JP2012173646A - Toner, and toner container, developer, developing device, image forming apparatus, and process cartridge - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner and the like being excellent in temperature fixability, sticking resistance and reduction of background staining and allowing an adhesion step at low temperature in which a shell layer is adhered to a core particle when manufacturing a toner.SOLUTION: A toner has a core particle containing at least a binder resin, a colorant and a mold-releasing agent and a shell layer formed of a vinyl resin fine particle on the surface of the core particle, where the binder resin contains at least a crystalline polyester resin and an amorphous polyester resin; the glass-transition temperature of the vinyl resin fine particles is 60°C to 80°C; and a component of the vinyl resin fine particle comprises 80 mass% or more of an aromatic compound having a vinyl polymerizable functional group and 5 mass% or more of a compound having a vinyl polymerizable functional group and an ester bond, and comprises no compound having a vinyl polymerizable functional group and an acid group.

Description

  The present invention relates to a toner, a toner container containing the toner, a developer containing the toner, a developing device containing the developer, an image forming apparatus having the developing device, and a process cartridge having the developing device. .

  Image formation by electrophotography generally forms an electrostatic image on a photoreceptor (electrostatic image carrier), develops the electrostatic image 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.

  In recent years, from the viewpoint of energy saving, development of technology that enables low-temperature fixing has been developed. For example, a melt-miscible substance (for example, a crystalline polyester resin) that is compatible with a resin and exhibits a plastic effect. By adding it to the toner, the glass transition temperature (Tg) of the resin is lowered.

However, when the crystalline polyester resin is used for the toner, there are problems that blocking occurs in the developing device, the blocked toner is not fixed to the regulating blade, and the background is stained due to a decrease in chargeability.
Therefore, there is a demand for a toner that is excellent in low-temperature fixability, adhesion resistance, and background stains.

An electrostatic charge image developing toner having a core-shell structure in which a shell is provided on the surface of core particles containing a binder resin containing a crystalline polyester resin and an amorphous polyester resin, and a colorant. However, an electrostatic charge image developing toner including a copolymer resin obtained by copolymerizing a monomer mixture including a styrene monomer and a (meth) acrylic monomer has been proposed (see Patent Document 1). In the proposed technique, a copolymer resin obtained by copolymerizing styrene, n-butyl acrylate, and acrylic acid is used as the shell.
However, there is a problem that the shell made of the copolymer resin is not sufficiently attached to the core. Therefore, in this proposed technique, the adhesion process of attaching the shell to the core is improved at a high temperature of 96 ° C. to improve the adhesion of the shell to the core, but the adhesion process at a high temperature requires a lot of energy. Therefore, there is a problem that it is not desirable from the viewpoint of energy saving.

  Therefore, a toner that is excellent in low-temperature fixability, anti-sticking property, and background stain, and that can be attached at a low temperature to attach the shell layer to the core particles when the toner is produced, and a toner container containing the toner The present situation is that there is a need to provide a developer containing the toner, a developing device containing the developer, an image forming apparatus having the developing device, and a process cartridge having the developing device.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is a toner that is excellent in low-temperature fixability, anti-sticking property, and background stain, and that can perform an adhesion step of attaching a shell layer to core particles at the time of manufacturing the toner, and the toner. It is an object of the present invention to provide a toner container accommodated, a developer containing the toner, a developing device containing the developer, an image forming apparatus having the developing device, and a process cartridge having the developing device.

Means for solving the problems are as follows. That is,
<1> Core particles containing at least a binder resin, a colorant, and a release agent;
A toner having a shell layer formed of vinyl resin fine particles on the surface of the core particles,
The binder resin contains at least a crystalline polyester resin and an amorphous polyester resin;
The glass transition temperature of the vinyl resin fine particles is 60 ° C to 80 ° C,
The constituent component of the vinyl resin fine particles contains 80% by mass or more of an aromatic compound having a vinyl polymerizable functional group and 5% by mass or more of a compound having a vinyl polymerizable functional group and an ester bond, and is vinyl polymerizable. The toner does not contain a compound having a functional group and an acid group.
<2> The toner according to <1>, wherein the vinyl resin fine particles have a weight average molecular weight of 20,000 to 50,000.
<3> The toner according to any one of <1> to <2>, wherein the core particle and the shell layer form a continuous layer.
<4> The toner according to any one of <1> to <3>, wherein the binder resin further contains a modified polyester resin having at least one of a urethane bond and a urea bond.
<5> The toner according to any one of <1> to <4>, wherein the release agent is at least one selected from paraffins, synthetic esters, polyolefins, carnauba wax, and rice wax. .
<6> A toner container in which the toner according to any one of <1> to <5> is accommodated.
<7> A developer containing the toner according to any one of <1> to <5>.
<8> a developer carrier that carries on its surface a developer to be supplied to the image carrier;
Developer supplying means for supplying the developer to the surface of the developer carrying member;
At least developer storage means for storing the developer,
A developing device in which the developer according to <7> is stored in the developer storing means.
<9> an image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the image carrier;
Developing means for developing the electrostatic latent image with a developer to form a visible image;
Transfer means for transferring the visible image to a recording medium;
And at least fixing means for fixing the transferred image transferred to the recording medium,
The image forming apparatus is characterized in that the developing unit is the developing device according to <8>.
<10> A process cartridge having at least an image carrier and the developing device according to <8>, wherein the process cartridge is detachable from a main body of the image forming apparatus.

  According to the present invention, it is possible to solve the above-mentioned problems, and is excellent in low-temperature fixability, anti-sticking property, and background stain, and has an adhesion process for attaching a shell layer to core particles at the time of producing toner. , A toner container containing the toner, a developer containing the toner, a developing device containing the developer, an image forming apparatus having the developing device, and a process cartridge having the developing device Can be provided.

FIG. 1 is a schematic cross-sectional view showing the configuration of the developing device of the present invention. FIG. 2 is a schematic sectional view showing an example of the image forming apparatus of the present invention. FIG. 3 is a schematic sectional view showing an example of a fixing device used in the image forming method according to the present invention. FIG. 4 is a schematic view showing an example of a multicolor image forming apparatus to which the image forming apparatus of the present invention is applied. FIG. 5 is a schematic view showing an example of a revolver type full-color image forming apparatus to which the image forming apparatus of the present invention is applied. FIG. 6 is a schematic sectional view showing an example of the process cartridge of the present invention. FIG. 7 is a cross-sectional photograph showing a state in which the core particles and the shell layer form a continuous layer in the toner of Example 1. FIG. 8 is a cross-sectional photograph of the toner of Comparative Example 1.

(toner)
The toner of the present invention includes at least core particles and a shell layer, and further includes other components as necessary.

<Core particles>
The core particles contain at least a binder resin, a colorant, and a release agent, and further contain other components as necessary.
The core particles are preferably core particles obtained by dispersing, in an aqueous medium, an oil phase in which at least a binder resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent.

-Binder resin-
As the binder resin, a modified polyester resin containing at least a crystalline polyester resin and an amorphous polyester resin, preferably having at least one of a urethane bond and a urea bond, and, if necessary, other resins Containing.

--- Crystalline polyester resin--
The crystalline polyester resin is obtained using a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester.
In the present invention, the crystalline polyester resin, as described above, uses a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester. A polyester resin modified, for example, a polyester prepolymer described later, and a modified polyester resin obtained by crosslinking and / or elongation reaction of the polyester prepolymer (that is, at least urethane bond and urea bond). The modified polyester resin having any of them is not included in the crystalline polyester resin in the present invention and is treated as a modified polyester resin.
When the core particles contain the crystalline polyester resin, the toner has excellent low-temperature fixability.

There is no restriction | limiting in particular as said polyhydric alcohol component, According to the objective, it can select suitably, For example, a C2-C12 aliphatic diol compound is mentioned. Examples of the aliphatic diol compound having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 1,4-butenediol and the like. Among these, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol are preferable, and 1,8-octanediol and 1,10-decanediol are more 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 said polyvalent carboxylic acid component, According to the objective, it can select suitably, For example, aromatic dicarboxylic acid, C2-C12 saturated dicarboxylic acid, these derivatives, etc. are mentioned. .
Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and the like.
Examples of the saturated dicarboxylic acid having 2 to 12 carbon atoms include 1,4-butanedioic acid, 1,6-hexanedioic acid (adipic acid), 1,8-octanedioic acid, and 1,10-decanedioic acid. 1,12-dodecanedioic acid and the like.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as an acid value of the said crystalline polyester resin, Although it can select suitably according to the objective, 5 mgKOH / g or more is preferable and 10 mgKOH / g or more is more preferable.
The acid value can be measured, for example, according to the measurement method described in JIS K0070-1992. Specifically, it can be calculated as follows. That is, titration is performed with a 0.1 mol / L potassium hydroxide ethanol solution that has been standardized in advance, and the acid value can be obtained from the consumption amount of the potassium hydroxide ethanol solution by the following formula.
Acid value = KOH (number of mL) × N × 56.1 / sample mass (In the above formula, N represents a factor of a 0.1 mol / L potassium hydroxide ethanol solution.)

  The melting point of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, in the differential heat curve obtained by differential scanning calorimetry (DSC), the endothermic amount is maximal. The temperature of the endothermic peak (hereinafter sometimes referred to as “peak top”) is preferably 50 ° C. or higher and 150 ° C. or lower. When the melting point is less than 50 ° C., the heat storage stability of the toner is deteriorated and solidifies during storage, and the fluidity may be deteriorated. When the melting point is higher than 150 ° C., the release agent is finely dispersed during fixing. And the image surface releasability is poor and contamination by the release agent cannot be prevented, and uneven glossiness and solid image surface roughness may occur.

  There is no restriction | limiting in particular as content of the said crystalline polyester resin, Although it can select suitably according to the objective, 3 mass%-15 mass% are preferable. When the content of the crystalline polyester resin is less than 3% by mass, the low-temperature fixability may be deteriorated, and when it exceeds 15% by mass, the heat resistant storage stability may be inferior.

--- Amorphous polyester resin--
The amorphous polyester resin is obtained using a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester.
In the present invention, the amorphous polyester resin uses, as described above, a polyhydric alcohol component and a polyvalent carboxylic acid component such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester. Obtained by modifying a polyester resin, for example, a polyester prepolymer described later, and a modified polyester resin obtained by crosslinking and / or elongation reaction of the polyester prepolymer (that is, urethane bond and urea bond). In the present invention, the modified polyester resin having at least one is not included in the amorphous polyester resin, but is treated as a modified polyester resin.

  Examples of the polyhydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxy). Alkylene) (2 to 3 carbon atoms) oxide (average number of added moles 1 to 10) adduct of bisphenol A such as phenyl) propane; ethylene glycol, propylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated Bisphenol A, sorbitol, or their alkylene (C2-C3) oxide (average addition mole number 1-10) adduct etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polyvalent carboxylic acid component include dicarboxylic acids such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid and maleic acid; alkyl groups having 1 to 20 carbon atoms such as dodecenyl succinic acid and octyl succinic acid; Examples thereof include succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms; trimellitic acid and pyromellitic acid; anhydrides of these acids and alkyl (C1 to C8) esters of these acids. These may be used individually by 1 type and may use 2 or more types together.

  The amorphous polyester resin, the polyester prepolymer described later, and a resin obtained by crosslinking and / or elongation reaction of the polyester prepolymer (that is, a modified polyester resin having at least one of a urethane bond and a urea bond) It is preferable that at least a part is compatible. When these are compatible, low-temperature fixability and high-temperature offset resistance can be improved. For this reason, the polyhydric alcohol component and polyvalent carboxylic acid component constituting the amorphous polyester resin and the polyhydric alcohol component and polycarboxylic acid component constituting the prepolymer described later have similar compositions. Is preferred.

There is no restriction | limiting in particular as glass transition temperature (Tg) of the said amorphous polyester resin, Although it can select suitably according to the objective, 40 to 70 degreeC is preferable and 45 to 65 degreeC is more preferable. When the glass transition temperature is less than 40 ° C., the heat resistant storage stability of the toner and durability against stress such as agitation in the developing device may be inferior. May become inferior in low-temperature fixability.
The glass transition temperature is a glass transition temperature measured by differential scanning calorimetry (DSC), and can be measured using, for example, a TG-DSC system TAS-100 manufactured by Rigaku Corporation.

