressure. The ring-opening polymerization was carried out for a period of time, and the reaction was further carried out at 130 ° C. for 1 hour under normal pressure. In addition, the lactide in a table | surface is a lactide of lactic acid.
The taken-out resin was cooled to room temperature, and then pulverized to obtain polyester diols (b11) -1 to 3 having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer.
Each of these polyester diols (b11) -1 to 3 and polyester diols (b12) -1 to 3 obtained by dehydration condensation using the raw materials shown in the column of polyester diol (b12) in Table 3 in methyl ethyl ketone. After dissolution, IPDI was added as an extender and subjected to an extension reaction at 50 ° C. for 6 hours, and then the solvent was distilled off to obtain [Resin b-1] to [Resin b-3] of Production Examples 4 to 6. It was.

[Production Examples 7 to 9] -Production of resin (b)-
L-lactide, D-lactide, and ε-caprolactone were added to a four-necked flask in the number of parts shown in Table 4, and heated and melted at 120 ° C. for 20 minutes in a nitrogen atmosphere. In addition, the mixture was reacted at 190 ° C. for 3 hours. Thereafter, residual lactide and caprolactone were distilled off under reduced pressure to obtain [Resin b-4] to [Resin b-6]. The lactide is lactic acid lactide.

[Production Example 10] Synthesis of polyester prepolymer
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 720 parts of an ethylene oxide 2-mole adduct of bisphenol A, 90 parts of a propylene oxide 2-mole adduct of bisphenol A, 290 parts of terephthalic acid, 25 trimellitic anhydride And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure, and then reacted for 7 hours under reduced pressure of 10 to 15 mmHg to synthesize an intermediate polyester resin.
The obtained intermediate polyester resin has a number average molecular weight (Mn) of 2,500, a weight average molecular weight (Mw) of 10,700, a peak molecular weight of 3,400, a glass transition temperature (Tg) of 57 ° C., an acid value. Was 0.4 mgKOH / g, and the hydroxyl value was 49 mgKOH / g.
Next, 400 parts of intermediate polyester resin, 95 parts of isophorone diisocyanate, and 580 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 8 hours. Prepolymer] was synthesized.
The obtained polyester prepolymer had a free isocyanate content of 1.42% by mass.

[Production Example 11] Synthesis of ketimine compound
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts of isophoronediamine and 70 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound.
The obtained ketimine compound had an amine value of 423 mgKOH / g.

[Production Example 12] -Production of master batch-
1000 parts of water, DBP oil absorption 42 ml / 100 g, pH 9.5 carbon black (Printtex 35, manufactured by Degussa) 530 parts, resin (b) 1200 parts, Henschel mixer (made by Mitsui Mining) Used and mixed.
The resulting mixture was kneaded at 150 ° C. for 30 minutes using a two-roll, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

[Production Example 13] -Production of resin fine particle dispersion-
In a reaction vessel in which a stir bar and a thermometer are set, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 20 minutes, a white emulsion was obtained.
This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours.
Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 6 hours, and an aqueous dispersion of a vinyl resin (a copolymer of styrene-methacrylic acid-butyl methacrylate-alkylallylsulfosuccinate sodium salt) [fine particle dispersion ] Was obtained.
The volume average particle size of the above [fine particle dispersion] measured with a dynamic light scattering particle size distribution analyzer ELS-800 (manufactured by Otsuka Electronics Co., Ltd.) was 0.08 μm. Moreover, the glass transition temperature by the flow tester measurement of the resin part which dried and isolated a part of said [fine particle dispersion] was 74 degreeC.

[Production Example 14] -Preparation of aqueous medium-
300 parts of ion-exchanged water, 300 parts of the above-mentioned [fine particle dispersion], and 0.2 part of sodium dodecylbenzenesulfonate were mixed and stirred to dissolve uniformly, thereby preparing [Aqueous Medium Phase 1].

[Production Example 15] -Preparation of resin solution-
In the reaction vessel, [Resin b-1] to [Resin b-6], [Polyester prepolymer], and 80 parts of ethyl acetate were added and stirred in the number of parts shown in Table 5 to prepare resin solutions 1 to 6. .

[Production Example 16] -Preparation of emulsion-
10 parts of resin 1 as resin (a) in resin solution 1, 5 parts of carnauba wax [molecular weight 1,800, acid value 2.7 mgKOH / g, penetration 1.7 mm (40 ° C.)], and master batch 5 parts was added, and using a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.) under the condition that 80% by volume of zirconia beads having a particle diameter of 0.5 mm were filled at a liquid feeding speed of 1 kg / hour, a disk peripheral speed of 6 m / second. 3 passes. Further, 2.5 parts of a ketimine compound was added and dissolved to obtain a toner material liquid.
Next, 150 parts of [Aqueous medium phase 1] is placed in a container, and 100 parts of the toner material liquid is added while stirring at 12,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.). The mixture was mixed for 10 minutes to obtain an emulsified slurry.
Furthermore, 100 parts of the emulsified slurry was charged in a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 10 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.

