JP2006208609A - Toner and image forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which is good in various properties such as fluidity and fixing property, satisfies both of excellent low-temperature fixing property and hot storage resistance, and gives high image quality, and to provide an image forming method using the toner. <P>SOLUTION: The toner contains a resin and satisfies the formula (1): Tg2r>Tg2t and the formula (2): Tg1t-Tg2t>Tg1r-Tg2r, wherein Tg1r and Tg2r are respective peaks in the first temperature up of the resin and in the second temperature up of the resin on the DSC measurement of the resin; and Tg1t and Tg2t are respective peaks coming from the resin in the first temperature up of the toner and in the second temperature up of the toner on the DSC measurement of the toner containing the resin. Preferably the toner also contains a plasticizer for the resin compatible with the resin in heating and the plasticizer has a melting point (Tm) of 30 to <120°C. Preferably the toner also contains a trivalent or higher valence crosslinking agent. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a copying machine, a laser printer, a plain paper fax machine, a direct or indirect electrophotographic multicolor developing system using an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like. The present invention relates to a toner suitably used in a full-color copying machine, a full-color laser printer, a full-color plain paper fax machine, and the like, and a developer, a toner-containing container, a process cartridge, an image forming apparatus, and an image forming method using the toner.

  In image formation by electrophotography or the like, generally, an electrostatic image is formed on a photoreceptor (electrostatic image carrier), and the electrostatic image is developed with a developer to form a visible image (toner image). The visible image is transferred to a recording medium such as paper and fixed to form a fixed image (see Patent Document 1). As the developer, a one-component developer using a magnetic toner or a non-magnetic toner alone and a two-component developer composed of a toner and a carrier are known.

  As the fixing method in the electrophotographic method, a heated heat roller method in which a heating roller is directly pressed against a toner image on a recording medium and fixed is widely used because of its energy efficiency. However, in the case of the heating heat roller system, there is a problem that a large amount of electric power is required for the fixing. For this reason, from the viewpoint of energy saving, various studies have been made to reduce the power consumption of the heating roller. For example, the output of the heater for the heating roller is weakened when the image is not output, and the heater is turned off when the image is output. A method of increasing the output to raise the temperature of the heating roller is generally used. However, in this case, in order to raise the temperature of the heating roller to the temperature necessary for fixing from the sleep time, a waiting time of about several tens of seconds is required, and this waiting time becomes a stress for the user. In addition, when the image is not output, it is desired to further reduce power consumption by completely turning off the heater. In order to achieve these demands, it is considered essential to lower the fixing temperature of the toner itself and lower the toner fixing temperature when it can be used.

In order to achieve low-temperature fixing of the toner, it is necessary to control the thermal characteristics of the resin itself. For example, a melt-miscible substance (hereinafter referred to as a plasticizer) that is compatible with the resin and exhibits a plastic effect. It has been practiced to reduce the glass transition temperature (Tg) of the resin by adding it to the toner. However, if Tg is lowered too much, the heat-resistant storage stability is deteriorated, and if the flow tester method 1/2 temperature (F _1/2 ) is lowered too much, problems such as lowering the hot offset occurrence temperature occur, and the relationship is a trade-off. The development of a toner that can achieve both a low-temperature fixability and a heat-resistant storage stability at good levels has been a long-standing problem.

Thus, for the purpose of achieving both low-temperature fixability and heat-resistant storage stability, for example, Patent Document 2 describes a toner in which resin protrusions containing no plasticizer are present on the toner particle surface. In this case, although the protrusions are provided, the inside of the toner is mainly composed of a low Tg resin, and it is difficult to achieve both low-temperature fixability and heat-resistant storage stability at a good level.
For example, Patent Document 3 discloses a toner containing a binder that does not separate and precipitate in the wax when the wax having a melting point of 20 to 150 ° C. is dissolved in the wax as a solvent and further rapidly cooled. Are listed. According to the toner, since the wax exhibits a plastic effect on a resin having a melting point higher than the fixing temperature, it can be fixed at a low temperature, but is produced by a pulverization method including a melt-kneading step. A plasticizing effect has already been exhibited at the time of production, and the heat resistant storage stability is not sufficient.
For example, Patent Document 4 describes a toner containing two types of waxes, a compatible wax and an incompatible wax, with respect to a resin monomer. However, the toner described in Patent Document 4 is mainly intended for a toner for a one-component developer, and is intended to uniformly disperse a magnetic substance in the toner, and is a wax having compatibility with the toner. Although the plasticizing effect is mentioned, it is intended only to assist the dispersion of the magnetic material. In addition, since the toner manufacturing process includes a heating process at a temperature higher than the melting point of the compatible wax, a plasticizing effect is already manifested during the manufacturing process as in the toner described in Patent Document 3. There is a problem that heat-resistant storage stability deteriorates.
For example, Patent Document 5 describes a toner containing a polyfunctional ester compound that is compatible with a resin monomer. However, in the toner, only the melting point of the resin monomer and the melting point of the polyfunctional ester compound are just the same, and the glass transition temperature (Tg) of the toner is Since the plastic effect by the polyfunctional ester compound has already been developed, it is impossible to sufficiently achieve both low-temperature fixability and heat-resistant storage stability.

  Therefore, for the purpose of achieving both low-temperature fixability and heat-resistant storage stability, for example, a microcapsule toner having a shell portion formed of a high melting point compound and a core portion formed of a colored phase that is liquid at room temperature is provided. Proposed. As an example of this, for example, a copolymer having a microphase separation structure composed of a dispersed phase and a continuous phase and having compatibility with both phases is used as a core portion to improve the stability of an image after fixing. There is known a microcapsule toner that can be used (see Patent Document 6). However, the toner formed in such a configuration still needs to be pressurized for fixing, and also has problems such as toner stability, image disturbance, and glossiness reduction. It is difficult to develop the characteristics that are achieved.

  Therefore, it has both excellent low-temperature fixability and heat-resistant storage stability, good properties such as fluidity and fixability, good quality, high-quality images can be obtained, and power saving and standby time At present, the toner that can be shortened and the related technology using the toner have not been provided.

US Pat. No. 2,297,691 JP-A-6-258861 JP 2002-221825 A JP 2002-202627 A JP 2001-281909 A JP-A-6-19182

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, the present invention has various properties such as fluidity and fixability, and has both excellent low-temperature fixability and heat-resistant storage stability, and can provide high image quality, and the toner can be used to improve image quality. An object is to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method.

As a result of intensive studies in view of the above problems, the present inventors have obtained the following knowledge. That is, a plasticizer that exhibits a plasticizing effect by being compatible with the binder resin in the toner is present in the toner in a state independent of the binder resin (in a state where it is not compatible). The glass transition temperature (Tg) and F1 _{/ 2} temperature of the binder resin therein can be maintained at a high level to exhibit excellent heat-resistant storage stability. It is a finding that a plastic effect can be exhibited by compatibilizing with an agent, and the glass transition temperature (Tg) and the F1 _{/ 2} temperature can be lowered to exhibit excellent low-temperature fixability.

The present invention is based on the above findings of the present inventors, and means for solving the above problems are as follows. That is,
<1> A toner containing a resin, wherein the first temperature rise peak of the resin is Tg1r and the second temperature rise of the resin is Tg2r when the resin is subjected to DSC measurement. When the DSC measurement was performed, the peak derived from the resin at the first temperature increase of the toner was Tg1t, and the peak derived from the resin at the second temperature increase of the toner was Tg2t. And a toner satisfying the formula (2).
Tg2r> Tg2t (1)
Tg1t-Tg2t> Tg1r-Tg2r (2)
<2> The toner according to <1>, wherein Tg2r−Tg2t> 10 (° C.).
<3> The toner according to any one of <1> to <2>, wherein Tg1r−Tg1t <5 (° C.).
<4> Any one of <1> to <4>, including a plasticizer of the resin that is compatible with the resin when heated, and having a melting point (Tm) of the plasticizer of 30 ° C. or higher and lower than 120 ° C. The toner described in 1.
<5> The toner according to <4>, wherein the plasticizer has a melting point of 50 ° C. or higher and lower than 80 ° C.
<6> The toner according to any one of <4> to <5>, wherein the toner contains 5 to 30% by mass of a plasticizer.
<7> The toner according to any one of <1> to <6>, wherein the resin has an acidic group and includes at least one of a metal salt and a complex that causes a crosslinking reaction with the acidic group.
<8> The toner according to any one of <4> to <7>, wherein Tg1r> Tm, and 100 ° C.> Tg1r ≧ 60 ° C.
<9> The toner according to any one of <1> to <8>, comprising a trivalent or higher valent crosslinking agent.
<10> The toner according to <9>, wherein the trivalent or higher valent crosslinking agent is a trivalent or higher valent salicylic acid metal compound.
<11> The toner according to any one of <9> to <10>, wherein the toner contains 0.05 to 10% by mass of a trivalent or higher valent crosslinking agent.
<12> The toner according to any one of <1> to <11>, wherein the resin has a hydroxyl value of 20 mgKOH / g or more.
<13> The toner according to any one of <1> to <12>, wherein the toner material is granulated after the toner material is dissolved or dispersed in an aqueous medium to prepare an emulsion or dispersion. It is.
<14> The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The toner according to <13>, which is performed.
<15> The toner according to any one of <13> to <14>, wherein the solution or dispersion of the toner material is prepared by dissolving or dispersing the toner material in an organic solvent.
<16> The toner according to <15>, wherein the organic solvent is removed during or after granulation of the toner.
<17> The toner according to any one of <15> to <16>, wherein the organic solvent is an ester solvent.
<18> The toner according to any one of <1> to <17>, which is produced at 10 to 100 ° C.
<19> The toner according to any one of <1> to <18>, which is manufactured at 20 to 60 ° C.
<20> The toner according to any one of <4> to <19>, wherein the toner contains a plasticizer in a dispersed state, and the dispersion diameter of the plasticizer is 10 nm to 3 μm.
<21> The toner according to any one of <15> to <20>, wherein the solubility of the plasticizer in an organic solvent at 25 ° C. or less is 1% by mass or less.
<22> The toner according to any one of <15> to <21>, wherein the solubility of the plasticizer in the organic solvent at 60 ° C. or higher is 5% by mass or more.

<23> A developer comprising the toner according to any one of <1> to <22>.
<24> A toner-containing container filled with the toner according to any one of <1> to <22>.
<25> An electrostatic latent image carrier and an electrostatic latent image formed on the electrostatic latent image carrier are developed using the toner according to any one of <1> to <22> to be a visible image And a developing means for forming a process cartridge.
<26> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to <1> to <22> Developing means for developing a visible image by developing using any of the toners, Transfer means for transferring the visible image to a recording medium, Fixing means for fixing the transferred image transferred to the recording medium, An image forming apparatus having at least
<27> An image carrier, a toner supply unit that supplies the toner according to any one of <1> to <22> on the image carrier, and the toner brought into contact with the image carrier Visible image temporary fixing means for applying a heat corresponding to the image signal to form a visible image with the toner at the site to which the heat is applied, and temporarily fixing the visible image on the image carrier; An image forming apparatus comprising at least heat welding means for transferring and heat-welding the fixed visible image to a recording medium.
<28> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image using the toner according to any one of <1> to <22> An image 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 It is a forming method.
<29> A toner supplying step of supplying the toner according to any one of <1> to <22> on the image carrier, and heat corresponding to an image signal for the toner brought into contact with the image carrier A visible image temporary fixing step of forming a visible image with the toner at the site to which the heat is applied, and temporarily fixing the visible image on the image carrier, and the temporarily fixed visible An image forming method comprising at least a heat welding step of transferring an image onto a recording medium and heat welding.

The toner of the present invention contains a resin, and when the DSC measurement of the resin is performed, the first peak of temperature rise of the resin is Tg1r, and the second peak of temperature rise of the resin is Tg2r. When the DSC measurement of the toner containing toner is Tg1t, the peak derived from the resin at the first temperature increase of the toner is Tg1t, and the peak derived from the resin at the second temperature increase of the toner is Tg2t. (1) and Formula (2) are satisfied.
Tg2r> Tg2t (1)
Tg1t-Tg2t> Tg1r-Tg2r (2)
Since the toner satisfies the formula (1), the glass transition temperature can be reduced, and since the formula (2) is satisfied, the glass transition temperature is reduced when heated. That is, it has a high glass transition temperature during storage, and the glass transition temperature decreases during heating. For this reason, both excellent low-temperature fixability and heat-resistant storage stability are achieved. When image formation is performed using the toner, high image quality can be obtained even under low-temperature fixing conditions.
An embodiment comprising a plasticizer that is compatible with the resin at the time of heating, wherein the plasticizer has a melting point (Tm) of 30 ° C. or higher, the resin has an acidic group, and a crosslinking reaction with the acidic group An embodiment containing at least one of a metal salt and a complex that causes a toner, an embodiment containing a trivalent or higher-valent cross-linking agent, and a toner after dissolving or dispersing a toner material in an aqueous medium to prepare an emulsion or dispersion. The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound, and the granulation includes the active hydrogen group-containing compound, An embodiment in which the active hydrogen group-containing compound and a polymer capable of reacting are reacted to produce particles having at least the adhesive substrate while producing an adhesive substrate is preferable.

  The developer of the present invention contains the toner of the present invention. For this reason, when an image is formed by electrophotography using the developer, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  The toner container of the present invention is filled with the toner of the present invention. Therefore, when an image is formed by electrophotography using the toner of the present invention filled in the toner-containing container, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  The process cartridge of the present invention comprises an electrostatic latent image carrier, and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a visible image. At least. The process cartridge can be attached to and detached from the image forming apparatus, is excellent in convenience, and uses the toner of the present invention, so that a high-quality image with high image density and high sharpness can be formed even under low-temperature fixing conditions.

  One aspect of the image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image. Development means for forming a visible image by developing with the toner of the present invention, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium Have at least. In the image forming apparatus, the electrostatic latent image forming unit forms an electrostatic latent image on the electrostatic latent image carrier. The developing means develops the electrostatic latent image using the toner of the present invention to form a visible image. The transfer means transfers the visible image to a recording medium. The fixing unit fixes the transferred image transferred to the recording medium. As a result, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  According to another aspect of the image forming apparatus of the present invention, an image carrier, a toner supply unit that supplies the toner of the present invention on the image carrier, and an image with respect to the toner brought into contact with the image carrier. Visible image temporary fixing means for applying a heat corresponding to a signal to form a visible image with toner at a portion to which the heat is applied, and temporarily fixing the visible image on the image carrier; And at least heat welding means for transferring the visible image to a recording medium for heat welding. In the image forming apparatus, the toner supply unit supplies the toner of the present invention onto the image carrier. The visible image temporary fixing means applies heat according to an image signal to the toner brought into contact with the image carrier to form a visible image with the toner at a portion to which the heat is applied, A visible image is temporarily fixed on the image carrier. The thermal welding means transfers the temporarily fixed visible image to a recording medium and thermally welds it. As a result, it is not necessary to form an electrostatic latent image on the photoconductor, and a high-quality image with high image density and high sharpness can be formed at high speed.

  One aspect of the image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, and developing the electrostatic latent image using the toner of the present invention. Development step for forming a visible image, a transfer step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. In the image forming apparatus, an electrostatic latent image is formed on the electrostatic latent image carrier in the electrostatic latent image forming step. In the developing step, the electrostatic latent image is developed using the toner of the present invention to form a visible image. In the transfer step, the visible image is transferred to a recording medium. In the fixing step, the transferred image transferred to the recording medium is fixed. As a result, a high-quality image with high image density and high sharpness is formed even under low-temperature fixing conditions.