  There is no restriction | limiting in particular as content of the said amorphous polyester resin, Although it can select suitably according to the objective, 50 mass parts-95 mass parts are preferable with respect to 100 mass parts of said toners, 60 masses Part to 90 parts by mass is more preferable. When the content is less than 50 parts by mass, the dispersibility of the pigment and the release agent in the toner is deteriorated, and image fogging and disturbance may easily occur. Since the content of the polyester resin is reduced, the low-temperature fixability may be inferior. When the content is in the more preferable range, it is advantageous in that it is excellent in all of high image quality, high stability, and low temperature fixability.

--Modified polyester resin--
By using a modified polyester resin having at least one of the urethane bond and the urea bond, an appropriate cross-linked structure can be provided in the toner.
The modified polyester resin having at least one of the urethane bond and the urea bond (hereinafter sometimes referred to as “modified polyester resin”) is not particularly limited and may be appropriately selected depending on the purpose. A resin obtained by subjecting a polyester resin having a functional group capable of reacting with the active hydrogen group of the active hydrogen group-containing compound to an extension reaction or a crosslinking reaction using the active hydrogen group-containing compound is preferable.

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent, or the like when a polyester resin having a functional group capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in an 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 according to the purpose. For example, a functional group capable of reacting with the active hydrogen group-containing compound is used. When the polyester resin having an isocyanate group-containing polyester prepolymer (A), which will be described later, is an amine in that the isocyanate group-containing polyester prepolymer (A) can be increased in molecular weight by a reaction such as an extension reaction or a crosslinking reaction. Class (B) 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.

There is no restriction | limiting in particular as said amine (B), According to the objective, it can select suitably, For example, diamine (B1), trivalent or more polyamine (B2), amino alcohol (B3), amino mercaptan ( B4), amino acid (B5), and those obtained by blocking the amino group of B1 to B5 (B6). These may be used individually by 1 type and may use 2 or more types together.
Among these, the amines are particularly preferably diamine (B1), a mixture of diamine (B1) and a small amount of trivalent or higher polyamine (B2).

There is no restriction | limiting in particular as said diamine (B1), According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine etc. are mentioned.
Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, and 4,4′diaminodiphenylmethane.
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.
The trivalent or higher polyamine (B2) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The amino alcohol (B3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The amino mercaptan (B4) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include minoethyl mercaptan and aminopropyl mercaptan.
The amino acid (B5) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
There is no restriction | limiting in particular as what blocked the amino group of said (B1)-(B5), According to the objective, it can select suitably, For example, any one of said (B1) to (B5) And ketimine compounds and oxazolidone compounds obtained from these amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

--- Polyester resin having functional group capable of reacting with active hydrogen group-containing compound ---
The polyester resin having a functional group capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “polyester prepolymer”) includes a polyester resin having at least a site capable of reacting with the active hydrogen group-containing compound. If it is, there will be no restriction | limiting in particular, According to the objective, it can select suitably.

There is no restriction | limiting in particular as a functional group which can react with the said active hydrogen group in the said polyester prepolymer, It can select suitably from well-known substituents etc., for example, an isocyanate group, an epoxy group, carboxylic acid, acid And a chloride group. These may be contained singly or in combination of two or more.
Among these, the functional group capable of reacting with the active hydrogen group-containing compound is particularly preferably an isocyanate group.

  There is no restriction | limiting in particular as a manufacturing method of an isocyanate group containing polyester prepolymer (A), According to the objective, it can select suitably. For example, the polyol (A1) and the polycarboxylic acid (A2) are heated to 150 ° C. to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxy titanate or dibutyltin oxide, and the pressure is reduced as necessary. Generate. Water is distilled off to obtain a polyester having a hydroxyl group. Subsequently, it can obtain by making polyisocyanate (A3) react with polyester which has a hydroxyl group at 40 to 140 degreeC.

  There is no restriction | limiting in particular as said polyol (A1), According to the objective, it can select suitably, For example, the mixture of a diol, a trihydric or more polyol, a diol, and a trihydric or more polyol etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, the polyol is preferably the diol alone or a mixture of the diol and a small amount of the trivalent or higher polyol.

The diol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol); alkylene ether glycol (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diol (1,4-cyclohexanedimethanol, Hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.); alkylene oxides of the alicyclic diols (ethylene oxide, propylene oxide) De, butylene oxide, etc.) adducts; alkylene oxide (ethylene oxide of the bisphenols, propylene oxide, and the like butylene oxide, etc.) adducts. These may be used individually by 1 type and may use 2 or more types together.
Among these, the diol is an alkylene glycol having 2 to 12 carbon atoms, an alkylene oxide adduct of bisphenols (for example, bisphenol A ethylene oxide 2 mol adduct, bisphenol A propylene oxide 2 mol adduct, bisphenol A propylene oxide 3). Mole adducts etc. are preferred.

  The trivalent or higher polyol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyhydric aliphatic alcohol (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); Trihydric or higher phenols (phenol novolak, cresol novolak, etc.); trihydric or higher polyphenol alkylene oxide adducts and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as said polycarboxylic acid (A2), According to the objective, it can select suitably, For example, alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); Alkenylene dicarboxylic acid (maleic acid, maleic acid) Fumaric acid, etc.); aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, etc.). These may be used individually by 1 type and may use 2 or more types together. Among these, the polycarboxylic acid (2) is preferably an alkenylene dicarboxylic acid having 4 to 20 carbon atoms and an aromatic dicarboxylic acid having 8 to 20 carbon atoms.

The trivalent or higher polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an aromatic polycarboxylic acid having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.
In place of polycarboxylic acid, an anhydride or lower alkyl ester of polycarboxylic acid can also be used. There is no restriction | limiting in particular as said lower alkyl ester, According to the objective, it can select suitably, For example, methyl ester, ethyl ester, isopropyl ester etc. are mentioned.

  The mixing ratio of the polyol (A1) and the polycarboxylic acid (A2) is not particularly limited and may be appropriately selected depending on the intended purpose. The hydroxyl group [OH] of the polyol (A1) and the polycarboxylic acid may be selected. The equivalent ratio [OH] / [COOH] of the carboxyl group [COOH] in (A2) is preferably 2/1 to 1/1, more preferably 1.5 / 1 to 1/1, and 1.3 / 1 to 1.02 / 1 is particularly preferred.

  There is no restriction | limiting in particular as said polyisocyanate (A3), According to the objective, it can select suitably, For example, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic diisocyanate, araliphatic diisocyanate, isocyanurates And those blocked with these phenol derivatives, oximes, caprolactams, and the like.

  The aliphatic polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, deca Examples include methylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.

  The alicyclic polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.

  The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, diphenylene-4,4′-diisocyanate, 4 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate and the like.

The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.
There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris-isocyanate alkyl-isocyanurate, a triisocyanate cycloalkyl-isocyanurate, etc. are mentioned.
These may be used individually by 1 type and may use 2 or more types together.

  The mixing ratio of the polyisocyanate (A3) and the polyester having a hydroxyl group is not particularly limited and may be appropriately selected depending on the intended purpose. The isocyanate group [NCO] of the polyisocyanate (A3) and the The equivalent ratio [NCO] / [OH] of the hydroxyl group [OH] of the polyester having a hydroxyl group is preferably 5/1 to 1/1, more preferably 4/1 to 1.2 / 1, and 2.5 / 1 to 1.5 / 1 is particularly preferred. When the [NCO] / [OH] exceeds 5, the remaining polyisocyanate compound may adversely affect the chargeability of the toner.

  The modified polyester resin comprises an aqueous medium comprising a compound having an active hydrogen group such as the amines (B) and a polyester resin having a functional group capable of reacting with an active hydrogen group-containing compound such as the polyester prepolymer (A). It can be obtained by reacting in.

When the polyisocyanate (A3) and the amines (B) are reacted, a solvent can be used as necessary.
The usable solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (Ethyl acetate and the like); amides (dimethylformamide, dimethylacetamide and the like), ethers (tetrahydrofuran and the like) and the like which are inert to the isocyanate (3). These may be used individually by 1 type and may use 2 or more types together.

  The mixing ratio of the amines (B) and the polyester prepolymer (A) having an isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. The equivalent ratio ([NCO] / [NHx]) of the isocyanate group [NCO] of the polymer (A) to the amino group [NHx] of the amines (B) is preferably 1/2 to 2/1, 1.5-1.5 / 1 is more preferable, and 1 / 1.2-1.2 / 1 is particularly preferable.

A reaction terminator can be used to stop the elongation reaction, the crosslinking reaction, and the like in the active hydrogen group-containing compound and the polyester resin having a functional group capable of reacting with the active hydrogen group-containing compound.
The reaction terminator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.) Etc. These may be used individually by 1 type and may use 2 or more types together.

-Other resins-
There is no restriction | limiting in particular as said other resin, According to the objective, it can select suitably, For example, a styrene-acryl resin, a polyol resin, a vinyl resin, a polyurethane resin, an epoxy resin, a polyamide resin, a polyimide resin, silicon Resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, polycarbonate resin and the like.
These may be used individually by 1 type and may use 2 or more types together.

-Colorant-
The colorant is not particularly limited and may be appropriately selected depending on the intended purpose. , Copper phthalocyanine, malachite green oxalate, lamp black, rose bengal, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 184, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 74, C.I. I. Solvent Yellow 162, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185, C.I. I. Pigment blue 15: 1, C.I. I. And CI Pigment Blue 15: 3.

  There is no restriction | limiting in particular as content of the said colorant, Although it can select suitably according to the objective, 2 mass parts-15 mass parts are preferable with respect to 100 mass parts of resin parts in a toner.

  The colorant is preferably used as a master batch combined with a resin from the viewpoint of dispersibility. There is no restriction | limiting in particular as content of the said masterbatch, Although it can select suitably according to the objective, The quantity of the said coloring agent is 2-15 mass parts with respect to 100 mass parts of resin parts in a toner. An amount that provides parts by mass is preferred. There is no restriction | limiting in particular as content of the coloring agent in the said masterbatch, Although it can select suitably according to the objective, 20 mass%-40 mass% are preferable.

-Release agent-
As the releasing agent, it is preferable to use a substance such as wax or silicone oil, which has a sufficiently low viscosity when heated in the fixing process and hardly dissolves or swells on the surface of the fixing member. In view of storage stability, it is more preferable to use a wax that exists as a solid in the toner during normal storage.

Examples of the wax include paraffins, synthetic esters, polyolefins, paraffins, natural plant waxes, natural mineral waxes, and fatty acid amide synthetic waxes.
Examples of the paraffins include paraffin wax and sazol wax.
Examples of the synthetic esters include trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, trimellit Examples include tristearyl acid, distearyl maleate, and octadecyl stearate.
Examples of the polyolefins include polyethylene wax and polypropylene wax.
Examples of the natural plant wax include carnauba wax, rice wax, and candelilla wax.
Examples of the natural mineral wax include montan wax, ozokerite, and ceresin.
Examples of fatty acid amide synthetic waxes include stearic acid amide.
Among these, paraffins, synthetic esters, polyolefins, carnauba wax and rice wax are preferable.
These may be used individually by 1 type, and may use 2 or more types together.

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

<Shell layer>
The shell layer is formed of vinyl resin fine particles. The shell layer is formed on the surface of the core particle.
Whether or not the vinyl resin fine particles are formed on the surface of the core particles can be confirmed, for example, by observing the toner using a scanning electron microscope (SEM).

-Vinyl resin fine particles-
The vinyl resin fine particles are obtained from a vinyl resin obtained by polymerizing an aromatic compound having a vinyl polymerizable functional group and a monomer mixture containing at least a compound having a vinyl polymerizable functional group and an ester bond. Become.