Next, 100 parts of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice.
To the obtained filter cake, 20 parts of a 10% by mass aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice.
After adding 20 parts of 10% by mass hydrochloric acid to the obtained filter cake and mixing for 10 minutes at 12,000 rpm using a TK homomixer, fluorine-based quaternary ammonium salt compound, Fgent 310 (Neos) Was added as a 5% by mass ethanol solution so as to correspond to 0.1 part with respect to 100 parts of the solid content of the toner, stirred for 10 minutes, and then filtered.
To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered twice.
The obtained filter cake was dried at 40 ° C. for 36 hours using a circulating dryer, and sieved with a mesh having a mesh opening of 75 μm to prepare toner base particles 1.

Toner base particles 2 to 13 were produced in the same manner as toner base particles 1 except that the type of resin solution, the type of resin (a), and the blending amount thereof were changed as shown in Table 6.

-Preparation of toner-
100 parts of toner base particles 1 to 13 and 1.0 part of hydrophobic silica (H2000, manufactured by Clariant Japan) as an external additive were added to a peripheral speed of 30 m / second using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was subjected to 5 cycles of mixing for 30 seconds and resting for 1 minute, followed by sieving with a mesh having an opening of 35 μm to prepare toners 1 to 13 of Examples , Reference Examples and Comparative Examples.

-Fabrication of carrier-
To 100 parts of toluene, 100 parts of silicone resin (organostraight silicone), 5 parts of γ- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts of carbon black are added and dispersed for 20 minutes with a homomixer. A layer coating solution was prepared.
Next, using a fluidized bed type coating apparatus, the resin layer coating solution was applied to the surface of 1,000 parts of spherical magnetite having a volume average particle size of 50 μm to prepare a carrier.

-Production of developer-
Each developer of Example, Reference Example, Comparative Example, and Reference Comparative Example was prepared by mixing 5 parts of each of the toners 1 to 13 and 95 parts of the carrier.

  Next, fixability, image density, haze degree and heat-resistant storage stability were evaluated using the toner or developer as follows. The results are shown in Table 7.

<Fixability>
Plain paper and cardboard are used by changing the temperature of the fixing belt using an apparatus in which the fixing unit of an electrophotographic copying machine (MF-200, manufactured by Ricoh) is using a Teflon (registered trademark) roller as a fixing roller. A solid image having a toner adhesion amount of 0.85 ± 0.1 mg / cm ² was formed on the transfer paper type 6200 (manufactured by Ricoh Company) and copy printing paper <135> (manufactured by NBS Ricoh Company). At this time, the upper limit temperature at which hot offset does not occur on plain paper was taken as the fixing upper limit temperature. Further, the lower limit temperature at which the residual ratio of the image density after rubbing the solid image with a pad was 70% or more was defined as the minimum fixing temperature.
[Evaluation criteria for maximum fixing temperature]
A: 190 ° C. or higher B: 180 ° C. or higher and lower than 190 ° C. C: 170 ° C. or higher and lower than 180 ° C. D: Less than 170 ° C. [Evaluation criteria for minimum fixing temperature]
A: Less than 130 ° C. B: 130 ° C. or more and less than 140 ° C. C: 140 ° C. or more and less than 150 ° C. D: 150 ° C. or more

<Image density>
Using a tandem color image forming apparatus (image Neo Neo 450, manufactured by Ricoh Co., Ltd.), the surface temperature of the fixing roller is set to 160 ± 2 ° C. A solid image of 0.000 ± 0.05 mg / cm ² was formed. The image density of arbitrary six places of the obtained solid image was measured using a spectrometer (938 Spectrodensitometer, manufactured by X-Rite), and the image density (average value) was obtained and evaluated according to the following criteria. .
〔Evaluation criteria〕
A: 2.0 or more B: 1.70 or more and less than 2.0 C: less than 1.70

<Haze degree>
As an image sample for evaluation of fixability, a monochrome image sample developed on an OHP sheet type PPC-DX (manufactured by Ricoh Co., Ltd.) at a fixing belt temperature of 160 ° C. is prepared, and the haze degree is calculated by a direct reading haze degree computer (HGM). -2DP type, manufactured by Suga Test Instruments Co., Ltd.).
The haze degree (%) is also referred to as haze and is measured as a measure of the transparency of the toner. The lower this value, the higher the transparency and the better the color developability when an OHP sheet is used.
〔Evaluation criteria〕
A: Less than 20% B: 20% or more and less than 30% C: 30% or more

<Heat resistant storage stability (Penetration)>
Each toner was filled in a 50 ml glass container, placed in a constant temperature bath at 50 ° C., and left for 20 hours. Thereafter, each toner was cooled to room temperature, the penetration (mm) was measured by a penetration test (JIS K2235-1991), and the heat resistant storage stability was evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large.
〔Evaluation criteria〕
A: 20 mm or more B: 15 mm or more and less than 20 mm C: 10 mm or more and less than 15 mm D: less than 10 mm

As can be seen from the results of Table 7, in the toner of the comparative example consisting only of the resin having a polyhydroxycarboxylic acid skeleton, the evaluation of the minimum fixing temperature was D. The toners of Examples containing a crystalline resin having no carboxylic acid skeleton were good in all items including the minimum fixing temperature.