  According to another aspect of the image forming method of the present invention, a toner supplying step of supplying the toner of the present invention onto an image carrier, and heat corresponding to an image signal is applied to the toner abutted on the image carrier. A visible image temporary fixing step in which a visible image is formed by toner applied to the portion to which the heat is applied, and the visible image is temporarily fixed on the image bearing member; and the temporarily fixed visible image At least a heat welding step of transferring the material to a recording medium and heat welding. In the image forming method, the toner of the present invention is supplied onto the image carrier in the toner supply step. In the visible image temporary fixing step, heat corresponding to an image signal is applied to the toner brought into contact with the image carrier, and a visible image is formed by the toner of the portion to which the heat is applied, A visible image is temporarily fixed on the image carrier. In the thermal welding step, the temporarily fixed visible image is transferred to the recording medium and thermally welded. As a result, it is not necessary to form an electrostatic latent image on the photoconductor, and a high-quality image with high image density and high sharpness can be formed at high speed.

  According to the present invention, various conventional problems can be solved, fluidity, fixability and other properties are good, and both excellent low-temperature fixability and heat-resistant storage stability can be achieved, and high image quality can be obtained. In addition, it is possible to provide a developer, a container containing toner, a process cartridge, an image forming apparatus, and an image forming method capable of improving image quality using the toner.

(toner)
The toner of the present invention contains a resin, and when the DSC measurement of the resin is performed, the first peak of temperature rise of the resin is Tg1r, and the second peak of temperature rise of the resin is Tg2r. When the DSC measurement of the toner containing toner is Tg1t, the peak derived from the resin at the first temperature increase of the toner is Tg1t, and the peak derived from the resin at the second temperature increase of the toner is Tg2t. It satisfies (1) and formula (2), preferably contains a trivalent or higher valent crosslinking agent and plasticizer, and further contains other components such as a colorant, a release agent, and a charge control agent as necessary. Become.
Tg2r> Tg2t (1)
Tg1t-Tg2t> Tg1r-Tg2r (2)

-Resin-
The resin is not particularly limited as long as the formulas (1) and (2) are satisfied, and can be appropriately selected according to the purpose. Examples thereof include known binder resins.
The formula (1) indicates that the glass transition temperature of the toner is lower than the glass transition temperature of the resin, and the formula (2) indicates that the glass transition temperature is decreased when the toner is heated. means.
The Tg2r needs to be larger than the Tg2t, and the difference Tg2r−Tg2t preferably satisfies Tg2r−Tg2t> 10 (° C.). As the difference (Tg2r−Tg2t) is increased, the heat characteristic value of the resin is significantly decreased by heating at the time of fixing, and the lower limit temperature of fixing of the toner can be decreased, and the difference is less than 10 ° C. In some cases, the low-temperature fixability is not sufficient.
At this time, Tg1r-Tg1t preferably satisfies Tg1r-Tg1t <5 (° C.). When the difference (Tg1r−Tg1t) is less than 5 (° C.), the glass transition temperature of the resin alone and the toner during storage are close, and heat resistant storage stability can be maintained at a higher level.

  When the toner of the present invention contains the plasticizer, when the resin is subjected to DSC measurement, the first temperature rise Tg1r of the resin is Tg1r> Tm with respect to the melting point Tm of the plasticizer. And it is preferable that 100 ° C.> Tg1r ≧ 60 ° C. That is, the peak Tgr1 of the first temperature rise of the resin is preferably a low temperature from the viewpoint of low-temperature fixability, but when it is lower than the melting point of the plasticizer, 100 ° C.> Tg1r ≧ 60 ° C. The temperature may be high within the range satisfying.

In the toner of the present invention, it is preferable that the resin has an acidic group and contains a crosslinking agent that causes a crosslinking reaction with the acidic group. By including the metal salt or complex, the crosslinking reaction proceeds during heating, and the occurrence of copy blocking can be prevented.
Examples of the resin having an acidic group include those containing an acidic group such as a carboxyl group and a sulfonic acid group, and those obtained by excessively blending and synthesizing an acid component of a copolymer of acrylic acid or methacrylic acid or a polyester resin. Among these, those containing a carboxyl group, a sulfonic acid group and the like are preferable. Further, a monofunctional monomer may be introduced into the polyester for the purpose of blocking the polar group at the end of the polyester polymer and improving the environmental stability of the toner charging characteristics. Examples of the monofunctional monomer include benzoic acid, chlorobenzoic acid, bromobenzoic acid, parahydroxybenzoic acid, sulfobenzoic acid monoammonium salt, sulfobenzoic acid monosodium salt, cyclohexylaminocarbonylbenzoic acid, and n-dodecyl. Aminocarbonylbenzoic acid, tertiary butylbenzoic acid, naphthalenecarboxylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, salicylic acid, thiosalicylic acid, phenylacetic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, octanecarboxylic acid, lauric acid Monocarboxylic acids such as stearyl acid and lower alkyl esters thereof, or monoalcohols such as aliphatic alcohols, aromatic alcohols, and alicyclic alcohols.

  The resin preferably has a hydroxyl value of 20 mgKOH / g or more. When the hydroxyl value is 20 mgKOH / g, the hot offset property is excellent. This is presumably because the hydroxyl value constitutes three-dimensionally a site that reacts easily with a crosslinking structure with a crosslinking agent described later and a weak crosslinking.

-Crosslinking agent-
The crosslinking agent is preferably at least one of a metal salt and a complex, for example.
The metal salt and complex are preferably at least one selected from, for example, metal salts of salicylic acid derivatives, acetylacetonate metal salts, and complexes. The metal is not particularly limited as long as it is a polyvalent ion metal, and examples thereof include zinc, iron, zirconium, and chromium.

The crosslinking agent is preferably trivalent or higher. By including the trivalent or higher valent crosslinking agent, the hot offset resistance is improved. This is because when a trivalent or higher valent crosslinking agent is contained, the metal complex reacts with a portion having high reactivity between the resin and the mold release agent described later, thereby forming a mild crosslinked structure, thereby preventing hot offset resistance. This is considered to be due to the improvement effect.
Preferred examples of the trivalent or higher valent crosslinking agent include trivalent or higher valent salicylic acid metal compounds. Specifically, a salicylic acid metal compound represented by the following structural formula (1) is preferable.

ただし、前記構造式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、水素原子、炭素数１〜１８のアルキル基、及びアリル基のいずれかであるのが好ましく、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一であってもよいし、異なっていてもよい。Ｒ^１とＲ^２、Ｒ^２とＲ^３、及びＲ^３とＲ^４のいずれかは、結合により置換基を有していてもよい芳香族環又は脂肪族環を形成するものであってもよい。Ｍは金属を表し、ｍは３以上の整数であり、ｎは２以上の整数である。
中心金属である前記Ｍとしては、３価以上の金属である限り特に制限はなく、目的に応じて適宜選択することができるが、Ｆｅ、Ｎｉ、Ａｌ、Ｔｉ及びＺｒが好ましい。これらの中でも、人体に対する安全性等の点で、Ｆｅが特に好ましい。

However, in the structural formula (1), R ¹ , R ² , R ³ and R ⁴ are preferably any one of a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and an allyl group, and R ¹ , R ² , R ³ and R ⁴ may be the same or different. Any of R ¹ and R ² , R ² and R ³ , and R ³ and R ⁴ may form an aromatic ring or an aliphatic ring which may have a substituent by a bond. . M represents a metal, m is an integer of 3 or more, and n is an integer of 2 or more.
The M which is a central metal is not particularly limited as long as it is a trivalent or higher metal, and can be appropriately selected according to the purpose, but Fe, Ni, Al, Ti and Zr are preferable. Among these, Fe is particularly preferable in terms of safety to the human body.

  As content of the said crosslinking agent, 0.05-10 mass parts is preferable with respect to 100 mass parts of toner, for example, and 0.5-5 mass parts is more preferable. If the content is less than 0.05 parts by mass, the hot offset resistance may be inferior. If it exceeds 10 parts by mass, the hot offset resistance may be excellent, but the low-temperature fixability may be inferior.

-Plasticizer-
The plasticizer is a plasticizer of the resin that is compatible with the resin when heated. As the plasticizer, the greater the change in the glass transition temperature when it is compatible with the resin, the lower the temperature can be fixed. Therefore, 5 parts by mass was added to 100 parts by mass of the resin to achieve compatibility. In some cases, it is preferable to be able to lower the glass transition temperature Tg2r of the single resin by 5 ° C. or more.
As the melting point (Tm) of the plasticizer, it has excellent heat-resistant storage stability by being placed in a state where the resin and the plasticizer exist independently during storage (incompatible state), and fixing. It is preferably 30 ° C. or more and less than 120 ° C., preferably 50 ° C. or more, in that the resin and the plasticizer are quickly compatible with each other by heating, and a low-temperature fixability at a high level can be realized. More preferably, it is less than 80 ° C. When the melting point (Tm) is less than 30 ° C., the heat-resistant storage stability may be inferior, and when it is 120 ° C. or more, the compatibility during heating may be insufficient and the low-temperature fixability may be inferior.

The plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acid esters, esters of aromatic acids such as phthalic acid, phosphoric esters, maleic esters, fumaric esters, itaconic acids. Esters, other esters, benzyl, benzoin compounds, ketones such as benzoyl compounds, hindered phenol compounds, benzotriazole compounds, aromatic sulfonamide compounds, aliphatic amide compounds, long chain alcohols, long chain dialcohols, long chains Carboxylic acid, long chain dicarboxylic acid, etc. are mentioned.
Specifically, dimethyl fumarate, monoethyl fumarate, monobutyl fumarate, monomethyl itaconate, monobutyl itaconate, diphenyl adipate, dibenzyl terephthalate, dibenzyl isophthalate, benzyl, benzoin isopropyl ether, 4-benzoylbiphenyl , 4-benzoyldiphenyl ether, 2-benzoylnaphthalene, dibenzoylmethane, 4-biphenylcarboxylic acid, stearyl stearamide, oleyl stearamide, stearoleoleamide, octadecanol, n-octyl alcohol, tetracosanoic acid, eicosane Acid, stearic acid, lauric acid, nonadecanoic acid, palmitic acid hydroxyoctanoic acid, docosanoic acid, described in JP-A-2002-105414 The compounds of the general formula (1) to (17), and the like.

The plasticizer is preferably contained in the toner in a dispersed state. The dispersion diameter of the plasticizer is, for example, 10 nm to 3 μm, more preferably 50 nm to 1 μm, in the maximum direction.
If the dispersion diameter is less than 10 nm, the heat-resistant storage stability may be inferior due to an increase in the contact surface area between the plasticizer and the resin. If the dispersion diameter exceeds 3 μm, the phase with the resin during heating during fixing may be inferior. Insufficient dissolution may result in poor low temperature fixability.
The method for measuring the dispersion diameter of the plasticizer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the toner is embedded in an epoxy resin and sliced to about 100 μm, and ruthenium tetroxide. After observing the dispersion state of the plasticizer by observing with a transmission electron microscope (TEM) at a magnification of 10,000, taking a photograph, and evaluating the photograph, the dispersion diameter is determined. Can be measured. When it is confirmed that the plasticizer dispersion is present in the particles, it can be determined that the plasticizer is not contained in the toner in a dispersed state.

As the solubility of the plasticizer, for example, the solubility in an organic solvent at 25 ° C. or less is preferably 1% by mass or less, and more preferably 0.1% by mass or less. If the solubility exceeds 1% by mass, the resin and the plasticizer may become compatible during production in the toner production method described later.
Moreover, as the solubility of the plasticizer, for example, the solubility in an organic solvent at 60 ° C. or higher is preferably 5% by mass or more, and more preferably 20% by mass or more. When the solubility is less than 5% by mass, the plasticizer is not dissolved in the organic solvent by heating, so that the dispersion state in the toner may be deteriorated.
The solubility of the plasticizer in the organic solvent can be determined by measuring the amount (g) of the plasticizer dissolved in 100 g of the organic solvent at each measurement temperature.

  The content of the plasticizer in the toner is 5 to 30% by mass in terms of achieving both low-temperature fixability and heat-resistant storage stability and maintaining toner characteristics such as chargeability and resolution at a high level. Preferably, 10 to 20% by mass is more preferable. When the content is less than 5% by mass, the low-temperature fixability may be inferior, and when it exceeds 30% by mass, the area of the plasticizer on the toner surface may increase and the fluidity may be inferior.

As a method for measuring the glass transition temperature and melting point of the resin, the toner, and the plasticizer, for example, using a DSC system (differential scanning calorimeter) (“DSC-60”; manufactured by Shimadzu Corporation), the following method is used. Can be measured.
Regarding the glass transition temperature (Tg1r and Tg1t) of the resin and toner at the first temperature increase, first, about 5.0 mg of resin or toner (sample) is placed in an aluminum sample container, and the sample container is placed on a holder unit. Set in an electric furnace. Next, the sample is heated from 20 ° C. to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere, and a DSC curve is measured with a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation). The obtained DSC curve can be calculated from the intersection of the tangent line between the curve before the inflection point of the resin (or toner) and the curve after the inflection point using an analysis program in the DSC-60 system. At the same time, the melting point (Tm) of the plasticizer can be determined from the peak value derived from the plasticizer. When the melting point of the plasticizer overlaps with the peak of other substances (resin, wax, etc.) in the toner, the melting point of the plasticizer can be obtained by performing DSC measurement on the plasticizer alone. it can.
Regarding the glass transition temperatures (Tg2r and Tg2t) of the resin and toner in the second temperature increase, after the first temperature increase, the temperature is decreased from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further in a nitrogen atmosphere. Then, the sample is heated to 150 ° C. at a heating rate of 10 ° C./min, and the DSC curve is measured with a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation). The obtained DSC curve can be calculated from the intersection of the tangent line between the curve before the inflection point of the resin (or toner) and the curve after the inflection point using an analysis program in the DSC-60 system. At this time, the endothermic peak derived from the plasticizer disappears or decreases due to the compatibility between the resin and the plasticizer. The compatibility between the resin and the plasticizer can be determined from the change in the area of the endothermic peak.

-Other ingredients-
The other components are not particularly limited and may be appropriately selected depending on the purpose. For example, colorants, mold release agents, charge control agents, inorganic fine particles, fluidity improvers, cleaning improvers, magnetic properties, and the like. Examples include materials, metal soaps, and the like.

The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Ash Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.
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 not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed, and when the content exceeds 15% by mass, a poor dispersion of the pigment in the toner occurs. The characteristics may be degraded.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate, polybutyl methacrylate , Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic ring Aromatic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polymer of styrene or a substituted product thereof include polyester resin, polystyrene, poly p-chlorostyrene, polyvinyl toluene, and the like. Examples of the styrene copolymer include a styrene-p-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene copolymer, and a styrene-methyl acrylate copolymer. Polymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene- Butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene An acrylonitrile-indene copolymer, Styrene - maleic acid copolymer, styrene - maleic acid ester copolymer, and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant under high shear. 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. This flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin side to remove moisture and organic solvent components. For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

There is no restriction | limiting in particular as said mold release agent, Although it can select suitably according to the objective, The low melting-point mold release agent whose melting | fusing point is 50-120 degreeC is preferable. The low melting point release agent, when dispersed with the resin, effectively acts as a release agent between the fixing roller and the toner interface, thereby preventing oilless (release agent such as oil on the fixing roller). Even if it is not applied), the hot offset property is good.
Suitable examples of the mold release agent include waxes and waxes.
Examples of the waxes and waxes include plant waxes such as carnauba wax, cotton wax, wood wax and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin and micro wax And natural waxes such as petroleum waxes such as crystallin and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers; Furthermore, fatty acid amides such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; poly-n-stearyl methacrylate, poly-n-lauryl which are low molecular weight crystalline polymer resins A homopolymer or copolymer of polyacrylate such as methacrylate (for example, a copolymer of n-stearyl acrylate-ethyl methacrylate, etc.); a crystalline polymer having a long alkyl group in the side chain, or the like may be used.
These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50-120 degreeC is preferable and 60-90 degreeC is more preferable.
When the melting point is less than 50 ° C., the wax may adversely affect the heat resistant storage stability, and when it exceeds 120 ° C., a cold offset may easily occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps, more preferably 10 to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point of the wax.
If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability may not be obtained.

