JP2010128002A - Electrostatic charge image developing toner, method for producing the same, and developer, image forming apparatus and image forming method using the electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which excels in long-term charge stability, can prevent fogging and toner scattering, as a full-color toner, achieves a high image density and excels in transparency, satisfies cleaning property, and excels in transferability and graininess, a method for producing the same, and a developer, an image forming apparatus and an image forming method using the electrostatic charge image developing toner. <P>SOLUTION: The electrostatic charge image developing toner is produced from a system in which oil droplets containing at least a binder resin and a pigment are dispersed in an aqueous phase, and the toner contains a polycondensate obtained by the polycondensation reaction of phenols and aldehydes. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like, a method for producing the same, and the electrostatic charge image developing toner. The present invention relates to a used developer, an image forming apparatus, and an image forming method.

In recent years, the strong demand for higher image quality and higher speed from the market has spurred the development of an electrophotographic apparatus suitable for it and toner used for it.
It is essential that the toner corresponding to the high speed has a charge performance for quickly reaching the desired charge level after the replenishment of the electrostatic charge.
In addition to the polarity and magnitude of the electrostatic charge, important criteria for determining the quality of the toner include that the desired charge level is reached quickly and that the charge level does not change over a long excitation period. It is done. Another important criterion is that the toner is insensitive to environmental changes such as temperature and atmospheric humidity.
Further, it is essential that the toner corresponding to high image quality is composed of toner particles having a small particle diameter and a uniform particle diameter. If the particle diameters of the toner particles are uniform and the particle size distribution is sharp, the behavior of the toner particles during development is uniform, and the reproducibility of minute dots is significantly improved.

However, the conventional pulverized toner has a problem in that it requires a large amount of energy and a classification process to produce a toner having a small particle size and a uniform particle size, and the productivity is poor.
In addition, a charge control agent may be used to control the charge to the desired charge level. In that case, a step of kneading into the toner together with the binder resin and a step of driving onto the toner surface are required. For this reason, there are problems that the number of steps increases and that the charge control agent needs to be added in an amount greater than the physical amount required, resulting in high costs.

Under such circumstances, various methods for improving these problems have been proposed by a polymerized toner method different from the conventional pulverization method.
In addition to suspension polymerization, there are emulsion polymerization method and dissolution suspension method, etc., but in the emulsion polymerization method, complete removal of styrene monomer and removal of emulsifier and dispersant are difficult in the emulsion polymerization method. As environmental problems have been highlighted, the problem of toner has been increasing. In addition, the toner obtained by the emulsion polymerization method has a weak adhesion of the charge control agent, and due to the movement of silica to the concave portion formed on the surface of the toner in use, the problem of contamination of the photoreceptor by the toner and the fixing roller The toner adhesion problem tends to occur.
On the other hand, the dissolution suspension method has the merit of using a polyester resin that can be fixed at low temperature, but in order to achieve oil-less fixing, polymer control is performed to widen the mold release width. Since a high molecular weight component is added in the process of dissolving or dispersing the pigment in the solvent, the liquid viscosity increases and the productivity is likely to decrease.

  And the above-mentioned problems have not been solved yet. In the dissolution suspension method, in Patent Document 1, it is disclosed that the toner is formed into a spherical shape and the surface thereof is made uneven to improve the cleaning. Because it is a non-standard amorphous toner, it lacks charging stability, and it is difficult to design a high molecular weight to ensure basic durability and releasability, and a toner of satisfactory quality cannot be obtained. There's a problem.

  In Patent Document 2, a specific compound powder and a specific inorganic fine powder having a predetermined specific surface area are added to the toner particles, thereby exhibiting preferable charging characteristics, and in particular, pulverization excellent in environmental dependency of image density. Although it is disclosed that a toner can be obtained, in practice, it is insufficient to achieve both high image quality and charging characteristics.