  The constituent component of the vinyl resin fine particles contains an aromatic compound having a vinyl polymerizable functional group in an amount of 80% by mass or more, preferably in the range of 80% by mass to 95% by mass, and 80% by mass to 90% by mass. It is more preferable to include within the range. When the proportion of the aromatic compound having a vinyl polymerizable functional group in the constituent component of the vinyl resin fine particles is less than 80% by mass, the chargeability of the obtained toner becomes poor. When the ratio of the aromatic compound having a vinyl polymerizable functional group in the constituent component of the vinyl resin fine particles is within the more preferable range, it is advantageous in that the charging property is excellent.

  The constituent component of the vinyl resin fine particles contains 5% by mass or more of a compound having a vinyl polymerizable functional group and an ester bond, and preferably contains 5% by mass to 20% by mass. More preferably, it is contained within the range of mass%. When the proportion of the compound having a vinyl polymerizable functional group and an ester bond in the constituent components of the vinyl resin fine particles is less than 5% by mass, the compatibility between the shell layer and the core particles is reduced, and the shell layer Causes withdrawal. When the ratio of the compound having a vinyl polymerizable functional group and an ester bond in the constituent components of the vinyl resin fine particles is within the more preferable range, it is advantageous in terms of improving the adhesion between the core particle and the shell layer. It is.

The constituent component of the vinyl resin fine particles does not include a compound having a vinyl polymerizable functional group and an acid group. When the constituent component of the vinyl resin fine particles contains a compound having the vinyl polymerizable functional group and an acid group, the sticking resistance is lowered.
The reason why the anti-sticking property is lowered when the constituent component of the vinyl resin fine particles includes the compound having the vinyl polymerizable functional group and the acid group is high in the aqueous phase of the vinyl resin fine particles, It is considered that it is difficult to form the vinyl resin fine particles on the surface of the core particles during the production of the toner. That is, when the constituent component of the vinyl resin fine particle includes the compound having the vinyl polymerizable functional group and the acid group, the oil phase containing the core particle is dispersed in the aqueous medium when the toner is manufactured. When the resin fine particle dispersion in which the vinyl resin fine particles are dispersed in an aqueous medium is added to the core particle dispersion, the vinyl resin fine particles are unlikely to move from the aqueous phase to the oil phase. It is considered that it is difficult to form the resin fine particles on the surface of the core particle. Further, it is considered that even if the vinyl resin fine particles are formed on the surface of the core particles, they are easily detached.
In other words, the component of the vinyl resin fine particles does not contain the compound having the vinyl polymerizable functional group and the acid group, so that the stability of the vinyl resin fine particles in the aqueous phase is reduced, and the toner It is considered that it becomes easy to form the vinyl resin fine particles on the surface of the core particles during the production. That is, since the constituent component of the vinyl resin fine particles does not include the compound having the vinyl polymerizable functional group and the acid group, the oil phase containing the core particles is an aqueous medium in the production of the toner. When the resin fine particle dispersion in which the vinyl resin fine particles are dispersed in an aqueous medium is introduced into the core particle dispersion liquid dispersed therein, the vinyl resin fine particles are easily transferred from the aqueous phase to the oil phase. As a result, it is considered that the vinyl resin fine particles can be easily formed on the surface of the core particles.

Here, it is confirmed that the vinyl resin fine particles do not contain the compound having the vinyl polymerizable functional group and the acid group as a constituent component when the acid value is measured, which is below the detection limit. Can do.
The acid value can be measured, for example, according to the measurement method described in JIS K0070-1992. Specifically, it can be calculated as follows. That is, titration is performed with a 0.1 mol / L potassium hydroxide ethanol solution that has been standardized in advance, and the acid value can be obtained from the consumption amount of the potassium hydroxide ethanol solution by the following formula.
Acid value = KOH (number of mL) × N × 56.1 / sample mass (In the above formula, N represents a factor of a 0.1 mol / L potassium hydroxide ethanol solution.)
In this case, the detection limit means a state in which the sample solution is colored by the indicator when a sample amount is 20 g and one drop of a 0.1 mol / L potassium hydroxide ethanol solution is dropped onto the sample solution by a burette.

--Aromatic compound having vinyl polymerizable functional group--
The polymerizable functional group in the aromatic compound having a vinyl polymerizable functional group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, vinyl group, isopropenyl group, allyl group, acryloyl group And a methacryloyl group.
Examples of the aromatic compound having a vinyl polymerizable functional group include styrene, α-methylstyrene, 4-methylstyrene, 4-ethylstyrene, 4-tert-butylstyrene, 4-methoxystyrene, 4-ethoxystyrene, 4 -Carboxystyrene or its metal salt, 4-styrenesulfonic acid or its metal salt, 1-vinylnaphthalene, 2-vinylnaphthalene, allylbenzene, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, vinyl benzoate, phenoxyalkylene Examples include glycol acrylate, phenoxyalkylene glycol methacrylate, phenoxy polyalkylene glycol acrylate, and phenoxy polyalkylene glycol methacrylate.
Among these, styrene is preferable because it is easily available, has excellent reactivity, and high chargeability.
In addition, in the present invention, a compound having a vinyl polymerizable functional group, an aromatic group, and an ester bond in the molecule, such as benzyl acrylate and phenoxyalkylene glycol acrylate, is an aromatic compound having a vinyl polymerizable functional group. Among the compounds having a vinyl polymerizable functional group and an ester bond, it belongs to an aromatic compound having a vinyl polymerizable functional group.

--Compound having vinyl polymerizable functional group and ester bond--
Examples of the compound having a vinyl polymerizable functional group and an ester bond include vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinyl. Benzoate, cyclohexyl methacrylate, vinyl methoxyacetate, ethyl-α-ethoxy acrylate, methoxydiethylene glycol methacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms, dialkyl fumarate (two alkyl groups have 2 carbon atoms A dialkyl maleate (2 alkyl groups are straight chain, branched chain and alicyclic having 2 to 8 carbon atoms). Any group of the formula), poly (me ) Allyloxy alkanes, vinyl monomers having a polyalkylene glycol chain, such as poly (meth) acrylates of polyhydric alcohols.

Examples of the (meth) alkyl acrylate having an alkyl group having 1 to 50 carbon atoms include methyl acrylate, ethyl acrylate, propyl acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, hexadecyl acrylate, and heptadecyl. Examples thereof include acrylates, eicosyl acrylates, and compounds obtained by replacing these acrylates with methacrylates.
Examples of the poly (meth) allyloxyalkane include diaryloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, and tetrametaallyloxyethane.
Examples of the vinyl monomer having a polyalkylene glycol chain include polyethylene glycol (molecular weight 300) monoacrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mol adduct acrylate, and lauryl alcohol ethylene oxide 30 mol addition. Product acrylates, and compounds obtained by replacing these acrylates with methacrylates.
Examples of poly (meth) acrylates of the polyhydric alcohols include ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, and methacrylates of these acrylates. And the like.

--Compound having vinyl polymerizable functional group and acid group--
Examples of the acid group of the compound having a vinyl polymerizable functional group and an acid group include a carboxyl group, a sulfonyl group, and a phosphonyl group.
Examples of the compound having a vinyl polymerizable functional group and an acid group include a carboxyl group-containing vinyl monomer and a salt thereof, a sulfonic acid group-containing vinyl monomer, a vinyl sulfate monoester and a salt thereof, and a phosphate group-containing vinyl. System monomers and salts thereof.
Examples of the carboxyl group-containing vinyl monomers and salts thereof include acrylic acid, methacrylic acid, maleic acid, monoalkyl maleate, fumaric acid, monoalkyl fumarate, crotonic acid, itaconic acid, monoalkyl itaconic acid, glycol itaconic acid mono Examples include ether, citraconic acid, monoalkyl citraconic acid, cinnamic acid, and salts thereof.
Among these, representative examples include acrylic acid, methacrylic acid, maleic acid, monoalkyl maleate, fumaric acid, and monoalkyl fumarate.
In addition, in the present invention, a compound having a vinyl polymerizable functional group, an acid group, and an ester bond in the molecule, such as monoalkyl maleate, is a compound having a vinyl polymerizable functional group and an acid group, vinyl Among the compounds having a polymerizable functional group and an ester bond, it belongs to a compound having a vinyl polymerizable functional group and an acid group.

There is no restriction | limiting in particular as a weight average molecular weight of the said vinyl resin fine particle, Although it can select suitably according to the objective, 20,000-50,000 are preferable. When the weight average molecular weight is less than 20,000, the mechanical strength of the toner is weak and brittle, causing a significant change in chargeability, contamination such as adhesion to peripheral members, and accompanying quality problems. Sometimes. When the weight average molecular weight exceeds 50,000, the low-temperature fixability may be lowered. When the weight average molecular weight is within the particularly preferable range, both low-temperature fixability and anti-sticking property can be achieved at a high level.
The said weight average molecular weight is a molecular weight measured by GPC (gel permeation chromatography), for example, can be measured using GPC-150C (made by Waters).

The glass transition temperature (Tg) of the vinyl resin fine particles is 60 ° C to 80 ° C, preferably 60 ° C to 75 ° C, and more preferably 60 ° C to 70 ° C. By setting the glass transition temperature to 60 ° C. to 80 ° C., the toner can achieve both excellent low-temperature fixability due to the core particles containing the crystalline polyester resin and anti-sticking property.
The glass transition temperature is a glass transition temperature measured by differential scanning calorimetry (DSC), and can be measured using, for example, a TG-DSC system TAS-100 manufactured by Rigaku Corporation.

There is no restriction | limiting in particular as a volume average particle diameter of the said vinyl resin fine particle, Although it can select suitably according to the objective, 80 nm-120 nm are preferable.
The volume average particle diameter of the vinyl resin fine particles can be measured using, for example, UPA-150EX (manufactured by Nikkiso Co., Ltd.).

--- Method for producing vinyl resin fine particles--
There is no restriction | limiting in particular as a manufacturing method of the said vinyl resin fine particle, According to the objective, it can select suitably, For example, the following (a)-(f) etc. are mentioned.
(A) A method of producing a dispersion of vinyl resin fine particles by reacting a monomer mixture by a polymerization reaction such as a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method.
(B) A method of producing vinyl resin fine particles by polymerizing a monomer mixture in advance, pulverizing the obtained resin using a mechanical pulverizer such as a mechanical rotary type or a jet type, and then classifying.
(C) A method of producing vinyl resin fine particles by polymerizing a monomer mixture in advance and spraying a resin solution obtained by dissolving the obtained resin in a solvent in a mist form.
(D) Precipitating vinyl resin fine particles by polymerizing the monomer mixture in advance and adding the solvent to the resin solution obtained by dissolving the obtained resin in the solvent or by cooling the resin solution previously heated and dissolved in the solvent And then producing a vinyl resin fine particle by removing the solvent.
(E) A vinyl resin solution obtained by polymerizing a monomer mixture in advance and dissolving the obtained resin in a solvent is dispersed in an aqueous medium in the presence of a suitable dispersant, and the solvent is removed by heating or decompression. How to remove.
(F) A method in which a monomer mixture is polymerized in advance, a suitable emulsifier is dissolved in a vinyl resin solution obtained by dissolving the obtained resin in a solvent, and then water is added to perform phase inversion emulsification.
Among these, the method (a) is preferable because it is easy to produce and the vinyl resin fine particles can be obtained as a dispersion, so that it can be smoothly applied to the next step.

  In the method (a), when the polymerization reaction is performed, a dispersion stabilizer is added to the aqueous medium, or the dispersion stability of the vinyl resin fine particles obtained by polymerization in the monomer that performs the polymerization reaction is increased. It is preferable to add a monomer that can be imparted (so-called reactive emulsifier), or to use these two means in combination to impart dispersion stability to the resulting vinyl resin fine particles. If the dispersion stabilizer and reactive emulsifier are not used, the dispersion state of the particles cannot be maintained, so the vinyl resin cannot be obtained as fine particles, or the resulting vinyl resin fine particles have low dispersion stability and are stored. The toner particles that are ultimately unstable because of poor stability and agglomeration during storage, or because the dispersion stability of the particles in the resin fine particle adhesion process is reduced, and the core particles tend to agglomerate and coalesce. The uniformity of the diameter, shape, surface, etc. may deteriorate.