There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 0-40 mass% is preferable and 3-30 mass% is more preferable.
When the content exceeds 40% by mass, the fluidity of the toner may be deteriorated.

The charge control agent is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments , Rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine activators, salicylic acid metal salts And metal salts of salicylic acid derivatives. These may be used individually by 1 type and may use 2 or more types together.
Commercially available products may be used as the charge control agent. Examples of the commercially available products include bontron 03 of a nigrosine dye, bontron P-51 of a quaternary ammonium salt, and bontron S-34 of a metal-containing azo dye. , Oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302 TP-415 (made by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (Above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Japan) Ritto Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, polymer compounds having a functional group such as quaternary ammonium salts, and the like.

  The content of the charge control agent in the toner varies depending on the type of the resin, the presence or absence of an additive, a dispersion method, and the like, and cannot be generally defined. For example, with respect to 100 parts by mass of the binder resin, 0.1-10 mass parts is preferable and 0.2-5 mass parts is more preferable. When the content is less than 0.1 parts by mass, the charge controllability may not be obtained. When the content exceeds 10 parts by mass, the chargeability of the toner becomes too large, and the effect of the main charge control agent is reduced. As a result, the electrostatic attractive force with the developing roller increases, which may lead to a decrease in developer fluidity and a decrease in image density.

The inorganic fine particles can be used as an external additive for imparting fluidity, developability, chargeability and the like to toner particles.
The inorganic fine particles are not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Examples include silicon and silicon nitride. These may be used individually by 1 type and may use 2 or more types together.
The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. The specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The content of the inorganic fine particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass.

The fluidity improver means a material that can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, Examples thereof include a silane coupling agent having an alkyl fluoride group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. It is particularly preferable that the silica and the titanium oxide are surface-treated with such a fluidity improver and used as hydrophobic silica and hydrophobic titanium oxide.
The cleaning improver is added to the toner in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. For example, a fatty acid metal salt such as zinc stearate, calcium stearate, stearic acid, Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as methyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

The toner of the present invention can be produced using a known method such as a suspension polymerization method, an emulsion polymerization method, or a dissolution suspension method. For example, the toner material is dissolved or dispersed in an aqueous medium. It can be obtained by granulating a toner after preparing an emulsified or dispersed liquid.
As a preferred embodiment of the toner of the present invention, a solution or dispersion of a toner material containing at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound is emulsified or dispersed in an aqueous medium. And a toner obtained by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium to produce particles containing at least an adhesive substrate. .
Here, as a temperature at the time of manufacturing the toner of the present invention, for example, 10 to 100 ° C. is preferable, and 20 to 60 ° C. is more preferable. When the production temperature exceeds 100 ° C., the resin and the plasticizer are compatible with each other by heating, and it may be impossible to achieve both low-temperature fixability and heat-resistant storage stability.
Hereinafter, the toner of a preferred embodiment of the present invention will be described.

-Dissolution or dispersion of toner material-
The solution or dispersion of the toner material is obtained by dissolving or dispersing the toner material in a solvent.
The toner material is not particularly limited as long as the toner can be formed, and can be appropriately selected according to the purpose. Examples thereof include an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. (Prepolymer) at least, preferably including the plasticizer, and further including other components such as an unmodified polyester resin, a release agent, a colorant, and a charge control agent as necessary. Become.

The solution or dispersion of the toner material is preferably prepared by dissolving or dispersing the toner material in the organic solvent. The organic solvent is preferably removed during or after the toner granulation.
The organic solvent is not particularly limited as long as it is a solvent that can dissolve or disperse the toner material, and can be appropriately selected according to the purpose. For example, the boiling point is less than 150 ° C. in terms of ease of removal. Volatile ones are preferred, for example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, acetic acid Examples include ethyl, methyl ethyl ketone, methyl isobutyl ketone, and the like, and ester solvents are preferable, and ethyl acetate is particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent, According to the objective, it can select suitably, For example, 40-300 mass parts is preferable with respect to 100 mass parts of said toner materials, and 60-140 mass parts is preferable. More preferably, 80-120 mass parts is still more preferable.
In the method for producing a toner according to the preferred embodiment of the present invention, the dissolution or dispersion of the toner material can be reacted with the active hydrogen group-containing compound and the active hydrogen group-containing compound in the organic solvent. It can be performed by dissolving or dispersing a toner material such as a polymer, the unmodified polyester resin, the release agent, the colorant, the charge control agent, and the active hydrogen in the toner material. Components other than the polymer (prepolymer) capable of reacting with the group-containing compound may be added and mixed in the aqueous medium in the preparation of the aqueous medium described later, or the solution or dispersion of the toner material may be added. When added to the aqueous medium, it may be added to the aqueous medium together with the dissolved or dispersed liquid.

-Active hydrogen group-containing compound-
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polymer capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in the aqueous medium.
The active hydrogen group-containing compound is not particularly limited as long as it has an active hydrogen group, and can be appropriately selected depending on the purpose. For example, the polymer capable of reacting with the active hydrogen group-containing compound is In the case of the isocyanate group-containing polyester prepolymer (A), the amines (B) can be increased in molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the isocyanate group-containing polyester prepolymer (A). Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, an alcoholic hydroxyl group is particularly preferable.

The amines (B) are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamine (B1), trivalent or higher polyamine (B2), amino alcohol (B3), and amino mercaptan. (B4), amino acid (B5), and those obtained by blocking the amino groups of B1 to B5 (B6).
These may be used individually by 1 type and may use 2 or more types together. Among these, diamine (B1), a mixture of diamine (B1) and a small amount of a trivalent or higher polyamine (B2) are particularly preferable.

Examples of the diamine (B1) include aromatic diamines, alicyclic diamines, aliphatic diamines, and the like. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, and the like. Examples of the alicyclic diamine include 4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, and isophoronediamine. Examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, and hexamethylene diamine.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
Examples of the block (B6) in which the amino group of B1 to B5 is blocked include, for example, a ketimine obtained from any of the amines (B1) to (B5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) Compounds, oxazolyzone compounds, and the like.

  In addition, a reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, etc. between the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound. Use of the reaction terminator is preferable in that the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Examples of the reaction terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) or those blocked (ketimine compounds).

As a mixing ratio of the amines (B) and the isocyanate group-containing polyester prepolymer (A), the isocyanate group [NCO] in the isocyanate group-containing prepolymer (A) and the amines (B) The mixing equivalent ratio ([NCO] / [NHx]) of the amino group [NHx] is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, It is particularly preferably 1.5 to 1.5 / 1.
When the mixing equivalent ratio ([NCO] / [NHx]) is less than 1/3, the low-temperature fixability may be lowered. When the mixing equivalent ratio exceeds 3/1, the molecular weight of the urea-modified polyester resin becomes low. The hot offset resistance may be deteriorated.

--Polymer capable of reacting with active hydrogen group-containing compound--
The polymer capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) is not particularly limited as long as it has at least a site capable of reacting with the active hydrogen group-containing compound. However, it can be appropriately selected from known resins, and examples thereof include polyol resins, polyacrylic resins, polyester resins, epoxy resins, and derivative resins thereof.
These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is particularly preferable in terms of high fluidity and transparency during melting.

The site capable of reacting with the active hydrogen group-containing compound in the prepolymer is not particularly limited and may be appropriately selected from known substituents. For example, an isocyanate group, an epoxy group, a carboxylic acid, An acid chloride group, and the like.
These may be contained singly or in combination of two or more. Among these, an isocyanate group is particularly preferable.

Among the prepolymers, it is easy to adjust the molecular weight of the polymer component, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. It is particularly preferable that it is a urea bond-forming group-containing polyester resin (RMPE) in that it can be secured.
As said urea bond production | generation group, an isocyanate group etc. are mentioned, for example. When the urea bond generating group in the urea bond generating group-containing polyester resin (RMPE) is the isocyanate group, the isocyanate group-containing polyester prepolymer (A) and the like are particularly preferable as the polyester resin (RMPE). It is done.

  The isocyanate group-containing polyester prepolymer (A) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of a polyol (PO) and a polycarboxylic acid (PC), And what made the said active hydrogen group containing polyester resin react with polyisocyanate (PIC), etc. are mentioned.

  There is no restriction | limiting in particular as said polyol (PO), According to the objective, it can select suitably, For example, diol (DIO), trihydric or more polyol (TO), diol (DIO), and trihydric or more polyol A mixture with (TO), etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the diol (DIO) alone or a mixture of the diol (DIO) and a small amount of the trivalent or higher polyol (TO) is preferable.

Examples of the diol (DIO) include alkylene glycols, alkylene ether glycols, alicyclic diols, alkylene oxide adducts of alicyclic diols, bisphenols, alkylene oxide adducts of bisphenols, and the like.
The alkylene glycol is preferably one having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like. Can be mentioned. Examples of the alkylene ether glycol include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, and the like. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the alkylene oxide adduct of the alicyclic diol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the alicyclic diol. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide adduct of the bisphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the bisphenol.
Among these, alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols and the like are preferable, and alkylene oxide adducts of bisphenols, alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. Mixtures are particularly preferred.

The trivalent or higher polyol (TO) is preferably 3 to 8 or higher, for example, a trivalent or higher polyhydric aliphatic alcohol, a trivalent or higher polyphenol, a trivalent or higher polyphenol. And alkylene oxide adducts.
Examples of the trihydric or higher polyhydric aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak, and the like. Examples of the alkylene oxide adduct of the trihydric or higher polyphenol include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the trihydric or higher polyphenol.

  The mixture mass ratio (DIO: TO) of the diol (DIO) and the trivalent or higher polyol (TO) in the mixture of the diol (DIO) and the trivalent or higher polyol (TO) is 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

There is no restriction | limiting in particular as said polycarboxylic acid (PC), Although it can select suitably according to the objective, For example, dicarboxylic acid (DIC), trivalent or more polycarboxylic acid (TC), dicarboxylic acid (DIC) ) And a tri- or higher valent polycarboxylic acid.
These may be used individually by 1 type and may use 2 or more types together. Among these, dicarboxylic acid (DIC) alone or a mixture of DIC and a small amount of trivalent or higher polycarboxylic acid (TC) is preferable.
Examples of the dicarboxylic acid include alkylene dicarboxylic acid, alkenylene dicarboxylic acid, aromatic dicarboxylic acid, and the like.
Examples of the alkylene dicarboxylic acid include succinic acid, adipic acid, and sebacic acid. As said alkenylene dicarboxylic acid, a C4-C20 thing is preferable, For example, a maleic acid, a fumaric acid, etc. are mentioned. As said aromatic dicarboxylic acid, a C8-C20 thing is preferable, For example, a phthalic acid, an isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.
Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (TO) is preferably a trivalent to octavalent or higher one, and examples thereof include aromatic polycarboxylic acids.
The aromatic polycarboxylic acid preferably has 9 to 20 carbon atoms, and examples thereof include trimellitic acid and pyromellitic acid.

  As the polycarboxylic acid (PC), the dicarboxylic acid (DIC), the trivalent or higher polycarboxylic acid (TC), and a mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid, Any acid anhydride or lower alkyl ester selected from can also be used. Examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

  Mixing mass ratio (DIC: TC) of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) in the mixture of the dicarboxylic acid (DIC) and the trivalent or higher polycarboxylic acid (TC) There is no restriction | limiting in particular, According to the objective, it can select suitably, For example, 100: 0.01-10 are preferable and 100: 0.01-1 are more preferable.

  The mixing ratio for the polycondensation reaction between the polyol (PO) and the polycarboxylic acid (PC) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, in the polyol (PO) The equivalent ratio ([OH] / [COOH]) of the hydroxyl group [OH] to the carboxyl group [COOH] in the polycarboxylic acid (PC) is usually preferably 2/1 to 1/1. More preferably, it is 0.5 / 1 to 1/1, and particularly preferably 1.3 / 1 to 1.02 / 1.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyol (PO), Although it can select suitably according to the objective, For example, 0.5-40 mass% is preferable. 1-30 mass% is more preferable, and 2-20 mass% is especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In some cases, the low-temperature fixability may deteriorate.

The polyisocyanate (PIC) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic diisocyanates, araliphatic diisocyanates, and isocyanurates. And those blocked with phenol derivatives, oximes, caprolactams, and the like.
Examples of the aliphatic polyisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, Examples include tetramethylhexane diisocyanate. Examples of the alicyclic polyisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 3- Examples thereof include methyldiphenylmethane-4,4′-diisocyanate and diphenyl ether-4,4′-diisocyanate. Examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Examples of the isocyanurates include tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, and the like.
These can be used alone or in combination of two or more.

As a mixing ratio when the polyisocyanate (PIC) and the active hydrogen group-containing polyester resin (for example, a hydroxyl group-containing polyester resin) are reacted, the isocyanate group [NCO] in the polyisocyanate (PIC) and the hydroxyl group-containing component are used. The mixing equivalent ratio ([NCO] / [OH]) with the hydroxyl group [OH] in the polyester resin is usually preferably 5/1 to 1/1, and preferably 4/1 to 1.2 / 1. More preferred is 3/1 to 1.5 / 1.
When the isocyanate group [NCO] exceeds 5, low-temperature fixability may be deteriorated, and when it is less than 1, offset resistance may be deteriorated.

There is no restriction | limiting in particular as content in the said isocyanate group containing polyester prepolymer (A) of the said polyisocyanate (PIC), Although it can select suitably according to the objective, For example, 0.5-40 mass% is Preferably, 1-30 mass% is more preferable, and 2-20 mass% is still more preferable.
When the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, Low temperature fixability may deteriorate.

As an average number of the isocyanate groups contained per molecule of the isocyanate group-containing polyester prepolymer (A), 1 or more is preferable, 1.2 to 5 is more preferable, and 1.5 to 4 is more preferable.
When the average number of the isocyanate groups is less than 1, the molecular weight of the polyester resin (RMPE) modified with the urea bond-forming group is lowered, and the hot offset resistance may be deteriorated.

  The weight average molecular weight (Mw) of the polymer capable of reacting with the active hydrogen group-containing compound is 3,000 to 40,000 in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). Preferably, 4,000 to 30,000 is more preferable. When the weight average molecular weight (Mw) is less than 3,000, the heat resistant storage stability may be deteriorated, and when it exceeds 40,000, the low temperature fixability may be deteriorated.

The measurement of the molecular weight distribution by the gel permeation chromatography (GPC) can be performed, for example, as follows.
That is, first, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran (THF) as a column solvent is allowed to flow at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran sample solution of a resin whose sample concentration is adjusted to 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of the calibration curve created by several monodisperse polystyrene standard samples and the count number. Examples of standard polystyrene samples for preparing the calibration curve include Pressure Chemical Co. Or Toyo Soda Kogyo Co., Ltd. having 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, 8.6 It is preferable to use those of × 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.

-Aqueous medium-
The aqueous medium is not particularly limited and may be appropriately selected from known ones. Examples thereof include water, solvents miscible with water, and mixtures thereof. Among these, Is particularly preferred.
The solvent miscible with water is not particularly limited as long as it is miscible with water, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones.
Examples of the alcohol include methanol, isopropanol, ethylene glycol and the like. Examples of the lower ketones include acetone and methyl ethyl ketone.
These may be used individually by 1 type and may use 2 or more types together.