JP 9-15903 A Japanese Patent No. 2682331

An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention is excellent in charging stability over a long period of time, can prevent fogging and toner scattering, and as a full-color toner, it can provide a high image density, excellent transparency, satisfactory cleaning properties, and transferability. An object of the present invention is to provide an electrostatic image developing toner excellent in graininess and a method for producing the same, and a developer, an image forming apparatus and an image forming method using the electrostatic image developing toner.
Furthermore, the present invention provides (1) a toner for developing electrostatic images produced by a dissolution suspension method and a monomer suspension method, which has good charging performance and high reliability. (2) To provide an electrostatic image developing toner excellent in low temperature fixability, (3) To provide an electrostatic image developing toner capable of achieving the same problems (1) to (2), (4) ) Providing toner for developing electrostatic images with excellent transfer efficiency and low transfer residual toner to obtain high quality images, (5) Low power consumption and high transferability and OHP transmission required for color images (6) (1) to (5) production method of electrostatic image developing toner, development using the electrostatic image developing toner Agent, image forming apparatus, and image forming method , It is an object of the present invention.

In order to solve the above-mentioned problems, the present inventors have made extensive studies and obtained the following knowledge.
The manufacturing method used for manufacturing the toner for developing an electrostatic charge image of the present invention is a so-called dissolution suspension method in which a binder resin, a pigment, and other toner materials are dissolved or dispersed using an organic solvent and emulsified or dispersed in an aqueous medium. This is a manufacturing method in which toner is dispersed. Usually, the charge control of the toner is carried out by incorporating a charge control agent into the toner material and incorporating it into the toner.
However, when the charge control agent used has good compatibility with water or is soluble in water, the charge control agent often does not enter the finished toner. On the other hand, when the hydrophobicity is strong, the charge control agent enters even inside the toner. Since the charging phenomenon occurs mainly on the toner surface, a predetermined charging performance cannot be obtained.
In addition, many organic pigments have a nitrogen-containing functional group. To adjust the viscoelasticity of the resin used, a method in which urea and urethane bonds are introduced into the resin has been proposed. Easy to block.
Further, when organic or inorganic fine particles or surfactants are added to the aqueous phase in order to adjust the emulsion stability and particle size during the production of the toner, they remain on the toner surface and inhibit the charging performance.
In addition, many charge control agents are usually insoluble in an organic solvent, and it is necessary to use the charge control agent by dispersing it below the toner size.
The present inventors have also found that the above-mentioned problems can be solved by including a polycondensate obtained by a polycondensation reaction from phenols and aldehydes.
That is, the polycondensate has a property that its polarity is easily oriented at the oil-water interface in the dissolution suspension method, and can be present on the toner surface while being held by the toner.
For this reason, it is considered that even if the charge-inhibiting substance such as the resin or pigment is present, the charging performance can be exerted, and the adverse effect of the chargeability can be reduced and canceled.
In addition, the polycondensate is often soluble in an organic solvent, and is effective in a small amount.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> It is produced from a system in which at least oil droplets containing a binder resin and a pigment are dispersed in an aqueous phase, and contains a polycondensate obtained by a polycondensation reaction of phenols and aldehydes. An electrostatic charge image developing toner.
<2> From an emulsion or dispersion obtained by emulsifying or dispersing, in an aqueous medium, a solution or dispersion obtained by dissolving or dispersing a toner composition containing at least a binder resin and a pigment in an organic solvent. Is a toner for developing an electrostatic charge image, which contains a polycondensate produced by polycondensation reaction of phenols and aldehydes.
<3> A cross-linking agent obtained by dispersing, in an aqueous medium, a solution or dispersion obtained by dissolving or dispersing a toner composition containing at least a modified polyester resin capable of urea bonding and a pigment in an organic solvent. Or a polycondensate produced by removing a solvent from a dispersion obtained by reacting with an extender and obtained by a polycondensation reaction of phenols and aldehydes. This is a charge image developing toner.
<4> From <1> above, wherein a kneaded complex obtained by kneading a polycondensate obtained by a polycondensation reaction of phenols and aldehydes with a binder resin is dissolved or dispersed in an organic solvent. <3> The toner for developing an electrostatic charge image according to any one of the above.
<5> Phenols have one phenolic hydroxyl group, and hydrogen is bonded to the ortho position of the phenolic hydroxyl group, p-alkylphenol, p-aralkylphenol, p-phenylphenol, p-hydroxybenzoic acid Bisphenols having at least one phenol compound (A) selected from the group consisting of acid esters, two or more phenolic hydroxyl groups, and hydrogen bonded to the ortho position of the phenolic hydroxyl groups, <1> to <4>, comprising at least one phenol compound (B) selected from the group consisting of trisphenols and tetrakisphenols, wherein the aldehyde comprises at least one of paraformaldehyde and formaldehyde The electrostatic charge image developing toner according to any one of the above.
<6> The electrostatic charge image developing toner according to <5>, wherein the phenol compound (B) is a bisphenol.
<7> The volume average particle diameter (Dv) of the toner particles is 3 μm to 8 μm, and the ratio Dv / Dn of the volume average particle diameter (Dv) to the number average particle diameter (Dn) is 1.25 or less. <1> to <6> The electrostatic image developing toner according to any one of <6>.
<8> The electrostatic image developing toner according to any one of <1> to <7>, wherein the toner particles have an average circularity of 0.960 to 0.980.
<9> A method for producing an electrostatic image developing toner, comprising producing the electrostatic image developing toner according to any one of <1> to <8>.
<10> A developer comprising the electrostatic image developing toner according to any one of <1> to <8> and a carrier.
<11> An image forming apparatus using the electrostatic image developing toner according to any one of <1> to <8>.
<12> An image forming method using the electrostatic charge developing toner according to any one of <1> to <8>.