There is no restriction | limiting in particular as said dispersion stabilizer, According to the objective, it can select suitably, For example, surfactant, an inorganic dispersing agent, etc. are mentioned.
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphate esters; alkylamines Salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Cationic surfactants such as quaternary ammonium salt types; Nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives; Alanine, Dodecyldi (aminoethyl) glycine, Di (octylaminoethyl) glycine, N-alkyl-N , - such as amphoteric surfactants such as dimethyl ammonium betaine and the like.
The inorganic dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

The core particles and the shell layer preferably form a continuous layer.
Here, “forming a continuous layer” means a state in which there is no gap at the boundary between the core particle and the shell layer.
The continuous layer is formed by introducing a resin fine particle dispersion in which vinyl resin fine particles are dispersed in an aqueous medium into a core particle dispersion in which the core particles containing an organic solvent are dispersed in an aqueous medium. obtain. That is, in the resin fine particle adhesion step described later, a resin fine particle dispersion in which the vinyl resin fine particles are dispersed in an aqueous medium is introduced into the core particle dispersion, and a shell made of the vinyl resin fine particles is formed on the surface of the core particles. When preparing the particles in which the layer is formed, the vinyl resin fine particles attached to the surface of the core particles adhere to the core particles while being dissolved or swollen by the organic solvent contained in the core particles, The core particles and the shell layer form a continuous layer. In addition, although the organic solvent is contained in the shell layer after the resin fine particle adhesion process, the organic solvent is removed from the shell layer by the solvent removal process described later.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, an external additive etc. are mentioned.

<Toner production method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but includes at least an oil phase preparation step, a dispersion preparation step, and a resin fine particle adhesion step, and further if necessary. In addition, a production method (so-called dissolution suspension method) including other steps such as a solvent removal step, an aging step, a washing step, and a drying step is preferable.

-Oil phase preparation process-
The oil phase preparation step is not particularly limited as long as it is a step of preparing an oil phase in which at least a binder resin, a colorant, and a release agent are dissolved or dispersed in an organic solvent, depending on the purpose. It can be selected appropriately.

As the oil phase preparation step, for example, the binder resin, the colorant, the release agent, and the charge control agent are gradually added to the organic solvent while stirring the organic solvent. Then, there is a method of dissolving or dispersing. When using a pigment as the colorant, or when adding an organic solvent that is difficult to dissolve in an organic solvent such as the charge control agent, the particles are made smaller prior to addition to the organic solvent. It is preferable.
Making the colorant into a masterbatch is also one suitable means, and the same method can be applied to the mold release agent and the charge control agent.

As another method, it is also possible to add a dispersion aid as necessary in the organic solvent and disperse the colorant, the release agent, the charge control agent, etc. in a wet manner to obtain a wet master. is there.
Further, as another method, if a material that melts below the boiling point of the organic solvent is dispersed, a dispersion aid is added in the organic solvent as necessary, and the mixture is heated while stirring with the dispersoid. It is possible to perform a method in which, after once dissolved, crystallization is performed by cooling while applying stirring or shearing to produce fine crystals of dispersoids.

  The colorant dispersed using the above method, the release agent, and if necessary, the charge control agent may be further dispersed after being dissolved or dispersed together with the binder resin in the organic solvent. . For the dispersion, a known disperser such as a bead mill or a disk mill can be used.

  Also, a polyester having a functional group capable of reacting with the active hydrogen group of the active hydrogen group-containing compound in the oil phase for the purpose of increasing the mechanical strength of the obtained toner or preventing high temperature offset during fixing. The toner is preferably produced in a state in which the resin is dissolved, that is, the oil phase contains a polyester resin having a functional group capable of reacting with the active hydrogen group of the active hydrogen group-containing compound.

--Organic solvent--
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, It is preferable that a boiling point is less than 100 degreeC from the point from which subsequent organic solvent removal becomes easy. Examples of such an organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, Examples include ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone.
These may be used individually by 1 type and may use 2 or more types together.
When the binder resin to be dissolved or dispersed in the organic solvent is a resin having a polyester skeleton, an ester solvent such as methyl acetate, ethyl acetate, or butyl acetate, or a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone is used. Is preferable from the viewpoint of excellent solubility. Of these, methyl acetate, ethyl acetate, and methyl ethyl ketone, which have high solvent removability, are particularly preferable.

-Dispersion preparation process-
The dispersion preparation step is not particularly limited as long as it is a step of dispersing the oil phase in an aqueous medium and preparing a core particle dispersion in which core particles made of the oil phase are dispersed in the aqueous medium. Can be appropriately selected according to the purpose.

  The dispersion method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, using a known facility such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, or an ultrasonic wave. A method of dispersing is mentioned. In order to make the particle diameter of the core particles 2 μm to 20 μm, dispersion using a high-speed shearing disperser is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is preferably 1,000 rpm to 30,000 rpm, and more preferably 5,000 rpm to 20,000 rpm. There is no restriction | limiting in particular as dispersion time, According to the objective, it can select suitably, However, In the case of a batch system, 0.1 minute-5 minutes are preferable. When the dispersion time exceeds 5 minutes, particles having an undesirably small diameter may remain, or the dispersion may be in an overdispersed state, resulting in unstable system and generation of aggregates and coarse particles. . There is no restriction | limiting in particular as temperature at the time of dispersion | distribution, Although it can select suitably according to the objective, 0 to 40 degreeC is preferable and 10 to 30 degreeC is more preferable. When the temperature at the time of dispersion is less than 0 ° C., the viscosity of the dispersion increases, and shear energy necessary for dispersion increases, so that the production efficiency may decrease. When the temperature at the time of dispersion exceeds 40 ° C., molecular motion becomes active, so that dispersion stability is lowered, and aggregates and coarse particles may be easily generated.

--- 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 mentioned.
The aqueous medium may be water alone or an organic solvent miscible with water. Examples of water-miscible organic solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. .

The aqueous medium preferably contains a surfactant.
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, and disulfonates. Agent: alkylamine salt, amino alcohol fatty acid derivative, polyamine fatty acid derivative, amine salt type such as imidazoline, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, chloride Cationic surfactants such as quaternary ammonium salts such as benzethonium; nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives; alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N Alkyl -N, such amphoteric surfactants such as N- dimethyl ammonium betaine and the like. Among these, in order to efficiently disperse oil droplets containing a solvent, a disulfonate having a high HLB is preferable.
There is no restriction | limiting in particular as content of the said surfactant, Although it can select suitably according to the objective, The density | concentration in the said aqueous medium has preferable 1 mass%-10 mass%, 2 mass%- 8 mass% is more preferable, and 3 mass%-7 mass% is especially preferable. When the concentration is less than 1% by mass, the oil droplets may not be stably dispersed and the oil droplets may become coarse,
If it exceeds 10% by mass, the oil droplets may become too small, or a reverse micelle structure may be formed, and the dispersion stability may be lowered, resulting in coarsening of the oil droplets.

-Resin fine particle adhesion process-
In the resin fine particle adhesion step, a resin fine particle dispersion in which the vinyl resin fine particles are dispersed in an aqueous medium is introduced into the core particle dispersion, and a shell made of the vinyl resin fine particles is formed on the surface of the core particles. If it is the process of preparing the particle in which the layer was formed, there will be no restriction | limiting in particular, According to the objective, it can select suitably.
There is no restriction | limiting in particular as the time of injection | throwing-in of the said resin fine particle dispersion, Although it can select suitably according to the objective, 30 seconds or more are preferable and 30 seconds-60 minutes are more preferable. If the charging time is less than 30 seconds, the dispersion system may change abruptly to cause agglomerated particles or uneven adhesion of vinyl resin fine particles. If the charging time exceeds 60 minutes, it is not preferable from the viewpoint of production efficiency.

  In the resin fine particle attaching step, the vinyl resin fine particles adhere to the core particles with sufficient strength when the vinyl resin fine particles adhere to the droplets of the core particles. The vinyl resin fine particle interface and the contact surface are sufficiently formed to be freely deformable, and the vinyl resin fine particle swells or dissolves with an organic solvent, and the vinyl resin fine particle and the resin in the core particle This is thought to be due to the situation where it is easy to bond. Therefore, it is important that the organic solvent is sufficiently present in the system in this state. Specifically, the content of the organic solvent is a solid content in the state of the core particle dispersion (the binder resin, the colorant, the release agent, and the charge control agent as necessary). 50 mass%-150 mass% is preferable with respect to 70 mass%-125 mass%. When the content exceeds 150% by mass, the amount of toner obtained in a single production process is reduced and the production efficiency is lowered, and when there is a large amount of organic solvent, the dispersion stability is lowered and stable production becomes difficult. There is.

  There is no restriction | limiting in particular as temperature when making the said vinyl resin fine particle adhere to the said core particle, Although it can select suitably according to the objective, 10 to 60 degreeC is preferable and 20 to 45 degreeC is more. preferable. If the temperature is less than 10 ° C., the viscosity of the dispersion becomes high, and adhesion of the vinyl resin fine particles may be insufficient. If the temperature exceeds 60 ° C., the energy required for production increases, so that the environmental burden on the production increases, and in addition, it does not have an acid value (that is, vinyl polymerizable functional groups and acid groups are included in the constituent components). The vinyl resin fine particles may be present on the surface of the droplets, and dispersion may become unstable and coarse particles may be generated.

--Resin fine particle dispersion--
The resin fine particle dispersion is not particularly limited as long as it is a dispersion in which the vinyl resin fine particles are dispersed in an aqueous medium, and can be appropriately selected according to the purpose.

---- 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 mentioned.
The aqueous medium may be water alone or an organic solvent miscible with water. Examples of water-miscible organic solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. .

-Solvent removal step-
The solvent removal step is not particularly limited as long as it is a step of removing the organic solvent from the particle dispersion obtained in the resin fine particle adhesion step, and can be appropriately selected according to the purpose. A method of gradually evaporating and removing the organic solvent in the droplets by gradually raising the temperature while stirring the particle dispersion, and spraying the particle dispersion in a dry atmosphere while stirring the organic solvent in the droplets Examples thereof include a method of completely removing the solvent, a method of evaporating and removing the organic solvent by reducing the pressure of the particle dispersion while stirring. The latter two means can be used in combination with the first means.
There is no restriction | limiting in particular as dry atmosphere in which the dispersion liquid of the said particle | grain is sprayed, According to the objective, it can select suitably, For example, the gas which heated air, nitrogen, a carbon dioxide gas, combustion gas etc. is mentioned.
There is no restriction | limiting in particular as temperature of the said dry atmosphere, Although it can select suitably according to the objective, Temperature more than the boiling point of the highest boiling point solvent is preferable.
The spraying is performed using, for example, a spray dryer, a belt dryer, a rotary kiln, or the like. When these are used, the target quality can be sufficiently obtained in a short time.

-Aging process-
When the oil phase contains a polyester resin having a functional group capable of reacting with the active hydrogen group of the active hydrogen group-containing compound, the polyester having a functional group capable of reacting with the active hydrogen group of the active hydrogen group-containing compound It is preferable to perform an aging step in order to advance the elongation and crosslinking reaction of the resin.
The aging step is preferably performed after the solvent removal step and before the washing step.
There is no restriction | limiting in particular as an aging time in the said aging process, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as reaction temperature in the said ripening process, Although it can select suitably according to the objective, 0 to 65 degreeC is preferable and 35 to 50 degreeC is more preferable.