  The aqueous medium can be prepared, for example, by dispersing resin fine particles in the aqueous medium. There is no restriction | limiting in particular as the addition amount in this aqueous medium of this resin fine particle, According to the objective, it can select suitably, For example, 0.5-10 mass% is preferable.

The resin fine particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. It may be a thermosetting resin, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin. , Etc.
These may be used individually by 1 type and may use 2 or more types together. Among these, at least one selected from a vinyl resin, a polyurethane resin, an epoxy resin, and a polyester resin is preferable because an aqueous dispersion of fine spherical resin resin particles can be easily obtained.
The vinyl resin is a polymer obtained by homopolymerizing or copolymerizing a vinyl monomer. For example, a styrene- (meth) acrylic acid ester resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylic acid ester polymer. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
Moreover, as the resin fine particles, a copolymer comprising a monomer having at least two unsaturated groups can be used.
The monomer having at least two unsaturated groups is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a sodium salt of ethylene oxide methacrylate adduct sulfate (“Eleminol RS-30”). "; Manufactured by Sanyo Chemical Industries Ltd.), divinylbenzene, 1,6-hexanediol acrylate and the like.

  The resin fine particles can be obtained by polymerization according to a known method appropriately selected according to the purpose, but is preferably obtained as an aqueous dispersion of the resin fine particles. The method for preparing the aqueous dispersion of the resin fine particles is, for example, (1) In the case of the vinyl resin, a vinyl monomer is used as a starting material and is selected from suspension polymerization, emulsion polymerization, seed polymerization, and dispersion polymerization. (2) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., a precursor (monomer, oligomer). Or the like, or a solvent solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant, and then heated or added with a curing agent to be cured to produce an aqueous dispersion of resin fine particles (3) ) In the case of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin, etc., it may be a precursor (monomer, oligomer, etc.) or a solvent solution thereof (liquid). (4) Preliminary polymerization reaction (addition polymerization, ring-opening polymerization, polyaddition, addition) After the resin prepared by any polymerization reaction mode such as condensation and condensation polymerization is pulverized using a mechanical pulverizer or jet type pulverizer and then classified to obtain resin fine particles , A method of dispersing in water in the presence of an appropriate dispersant, (5) prepared in advance by a polymerization reaction (any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) (6) A polymerization reaction (addition polymerization) in advance, in which resin fine particles are obtained by spraying a resin solution in which the resin is dissolved in a solvent to obtain resin fine particles and then dispersing the resin fine particles in water in the presence of an appropriate dispersant. , Ring-opening polymerization, polyaddition, addition condensation The resin fine particles can be obtained by adding a poor solvent to a resin solution obtained by dissolving a resin prepared in a solvent by a polymerization reaction method such as condensation polymerization or by cooling a resin solution previously dissolved in a solvent by heating. And then removing the solvent to obtain resin particles, and then dispersing the resin particles in water in the presence of a suitable dispersant. (7) Polymerization reaction (addition polymerization, ring-opening polymerization, heavy polymerization) in advance (Any polymerization reaction mode such as addition, addition condensation, and condensation polymerization may be used.) A resin solution prepared by dissolving a resin prepared in a solvent in a solvent is dispersed in an aqueous medium and then heated or heated. (8) A resin prepared in advance by a polymerization reaction (which may be any polymerization reaction mode such as addition polymerization, ring-opening polymerization, polyaddition, addition condensation or condensation polymerization) is used as a solvent. In the dissolved resin solution A method of dissolving a suitable emulsifier and then adding water to carry out phase inversion emulsification is preferable.

-Emulsification or dispersion-
In the dissolution or dispersion of the toner material in the aqueous medium, the dissolution or dispersion of the toner material is preferably dispersed in the aqueous medium while stirring. The dispersion method is not particularly limited and can be appropriately selected depending on the purpose. For example, the dispersion method can be performed using a known disperser, and the disperser includes the low-speed shear disperser. And the high-speed shearing disperser.

  In the method for producing a toner according to the preferable aspect of the present invention, when the emulsification or dispersion is performed, the active hydrogen group-containing compound and the polymer capable of reacting with the active hydrogen group-containing compound are subjected to an extension reaction or a crosslinking reaction. An adhesive substrate (the resin) is generated.

-Adhesive substrate-
The adhesive substrate exhibits adhesiveness to a recording medium such as paper, and is formed by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound in the aqueous medium. It may contain at least a polymer and may further contain a binder resin appropriately selected from known binder resins.

There is no restriction | limiting in particular as a weight average molecular weight of the said adhesive base material, Although it can select suitably according to the objective, For example, 3,000 or more are preferable and 5,000-1,000,000 are more preferable. 7,000 to 500,000 are particularly preferred.
When the weight average molecular weight is less than 3,000, the hot offset resistance may be deteriorated.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said adhesive base material, Although it can select suitably according to the objective, For example, 30-70 degreeC is preferable and 40-65 degreeC is more preferable. In the toner, since a polyester resin subjected to a crosslinking reaction and an extension reaction coexists, the toner exhibits good storage stability even when the glass transition temperature is lower than that of a conventional polyester toner.
When the glass transition temperature (Tg) is less than 30 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient.

  The glass transition temperature can be measured by, for example, the following method using a TG-DSC system TAS-100 (manufactured by Rigaku Corporation). First, about 10 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. After heating from room temperature to 150 ° C. at a rate of temperature increase of 10 ° C./min, the sample is left at 150 ° C. for 10 minutes, and the sample is cooled to room temperature and left for 10 minutes. Then, the DSC curve is measured with a differential scanning calorimeter (DSC) after heating to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. From the obtained DSC curve, using the analysis system in the TG-DSC system TAS-100 system, the glass transition temperature (Tg) is calculated from the contact point between the tangent line of the endothermic curve near the glass transition temperature (Tg) and the baseline. can do.

Specific examples of the adhesive substrate are not particularly limited and may be appropriately selected depending on the intended purpose. Particularly preferred are polyester resins.
There is no restriction | limiting in particular as said polyester-type resin, Although it can select suitably according to the objective, For example, a urea modified polyester-type resin etc. are mentioned especially suitably.
The urea-modified polyester-based resin includes an amine (B) as the active hydrogen group-containing compound and an isocyanate group-containing polyester prepolymer (A) as a polymer that can react with the active hydrogen group-containing compound. It is obtained by reacting in a medium.
The urea-modified polyester resin may contain a urethane bond in addition to the urea bond. In this case, the molar ratio of the urea bond to the urethane bond (urea bond / urethane bond) is particularly limited. However, 100/0 to 10/90 is preferable, 80/20 to 20/80 is more preferable, and 60/40 to 30/70 is particularly preferable.
When the urea bond is less than 10, the hot offset resistance may be deteriorated.

  Preferable specific examples of the urea-modified polyester resin include the following (1) to (10), that is, (1) a polyester pre-reacted polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate. A mixture of a polymer urealated with isophorone diamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid, and (2) a polycondensate of bisphenol A ethylene oxide 2 mol adduct and isophthalic acid A mixture of a polyester prepolymer reacted with diisocyanate and uread with isophoronediamine, a bicondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (3) bisphenol A ethylene oxide 2 mol A polyester prepolymer obtained by reacting an adduct / bisphenol A propylene oxide 2 mol adduct and a polycondensate of terephthalic acid with isophorone diisocyanate, and urethanized with isophorone diamine, and bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene. Mixture of oxide 2 mol adduct and polycondensate of terephthalic acid, (4) Bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate were reacted with isophorone diisocyanate. A mixture of a polyester prepolymer uread with isophoronediamine, a bisphenol A propylene oxide 2-mole adduct and a polycondensate of terephthalic acid, (5) bisphenol A A polyester prepolymer obtained by reacting a polycondensate of tylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate and uread with hexamethylenediamine, and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid (6) Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide with 2 mol of bisphenol A and isophorone diisocyanate with urea and hexamethylenediamine and 2 mol of bisphenol A ethylene oxide. Product / bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate, (7) bisphenol A ethylene oxide 2 mol adduct and terephthalic acid polycondensate A mixture of a polyester prepolymer reacted with socyanate with urethanized with ethylenediamine and a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid, (8) bisphenol A ethylene oxide 2 mol adduct and isophthalic acid (9) Bisphenol A ethylene, a mixture of a polyester prepolymer obtained by reacting a polycondensate of bisphenol with diphenylmethane diisocyanate and uread with hexamethylene diamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, Polyester prepolymer obtained by reacting polycondensate of oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid / dodecenyl succinic anhydride with diphenylmethane diisocyanate Mixture of uremer with hexamethylenediamine and bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid polycondensate, (10) bisphenol A ethylene oxide 2-mole addition And a mixture of a polyester prepolymer obtained by reacting a polycondensate of isophthalic acid and toluene diisocyanate with urea diisocyanate with hexamethylenediamine, a bicondensate of bisphenol A ethylene oxide and a polycondensate of isophthalic acid, etc. Preferably mentioned.

---- Binder resin ---
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, although a polyester resin etc. are mentioned, Undenatured polyester resin (unmodified polyester resin) is especially preferable.
When the unmodified polyester resin is contained in the toner, low-temperature fixability and glossiness can be improved.
Examples of the unmodified polyester resin include those similar to the urea bond-forming group-containing polyester resin, that is, a polycondensate of a polyol (PO) and a polycarboxylic acid (PC). The unmodified polyester resin is partially compatible with the urea bond-forming group-containing polyester resin (RMPE), that is, has a similar structure that is compatible with each other. It is preferable in terms of resistance to hot offset.

The weight average molecular weight (Mw) of the unmodified polyester resin is preferably 1,000 to 30,000, preferably 1,500 to 15, in terms of molecular weight distribution by GPC (gel permeation chromatography) soluble in tetrahydrofuran (THF). 1,000 is more preferable. When the weight average molecular weight (Mw) is less than 1,000, the heat resistant storage stability may be deteriorated. Therefore, the content of the component having the weight average molecular weight (Mw) of less than 1,000 as described above. Needs to be 8 to 28% by mass. On the other hand, when the weight average molecular weight (Mw) exceeds 30,000, the low-temperature fixability may be deteriorated.
The glass transition temperature of the unmodified polyester resin is preferably 35 to 70 ° C. When the glass transition temperature is less than 35 ° C., the heat resistant storage stability of the toner may be deteriorated, and when it exceeds 70 ° C., the low-temperature fixability may be insufficient.
The hydroxyl value of the unmodified polyester resin is preferably 5 mgKOH / g, more preferably 10 to 120 mgKOH / g, and still more preferably 20 to 80 mgKOH / g. If the hydroxyl value is less than 5, it may be difficult to achieve both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester resin is usually 1.0 to 30.0 mgKOH / g, preferably 5.0 to 20.0 mgKOH / g. Generally, it becomes easy to be negatively charged by giving an acid value to the toner.
When the unmodified polyester resin is contained in the toner, the mixing mass ratio (RMPE / PE) of the urea bond-forming group-containing polyester resin (RMPE) and the unmodified polyester resin (PE) is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable.
When the mixing mass ratio of the unmodified polyester resin (PE) exceeds 95, the hot offset resistance may be deteriorated, and when it is less than 75, the low-temperature fixability and the glossiness of the image may be deteriorated. .

  As content of the said unmodified polyester resin in the said binder resin, 50-100 mass% is preferable, for example, and 55-95 mass% is more preferable. When the content is less than 50% by mass, low-temperature fixability, fixed image strength, glossiness, and the like may be deteriorated.

  The adhesive substrate (for example, the urea-modified polyester resin) includes, for example, (1) a polymer that can react with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)). A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium together with the active hydrogen group-containing compound (for example, the amines (B)) to form the oil droplets, and both in the aqueous medium. (2) A solution or dispersion of the toner material is emulsified or dispersed in the aqueous medium to which the active hydrogen group-containing compound has been added in advance. It may be formed by forming droplets and subjecting both to extension reaction or crosslinking reaction in the aqueous medium, or (3) dissolving or dispersing the toner material in the aqueous medium After the addition and mixing in the system medium, the active hydrogen group-containing compound is added, the oil droplets are formed, and they are produced by subjecting both to an extension reaction or a crosslinking reaction from the particle interface in the aqueous medium. Good. In the case of (3), a modified polyester resin is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided in the toner particles.

  The reaction conditions for producing the adhesive base material by the emulsification or dispersion are not particularly limited, depending on the combination of the polymer capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours.

  Examples of a method for stably forming the dispersion containing a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)) in the aqueous medium include, for example, the aqueous system. In a medium, a polymer capable of reacting with the active hydrogen group-containing compound (for example, the isocyanate group-containing polyester prepolymer (A)), the colorant, the release agent, the charge control agent, and the unmodified polyester resin And the like. A method in which a solution or dispersion of the toner material prepared by dissolving or dispersing the toner material in the organic solvent is added and dispersed by shearing force.

In the emulsification or dispersion, the amount of the aqueous medium used is preferably 50 to 2,000 parts by mass, more preferably 100 to 1,000 parts by mass with respect to 100 parts by mass of the toner material.
If the amount used is less than 50 parts by mass, the toner material may be poorly dispersed and toner particles having a predetermined particle size may not be obtained. If the amount used exceeds 2,000 parts by mass, the production cost will be high. May be.

In the emulsification or dispersion, if necessary, it is preferable to use a dispersant from the viewpoint of stabilizing the oil droplets and sharpening the particle size distribution while obtaining a desired shape.
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a sparingly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.
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 perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 carbon atoms). -11) Oxy] -1-alkyl (carbon number 3-4) sodium sulfonate, 3- [omega-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-hydroxy Ethyl) perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number) 6-16) Ethyl phosphate and the like. Examples of commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, FC- 129 (manufactured by Sumitomo 3M); Unidyne DS-101, DS-102 (manufactured by Daikin Industries); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (large) Nihon Ink Co., Ltd.); Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products Co.); Footent F-100, F150 (Neos) Manufactured) and the like.

  Examples of the cationic surfactant include amine salt type surfactants and quaternary ammonium salt type cationic surfactants. Examples of the amine salt type surfactant include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, and the like. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Among the cationic surfactants, aliphatic quaternary ammonium such as aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, perfluoroalkyl (6 to 10 carbon atoms) sulfonamidopropyltrimethylammonium salt, etc. Salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and the like. Commercially available products of the cationic surfactant include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.); Florard FC-135 (manufactured by Sumitomo 3M); F-824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products); Footgent F-300 (manufactured by Neos).

Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives.
Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Examples of the poorly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Examples of the polymeric protective colloid include acids, (meth) acrylic monomers containing hydroxyl groups, vinyl alcohol or ethers of vinyl alcohol, esters of vinyl alcohol and compounds containing carboxyl groups, amides Examples thereof include homopolymers or copolymers of compounds or their methylol compounds, chlorides, those having a nitrogen atom or a heterocyclic ring thereof, polyoxyethylenes, celluloses, and the like.
Examples of the acids 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 containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate Glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide and the like. Examples of the vinyl alcohol or ethers with vinyl alcohol include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and the like. Examples of the esters of vinyl alcohol and a compound containing a carboxyl group include vinyl acetate, vinyl propionate, and vinyl butyrate. Examples of the amide compound or these methylol compounds include acrylamide, methacrylamide, diacetone acrylamide acid, or these methylol compounds. Examples of the chlorides include acrylic acid chloride and methacrylic acid chloride. Examples of the homopolymer or copolymer such as those having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethylene imine. Examples of the polyoxyethylene are polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene Examples thereof include oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester. Examples of the celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and the like.

In preparing the dispersion, a dispersion stabilizer can be used as necessary.
Examples of the dispersion stabilizer include acids that are soluble in acids and alkalis such as calcium phosphate.
When the dispersion stabilizer is used, the calcium phosphate salt can be removed from the fine particles by a method of dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water or a method of decomposing with an enzyme.