  The toner of the present invention has excellent thermal characteristics (particularly low-temperature fixability) and can provide good image quality. Therefore, it can be used for electrophotographic image forming such as copying machines, electrostatic printing, printers, facsimiles, and electrostatic recording. Suitable as a toner.

(About Figure 1)
DESCRIPTION OF SYMBOLS 10 Intermediate transfer body 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Tandem image forming unit 21 Exposure device 22 Secondary transfer device 23 Roller 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet reversing device 30 Document table 32 Contact glass 33 First traveling body 34 Second traveling body 35 Imaging lens 36 Reading sensor 40 Photosensitive body 42 Paper feed roller 43 Paper bank 44 Paper feed cassette 45 Separating roller 46 Paper feed Path 47 conveying roller 48 sheet feeding path 49 registration roller 55 switching claw 56 discharging roller 57 sheet discharging tray 62 primary transfer apparatus 100 copying apparatus main body 200 sheet feeding table 300 scanner 400 automatic document conveying apparatus (ADF)
(About Figure 2)
DESCRIPTION OF SYMBOLS 1 Process cartridge 2 Photoconductor 3 Charging means 4 Developing means 5 Cleaning means

JP-A-9-319144 JP 2002-284881 A JP 2003-140381 A Japanese Patent Laid-Open No. 7-120975 Japanese Patent Laid-Open No. 9-274335 JP 2001-166537 A JP 7-33861 A JP 59-96123 A JP 2008-262179 A JP 2006-267980 A JP 2006-276074 A

Claims (12)

An electrostatic latent image developing toner containing at least a binder resin, a colorant, and a release agent,
The binder resin comprises a resin (a) having no polyhydroxycarboxylic acid skeleton composed of an optically active monomer, and a resin (b) having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer,
The resin (a) is a polyester resin having crystallinity,
Polyhydroxycarboxylic acid skeleton of the resin (b) is a monomer component terms, the optical purity X (%) = | X ( L member) -X (D body) | is Ri der 80% or less,
[However, X (L isomer) represents the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer) represents the D isomer ratio (mol%) in terms of optically active monomer). ]
The resin (b) is a straight chain obtained by reacting a polyester diol (b11) having a polyhydroxycarboxylic acid skeleton composed of an optically active monomer and a polyester diol (b12) other than (b11) together with an extender. A toner for developing an electrostatic latent image, comprising a polyester resin (b1) .   The DSC endothermic peak temperature when the resin (a) is heated from -20 ° C to 150 ° C at a heating rate of 10 ° C / min is 50 to 150 ° C. Toner for developing latent charge image. The electrostatic charge latent image developing toner according to claim 1, wherein the resin (a) is represented by the following general formula (1).

(In the above formula, n and m represent the number of repeating units, p represents an integer of 1 to 3, R ¹ and R ² may be the same as or different from each other, and may be a hydrogen atom or a hydrocarbon group. Represents.)   4. The electrostatic charge latent image developing device according to claim 1, wherein the polyhydroxycarboxylic acid skeleton of the resin (b) is a skeleton obtained by copolymerizing a hydroxycarboxylic acid having 3 to 6 carbon atoms. toner. The electrostatic latent image developing toner according to claim 4 , wherein a mass ratio of (b11) to (b12) is 31:69 to 90:10. The mass ratio of the resin (a) and resin (b) is from 1: 99 to 30: electrostatic latent image developing toner according to any one of claims 1 to 5, characterized in that it is 70. It is characterized by granulating a toner for developing an electrostatic latent image by emulsifying or dispersing a solution or dispersion in which at least a binder resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent in an aqueous medium. A method for producing a toner for developing an electrostatic latent image according to any one of claims 1 to 6 . Developer comprising the toner for electrostatic latent image developing according to any one of claims 1-6. The developer according to claim 8 , further comprising a carrier. An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image using a developer to form a visible image, transferring means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium and at least having an image forming apparatus bets, the developer, an image forming apparatus which is a developer according to claim 8 or 9. A charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic latent image using a developer An image forming method comprising at least a developing step for developing to form a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. An image forming method, wherein the developer is the developer according to claim 8 or 9 . An image forming apparatus main body having at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using a developer to form a visible image A process cartridge that is attachable to and detachable from the camera, wherein the developer is the developer according to claim 8 or 9 .

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