-Washing process-
The washing step is not particularly limited as long as it is a step for washing the particles following the solvent removal step or following the aging step, and can be appropriately selected according to the purpose.
Since the particle dispersion obtained by the above method contains toner base particles as well as secondary materials such as a dispersant such as a surfactant, washing is performed to remove only the toner base particles from the dispersion. I do.
There is no restriction | limiting in particular as the washing | cleaning method of the said particle | grain, According to the objective, it can select suitably, For example, the centrifugation method, the reduced pressure filtration method, the filter press method etc. are mentioned. Either method can provide a cake of toner base particles. If the cake cannot be sufficiently washed by a single operation, the obtained cake is dispersed again in an aqueous medium to form a slurry, and the toner can be obtained by any of the above methods. The step of taking out the base particles may be repeated, and if cleaning is performed by a vacuum filtration method or a filter press method, an aqueous medium is passed through the cake to wash away the secondary material that the toner base particles have embraced. Also good. As the aqueous medium used for the washing, water or a mixed solvent obtained by mixing water and alcohol such as methanol or ethanol is used, but water is preferably used in consideration of cost and environmental load due to waste water treatment.

-Drying process-
The drying step is not particularly limited as long as it is a step of drying the toner base particles after the washing step, and can be appropriately selected according to the purpose.
Since the toner base particles cleaned by the cleaning step contain a large amount of water, only toner base particles can be obtained by drying and removing the water from the particles.
The method for removing moisture from the toner base particles is not particularly limited and may be appropriately selected depending on the intended purpose. For example, spray dryer, vacuum freeze dryer, vacuum dryer, stationary shelf dryer, transfer Examples include a method using a dryer such as a type shelf dryer, a fluidized tank dryer, a rotary dryer, and a stirring dryer.
It is preferable to remove the water until the water content of the toner base particles is less than 1% by mass. In addition, if the toner base particles after moisture removal are softly agglomerated and inconvenience occurs, use a device such as a jet mill, Henschel mixer, super mixer, coffee mill, auster blender, or food processor. Crushing may be performed to loosen the soft agglomeration.

(Toner container)
The toner container of the present invention is a toner container in which the toner of the present invention is accommodated.
The toner container is not particularly limited as long as it contains the toner, and can be appropriately selected according to the purpose. For example, a toner container having a toner container body and a cap can be used. preferable.
The size, shape, structure, material and the like of the toner container body are not particularly limited, and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. There are spiral irregularities 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. Particularly preferred.
The material of the toner container main body is not particularly limited and can be appropriately selected according to the purpose. However, a material having good dimensional accuracy is preferable. A resin having a good dimensional accuracy is preferable. As the resin, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacryl resin, polycarbonate resin, ABS resin, polyacetal resin, etc. are preferable. The toner container is easy to store and transport. It is excellent in handleability and can be detachably attached to a process cartridge or an image forming apparatus of the present invention, which will be described later, and used for replenishing toner.

(Developer)
The developer of the present invention contains at least the toner of the present invention and, if necessary, other components such as a carrier.
The developer may be a one-component developer or a two-component developer.

<Career>
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 a core material is preferable.

−Core material−
There is no restriction | limiting in particular as a material of the said core material, According to the objective, it can select suitably, For example, 50 emu / g-90 emu / g manganese-strontium type material, manganese-magnesium type material, etc. are mentioned. . In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. When the volume average particle diameter is more than 150 μm, the specific surface area is decreased, and the toner In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

-Resin layer-
The material of the resin layer is not particularly limited and may be appropriately selected from known resins according to the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester Resin, polycarbonate resin, polyethylene, polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, Examples include fluoroterpolymers such as copolymers of tetrafluoroethylene, vinylidene fluoride, and monomers having no fluoro group, silicone resins, and the like.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said amino-type resin, According to the objective, it can select suitably, For example, a urea-formaldehyde resin, a melamine resin, a benzoguanamine resin, a urea resin, a polyamide resin, an epoxy resin etc. are mentioned.
There is no restriction | limiting in particular as said polyvinyl-type resin, According to the objective, it can select suitably, For example, an acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc. are mentioned. .
There is no restriction | limiting in particular as said polystyrene resin, According to the objective, it can select suitably, For example, a polystyrene, a styrene-acryl copolymer, etc. are mentioned.
The polyhalogenated olefin is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include polyvinyl chloride.
There is no restriction | limiting in particular as said polyester-type resin, According to the objective, it can select suitably, For example, a polyethylene terephthalate, a polybutylene terephthalate, etc. are mentioned.

  The resin layer may contain conductive powder or the like as necessary. There is no restriction | limiting in particular as said electrically conductive powder, According to the objective, it can select suitably, For example, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide, etc. are mentioned. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.

The resin layer is formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then coating and drying the coating solution on the surface of the core using a known coating method, followed by baking. Can do.
There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, a dip coating method, a spray method, a brush coating method etc. can be used.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and butyl cellosolve.
The baking may be an external heating method or an internal heating method. For example, a method using a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, The method to use etc. are mentioned.

  There is no restriction | limiting in particular as content of the resin layer in the said carrier, Although it can select suitably according to the objective, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer is thick and the carrier Fusion may occur between them, and the uniformity of the carrier may decrease.

(Developer)
The developing device of the present invention includes at least a developer carrying member, a developer supply unit, and a developer storage unit, and further includes other units as necessary.

<Developer carrier>
The developer carrier is not particularly limited as long as it is a carrier that supports the developer supplied to the image carrier on the surface, and can be appropriately selected according to the purpose. Examples thereof include a developing roller. .

<Developer supply means>
The developer supply means is not particularly limited as long as it is a means for supplying the developer to the surface of the developer carrying member, and can be appropriately selected according to the purpose. Examples thereof include a supply roller.

<Developer storage means>
The developer storage means is not particularly limited as long as it is a means for storing a developer, and can be appropriately selected according to the purpose.
The developer of the present invention is accommodated in the developer accommodating means.

An example of the configuration of the developing device will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing the configuration of the developing device of the present invention.
The developing device (4) includes a developing roller (4a) as a developer carrier, a supply roller (4b) as a developer supply means, a regulating blade (4c) as a developer layer regulating means, and a developer containing means. (4d). The developer in the container (4d) as the developer storage means is agitated by the supply roller (4b) as the developer supply means, and the developer carrier that supports the developer supplied to the image carrier on the surface. As a developing roller (4a). At this time, the supply roller (4b) and the developing roller (4a) are rotated in the reverse direction (counter rotation) at the nip portion. Further, the amount of developer on the developing roller (4a) is regulated by a regulating blade (4c) as a developer layer regulating means provided so as to be in contact with the developing roller (4a), and the developing on the developing roller (4a) is developed. A thin agent layer is formed. Further, the developer is rubbed between the supply roller (4b) and the nip portion of the developing roller (4a), the regulating blade (4c), and the developing roller (4a), and is controlled to an appropriate charge amount.

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

  The image forming method according to 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.

<Image carrier>
The image carrier (sometimes referred to as “photosensitive member” or “latent image carrier”) is not particularly limited in terms of material, shape, structure, size, and the like, and may be appropriately selected from known ones. However, the shape is preferably a drum shape, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine.

  Examples of the image carrier (photoreceptor) include a conductive support and an image carrier having at least a photosensitive layer on the conductive support, and further having other layers as necessary. .

  As the photosensitive layer, a single layer type in which a charge generation material and a charge transport material are mixed, a forward layer type in which a charge transport layer is provided on the charge generation layer, or a charge generation layer is provided on the charge transport layer. There is a reverse layer type. In order to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, etc. of the photoreceptor, an outermost surface layer can be provided on the photosensitive layer. An undercoat layer may be provided between the photosensitive layer and the conductive support. Moreover, an appropriate amount of a plasticizer, an antioxidant, a leveling agent or the like can be added to each layer as necessary.

The conductive support is not particularly limited as long as it has a volume resistance of 1.0 × 10 ¹⁰ Ω · cm or less, and can be appropriately selected according to the purpose. Metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, and metal oxides such as tin oxide and indium oxide coated with film or cylindrical plastic or paper by vapor deposition or sputtering, Alternatively, a plate made of aluminum, aluminum alloy, nickel, stainless steel or the like, and a tube subjected to surface treatment such as cutting, super-finishing, polishing, etc. after forming them into a drum shape by a method such as extrusion or drawing can be used. .
The drum-shaped support preferably has a diameter of 20 mm to 150 mm, more preferably 24 mm to 100 mm, and still more preferably 28 mm to 70 mm. When the diameter of the drum-shaped support is less than 20 mm, it may be physically difficult to arrange each step of charging, exposure, development, transfer, and cleaning around the drum. When the diameter exceeds 150 mm, The image forming apparatus may become large. In particular, when the image forming apparatus is a tandem type, since it is necessary to mount a plurality of photoconductors, the diameter is preferably 70 mm or less, and more preferably 60 mm or less. Further, an endless nickel belt or an endless stainless steel belt as disclosed in JP-A-52-36016 can also be used as the conductive support.

The undercoat layer of the photoconductor may be composed of a single layer or a plurality of layers. For example, (1) the resin is the main component, and (2) the white pigment and the resin are the main components. (3) A metal oxide film obtained by chemically or electrochemically oxidizing the surface of a conductive substrate. Among these, those containing a white pigment and a resin as main components are preferable.
Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide. Among these, titanium oxide is particularly excellent in preventing charge injection from a conductive support. preferable.
Examples of the resin include thermoplastic resins such as polyamide, polyvinyl alcohol, casein, and methyl cellulose; thermosetting resins such as acrylic, phenol, melamine, alkyd, unsaturated polyester, and epoxy. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular in the thickness of the said undercoat layer, According to the objective, it can select suitably, 0.1 micrometer-10 micrometers are preferable, and 1 micrometer-5 micrometers are more preferable.

  Examples of the charge generation material in the photosensitive layer include monoazo pigments, bisazo pigments, trisazo pigments, tetrakisazo pigments and other azo pigments, triarylmethane dyes, thiazine dyes, oxazine dyes, xanthene dyes, Cyanine dyes, styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indanthrone pigments, squarylium pigments, phthalocyanine pigments, etc. Organic pigments or dyes; selenium, selenium-arsenic, selenium-tellurium, cadmium sulfide, zinc oxide, titanium oxide, amorphous silicon, and other inorganic materials. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the charge transport material in the photosensitive layer include anthracene derivatives, pyrene derivatives, carbazole derivatives, tetrazole derivatives, metallocene derivatives, phenothiazine derivatives, pyrazoline compounds, hydrazone compounds, styryl compounds, styryl hydrazone compounds, enamine compounds, butadiene compounds, distyryl. Examples thereof include compounds, oxazole compounds, oxadiazole compounds, thiazole compounds, imidazole compounds, triphenylamine derivatives, phenylenediamine derivatives, aminostilbene derivatives, and triphenylmethane derivatives. These may be used individually by 1 type and may use 2 or more types together.

  As the binder resin used to form the photosensitive layer, it is electrically insulating and may be a known thermoplastic resin, thermosetting resin, photocurable resin, photoconductive resin, or the like. it can. Examples of the binder resin include polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, ethylene-vinyl acetate copolymer, polyvinyl butyral, Polyvinyl acetal, polyester, phenoxy resin, (meth) acrylic resin, polystyrene, polycarbonate, polyarylate, polysulfone, polyethersulfone, ABS resin and other thermoplastic resins, phenol resin, epoxy resin, urethane resin, melamine resin, isocyanate Examples thereof include thermosetting resins such as resins, alkyd resins, silicone resins, and thermosetting acrylic resins, polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene. These may be used individually by 1 type and may use 2 or more types together.

  The outermost surface layer of the photoreceptor is provided to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, and the like of the photoreceptor. As the outermost surface layer, a polymer having a mechanical strength higher than that of the photosensitive layer and a material in which an inorganic filler is dispersed in the polymer are suitable. The resin used for the outermost surface layer may be either a thermoplastic resin or a thermosetting resin, but the thermosetting resin has high mechanical strength and suppresses wear due to friction with the cleaning blade. This is particularly preferable because of its extremely high capacity. If the surface layer is thin, there is no problem even if it does not have the charge transport capability, but if the surface layer without the charge transport capability is formed thick, the sensitivity of the photoreceptor decreases, the potential increases after exposure, and the residual layer Since the potential rise is likely to occur, it is preferable to include the above-described charge transport material in the surface layer or to use a polymer having charge transport ability as the polymer used in the surface layer.