  In the preparation of the dispersion, a catalyst for the extension reaction or the crosslinking reaction can be used. Examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

The organic solvent is removed from the emulsified slurry obtained by the emulsification or dispersion.
The organic solvent is removed by (1) a method in which the temperature of the entire reaction system is gradually raised to completely evaporate and remove the organic solvent in the oil droplets, and (2) the emulsion dispersion is sprayed into a dry atmosphere. And a method of completely removing the water-insoluble organic solvent in the oil droplets to form toner fine particles and evaporating and removing the aqueous dispersant together.

  When the organic solvent is removed, toner particles are formed. The toner particles can be washed, dried, etc., and then classified as desired. The classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like in a liquid, and the classification operation may be performed after obtaining a powder after drying.

Thus, the obtained toner particles are mixed with particles of the colorant, release agent, charge control agent, etc., and further, a mechanical impact force is applied to the release agent from the surface of the toner particles. And the like can be prevented from being detached.
As the method for applying the mechanical impact force, for example, a method in which an impact force is applied to the mixture by blades rotating at a high speed, a mixture is introduced into a high-speed air stream and accelerated to appropriately collide particles or composite particles. The method of making it collide with a board, etc. are mentioned. As an apparatus used for this method, for example, an ong mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverization air pressure, a hybridization system (Nara Machinery Co., Ltd.) Product), kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, and the like.

The toner produced by the suspension polymerization method will be described below.
As described above, the toner produced by the suspension polymerization method is prepared by emulsifying or dispersing (suspending) a toner material in an aqueous medium after preparing the emulsion or dispersion (suspension). It can be obtained by granulating toner.

-Dissolution or dispersion of toner material-
In the suspension polymerization method, the solution or dispersion of the toner material is preferably in the polymerizable monomer or oil-soluble polymerization initiator, preferably the plasticizer, and if necessary, a colorant, a release agent, Other components such as a charge control agent are dissolved or dispersed. In addition, for example, in order to reduce the viscosity of the polymer produced by the polymerization reaction described later, an organic solvent, a polymer, a dispersant, and the like may be added as appropriate.

--Polymerizable monomer--
Examples of the polymerizable monomer include acrylic acids, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and maleic anhydride; The surface of toner particles by partially using amide, diacetone acrylamide, and their methylol compounds, acrylates and methacrylates having amino groups such as vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, ethyleneimine, dimethylaminoethyl methacrylate, etc. Functional groups can be introduced into the. It should be noted that a functional group can be introduced by adsorbing and remaining the dispersant on the surface of the toner particles by appropriately selecting a dispersant having an acid group or a basic group.
Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate Acrylic acid such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, etc. Esters: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenolic methacrylate , Dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, acrylamide, and the like.

  In addition to the polymerizable monomer, a resin may be used. For example, since the polymerizable monomer is soluble in water and cannot be emulsified by dissolution in an aqueous suspension, an amino group, a carboxylic acid group, a hydroxyl group, a sulfone group, a glycidyl group, a nitrile When a hydrophilic functional group-containing polymerizable monomer such as a group is to be introduced into the toner, a random copolymer of these with a vinyl compound such as styrene or ethylene, a block copolymer, a graft copolymer, etc. A resin in the form of a copolymer, a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine can be used.

Examples of the alcohol component and the acid component that form the polyester resin include the following.
Examples of the alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, Examples include 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, and the like. Polyhydric alcohols such as glycerin, pentaerythritol, sorbit, sorbitan, and oxyalkylene ethers of novolac type phenol resins may be used.
Examples of the acid component include divalent carboxylic acids such as benzene dicarboxylic acid such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, and the like. Alkyl dicarboxylic acids or anhydrides thereof; succinic acids substituted with alkyl or alkenyl groups having 6 to 18 carbon atoms or anhydrides thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or anhydrides thereof; Thing; etc. are mentioned. Further, polycarboxylic acids such as trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, benzophenonetetracarboxylic acid, and anhydrides thereof may be used.
As content of the said alcohol component and the said acid component in the said polyester resin, it is preferable that the said alcohol component is 45-55 mol%, and the said acid component is 55-45 mol%.

Two or more polyester resins may be used in combination as long as the physical properties of the toner particles obtained are not adversely affected. Moreover, physical properties can be adjusted, such as modification with silicone or a fluoroalkyl group-containing compound.
Here, when using the high molecular polymer containing such a polar functional group, the average molecular weight of the high molecular polymer is preferably 5,000 or more.

Furthermore, in addition to the polymerizable monomer, the following resins can be used. Examples of the resin include homopolymers of styrene such as polystyrene and polyvinyltoluene, and substituted products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid. Methyl copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer Polymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Coalescence, styrene-vinylmethylke Copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc .; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, Aromatic petroleum resin, and the like. These may be used individually by 1 type and may use 2 or more types together.
As addition amount of these resin, 1-20 mass parts is preferable with respect to 100 mass parts of said polymerizable monomers, for example. When the addition amount is less than 1 part by mass, the effect of adjusting the physical properties of the toner particles due to the addition may not be exhibited, and when it exceeds 20 parts by mass, the physical property design of the toner particles may be difficult.
Further, a polymer having a molecular weight different from the molecular weight range of the toner obtained by polymerizing the polymerizable monomer can be dissolved in the polymerizable monomer and polymerized.

--Oil-soluble polymerization initiator--
The oil-soluble polymerization initiator has a half-life of 0.5 to 30 hours during the polymerization reaction and is added in an amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Can give a polymer having a maximum between 10,000 and 100,000 in molecular weight, and can impart desirable strength and suitable dissolution characteristics to the toner.
The oil-soluble polymerization initiator is not particularly limited as long as it is oil-soluble, and can be appropriately selected according to the purpose. For example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2 , 2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyro Azo-based or diazo-based polymerization initiators such as nitriles; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butyl peroxide 2- And peroxide polymerization initiators such as ethyl hexanoate.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a coloring agent, a mold release agent, a charge control agent, a crosslinking agent etc. are mentioned.

There is no restriction | limiting in particular as said coloring agent, It can select suitably from well-known things, For example, carbon black, a yellow coloring agent, a magenta coloring agent, a cyan coloring agent is mentioned.
Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 168, 180 and the like are particularly preferable.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 and the like are particularly preferable.
Examples of the cyan colorant include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferable.
The said colorant may be used individually by 1 type, may use 2 or more types together, and can be used in the state of a solid solution. The colorant can be selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, dispersibility in the toner, and the like.
There is no restriction | limiting in particular as addition amount of the said coloring agent, According to the objective, it can select suitably, For example, 1-20 mass parts is preferable with respect to 100 mass parts of said resins.

  Examples of the release agent include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof; montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method, and polyolefins represented by polyethylene. And waxes, derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. These derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. . In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid and their compounds, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can also be used. .

  The charge control agent is not particularly limited and may be appropriately selected from known ones. However, when the toner is produced using a direct polymerization method, the polymerization inhibitory property is low and the toner can be applied to an aqueous medium. Those having substantially no lysate are particularly preferred. Specifically, examples of the negative charge control agent include metal compounds of aromatic carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, and dicarboxylic acid; metal salts or metal complexes of azo dyes or azo pigments And polymer type compounds having a sulfonic acid or carboxylic acid group in the side chain, boron compounds, urea compounds, silicon compounds, calixarene, and the like. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  As a method of adding the charge control agent to the toner, there are a method of adding it inside the toner base particles and a method of adding it externally. The amount of the charge control agent used is determined by the type of resin, the presence or absence of other additives, and the toner production method including the dispersion method, and is not uniquely limited. In this case, 0.1 to 10 parts by mass is preferable and 0.1 to 5 parts by mass is more preferable with respect to 100 parts by mass of the resin. In the case of the external addition method, 0.005 to 1.0 part by mass is preferable with respect to 100 parts by mass of toner, and 0.01 to 0.3 part by mass is more preferable.

The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. However, a compound having two or more polymerizable double bonds can be preferably used. For example, divinyl Aromatic divinyl compounds such as benzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline, divinyl ether, divinyl sulfide And divinyl compounds such as divinyl sulfone; and compounds having three or more vinyl groups. These may be used individually by 1 type and may use 2 or more types together.
As addition amount of the said crosslinking agent, 0.001-15 mass parts is preferable with respect to 100 mass parts of said polymerizable monomers, for example.

-Aqueous medium-
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water is mention | raise | lifted.
The aqueous medium preferably contains a dispersion stabilizer.
As the dispersion stabilizer, for example, known surfactants, organic dispersants, inorganic dispersants and the like can be used. Therefore, an inorganic dispersant is preferable in that it maintains a stable state even when the reaction temperature is changed, is easy to wash, and does not adversely affect the toner.
Examples of the inorganic dispersant include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; calcium metasuccinate, calcium sulfate and barium sulfate. And inorganic oxides such as inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite, and alumina.

The inorganic dispersant can be used as it is, but in order to obtain finer particles, the inorganic dispersant particles may be generated and used in the aqueous medium. For example, in the case of the calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed with high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At this time, water-soluble sodium chloride salt is by-produced at the same time. However, when the water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and ultrafine toner by emulsion polymerization is used. Is preferable because it is difficult to generate. However, since it becomes an obstacle when the residual polymerizable monomer is removed at the end of the polymerization reaction, it is preferable to replace the aqueous medium or desalinate with an ion exchange resin. The inorganic dispersant can be almost completely removed by dissolution with an acid or alkali after completion of the polymerization.
The inorganic dispersant is preferably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. When the inorganic dispersant is used, it is difficult to produce ultrafine particles but it is difficult to obtain a toner having a small particle diameter. Therefore, it is preferable to use 0.001 to 0.1 parts by mass of a surfactant in combination.
Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

-Suspension-
The suspension is performed by emulsifying or dispersing a solution or dispersion of the toner material in which the toner material is uniformly dissolved or dispersed in the aqueous medium. At this time, if a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used to disperse the toner particles to a desired size at a stretch, a toner having a sharp particle size distribution can be obtained.
The oil-soluble polymerization initiator may be added simultaneously with the addition of other additives in the polymerizable monomer, or the solution or dispersion of the toner material is suspended in the aqueous medium. You may mix just before making. Further, during the granulation of the toner, the oil-soluble polymerization initiator dissolved in the polymerizable monomer or solvent may be added immediately after the granulation of the toner and before the start of the polymerization reaction.

-Granulation-
The granulation is performed by polymerizing the polymerizable monomer.
As temperature in the said polymerization reaction, it is 40 degreeC or more, for example, and generally is 50-90 degreeC. When the polymerization is performed within the temperature range, the release agent, the wax, and the like that should be present inside the toner particles are precipitated by phase separation, and can be encapsulated. In order to consume the remaining polymerizable monomer, the reaction temperature may be set to 90 to 150 ° C., but as described above, when heated above the melting point of the plasticizer, the resin and the plasticizer are In order to achieve compatibility, it is necessary to react at a temperature below the melting point of the plasticizer. Specifically, the reaction is preferably carried out at 100 ° C. or less.
In the granulation, it is also possible to use a seed polymerization method in which the polymerized monomer is further adsorbed on the obtained polymer particles and then polymerized using the oil-soluble polymerization initiator. At this time, a polar compound can be dissolved or dispersed in the polymerizable monomer to be adsorbed.

After completion of the polymerization reaction, it is preferable to perform stirring using a normal stirrer at a stirring speed that maintains the particle state and prevents the particles from floating and settling.
The polymerized particles after the completion of the polymerization reaction are filtered and washed by a known method to remove excess surfactant, dried, and further mixed with inorganic fine powder to adhere to the particle surface. Thus, toner particles are obtained. At this time, it is preferable to remove coarse powder and fine powder by performing classification.

In the toner of the present invention, an inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably added as a fluidizing agent.
Examples of the inorganic fine powder include silica, alumina, titanium oxide and the like.
Examples of the silica include, for example, so-called dry silica produced by vapor phase oxidation of silicon halides or dry silica called fumed silica, so-called wet silica produced from water glass, etc. Is mentioned. Among these, dry silica is preferable because there are few silanol groups on the surface and inside the silica fine powder, and there are few production residues such as Na ₂ O and SO ₃ ^— . In dry silica, for example, by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds, composite fine powders of the silica and other metal oxides can be obtained. Composite fine powders can also be used.

In order to impart good fluidity to the toner, the inorganic fine powder preferably has a specific surface area measured by a BET method by nitrogen adsorption, for example, of 20 to 350 m ² / g, and preferably 25 to 300 m ² / g. Is more preferable.
The specific surface area can be calculated according to the BET method using a specific surface area measuring device ("Autosorb 1"; manufactured by Yuasa Ionics Co., Ltd.) by adsorbing nitrogen gas to the sample surface and using the BET multipoint method.

As content of the said inorganic fine powder, 0.1-3.0 mass% is preferable with respect to a toner base particle, for example. When the addition amount is less than 0.1% by mass, the fluidity may be insufficient, and when it exceeds 3.0% by mass, the fixability may be deteriorated.
The content of the inorganic fine powder can be quantified using, for example, a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

The inorganic fine powder is preferably hydrophobized in that it can maintain excellent characteristics even in a high temperature and high humidity environment.
Examples of the treating agent in the hydrophobic treatment include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. These may be used individually by 1 type and may use 2 or more types together.
As a method for the hydrophobization treatment, for example, a silylation reaction is performed as a first stage reaction, silanol groups are eliminated by chemical bonds, and then a hydrophobic thin film is formed on the surface with silicone oil as a second stage reaction. The method of hydrophobizing by this is mentioned.
As a viscosity at 25 degrees C of the said silicone oil, 10-200,000 mm < ² > / s is preferable, for example, and 3,000-80,000 mm < ² > / s is more preferable.
When the viscosity is less than 10 mm ² / s, the performance of powder the inorganic fine powder becomes unstable due to thermal and mechanical stresses, may affect the image quality, when it exceeds 200,000 mm ² / s, uniform It may be difficult to perform a hydrophobic treatment.

Preferred examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil.
As a method of using the silicone oil, for example, silica treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or a method of spraying silicone oil on silica is used. Alternatively, a method may be used in which after dissolving or dispersing silicone oil in a suitable solvent, silica fine powder is added and mixed to remove the solvent. Among these, the method using a sprayer is preferable in that the formation of aggregates of the inorganic fine powder is relatively small.
As a processing amount of the silicone oil, for example, 1 to 40 parts by mass is preferable and 3 to 35 parts by mass is more preferable with respect to 100 parts by mass of the silica.

  The toner of the present invention is not particularly limited with respect to various physical properties such as shape and size, and can be appropriately selected according to the purpose. However, the following volume average particle diameter (Dv), volume average It is preferable to have particle diameter (Dv) / number average particle diameter (Dn), penetration, low temperature fixability, offset non-occurrence temperature, and the like.

The volume average particle diameter (Dv) of the toner is preferably 3 to 8 μm, and more preferably 4 to 6 μm, for example.
When the volume average particle size is less than 3 μm, in the case of a two-component developer, the toner may be fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to a member such as a blade are likely to occur because the toner is thinned. When the thickness exceeds 8 μm, the resolution is high and high. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

The ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) in the toner is, for example, preferably 1.30 or less, and more preferably 1.00-1.30.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is less than 1.00, with the two-component developer, the toner is fused to the surface of the carrier during long-term stirring in the developing device, The chargeability of the carrier may be reduced, and the cleaning property may be deteriorated. In the case of a one-component developer, the filming of the toner on the developing roller and the thinning of the toner are performed. Toner fusion may occur easily, and if it exceeds 1.30, it will be difficult to obtain a high-resolution and high-quality image, and toner particles in the developer balance will be generated. Variation in diameter may be large.
When the ratio of the volume average particle diameter to the number average particle diameter (Dv / Dn) is 1.00 to 1.30, the storage stability, low-temperature fixability, and hot offset resistance are all excellent. In particular, when used in a full-color copying machine, the glossiness of the image is excellent. With two-component developers, there is little fluctuation in the toner particle diameter in the developer even if the toner balance for a long period of time is achieved, and good and stable developability can be obtained even with long-term stirring in the developing device. Even if the balance of the toner is carried out with the agent, fluctuations in the particle diameter of the toner are reduced, and there is no filming of the toner on the developing roller and no fusion of the toner to the member to the blade for thinning the toner. Even in the long-term use (stirring) of the developing device, good and stable developability can be obtained, so that a high-quality image can be obtained.