  Since the mechanical strength of the photosensitive layer and the outermost surface layer is generally greatly different, the outermost surface layer is worn away due to friction with the cleaning blade, and when the outermost layer disappears, the photosensitive layer is worn away immediately. It is important that the outermost surface layer has a sufficient thickness, preferably 0.1 μm to 12 μm, more preferably 1 μm to 10 μm, and particularly preferably 2 μm to 8 μm. When the thickness is less than 0.1 μm, it is too thin and is likely to be partially lost due to friction with the cleaning blade, and wear of the photosensitive layer may proceed from the lost portion. Decrease in sensitivity, increase in potential after exposure, and increase in residual potential are likely to occur. Particularly when a polymer having charge transport ability is used, the cost of the polymer having charge transport ability may be increased.

  The resin used for the outermost surface layer is preferably one that is transparent to writing light at the time of image formation and excellent in insulation, mechanical strength, and adhesion. For example, ABS resin, ACS resin, olefin-vinyl monomer Copolymer, chlorinated polyether, acrylic resin, allyl resin, phenol resin, polyacetal, polyimide, polyamide, polyamideimide, polyallylsulfone, polyethylene, polypropylene, polybutylene, butadiene-styrene copolymer, polyethylene terephthalate, polybutylene terephthalate , Polycarbonate, polyethersulfone, polymethylbentene, polyphenylene oxide, polysulfone, polystyrene, AS resin, polyurethane, polyvinyl chloride, polyvinylidene chloride, epoxy resin and the like. These polymers may be thermoplastic resins, but in order to increase the mechanical strength of the polymers, they are crosslinked with a crosslinking agent having a polyfunctional acryloyl group, carboxyl group, hydroxyl group, amino group, etc. By using a functional resin, the mechanical strength of the outermost surface layer is increased, and wear due to friction with the cleaning blade can be greatly reduced.

  The outermost surface layer preferably has a charge transporting capability. In order to provide the outermost surface layer with a charge transporting capability, the polymer used for the outermost surface layer and the above-described charge transporting material are mixed and used. A method using a polymer having a charge transporting capability for the outermost surface layer is conceivable, and the latter method is preferable because a high-sensitivity photoconductor and a small increase in residual potential can be obtained.

  The outermost surface layer preferably contains metal fine particles, metal oxide fine particles, and other fine particles in order to increase the mechanical strength of the outermost surface layer. Examples of the metal oxide include titanium oxide, tin oxide, potassium titanate, titanium nitride, zinc oxide, indium oxide, and antimony oxide. Examples of the other fine particles include fluorine resins such as polytetrafluoroethylene, silicone resins, or those obtained by dispersing inorganic materials in these resins for the purpose of improving wear resistance.

<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 image carrier.
The formation of the electrostatic latent image can be performed, for example, by charging the surface of the image carrier and then performing imagewise exposure, and can be performed by the electrostatic latent image forming unit. The electrostatic latent image forming unit includes, for example, at least a charger for charging the surface of the image carrier and an exposure unit for exposing the surface of the image carrier imagewise.

The charging can be performed, for example, by applying a voltage to the surface of the 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, corotrons and scorotrons.
The charger preferably has voltage applying means for applying a voltage having an AC component.

The exposure can be performed, for example, by exposing the surface of the image carrier imagewise using the exposure device.
The exposure device is not particularly limited as long as it can perform image-like exposure on the surface of the image carrier charged by the charger, and can be appropriately selected according to the purpose. Examples of the exposure apparatus include a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
In the present invention, an optical back side system in which imagewise exposure is performed from the back side of the image carrier may be adopted.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using a developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the developer, and can be performed by the developing unit.
The developing means is the developing device 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 image carrier (photosensitive member) with the transfer charger using the visible image, 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 image carrier is an intermediate transfer member used for image formation by a so-called intermediate transfer method in which a toner image formed on a photosensitive member is primarily transferred to perform color superposition and further transferred to a recording medium. It may be.

-Intermediate transfer member-
As the intermediate transfer member, a material having a volume resistance value of 1.0 × 10 ^{5 to} 1.0 × 10 ¹¹ Ω · cm is preferable. When the volume resistance value is less than 1.0 × 10 ⁵ Ω · cm, so-called transfer dust is generated in which the toner image is disturbed due to discharge when the toner image is transferred from the photosensitive member onto the intermediate transfer member. If it exceeds 1.0 × 10 ¹¹ Ω · cm, the counter charge of the toner image remains on the intermediate transfer member after the toner image is transferred from the intermediate transfer member to a recording medium such as paper. It may appear as an afterimage on the image.

As the intermediate transfer member, for example, a metal oxide such as tin oxide or indium oxide, a conductive particle such as carbon black, or a conductive polymer, alone or in combination, kneaded with a thermoplastic resin, and then an extrusion molded belt A cylindrical or cylindrical plastic can be used. In addition to this, the above-mentioned conductive particles and conductive polymer are added to a resin solution containing a thermally crosslinkable monomer or oligomer, if necessary, and subjected to centrifugal molding while heating to obtain an intermediate transfer member on an endless belt. You can also.
When the surface layer is provided on the intermediate transfer member, among the surface layer materials used for the surface layer of the photoreceptor described above, the composition excluding the charge transport material is appropriately adjusted in combination with a conductive substance, Can be used.

The transfer means (the primary transfer means and the secondary transfer means) includes at least a transfer device that peels and charges the visible image formed on the image carrier (photoconductor) to the recording medium side. It is preferable to have. 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 carried out 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 pressing 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.

<Static elimination process and static elimination means>
The neutralization step is a step of performing neutralization by applying a neutralization bias to the 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 image carrier. For example, a neutralization lamp or the like is preferable. It is done.

<Cleaning process and cleaning means>
The cleaning step is a step of removing the electrophotographic toner remaining on the image carrier and can be suitably performed by a cleaning unit.
The cleaning unit is preferably provided downstream of the transfer unit and upstream of the protective layer forming unit.
The cleaning means is not particularly limited, and may be selected from known cleaners as long as the electrophotographic toner remaining on the image carrier can be removed. For example, a magnetic brush cleaner, Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

<Recycling process and recycling means>
The recycling step is a step of recycling the toner removed by 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.

<Control process and control means>
The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
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 sequencers and computers.

FIG. 2 shows an example of the image forming apparatus of the present invention. In this image forming apparatus, a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 2 is housed in a main body housing (not shown), and around the latent image carrier (1). In addition, a charging device (2), an exposure device (3), a developing device (4) having the developer (T) of the present invention, a cleaning unit (5), an intermediate transfer member (6), a support roller (7), a transfer device. A roller (8), a developing roller (40), a thin layer forming member (41), a supply roller (42), a charge removing means (not shown) and the like are provided.
The image forming apparatus includes a paper feed cassette (not shown) that stores a plurality of recording papers (P) as an example of a recording medium, and the recording paper (P) in the paper feed cassette is a paper feed (not shown). After the timing is adjusted by a pair of registration rollers (not shown) one by one by a roller, the sheet is fed between a transfer roller (8) as a transfer means and an intermediate transfer body (6).
In this image forming apparatus, the latent image carrier (1) is rotated clockwise in FIG. 2 to uniformly charge the latent image carrier (1) with the charging device (2), and then the exposure device ( 3) to irradiate the laser modulated with the image data to form an electrostatic latent image on the latent image carrier (1), and to the developing device (4) on the latent image carrier (1) on which the electrostatic latent image is formed. ) To attach toner and develop. Next, a transfer bias is applied from the latent image carrier (1) on which the toner image is formed by the developing device (4) to the intermediate transfer member (6) to transfer the toner image onto the intermediate transfer member (6). By transferring the recording paper (P) between the intermediate transfer body (6) and the transfer roller (8), the toner image is transferred to the recording paper (P). Further, the recording paper (P) on which the toner image is transferred is conveyed to a fixing means (not shown).
The fixing unit includes a fixing roller heated to a predetermined fixing temperature by a built-in heater and a pressure roller pressed against the fixing roller with a predetermined pressure, and heats the recording paper conveyed from the transfer roller (8). After pressurizing and fixing the toner image on the recording paper on the recording paper, it is discharged onto a paper discharge tray (not shown).
On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred onto the recording paper by the transfer roller (8), and the cleaning unit (5) applies the surface to the surface of the latent image carrier (1). After the remaining toner is scraped off and removed, the charge is removed by a charge removal device (not shown). The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the static eliminator with the charging device (2), and then performs the next image formation in the same manner as described above.

  FIG. 3 is a schematic sectional view showing an example of a fixing device used in the image forming method according to the present invention. The fixing device may be a soft roller type fixing device having a fluorine surface layer composition as shown in FIG. This is because the heating roller (9) has an elastic body layer (11) made of silicone rubber and a PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) surface layer (12) on an aluminum core bar (10). The heater (13) is provided inside the aluminum cored bar. The pressure roller (14) has an elastic layer (16) made of silicone rubber and a PFA surface layer (17) on an aluminum cored bar (15). The recording paper (P) on which the unfixed image (18) is printed is passed as shown.

FIG. 4 is a schematic view showing an example of a multicolor image forming apparatus to which the image forming apparatus of the present invention is applied. FIG. 4 shows a tandem type full-color image forming apparatus.
In FIG. 4, the image forming apparatus stores a latent image carrier (1) that is driven to rotate in the clockwise direction in FIG. 4 in a main body housing (not shown), and around the latent image carrier (1). , Charging device (2), exposure device (3), developing device (4), cleaning unit (5), intermediate transfer member (6), support roller (7), transfer roller (8), heating roller (9), A pressure roller (14) and the like are arranged. Although not shown, the image forming apparatus includes a paper feeding cassette that stores a plurality of recording papers. The recording paper (P) in the paper feeding cassette is fed to a pair of registration rollers (not shown) one by one by a paper feeding roller (not shown). After the timing adjustment, the sheet is fed between the intermediate transfer member (6) and the transfer roller (8) and fixed by the fixing means (19).

  The full-color image forming apparatus rotates the latent image carrier (1) clockwise in FIG. 4 to uniformly charge the latent image carrier (1) with the charging device (2), and then exposes the exposure device (3). ) Is irradiated with a laser modulated with image data to form an electrostatic latent image on the latent image carrier (1), and a developing device (4) is formed on the latent image carrier (1) on which the electrostatic latent image is formed. Develop with toner attached. The full-color image forming apparatus transfers the toner image formed by attaching the toner to the latent image carrier with the developing device (4) from the latent image carrier (1) to the intermediate transfer member. This is performed for each of the four colors of cyan (C), magenta (M), yellow (Y), and black (K) to form a full-color toner image.

  FIG. 5 is a schematic view showing an example of a revolver type full-color image forming apparatus to which the image forming apparatus of the present invention is applied. In this image forming apparatus, a charging device (2), an exposure device (3), a developing device (4C, 4M, 4Y, 4K), a cleaning unit (5), and the like are arranged around the latent image carrier (1). In this case, the toners of a plurality of colors are successively developed on one latent image carrier (1) by switching the operation of the developing device. The color toner image on the intermediate transfer body (6) is transferred to the recording paper (P) by the transfer roller (8) supported by the support roller (7), and the recording paper (P) to which the toner image is transferred is transferred. The image is conveyed to a fixing unit to obtain a fixed image.

  On the other hand, the image forming apparatus further rotates the latent image carrier (1) on which the toner image is transferred to the recording paper (P) by the intermediate transfer member (6), and the latent image carrier (1) by the cleaning unit (5). ) The toner remaining on the surface is removed by scraping with a blade, and then the charge is removed by the charge removing unit. The image forming apparatus uniformly charges the latent image carrier (1) neutralized by the neutralization unit with the charging device (2), and then performs the next image formation as described above. The cleaning unit (5) is not limited to scraping off the residual toner on the latent image carrier (1) with a blade. For example, the cleaning unit (5) scrapes off the residual toner on the latent image carrier (1) with a fur brush. It may be a thing.

(Process cartridge)
The process cartridge of the present invention includes at least the image carrier and the developing device of the present invention, and further includes other means such as a charging unit, an exposure unit, a transfer unit, a cleaning unit, and a charge eliminating unit as necessary. .
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 above.