  The volume average particle diameter and the ratio (Dv / Dn) between the volume average particle diameter and the number average particle diameter are measured using, for example, a particle size measuring device “Multisizer II” manufactured by Beckman Coulter, Inc. Can do.

As the penetration, for example, the penetration measured by a penetration test (JIS K2235-1991) is preferably 15 mm or more, and more preferably 20 to 30 mm.
When the penetration is less than 15 mm, the heat resistant storage stability may be deteriorated.
The penetration can be measured according to JIS K2235-1991. Specifically, a 50 ml glass container is filled with toner and left in a thermostatic bath at 50 ° C. for 20 hours. The penetration can be measured by cooling the toner to room temperature and performing a penetration test. In addition, it has shown that the said heat-resistant preservation | save property is excellent, so that the said penetration value is large.

As the low temperature fixability, from the viewpoint of achieving both a reduction in the fixing temperature and the occurrence of no offset, it is preferable that the lower limit temperature for fixing is lower, and more preferable that the temperature at which no offset is generated is higher. As a temperature range in which both can be achieved, the minimum fixing temperature is less than 150 ° C., and the non-offset temperature is 200 ° C. or more.
The minimum fixing temperature is, for example, an image forming apparatus, a transfer sheet is set, a copy test is performed, and the obtained fixed image is rubbed with a pad. The roll temperature is the lower limit fixing temperature.
The offset non-occurrence temperature is set by, for example, using an image forming apparatus, setting a transfer paper, and each color of solid images of red, blue, and green as single colors of yellow, magenta, cyan, and black, and solid colors of each color. It can be determined by adjusting so that it is developed, adjusting the temperature of the fixing belt to be variable, and measuring the temperature at which no offset occurs.

  The coloration of the toner of the present invention is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner and yellow toner. This toner can be obtained by appropriately selecting the type of the colorant.

  The toner of the present invention has good properties such as fluidity and fixability, and achieves both excellent low-temperature fixability and heat-resistant storage stability. Therefore, the toner of the present invention can be suitably used in various fields, and can be more suitably used for image formation by electrophotography. The following toner-containing container, developer, and process of the present invention are described below. It can be particularly suitably used for a cartridge, an image forming apparatus and an image forming method.

(Developer)
The developer of the present invention contains at least the toner of the present invention and other components appropriately selected such as the carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the service life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner according to the present invention, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, and the filming of the toner on the developing roller or the toner is thinned. Therefore, toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time. Further, in the case of the two-component developer using the toner of the present invention, even if the balance of the toner over a long period of time is performed, the fluctuation of the toner particle diameter in the developer is small, and even in the long-term stirring in the developing device, Good and stable developability can be obtained.

  There is no restriction | limiting in particular as said 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 high magnetization 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, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

The core material has a volume average particle size of preferably 10 to 150 μm, and more preferably 40 to 100 μm.
When the average particle size (volume average particle size (D ₅₀ )) is less than 10 μm, in the distribution of carrier particles, the number of fine powder systems increases, and the magnetization per particle may be lowered to cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur. In the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester 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 a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate resin, poly Examples include acrylonitrile resin, polyvinyl acetate resin, polyvinyl alcohol resin, and polyvinyl butyral resin. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like, if 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 a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include a dipping method, a spray method, and a brush coating method.
There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, etc. are mentioned.
The baking 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. The method of using, the method of using a microwave, etc. are mentioned.

The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass.
When the amount is less than 0.01% by mass, the 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 thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the 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. For example, 90 to 98% by mass Is preferable, and 93-97 mass% is more preferable.

Since the developer of the present invention contains the toner, it has excellent properties such as fluidity and fixability, and has both excellent low-temperature fixability and heat-resistant storage stability, and stable high-quality images. Can be formed.
The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method. It can be particularly suitably used for containers, process cartridges, image forming apparatuses and image forming methods.

(Toner container)
The toner-containing container of the present invention is obtained by filling the container of the toner of the present invention or the developer.
There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body containing a toner and a cap etc. are mentioned suitably.
The size, shape, structure, material, etc. of the container body containing toner is not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. The spiral surface irregularities are formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.
The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
The toner-containing container of the present invention is easy to store and transport, has excellent handleability, and is preferably used for replenishing toner by being detachably attached to the process cartridge and image forming apparatus of the present invention described later. Can do.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and further having other means appropriately selected as necessary.
The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.
The process cartridge of the present invention can be detachably provided in various electrophotographic apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention described later.

(Image forming method and image forming apparatus)
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, preferably including a cleaning step, and further other steps appropriately selected as necessary. For example, a static elimination process, a recycling process, a control process, etc. are included.
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and preferably includes a cleaning unit. In addition, other means appropriately selected as necessary, for example, static elimination means, recycling means, control means and the like are provided.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the electrostatic latent image forming step can be performed by the electrostatic latent image forming means, and the developing step is the developing The transfer step can be performed by the transfer unit, the fixing step can be performed by the fixing unit, and the other steps can be performed by the other unit.

<Electrostatic latent image forming step and electrostatic latent image forming means>
The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. It is done. Among these, amorphous silicon and the like are preferable in terms of long life.

The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to.
The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.
The charger is not particularly limited and may be appropriately selected depending on the purpose. And non-contact chargers using corona discharge such as corotrons and corotrons.

The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.
The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.
The developing means is not particularly limited as long as it can be developed using, for example, the toner or developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developing unit capable of contacting or non-contacting the toner or the developer with the electrostatic latent image is provided, and includes the toner container according to the present invention. More preferred is a developing device.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the latent electrostatic image bearing member (photoconductor) of the visible image using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.
The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

<Fixing process and fixing means>
The fixing step is a step of fixing the visible image transferred to the recording medium using the fixing unit, and may be performed each time the toner of each color is transferred to the recording medium, or may be applied to the toner of each color. On the other hand, it may be performed simultaneously at the same time in a state of being laminated.
The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose, but a known heating and pressing unit is preferable. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt.
The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

The cleaning step is a step of removing the electrophotographic toner remaining on the electrostatic latent image carrier, and can be suitably performed by a cleaning unit.
The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

The recycling step is a step of recycling the electrophotographic color toner removed in the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

The control means is a process for controlling the respective steps, and can be suitably performed by the control means.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. An image forming apparatus 100 shown in FIG. 1 includes a photosensitive drum 10 (hereinafter referred to as “photosensitive member 10”) as the electrostatic latent image carrier, a charging roller 20 as the charging unit, and exposure as the exposure unit. The apparatus 30 includes a developing device 40 as the developing means, an intermediate transfer member 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a static elimination lamp 70 as the static elimination means.

  The intermediate transfer member 50 is an endless belt, and is designed to be movable in the direction of an arrow by three rollers 51 that are arranged inside and stretched. Part of the three rollers 51 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50. The intermediate transfer body 50 is provided with a cleaning device 90 having a cleaning blade in the vicinity thereof, and for transferring (secondary transfer) a developed image (toner image) to a transfer sheet 95 as a final transfer material. A transfer roller 80 serving as a transfer unit to which a transfer bias can be applied is disposed to face the transfer roller 80. Around the intermediate transfer member 50, a corona charger 52 for applying a charge to the toner image on the intermediate transfer member 50 is arranged between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is disposed between the contact portion and the contact portion between the intermediate transfer member 50 and the transfer paper 95.

  The developing device 40 includes a developing belt 41 as the developer carrying member, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C provided around the developing belt 41. . The black developing unit 45K includes a developer accommodating portion 42K, a developer supplying roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer accommodating portion 42Y, a developer supplying roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer accommodating portion 42M, a developer supplying roller 43M, and a developing roller 44M, and the cyan developing unit 45C includes a developer accommodating portion 42C and a developer supplying roller 43C. And a developing roller 44C. The developing belt 41 is an endless belt, is rotatably stretched around a plurality of belt rollers, and a part thereof is in contact with the photoconductor 10.

  In the image forming apparatus 100 shown in FIG. 1, for example, the charging roller 20 charges the photosensitive drum 10 uniformly. The exposure device 30 performs imagewise exposure on the photosensitive drum 10 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from the developing device 40 to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer member 50 by the voltage applied from the roller 51, and further transferred (secondary transfer) onto the transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. The residual toner on the photoconductor 10 is removed by the cleaning device 60, and the charge on the photoconductor 10 is temporarily removed by the charge eliminating lamp 70.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. The image forming apparatus 100 shown in FIG. 2 does not include the developing belt 41 in the image forming apparatus 100 shown in FIG. 1, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and Except for the fact that the cyan developing unit 45C is disposed directly opposite, it has the same configuration as the image forming apparatus 100 shown in FIG. In FIG. 2, the same components as those in FIG. 1 are denoted by the same reference numerals.

Another mode for carrying out the image forming method of the present invention by the image forming apparatus of the present invention will be described with reference to FIG. A tandem image forming apparatus 100 shown in FIG. 3 is a tandem color image forming apparatus. The tandem image forming apparatus 100 includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.
The copying apparatus main body 150 is provided with an endless belt-like intermediate transfer member 50 at the center. The intermediate transfer member 50 is stretched around the support rollers 14, 15 and 16, and can be rotated clockwise in FIG. 3. An intermediate transfer member cleaning device 17 for removing residual toner on the intermediate transfer member 50 is disposed in the vicinity of the support roller 15. The intermediate transfer body 50 stretched by the support roller 14 and the support roller 15 is a tandem type in which four image forming means 18 of yellow, cyan, magenta, and black are arranged in parallel and facing each other along the conveyance direction. A developing device 120 is disposed. An exposure device 21 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 22 is disposed on the side of the intermediate transfer member 50 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 22, a secondary transfer belt 24, which is an endless belt, is stretched around a pair of rollers 23, and the transfer paper conveyed on the secondary transfer belt 24 and the intermediate transfer body 50 are in contact with each other. Is possible. A fixing device 25 is disposed in the vicinity of the secondary transfer device 22. The fixing device 25 includes a fixing belt 26 that is an endless belt, and a pressure roller 27 that is pressed against the fixing belt 26.
In the tandem image forming apparatus 100, a sheet reversing device 28 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 22 and the fixing device 25. Yes.

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the document is set on the contact glass 32 of the scanner 300. 400 is closed.

  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 set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta and cyan is stored in each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means and cyan image forming means in the tandem developing device 120. ) And black, yellow, magenta and cyan toner images are formed in the respective image forming means. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 is photosensitive as shown in FIG. On the basis of the body 10 (the black photoreceptor 10K, the yellow photoreceptor 10Y, the magenta photoreceptor 10M, and the cyan photoreceptor 10C), the charger 60 that uniformly charges the photoreceptor, and each color image information. The photosensitive member is exposed to each color image corresponding image (L in FIG. 4), and an electrostatic latent image corresponding to each color image is formed on the photosensitive member. A developing device 61 that develops using color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image of each color toner, and the toner image is transferred to the intermediate transfer member 5. The image forming apparatus includes a transfer charger 62 for transferring the image on the surface, a photoconductor cleaning device 63, and a static eliminator 64, and each monochrome image (black image, yellow image, magenta image) based on image information of each color. And cyan images) can be formed. The black image, the yellow image, the magenta image, and the cyan image formed in this way are formed on the black photoconductor 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16, respectively. The black image, the yellow image formed on the yellow photoconductor 10Y, the magenta image formed on the magenta photoconductor 10M, and the cyan image formed on the cyan photoconductor 10C are sequentially transferred (primary transfer). Is done. Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feeding roller 150 is rotated to feed out the sheets (recording paper) on the manual feed tray 51, separated one by one by the separation roller 58, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet.
Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 22 and sent to the fixing device 25, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 55 and discharged by the discharge roller 56 and stacked on the paper discharge tray 57, or switched by the switching claw 55 and reversed by the sheet reversing device 28 and transferred again. After being guided to the position and recording an image on the back surface, the image is discharged by the discharge roller 56 and stacked on the discharge tray 57.

As the image forming method and the image forming apparatus of the present invention, those adopting the adhesive transfer method shown below can also be suitably used.
When the adhesive transfer method is adopted, the toner of the present invention needs to contain at least a heat-sensitive adhesive. The heat-sensitive adhesive comprises a solid plasticizer and a thermoplastic resin as essential components, and contains a tackifier as necessary.
The heat-sensitive adhesive does not show any adhesiveness at room temperature, but develops adhesiveness by heating and external load, and maintains the adhesiveness for a while after removing the heat source. First, the solid plasticizer is melted, and the thermoplastic resin and the tackifier are melted to develop tackiness. That is, the adhesiveness is caused by causing the solid plasticizer to be melted by heat and compatible with the thermoplastic resin, thereby plasticizing the thermoplastic resin.

The image forming method of the present invention using the adhesive transfer method includes at least a toner supplying step, a visible image temporary fixing step, and a heat welding step, and further other steps appropriately selected as necessary, for example, toner removal Including processes.
The adhesive transfer type image forming apparatus of the present invention comprises at least an image carrier, a toner supply unit, a visible image temporary fixing unit, and a heat welding unit, and further appropriately selected as necessary. It has other means, for example, toner removing means.

  The image forming method of the present invention using the adhesive transfer method can be preferably implemented by the image forming apparatus of the present invention using the adhesive transfer method, and the toner supplying step can be performed by the toner supplying means. The visual image temporary fixing step can be performed by the visible image temporary fixing unit, the thermal welding step can be performed by the thermal welding unit, and the other steps can be performed by the other unit.

<Toner supply step and toner supply means>
The toner supply step is a step of supplying the toner of the present invention onto the image carrier.
The image carrier is not particularly limited as to the material, shape, structure, size, etc., and can be appropriately selected from known ones. The shape is preferably an endless film. Examples of the material include a light-transmitting resin, and polycarbonate is preferable.

The toner supply means is not particularly limited and may be appropriately selected from known ones. For example, the toner supply unit and a container for storing the toner and the toner carrying unit are transported to the opposing portion of the image carrier. A toner supply device having at least a toner carrier, a replenishment member for replenishing the toner carrier with the toner in the container, and a layer thickness regulating member for equalizing the thickness of the toner on the toner carrier. Preferably mentioned.
The toner may be supplied by applying an electrostatic adhesive force to the toner of the present invention to replenish the toner carrier, or by applying a non-electrostatic adhesive force such as a magnetic force. The carrier may be replenished.

<Visible image temporary fixing step and visible image temporary fixing means>
In the temporary visible image fixing step, heat corresponding to an image signal is applied to the toner brought into contact with the image carrier to form a visible image with the toner at a portion to which the heat is applied, This is a step of temporarily fixing a visible image on the image carrier.
The visible image temporary fixing means preferably has at least viscosity imparting means for imparting viscosity to the toner.
As the viscosity applying means, for example, a laser beam scanning device having at least a laser light source, a collimator lens, a polygon mirror, an fθ lens, and a reflecting mirror is preferably exemplified. The laser beam scanning device can apply heat according to an image signal to the toner imagewise with a laser beam. A thermal head can be used instead of the laser beam.
Viscosity can be selectively imparted to the toner present at a position corresponding to the image portion on the toner carrier by the heat from the laser beam in the viscosity imparting means. A viscous visible image is formed, and the visible image is temporarily fixed on the image carrier.
Here, the application of the viscosity includes not only the case where the material that originally has no viscosity is made viscous, but also the case where the viscosity of the material that was originally viscous is further increased.
Note that the adhesion force of the temporarily fixed visible image to the image carrier is weaker than the adhesion force due to electrostatic force between the toner and the toner carrier, and the residual toner on the image carrier in the toner removal step described later. Is of a size that can be easily removed.

<Thermal welding process and thermal welding means>
The thermal welding process is a process in which the temporarily fixed visible image is transferred to a recording medium and thermally welded, and can be suitably performed by a thermal welding means.
The heat welding means is not particularly limited and may be appropriately selected according to the purpose. However, it is preferable to simultaneously transfer and fix the visible image onto the recording medium, for example, a heating roller is preferable. It is mentioned in.

The toner removing step is a step of removing toner existing in a part other than the visible image on the image carrier, and can be suitably performed by a toner removing unit.
The toner removing means is not particularly limited and may be selected as appropriate from known cleaners as long as the toner remaining on the image carrier can be removed. For example, a magnetic roller cleaner, A blade cleaner or the like is preferably used.

  One mode of carrying out the image forming method of the present invention by the image forming apparatus of the present invention adopting the adhesive transfer method will be described with reference to FIG. An image forming apparatus 500 shown in FIG. 5 includes an image carrier 510, a toner supply device 520 as the toner supply unit, a laser beam scanning device 530 as the viscosity applying unit in the visible image temporary fixing unit, and the A toner removing roller 540 as a toner removing unit and a heating roller 550 as the heat welding unit are provided.

  The image carrier 510 has an endless film shape, and is formed of polycarbonate as a light-transmitting resin film that transmits light in a predetermined wavelength range, and has a thickness of 0.02 to 0.2 mm. The image carrier 510 is designed to be movable in the direction of the arrow a when one of a roller 511 and a roller 512 that are arranged inside and stretches the image carrier 510 is rotated by driving means such as a motor. A cleaning device 514 having a cleaning roller 513 that is in contact with the roller 512 via the image carrier 510 is disposed in the vicinity of the roller 512. A blade 515 is disposed in contact with the cleaning roller 513.

The toner supply device 520 includes a case 521 that accommodates the toner T, a toner carrying roller 522 that carries the toner T to a portion facing the image carrier 510, and the toner T in the case 521 to the toner carrying roller 522. A replenishing roller 523 for replenishing and a blade 524 for uniformizing the layer thickness of the toner T carried on the toner carrying roller 522 are provided in the vicinity of the image carrier 510. The toner carrying roller 522 and the replenishing roller 523 are each designed to be rotatable in the arrow direction.
In addition, a toner removing roller 540 with the leading edge of the cleaning blade 541 in contact with the toner supply device 520 is disposed.

The laser beam scanning device 530 includes a laser light source and a collimator lens (not shown), a polygon mirror 531, an fθ lens 532, and a strip-shaped reflecting mirror 534 having substantially the same length as the width of the image carrier 510, The image carrier 510 is disposed on the back side of the image carrier 510 at a position where the toner T is supplied by the toner carrier roller 522. The laser beam scanning device 530 applies heat corresponding to the image signal to the toner T on the toner carrying roller 522 via the image carrier 510 in an image-like manner. In this example, the laser beam is irradiated from the back side of the image carrier 510. However, a laser beam scanning device 530 is disposed outside the image carrier 510, and the toner is directly passed through the image carrier 510. Thermal energy may be applied by irradiating T with laser light.
The heating roller 550 is disposed so as to face and separate from the roller 511 via the image carrier 510, and when the recording medium S is sent between the heating roller 550 and the roller 511 by the registration roller pair 551, The roller 511 is pressed against the image carrier 510.

In the image forming apparatus 500 employing the adhesive transfer method shown in FIG. 5, in the toner supply device 520, the toner T in the case 521 is replenished to the toner carrying roller 522 by the replenishing roller 523 and the toner carried on the toner carrying roller 522. The layer thickness of T is made uniform by the blade 524, and an appropriate amount of toner is guided to the opposing portion between the image carrier 510 and the toner carrier roller 522. At this time, the toner carrying roller 522 and the replenishing roller 523 are brought into contact with each other with a speed difference at the opposing portion so that the toner is frictionally charged (for example, negatively charged), and the toner carrying roller 522 is supplied to the replenishing roller 523. By applying a voltage having a positive potential to the toner T, an electrostatic adhesion force is applied to the toner T, and the toner T having the electrostatic adhesion force is supplied to the toner carrying roller 522.
Next, in the laser beam scanning device 530, heat corresponding to the image signal is irradiated imagewise to the toner T on the toner carrying roller 522 via the image carrier 510 by the laser beam. The toner T becomes viscous due to the thermal energy of the laser light applied to the toner T, and is temporarily fixed as a visible image on the surface of the image carrier 510. Further, after the visible image G is temporarily fixed on the image carrier 510, the toner (residual toner) existing in the portion (non-image portion) other than the visible image G on the image carrier 510 has a positive voltage. The toner is removed by the electrostatic attraction force of the applied toner removing roller 540. The toner removal roller 540 is provided for the purpose of removing toner when toner other than the toner that is originally temporarily fixed adheres to the non-image portion on the image carrier 510 and so-called scumming occurs. The suction force of the toner removing roller 540 is weaker than the temporary fixing force of the toner T to the image carrier 510. Further, when the amount of toner adhering to the non-image portion is small, the toner removing roller 540 may not be provided.

  On the downstream side of the facing portion between the image carrier 510 and the toner removing roller 540, the visible image G is transferred and fixed to the recording medium S by heat welding by the heating roller 550. Here, the recording medium S is fed from a sheet feeding device (not shown), sent to the heating roller 550 in accordance with the visible image forming area on the image carrier 510 by the registration roller pair 551, and heated from the back side. As a result, the visible image G is transferred and fixed. Note that the image carrier 510 after the transfer and fixing of the visible image is cleaned by the cleaning roller 513, and dust containing toner on the cleaning roller 513 is scraped off by the blade 515.

  In the image forming apparatus and the image forming method of the present invention, since the toner of the present invention has good characteristics such as fluidity and fixability and has both excellent low-temperature fixability and heat-resistant storage stability, Can be obtained efficiently.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

Example 1
<Adhesive substrate production process>
A toner was produced as follows.

-Dissolution of toner material or preparation of dispersion-
--- Synthesis of unmodified polyester (low molecular weight polyester)-
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 84 parts by mass of bisphenol A propion oxide 3 mol adduct, 274 parts by mass of terephthalic acid, and dibutyltin oxide 2 parts by mass were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, the reaction solution was reacted under reduced pressure of 10 to 15 mmHg for 5 hours to synthesize unmodified polyester.
The obtained unmodified polyester had a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 5,600, and a glass transition temperature (Tg) of 58 ° C.

-Preparation of master batch (MB)-
1000 parts by mass of water, 540 parts by mass of carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) and 1200 parts by mass of the unmodified polyester were combined with a Henschel mixer (Mitsui Mine). Mixed). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

-Preparation of plasticizer dispersion-
200 parts by mass of docosanoic acid (melting point = 78 ° C.) as a plasticizer, 400 parts by mass of a polyester resin, and 800 parts by mass of ethyl acetate are mixed and sent using a bead mill (“Ultraviscomil”; manufactured by Imex Corporation). The plasticizer was dispersed in three passes under the conditions of a liquid speed of 1 kg / hr, a disk peripheral speed of 6 m / s, and 80% by volume of 0.5 mm zirconia beads to prepare a plasticizer dispersion.
In addition, when the solubility of the plasticizer with respect to the organic solvent was measured at 25 degreeC, it was 0 mass%.

--Synthesis of prepolymer--
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,600, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 49.
Next, 411 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and reacted at 100 ° C. for 5 hours. Thus, a prepolymer (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained prepolymer was 1.60% by mass, and the solid content concentration of the prepolymer (after standing at 150 ° C. for 45 minutes) was 50% by mass.

--Synthesis of ketimine (the active hydrogen group-containing compound)-
In a reaction vessel equipped with a stir bar and a thermometer, 30 parts by mass of isophoronediamine and 70 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (the active hydrogen group-containing compound).
The amine value of the obtained ketimine compound (the active hydrogen machine-containing compound) was 423.

  In a beaker, 15 parts by mass of the prepolymer, 60 parts by mass of the unmodified polyester, 130 parts by mass of ethyl acetate, and 100 parts by mass of the plasticizer dispersion were stirred and dissolved. Next, 10 parts by mass of carnauba wax (molecular weight = 1,800, acid value = 2.5, penetration = 1.5 mm (40 ° C.)) and 10 parts by mass of the master batch were charged, and a bead mill (“Ultra Visco” Mill "; manufactured by Imex Co., Ltd.), a raw material solution was prepared by three passes under the condition that the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / s, and 80% by volume of 0.5 mm zirconia beads were filled, 2.7 parts by mass of the ketimine was added and dissolved to prepare a toner material solution or dispersion.

-Preparation of aqueous medium phase-
An aqueous medium phase was prepared by mixing and stirring 306 parts by mass of ion-exchanged water, 265 parts by mass of a 10% by mass tricalcium phosphate suspension, and 0.2 parts by mass of sodium dodecylbenzenesulfonate, and dissolving them uniformly.

-Preparation of emulsion or dispersion-
150 parts by mass of the aqueous medium phase is placed in a container, and stirred at a rotational speed of 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). To this, 100 parts by mass of the toner material dissolved or dispersed is added. The mixture was added and mixed for 10 minutes to prepare an emulsified dispersion (emulsified slurry).

-Removal of organic solvent-
100 parts by mass of the emulsified slurry was charged into a Kolben equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min.

-Cleaning and drying-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. To the obtained filter cake, 20 parts by mass of a 10% by mass aqueous sodium hydroxide solution was added, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered twice. Furthermore, 20 mass parts of 10 mass% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes), and then filtered. To the obtained filter cake, 300 parts by mass of ion-exchanged water was added, mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried with a circulating dryer at 45 ° C. for 48 hours and sieved with a mesh of 75 μm to obtain toner base particles of Example 1.

(Example 2)
In Example 1, the amount of the plasticizer dispersion added in the dissolution or dispersion of the toner material was changed from 100 parts by mass to 200 parts by mass. Toner base particles were produced.

(Example 3)
In Example 2, Example 5 was carried out in the same manner as Example 2 except that 5 parts by mass of 3-5 ditertbutylsalicylic acid Fe (III) complex was further added at the time of dissolving or preparing the dispersion of the toner material. 3 toner base particles were produced.

Example 4
In Example 1, toner base particles of Example 4 are produced in the same manner as in Example 1 except that the docosanoic acid used in the preparation of the plasticizer dispersion is changed to n-octadecyl alcohol (melting point = 57 ° C.). did.
In addition, when the solubility of the plasticizer with respect to the organic solvent was measured at 25 degreeC, it was 1 mass%.

(Example 5)
In Example 1, the plasticizer dispersion used in the dissolution of the toner material or preparation of the dispersion was replaced with 40 parts by mass of dibenzyl oxalate (melting point = 102 ° C.) having solubility in ethyl acetate. Toner base particles of Example 5 were produced in the same manner as in Example 1 except that 500 parts by mass of ethanol, which is a poor solvent for dibenzyl, was further added.
In addition, when the solubility of the plasticizer with respect to the organic solvent was measured at 25 degreeC, it was 5 mass%.

(Example 6)
A toner was produced by a suspension polymerization method as follows.

-Preparation of toner material dissolution or dispersion (monomer composition)-
100 parts by mass of a polymerizable monomer composed of 80.5 parts by mass of styrene and 19.5 parts by mass of n-butyl acrylate, carbon black (“Printex35”; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9. 5) 6 parts by mass, 1 part by mass of charge control agent (“Spiron Black TRH”; manufactured by Hodogaya Chemical Co., Ltd.), 0.4 parts by mass of divinylbenzene, 1.0 part by mass of t-dodecyl mercaptan, 10 parts by mass of Carnauba wax, poly 0.5 parts by mass of methacrylic acid ester macromonomer and plasticizer dispersion prepared by replacing the docosanoic acid with n-stearyl stearamide (melting point = 95 ° C.) in the plasticizer dispersion obtained in Example 1 50 parts by mass of the liquid was stirred and mixed at room temperature using a stirrer, and then uniformly dispersed by a media-type disperser. Things were prepared.

-Preparation of aqueous medium phase-
In an aqueous solution in which 9.5 parts by mass of magnesium chloride (water-soluble polyvalent metal salt) is dissolved in 250 parts by mass of ion-exchanged water at room temperature, sodium hydroxide (alkali metal hydroxide) is added to 50 parts by mass of ion-exchanged water. An aqueous solution in which 8 parts by mass was dissolved was gradually added with stirring at room temperature to prepare a magnesium hydroxide colloid (hardly water-soluble metal hydroxide colloid) dispersion.

-Granulation-
To the obtained magnesium hydroxide colloidal dispersion, the monomer composition is charged at room temperature and stirred and dispersed until the droplets are stabilized. Then, t-butylperoxy-is used as an oil-soluble polymerization initiator. 5 parts by weight of 2-ethylhexanoate was added. Then, high shear stirring was performed for 10 minutes at 15,000 rpm with a TK homomixer to granulate fine droplets composed of the monomer composition.

--Polymerization--
The granulated aqueous dispersion medium (suspension) of the monomer composition was charged into a reactor equipped with a stirring blade and heated to 90 ° C. to initiate a polymerization reaction. The polymerization reaction was continued for 10 hours, and then water-cooled to complete the polymerization reaction. Subsequently, filtration, washing, and drying were performed in the same manner as in Example 1 to produce toner base particles of Example 6.

(Comparative Example 1)
A toner was produced by a pulverization method as follows.

100 parts by mass of the unmodified polyester obtained in Example 1, 4.5 parts by mass of carnauba wax, 8 parts by mass of carbon black ("Printex35"; manufactured by Degussa, DBP oil absorption = 42 ml / 100 g, pH = 9.5) And 10 parts by mass of docosanoic acid are sufficiently stirred and mixed in a Henschel mixer, then heated and melted at 130 ° C. for 30 minutes using a roll mill, and further cooled to room temperature. Coarsely pulverized to ˜400 μm. Next, a finely pulverized apparatus that directly pulverizes the coarsely pulverized product against the impingement plate using a jet stream, and a finely pulverized powder obtained by the finely pulverized apparatus forms a swirl flow in the classification chamber, and Crushing and classification were performed using an IDS-2 type pulverizing and classifying apparatus (manufactured by Nippon Pneumatic Industry Co., Ltd.) integrally having an air classifier that was separated by centrifugation, and toner base particles were obtained after classification.
The desired particle size distribution is measured with a Coulter counter, the supply amount of the object to be crushed, the pressure and flow rate of the pulverizing high-pressure air, the hair on the collision member for pulverization, and the air when the air in the classifier is sucked It can be adjusted by changing the inflow position, the inflow direction, the exhaust blower pressure, and the like.

(Comparative Example 2)
Toner base particles of Comparative Example 2 were produced in the same manner as in Comparative Example 1, except that the amount of docosanoic acid added in Comparative Example 1 was changed from 10 parts by mass to 20 parts by mass.

(Comparative Example 3)
In Example 1, docosanoic acid in the preparation of the plasticizer dispersion was replaced with a benzotriazole derivative (“Eversorb75”; manufactured by Dainippon Ink Co., Ltd., melting point = 152 ° C.) that does not impart a plastic effect to the toner resin. Except for the above, toner base particles of Comparative Example 3 were produced in the same manner as in Example 1.