  For example, as shown in FIG. 6, the process cartridge includes a latent image carrier (1), and includes a charging device (2), a developing device (4), a transfer roller (8), and a cleaning unit (5). In addition, other means are provided as necessary. In FIG. 6, (L) shows exposure from the exposure apparatus, and (P) shows recording paper. As the latent image carrier (1), the same one as the image forming apparatus can be used. An arbitrary charging member is used for the charging device (2).

  Next, the image forming process using the process cartridge shown in the drawing will be described. The latent image carrier (1) is charged by the charging device (2) while being rotated in the direction of the arrow, and exposure by an exposure means (not shown) (not shown). L), an electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed with toner by the developing device (4), and the toner development is transferred onto the recording paper (P) by the transfer roller (8) and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by the cleaning unit (5), further neutralized by a neutralizing unit (not shown), and the above operation is repeated again.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited by these Examples.
Hereinafter, “parts” and “%” indicate parts by mass and mass% unless otherwise specified.
In the following, the case where the toner of the present invention is used as a one-component developer was evaluated. However, the toner of the present invention can be used as a two-component developer by using a suitable external treatment and a suitable carrier. Can be used.

  First, a method for measuring physical properties used in Examples and Comparative Examples will be described.

<Measurement of volume average particle diameter of vinyl resin fine particles>
The volume average particle diameter of the vinyl resin fine particles was measured using UPA-150EX (manufactured by Nikkiso Co., Ltd.).
The measurement parameters are as follows.
-Particle permeability: transmission-Particle refractive index: 1.59
・ Particle shape: Spherical shape ・ Solvent type: WATER
Monodispersion: Invalid Under these conditions, the sample concentration was adjusted so that the loading index was in the range of 1 to 1.5.

<Molecular weight measurement (GPC)>
The molecular weight of the resin was measured by GPC (gel permeation chromatography) under the following conditions.
・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min Sample: 0.1 mL of a sample having a concentration of 0.05% to 0.6% was injected.
The number average molecular weight and the weight average molecular weight of the resin were calculated from the molecular weight distribution of the resin measured under the above conditions using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample. Standard polystyrene samples for preparing calibration curves include Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580 were used. An RI (refractive index) detector was used as the detector.

<Glass transition temperature (Tg) measurement (DSC)>
As an apparatus for measuring Tg, a TG-DSC system TAS-100 manufactured by Rigaku Corporation was used. First, about 5 mg of a sample was placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. And after heating from room temperature to 150 degreeC with the temperature increase rate of 10 degree-C / min, after leaving to stand at 150 degreeC for 10 minutes, the sample was cooled to room temperature and left to stand for 10 minutes. Subsequently, it was heated again to 150 ° C. at a heating rate of 10 ° C./min in a nitrogen atmosphere. The amount of heat during this heating was measured to determine Tg. Tg was calculated from the tangent of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.

(Production Example 1)
<Manufacture of dispersion of vinyl resin fine particles 1>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 190 parts of styrene monomer, 10 parts of methoxydiethylene glycol methacrylate, and 2 parts of n-octanethiol was added. The solution was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 1] having a volume average particle diameter of 110 nm.

(Production Example 2)
<Manufacture of dispersion liquid of vinyl resin fine particles 2>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 170 parts of styrene monomer, 30 parts of methoxydiethylene glycol methacrylate, and 1.4 parts of n-octanethiol were mixed. The liquid was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for an additional 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 2] having a volume average particle diameter of 108 nm.

(Production Example 3)
<Manufacture of dispersion liquid of vinyl resin fine particles 3>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 170 parts of styrene monomer, 30 parts of methoxydiethylene glycol methacrylate, and 2.0 parts of n-octanethiol were mixed. The liquid was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for an additional 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 3] having a volume average particle diameter of 100 nm.

(Production Example 4)
<Manufacture of dispersion of vinyl resin fine particles 4>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 160 parts of styrene monomer, 40 parts of methoxydiethylene glycol methacrylate, and 1.4 parts of n-octanethiol. The liquid was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for an additional 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersed liquid of vinyl resin fine particles 4] having a volume average particle diameter of 101 nm.

(Production Example 5)
<Manufacture of dispersion liquid of vinyl resin fine particles 5>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 190 parts of styrene monomer, 10 parts of n-butyl acrylate, and 2.0 parts of n-octanethiol The body mixture was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 5] having a volume average particle diameter of 101 nm.

(Production Example 6)
<Manufacture of dispersion liquid of vinyl resin fine particles 6>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution of 2.6 parts of potassium sulfate dissolved in 104 parts of ion-exchanged water was added, and 15 minutes later, 170 parts of styrene monomer, 30 parts of n-butyl acrylate, and 1.4 parts of n-octanethiol The body mixture was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 6] having a volume average particle diameter of 110 nm.

(Production Example 7)
<Manufacture of dispersion liquid of vinyl resin fine particles 7>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution of 2.6 parts of potassium sulfate dissolved in 104 parts of ion-exchanged water was added, and 15 minutes later, 170 parts of styrene monomer, 30 parts of n-butyl acrylate, and 2.0 parts of n-octanethiol The body mixture was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 7] having a volume average particle diameter of 107 nm.

(Production Example 8)
<Manufacture of dispersion of vinyl resin fine particles 8>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution of 2.6 parts of potassium sulfate dissolved in 104 parts of ion-exchanged water was added, and 15 minutes later, 160 parts of styrene monomer, 40 parts of n-butyl acrylate, and 1.4 parts of n-octanethiol The body mixture was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 8] having a volume average particle diameter of 108 nm.

(Production Example 9)
<Manufacture of dispersion of vinyl resin fine particles 9>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 170 parts of styrene monomer, 30 parts of methyl methacrylate, and 1.4 parts of n-octanethiol were mixed. The liquid was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for an additional 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersed liquid of vinyl resin fine particles 9] having a volume average particle diameter of 110 nm.

(Production Example 10)
<Manufacture of dispersion of vinyl resin fine particles 10>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution obtained by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 170 parts of styrene monomer, 30 parts of methyl methacrylate, and 2.0 parts of n-octanethiol were mixed. The liquid was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for an additional 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 10] having a volume average particle diameter of 109 nm.

(Production Example 11)
<Manufacture of dispersion liquid of vinyl resin fine particles 11>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution of 2.6 parts of potassium sulfate dissolved in 104 parts of ion-exchanged water is added, and 15 minutes later, 160 parts of styrene monomer, 40 parts of n-butyl acrylate, and 4.2 parts of n-octanethiol The body mixture was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction. Then, it cooled and the white [dispersion liquid of the vinyl resin fine particle 11] with a volume average particle diameter of 111 nm was obtained.

(Production Example 12)
<Production of dispersion liquid of vinyl resin fine particles 12>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 150 parts of styrene monomer, 30 parts of n-butyl acrylate, 20 parts of methyl methacrylate, and n-octanethiol 1 4 parts of the monomer mixture was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for an additional 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 12] having a volume average particle diameter of 111 nm.

(Production Example 13)
<Manufacture of dispersion liquid of vinyl resin fine particles 13>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 195 parts of styrene monomer, 5 parts of methyl methacrylate, and 4.2 parts of n-octanethiol were mixed. The liquid was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for an additional 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 13] having a volume average particle diameter of 110 nm.

(Production Example 14)
<Manufacture of dispersion liquid of vinyl resin fine particles 14>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 1.4 parts of n-octanethiol was added over 90 minutes. The solution was added dropwise, and then kept at 80 ° C. for another 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 14] having a volume average particle diameter of 104 nm.

(Production Example 15)
<Manufacture of dispersion liquid of vinyl resin fine particles 15>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 4.2 parts of n-octanethiol was added over 90 minutes. The solution was added dropwise, and then kept at 80 ° C. for another 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersion of vinyl resin fine particles 15] having a volume average particle diameter of 107 nm.

(Production Example 16)
<Manufacture of dispersion of vinyl resin fine particles 16>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution prepared by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, a monomer mixture of 200 parts of styrene monomer and 12.6 parts of n-octanethiol was added over 90 minutes. The solution was added dropwise, and then kept at 80 ° C. for another 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersed liquid of vinyl resin fine particles 16] having a volume average particle diameter of 110 nm.

(Production Example 17)
<Manufacture of dispersion of vinyl resin fine particles 17>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution obtained by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 152 parts of styrene monomer, 38 parts of n-butyl acrylate, 10 parts of methacrylic acid, and n-octanethiol. 2 parts of the monomer mixture was added dropwise over 90 minutes, and then kept at 80 ° C. for 60 minutes to cause a polymerization reaction. Thereafter, the mixture was cooled to obtain white [dispersed liquid of vinyl resin fine particles 17] having a volume average particle diameter of 110 nm.

(Production Example 18)
<Production of dispersion of vinyl resin fine particles 18>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution obtained by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 124 parts of styrene monomer, 74 parts of n-butyl acrylate, 2 parts of methacrylic acid, and n-octanethiol. 0 part of the monomer mixture was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for a further 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersed liquid of vinyl resin fine particles 18] having a volume average particle diameter of 110 nm.

(Production Example 19)
<Manufacture of dispersion liquid of vinyl resin fine particles 19>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 0.7 part of sodium dodecyl sulfate and 498 parts of ion-exchanged water are heated and dissolved at 80 ° C. with stirring. A solution obtained by dissolving 2.6 parts of potassium sulfate in 104 parts of ion-exchanged water was added, and 15 minutes later, 168 parts of styrene monomer, 30 parts of n-butyl acrylate, 2 parts of acrylic acid, and n-octanethiol. 0 part of the monomer mixture was added dropwise over 90 minutes, and then the polymerization reaction was continued at 80 ° C. for a further 60 minutes. Thereafter, the mixture was cooled to obtain white [dispersed liquid of vinyl resin fine particles 19] having a volume average particle diameter of 110 nm.

  Table 1 shows the monomer composition, molecular weight, and Tg of the vinyl resin fine particles in the dispersion of the vinyl resin fine particles 1 to 19 obtained above.

(Production Example 20)
<Synthesis of Amorphous Polyester Resin 1>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2-mole adduct, 400 parts of bisphenol A propylene oxide 2-mole adduct, 208 parts of terephthalic acid, 46 parts of adipic acid, And 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 mmHg to 18 mmHg for 7 hours, 20 parts of trimellitic anhydride is added to the reaction vessel, and the reaction is performed at 180 ° C under normal pressure until the softening point becomes 110 ° C. [Amorphous polyester resin 1] was synthesized. The obtained [Amorphous polyester resin 1] had a glass transition temperature of 63 ° C.

(Production Example 21)
<Synthesis of prepolymer>
682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, trimellitic anhydride 22 parts and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. under normal pressure for 8 hours. Next, the reaction was performed at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 49 mgKOH / g.
Next, 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer 1] was obtained.

(Production Example 22)
<Synthesis of Crystalline Polyester Resin 1>
146 parts of adipic acid, 175 parts of 1,10-decanediol, and 0.12 part of dibutyltin oxide were stirred at 180 ° C. for 6 hours in a nitrogen atmosphere. The mixture was then stirred for 4 hours while reducing the pressure to obtain [Crystalline Polyester Resin 1] having a weight average molecular weight of 16,700 and a number average molecular weight of 6,500.
Further, when the melting point of [Crystalline Polyester Resin 1] was measured using a differential scanning calorimeter (DSC), it had a clear peak and the peak top temperature was 69 ° C.

(Production Example 23)
<Synthesis of crystalline polyester resin 2>
Into a 5-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple, 2,300 g of 1,10-decanedioic acid, 2,530 g of 1,8-octanediol, and 4.9 g of hydroquinone The mixture was reacted at 180 ° C. for 10 hours, heated to 200 ° C., reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain a weight average molecular weight of 12,000, [Crystalline polyester resin 2] was obtained.
Further, when the melting point of [Crystalline Polyester Resin 2] was measured using a differential scanning calorimeter (DSC), it had a clear peak and the peak top temperature was 80 ° C.