(Comparative Example 4)
In Example 6, the toner of Comparative Example 4 was prepared in the same manner as in Example 6 except that the plasticizer dispersion in the preparation of the monomer composition was replaced with 10 parts by mass of dibehenyl phthalate (melting point = 57 ° C.). Base particles were produced.
In addition, when the solubility of the plasticizer with respect to the organic solvent was measured at 25 degreeC, it was 0 mass%.

(Comparative Example 5)
In Example 1, the plasticizer dispersion used in the dissolution or dispersion preparation of the toner material was replaced with 40 parts by mass of dibenzyl oxalate dissolved in ethyl acetate. Toner base particles of Comparative Example 5 were produced.
In addition, when the solubility of the plasticizer with respect to the organic solvent was measured at 25 degreeC, it was 10 mass%.

(Comparative Example 6)
In Example 1, the toner base material of Comparative Example 6 is the same as Example 1 except that the docosanoic acid used in the preparation of the plasticizer dispersion is changed to stearic acid-n-butyl (melting point = 24 ° C.). Particles were produced.

-External additive treatment-
1.0 part by mass of hydrophobic silica (“H2000”; manufactured by Clariant Japan) as an external additive was added to 100 parts by mass of the obtained toner base particles of Examples 1 to 6 and Comparative Examples 1 to 6 in a Henschel mixer. (Mitsui Mining Co., Ltd.) was used for 5 cycles of mixing at a peripheral speed of 30 m / s for 30 seconds and resting for 1 minute, sieving with a mesh of 35 μm, and the toners of Examples 1 to 6 and Comparative Examples 1 to 6 were used. Manufactured.

Next, a carrier was produced as follows.
To 100 parts by mass of toluene, 100 parts by mass of a silicone resin (“organostraight silicone”, 5 parts by mass of r- (2-aminoethyl) aminopropyltrimethoxysilane, and 10 parts by mass of carbon black were added, and the mixture was mixed with a homomixer for 20 minutes. A magnetic layer was prepared by coating the surface of 1,000 parts by mass of spherical magnetite having a particle diameter of 50 μm using a fluidized bed coating apparatus.

For the obtained toners of Examples 1 to 6 and Comparative Examples 1 to 6, the thermal characteristics, that is, (Tg2r-Tg2t), {(Tg2r-Tg1r)-(Tg2t-Tg1t)}, and (Tg1r-Tg1t). Was measured. The results are shown in Table 1.
The thermal characteristics were measured by the following method using a DSC system (differential scanning calorimeter) (“DSC-60”; manufactured by Shimadzu Corporation).
Regarding the glass transition temperature (Tg1r and Tg1t) of the resin and toner at the first temperature increase, first, about 5.0 mg of resin or toner (sample) is placed in an aluminum sample container, and the sample container is placed on a holder unit. It was set in an electric furnace. Subsequently, it heated from 20 degreeC to 150 degreeC by the temperature increase rate of 10 degree-C / min in nitrogen atmosphere, and the DSC curve was measured with the differential scanning calorimeter ("DSC-60"; Shimadzu Corporation make). From the obtained DSC curve, it calculated from the intersection of the tangent of the curve before the inflection point of the resin (or toner) and the curve after the inflection point using the analysis program in the DSC-60 system. At the same time, the melting point (Tm) of the plasticizer was determined from the peak value derived from the plasticizer.
Regarding the glass transition temperatures (Tg2r and Tg2t) of the resin and toner at the second temperature increase, after the first temperature increase, the resin is cooled from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min. Then, the sample was heated to 150 ° C. at a heating rate of 10 ° C./min, and the DSC curve was measured with a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation). From the obtained DSC curve, it calculated from the intersection of the tangent of the curve before the inflection point of the resin (or toner) and the curve after the inflection point using the analysis program in the DSC-60 system.

  5 parts by mass of each of the toners of Examples 1 to 6 and Comparative Examples 1 to 6 that have been subjected to external additive treatment and 95 parts by mass of the carrier are ball mill mixed, and each of the two components of Examples 1 to 6 and Comparative Examples 1 to 6 A developer was produced.

  Using each of the obtained developers, (a) fixability (offset generation temperature and fixing lower limit temperature), (b) heat-resistant storage stability, (c) fluidity, and (d) copy blocking are as follows. Evaluated. The results are shown in Tables 1 and 2.

(A) Fixability (offset generation temperature and fixing lower limit temperature)
A device that has been tuned so that the temperature and linear velocity can be adjusted by removing the silicone oil coating mechanism from the fixing unit of the tandem color electrophotographic apparatus (“Imagio Neo C350”; manufactured by Ricoh Co., Ltd.) and remodeling it to an oilless fixing system. Then, using a plain paper (“TYPE 6000 <70W>Y”; manufactured by Ricoh Co., Ltd.), the fixability (offset non-occurrence temperature and fixing lower limit temperature) was evaluated.
The tandem color electrophotographic apparatus can continuously print 35 sheets of A4 size paper per minute. At this time, the linear velocity of the fixing roller was set to 125 mm / s, and the evaluation was performed by changing the roller temperature.

<Offset generation temperature>
For image formation, the solid image of each single color of yellow, magenta, cyan, and black is printed on the plain paper using the tandem-type color electrophotographic apparatus in a single color of 0.85 ± 0.3 mg / cm ² . The toner was adjusted so as to be developed. The obtained image was fixed by changing the temperature of the heating roller, and the fixing temperature at which hot offset occurs (offset generation temperature) was measured and evaluated based on the following criteria.
〔Evaluation criteria〕
◎: 210 ° C or more ○: Less than 210 ° C 190 ° C or more △: Less than 190 ° C 170 ° C or more ×: Less than 170 ° C

<Fixing temperature limit>
For the image, the plain paper was set using the tandem type color electrophotographic apparatus, and a copy test was performed. The fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a dedicated cloth pad becomes 70% or more was defined as the minimum fixing temperature, and evaluation was performed based on the following criteria.
〔Evaluation criteria〕
◎: Less than 100 ° C ○: Less than 120 ° C 100 ° C or more △: Less than 140 ° C 120 ° C or more ×: 140 ° C or more

(B) Heat resistance storage (penetration)
Each toner was filled in a 50 ml glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the said penetration value is large, and when it is 5 mm or less, possibility that a problem in use will generate | occur | produce is high.
〔Evaluation criteria〕
○: Needle penetration 25 mm or more △: Needle penetration 15 mm or more and less than 25 mm ×: Needle penetration less than 15 mm

(C) Fluidity The measurement device uses a powder tester (manufactured by Hosokawa Micron), and on the vibration table, the following accessory parts are: Flute (3 types) Top>Medium> Bottom and (e) Osaba were set in this order, then fixed with a knob nut, and the shaking table was operated. And it measured based on the following conditions.
〔Measurement condition〕
Flute opening (top): 75 μm
Flute opening (middle): 45 μm
Flute opening (bottom): 22 μm
Swing scale: 1mm
Sampling amount: 10g
Vibration time: 30 seconds

After measurement under the above conditions, the degree of aggregation (%) of the toner was calculated based on the following formulas (3) to (6), and the fluidity was evaluated based on the following criteria.
A (%) = (weight of powder remaining on upper screen / sample collection amount) × 100 (3)
B (%) = (weight of powder remaining on middle stage sieve / sample collection amount) × 100 (4)
C (%) = (weight of powder remaining in lower screen / sample collection fee) × 100 (5)
Aggregation degree (%) = A + B + C (6)
〔Evaluation criteria〕
◎: Aggregation degree is less than 5% ○: Aggregation degree is less than 10% △: Aggregation degree is less than 20% ×: Aggregation degree is 20% or more

(D) Copy blocking 1,000 standard images having an image area ratio of 7% were continuously output, the adhesion state between the sheets was visually observed, and evaluated based on the following criteria.
〔Evaluation criteria〕
◎: The sheets are separated from each other without any problem. ○: Only the lower stacked sheets need to be separated. △: Although they are separated, they must be separated above and below the stacked sheets. It is in a state where it is difficult to separate. ×: Even if the stacked paper is squeezed up and down, it is in a state of being partially adhered.

なお、表２中、トナーの製法において、前記ＳＰＲは、トナー材料が活性水素基含有化合物と、該活性水素基含有化合物と反応可能な重合体とを少なくとも含み、前記トナー材料の溶解乃至分散液を水系媒体中に乳化乃至分散させて乳化乃至分散液を調製し、前記活性水素基含有化合物と、該活性水素基含有化合物と反応可能な重合体とを反応させて接着性基材を生成しつつ該接着性基材を少なくとも含む粒子を得ることによりトナーを造粒する方法を意味する。

In Table 2, in the toner production method, the SPR includes at least a toner material containing an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound. Is emulsified or dispersed in an aqueous medium to prepare an emulsified or dispersed liquid, and the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound are reacted to produce an adhesive substrate. It means a method of granulating toner by obtaining particles containing at least the adhesive substrate.

From the results of Tables 1 and 2, the following is clear. That is, in Example 1, a toner having excellent fluidity and heat-resistant storage stability, good fixability, and no copy blocking was obtained. In Example 2, since the concentration of the plasticizer is higher than that in Example 1, the minimum fixing temperature is excellent, and in Example 3, since the cross-linking reagent is added, the heat resistance, fluidity, and hot offset resistance are further improved. . In Example 4, since 1% by mass of the plasticizer is dissolved, the heat resistant storage stability and fluidity are slightly inferior to those of Example 1. In Example 5, since the poor solvent was added, the plasticizer was partially dissolved while being precipitated in the toner, and the heat resistant storage stability and fluidity were lowered. In Example 6, since the melting point of the plasticizer was low, it was found that the heat resistant storage stability and fluidity were not so high.
On the other hand, since the toners obtained in Comparative Examples 1 and 2 were produced by a pulverization method, it was found that the heat-resistant storage stability, fixability, and fluidity were inferior, and copy blocking might occur. In Comparative Example 3, since there is no plastic effect, the low-temperature fixability is inferior. In Comparative Example 4, since the resin and the plasticizer are compatible, the heat resistant storage stability and fluidity are poor. In Comparative Example 5, the plasticizer Since it is dissolved in an organic solvent, it was found that the heat resistant storage stability and fluidity were inferior. In Comparative Example 6, since the melting point of the plasticizer was low, it was melted at room temperature, and the heat resistant storage stability and fluidity deteriorated.

  The toner of the present invention is excellent in various properties such as fluidity and fixability, and has both excellent low-temperature fixability and heat-resistant storage stability. Therefore, the toner of the present invention is suitably used for high-quality image formation. The developer, toner-containing container, process cartridge, image forming apparatus and image forming method of the present invention using the toner of the present invention are suitably used for high-quality image formation.

FIG. 1 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 2 is a schematic explanatory view showing another example in which the image forming method of the present invention is carried out by the image forming apparatus of the present invention. FIG. 3 is a schematic explanatory view showing an example in which the image forming method of the present invention is implemented by the image forming apparatus (tandem color image forming apparatus) of the present invention. 4 is a partially enlarged schematic explanatory diagram of the image forming apparatus shown in FIG. FIG. 5 is a schematic explanatory view showing an example in which the image forming method of the present invention is carried out by the image forming apparatus (adhesive transfer method) of the present invention.

Explanation of symbols

10 Photoconductor (Photoconductor drum)
10K black photoconductor 10Y yellow photoconductor 10M magenta photoconductor 10C cyan photoconductor 14 support roller 15 support roller 16 support roller 17 intermediate transfer cleaning device 18 image forming means 20 charging roller 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 Exposure device 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer container 42Y Developer container 42M Developer container 42C Developer container 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K Developer roller 44Y Developer roller 44M Developer Roller 44C Development roller 45K Black development unit 45Y Yellow development unit 45M Magenta development unit 45C Cyan development unit 49 Registration roller 50 Intermediate transfer member 51 Roller 52 Corona charger 53 Constant current source 55 Switching claw 56 Discharge roller 57 Discharge tray 58 Separating roller 60 Cleaning device 61 Developing device 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 95 Transfer paper 100 Image forming device 120 Tandem type developer 130 Document base 142 Feed roller 143 Paper bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Carriage roller 148 Paper feed path 150 Copier main body 200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)
500 Image forming device (adhesive transfer method)
510 Image carrier 520 Toner supply device 530 Laser beam scanning device 540 Toner removal roller 550 Heating roller

Claims (22)

When the DSC measurement of the resin comprising the resin is performed, the first peak of temperature rise of the resin is Tg1r, the second peak of the temperature rise of the resin is Tg2r, and the DSC measurement of the toner containing the resin is performed. When the peak of the toner derived from the resin at the first temperature rise is Tg1t and the peak derived from the resin at the second temperature rise of the toner is Tg2t, the following formulas (1) and ( A toner characterized by satisfying 2).
Tg2r> Tg2t (1)
Tg1t-Tg2t> Tg1r-Tg2r (2)   The toner according to claim 1, wherein Tg2r−Tg2t> 10 (° C.).   The toner according to claim 1, wherein Tg1r−Tg1t <5 (° C.).   5. The toner according to claim 1, comprising a plasticizer of the resin that is compatible with the resin when heated, and having a melting point (Tm) of the plasticizer of 30 ° C. or higher and lower than 120 ° C. 6.   The toner according to claim 4, wherein the plasticizer has a melting point of 50 ° C. or higher and lower than 80 ° C.   The toner according to claim 4, comprising 5 to 30% by mass of a plasticizer.   The toner according to claim 1, wherein the resin has an acidic group and contains at least one of a metal salt and a complex that causes a crosslinking reaction with the acidic group.   The toner according to claim 4, wherein Tg1r> Tm, and 100 ° C.> Tg1r ≧ 60 ° C.   The toner according to claim 1, comprising a trivalent or higher valent crosslinking agent.   The toner according to claim 9, wherein the trivalent or higher valent crosslinking agent is a trivalent or higher valent salicylic acid metal compound.   The toner according to claim 9, comprising 0.05 to 10% by mass of a trivalent or higher valent crosslinking agent.   The toner according to claim 1, wherein the resin has a hydroxyl value of 20 mgKOH / g or more.   The toner according to claim 1, wherein the toner material is granulated after the toner material is dissolved or dispersed in an aqueous medium to prepare an emulsion or dispersion. The toner material includes at least an active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound,
By granulating, by reacting the active hydrogen group-containing compound and a polymer capable of reacting with the active hydrogen group-containing compound to produce an adhesive base material, particles containing at least the adhesive base material are obtained. The toner according to claim 13, which is performed.   The toner according to claim 13, wherein the toner material is dissolved or dispersed by dissolving or dispersing the toner material in an organic solvent.   The toner according to claim 1, wherein the toner is produced at 10 to 100 ° C.   The toner according to claim 1, which is produced at 20 to 60 ° C.   The toner according to claim 4, comprising a plasticizer in a dispersed state, wherein the plasticizer has a dispersion diameter of 10 nm to 3 μm.   The toner according to claim 15, wherein the solubility of the plasticizer in an organic solvent at 25 ° C. or less is 1% by mass or less.   The toner according to claim 15, wherein the plasticizer has a solubility of 5% by mass or more in an organic solvent at 60 ° C. or higher.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image is developed using the toner according to any one of claims 1 to 20 to be a visible image. An image forming method comprising: a developing step for forming the image; a transfer step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. A toner supply step for supplying the toner according to any one of claims 1 to 20 onto an image carrier, and applying heat according to an image signal to the toner brought into contact with the image carrier, the heat A visible image is temporarily formed on the image carrier, and the temporarily fixed visible image is transferred to a recording medium. And an image forming method characterized by comprising at least a heat welding step of heat welding.

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