(Production Example 23)
<Manufacture of master batch 1>
40 parts of PB15-3 (copper phthalocyanine, manufactured by DIC), 60 parts of [amorphous polyester resin 1], and 30 parts of water were mixed in a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. . This was kneaded for 45 minutes with two rolls set at a roll surface temperature of 130 ° C. and pulverized to a size of 1 mm with a pulverizer to obtain [Masterbatch 1].

Example 1
<Production of toner>
-Aqueous phase preparation process-
970 parts of ion-exchange water, 40 parts of a 25 wt% aqueous dispersion of organic resin fine particles (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt copolymer) for dispersion stabilization, dodecyl diphenyl ether When 95 parts of a 48.5% aqueous solution of sodium disulfonate and 98 parts of ethyl acetate were mixed and stirred, the pH reached 6.2. A 10% aqueous sodium hydroxide solution was added dropwise thereto to adjust the pH to 9.5 to obtain [Aqueous Phase 1].

-WAX dispersion preparation process-
In a container equipped with a stir bar and a thermometer, 20 parts of [Amorphous polyester resin 1], 12 parts of paraffin wax (melting point: 72 ° C.), 100 parts of ethyl acetate, and styrene-polyethylene polymer (Tg) as a wax dispersant. = 72 ° C., number average molecular weight 7,100) 6 parts, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, cooled to 30 ° C. in 1 hour, bead mill (ultra visco mill, Using a product of Imex Co., Ltd.), WAX dispersion was carried out under the conditions of 3 passes with a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and a 0.5 mm zirconia bead filled with 3 vol. ]

-Oil phase preparation process-
100 parts of [Amorphous Polyester Resin 1], 7 parts of [Crystalline Polyester Resin 1], 12 parts of [Masterbatch 1], 33 parts of [WAX Dispersion 1], and 80 parts of ethyl acetate were mixed with a TK homomixer (special machine After mixing at 8,000 rpm for 30 minutes, 15 parts of [Prepolymer 1] was added and mixed with TK homomixer at 8,000 rpm for 2 minutes to obtain [Oil Phase 1]. It was 58 weight% when solid content of the obtained [oil phase 1] was measured.

-Dispersion preparation process-
100 parts of [Oil Phase 1] is added to 100 parts of [Water Phase 1], and the temperature in the liquid is in the range of 20 ° C. to 23 ° C. by cooling in a water bath in order to suppress temperature rise due to shear heat of the mixer. , Adjusted at a rotation speed of 8,000 rpm to 15,000 rpm using a TK homomixer and mixed for 2 minutes. The mixture was stirred to obtain [core particle slurry 1] in which droplets of an oil phase serving as core particles were dispersed in an aqueous phase.

-Resin fine particle adhesion process-
[Vinyl resin fine particles 1] 0.37 parts at a liquid temperature of 22 ° C. while stirring [core particle slurry 1] with a three-one motor with an anchor blade attached at a rotational speed of 130 rpm to 350 rpm. And [resin fine particle dispersion 1] mixed with 1.09 parts of ion-exchanged water were added dropwise over 3 minutes. The rotation speed was adjusted between 200 rpm and 450 rpm, and stirring was continued for 30 minutes to obtain [Composite Particle Slurry 1].

-Solvent removal process-
[Composite particle slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours while stirring to obtain [Dispersion slurry 1].

-Cleaning and drying process-
[Dispersion Slurry 1] After filtering 100 parts under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 900 parts of ion-exchanged water was added to the filter cake of (1), ultrasonic vibration was applied, and the mixture was mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure. This operation was repeated so that the electric conductivity of the reslurry liquid was 10 μC / cm or less.
(3): 10% hydrochloric acid was added so that the reslurry solution of (2) had a pH of 4, and the mixture was directly filtered with a three-one motor for 30 minutes.
(4): 100 parts of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. This operation was repeated so that the reslurry liquid had an electric conductivity of 10 μC / cm or less to obtain [Filter Cake 1].
[Filtration cake 1] was dried at 45 ° C. for 48 hours in a circulating drier, and sieved with a mesh of 75 μm to obtain [Toner 1].
A sectional photograph of the obtained toner is shown in FIG. From the cross-sectional photograph of FIG. 7, it can be confirmed that there is no gap at the boundary between the core particle 100 and the shell layer 101, that is, a continuous layer is formed.

<Evaluation>
It used for the following evaluation. The results are shown in Table 2.
-Supernatant transparency-
1.6 g of [composite particle slurry] 10 minutes after addition of the resin fine particle dispersion in the resin fine particle adhering step is placed in a centrifuge tube containing 11 g of pure water, and the number of revolutions is measured with a centrifuge (CN-1040, manufactured by HSIANGTAI). It was rotated at 3,000 rpm for 5 minutes, and the transparency of the supernatant was evaluated.
Evaluation was made according to the following criteria for the transparency of the supernatant.
〔Evaluation criteria〕
◎: Transparent with no cloudiness ○: Slightly cloudy but almost transparent △: Cloudy and translucent ×: White and cloudy and opaque

-Chargeability (background stain)-
The toner was put in a Bk cartridge of IPSiO SP C220 (manufactured by Ricoh Co., Ltd.), the white paper when the white paper was printed out, and the photoreceptor were visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
A: No toner adheres to the white paper or the photoreceptor.
○: No toner adhesion is observed on the white paper, but a slight toner adhesion is observed when the photoreceptor is observed obliquely.
Δ: When the white paper is observed obliquely, the toner is slightly attached.
X: Adherence of toner is clearly observed on white paper.

-Fixability-
A toner was put into a modified IPSiO SP C220 (manufactured by Ricoh Co., Ltd.), and an unfixed solid image of 50 mm square was printed on the Ricoh Co., Ltd. type 6200Y eye paper with an adhesion amount of 10 g / m ² . 19 items were prepared.
Next, using the modified fixing unit, the system speed was set to 280 mm / sec, and the prepared unfixed solid image was passed through to fix the image. The test was performed by changing the fixing temperature from 120 ° C. to 200 ° C. in increments of 5 ° C. The fixed image was folded inward, spread again, and then rubbed lightly with an eraser. The lowest temperature at which the crease did not disappear was defined as the minimum fixing temperature, and evaluated according to the following criteria.
〔Evaluation criteria〕
: Fixing lower limit temperature is less than 130 ° C ○: Fixing lower limit temperature is 130 ° C or more and less than 140 ° C Δ: Fixing lower limit temperature is 140 ° C or more and less than 150 ° C ×: Fixing lower limit temperature is 150 ° C or more

-Fixing resistance-
Using IPSiO SP C220 (manufactured by Ricoh Co., Ltd.), 2,000 white solid images were output, and the toner adhered to the regulating blade was visually observed and evaluated according to the following criteria.
〔Evaluation criteria〕
◎: Very good level without toner adhesion ○: Level where toner adhesion is not noticeable and does not affect image quality △: Level where toner adhesion is present and affects image quality ×: Level where toner adhesion is noticeable and greatly affects image quality

(Examples 2 to 4)
<Production of toner>
A toner was prepared in the same manner as in Example 1 except that the vinyl resin fine particles in Example 1 were replaced with the vinyl resin fine particles shown in Table 2.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 5)
<Production of toner>
A toner was prepared in the same manner as in Example 2 except that [Prepolymer 1] was not added in the oil phase preparation step of Example 2.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Examples 6 to 9)
<Production of toner>
A toner was prepared in the same manner as in Example 1 except that the vinyl resin fine particles in Example 1 were replaced with the vinyl resin fine particles shown in Table 2.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 10)
<Production of toner>
A toner was prepared in the same manner as in Example 5 except that [Crystalline Polyester Resin 1] was replaced with [Crystalline Polyester Resin 2] in Example 5.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 11)
<Production of toner>
A toner was prepared in the same manner as in Example 2, except that [Crystalline Polyester Resin 1] was replaced with [Crystalline Polyester Resin 2] in Example 2.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Example 12)
<Production of toner>
A toner was prepared in the same manner as in Example 7, except that [Crystalline Polyester Resin 1] was replaced with [Crystalline Polyester Resin 2] in Example 7.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.

(Comparative Example 1)
In Example 1, a toner was produced in the same manner as in Example 1 except that the vinyl resin resin fine particles were not added (that is, the resin fine particle adhesion step was not performed).
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.
Further, a cross-sectional photograph of the obtained toner is shown in FIG.

(Comparative Examples 2 to 12)
A toner was prepared in the same manner as in Example 1 except that the vinyl resin fine particles in Example 1 were replaced with the vinyl resin fine particles shown in Table 2.
The obtained toner was evaluated in the same manner as in Example 1. The results are shown in Table 2.

In Table 2, abbreviations represent the following meanings.
Amorphous PE resin: Amorphous polyester resin Crystalline PE resin: Crystalline polyester resin

According to the evaluation results, the toners of Examples 1 to 12, which are the toners of the present invention, obtained very good results excellent in all of the background stain, the fixability and the anti-sticking property.
However, the toners of Comparative Examples 1 to 12 did not provide results that satisfy all of the background stain, the fixing property, and the anti-sticking property.

  The toner of the present invention is excellent in heat fixing property, anti-sticking property, and background stain, and can be applied at a low temperature to an adhesion step of attaching a shell layer to the core particles when the toner is produced. It is suitable as a toner used for electrophotographic image formation such as electroprinting, printer, facsimile, and electrostatic recording.

DESCRIPTION OF SYMBOLS 1 Latent image carrier 2 Charging device 3 Exposure device 4 Developing device 4a Developing roller 4b Supply roller 4c Restricting blade 4d Container 4C, 4M, 4Y, 4K Developing device 5 Cleaning unit 6 Intermediate transfer member 7 Support roller 8 Transfer roller 9 Heating roller DESCRIPTION OF SYMBOLS 10 Aluminum core metal 11 Elastic body layer 12 PFA surface layer 13 Heater 14 Pressure roller 15 Aluminum core metal 16 Elastic body layer 17 PFA surface layer 18 Unfixed image 19 Fixing means 40 Developing roller 41 Thin layer forming member 42 Supply roller 100 Core particle 101 Shell layer L Exposure P Recording paper T Developer

JP 2007-93809 A

Claims (10)

Core particles containing at least a binder resin, a colorant, and a release agent;
A toner having a shell layer formed of vinyl resin fine particles on the surface of the core particles,
The binder resin contains at least a crystalline polyester resin and an amorphous polyester resin;
The glass transition temperature of the vinyl resin fine particles is 60 ° C to 80 ° C,
The constituent component of the vinyl resin fine particles contains 80% by mass or more of an aromatic compound having a vinyl polymerizable functional group and 5% by mass or more of a compound having a vinyl polymerizable functional group and an ester bond, and is vinyl polymerizable. A toner comprising no compound having a functional group and an acid group.   The toner according to claim 1, wherein the vinyl resin fine particles have a weight average molecular weight of 20,000 to 50,000.   The toner according to claim 1, wherein the core particle and the shell layer form a continuous layer.   The toner according to claim 1, wherein the binder resin further contains a modified polyester resin having at least one of a urethane bond and a urea bond.   The toner according to claim 1, wherein the release agent is at least one selected from paraffins, synthetic esters, polyolefins, carnauba wax, and rice wax.   A toner container in which the toner according to claim 1 is contained.   A developer comprising the toner according to claim 1. A developer carrying member for carrying on the surface a developer to be supplied to the image carrier;
Developer supplying means for supplying the developer to the surface of the developer carrying member;
At least developer storage means for storing the developer,
A developing device, wherein the developer containing means contains the developer according to claim 7. An image carrier;
An electrostatic latent image forming means for forming an electrostatic latent image on the image carrier;
Developing means for developing the electrostatic latent image with a developer to form a visible image;
Transfer means for transferring the visible image to a recording medium;
And at least fixing means for fixing the transferred image transferred to the recording medium,
The image forming apparatus according to claim 8, wherein the developing unit is the developing device according to claim 8.   9. A process cartridge comprising at least an image carrier and a developing device according to claim 8, wherein the process cartridge is detachable from a main body of the image forming apparatus.