  According to the present invention, the conventional problems can be solved, charging stability is excellent over a long period, fog and toner scattering can be prevented, and as a full-color toner, high image density is obtained and transparency is excellent. In addition, an electrostatic charge image developing toner that satisfies cleaning properties, excellent transferability, and excellent graininess, a method for producing the same, a developer using the electrostatic charge image developing toner, an image forming apparatus, and an image forming method Can be provided.

(Static image developing toner)
The electrostatic image developing toner of the present invention contains at least a polycondensate obtained by a polycondensation reaction of phenols and aldehydes, a binder resin, and a pigment, and, if necessary, other toners. It contains a toner composition.

<Polycondensate obtained by polycondensation reaction of phenols and aldehydes>
There is no restriction | limiting in particular as a polycondensate obtained by the polycondensation reaction of the said phenols and aldehydes (henceforth a polycondensate), According to the objective, it can select suitably and can be used. In the present invention, the polycondensate is used as a negative charge control agent.

-Phenols-
There is no restriction | limiting in particular as said phenols, Although it can select suitably according to the objective, It has one phenolic hydroxyl group, and the phenolic compound which hydrogen has couple | bonded with the ortho position of the said phenolic hydroxyl group ( It preferably contains A) and a phenolic compound (B) having two or more phenolic hydroxyl groups and hydrogen bonded to the ortho position of the phenolic hydroxyl group.

--Phenol compound (A)-
There is no restriction | limiting in particular as said phenolic compound (A), Although it can select suitably according to the objective, It consists of p-alkylphenol, p-aralkylphenol, p-phenylphenol, p-hydroxybenzoic acid ester. It is preferably at least one selected from the group.
These may be used alone or in combination.

As said phenol compound (A), the compound shown by following formula (1) is mentioned, for example.

In formula (1), R ₁ and R ₃ each represent hydrogen, halogen, an alkyl group, an aralkyl group, a substituted or unsubstituted amino group, and the alkyl group includes a methyl group, an ethyl group, a butyl group, C1-C12 things, such as an octyl group and a dodecyl group, are preferable. Examples of the aralkyl group include a benzyl group and a cumyl group, and examples of the substituted amino group include —N (CH ₃ ) ₂ , —N (C ₂ H ₅ ) ₂ , —N (C ₃ H ₇ ) _{2 and the} like. Can be mentioned.

In formula (1), R ₂ is hydrogen, halogen, an alkyl group, —COC _m H _{2m + 1} (where m is an integer of 1 to 20), an aralkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted amino group. , A nitro group, an alicyclic group, —SO ₃ H, —Si (CH ₃ ) ₃ , an alkoxyl group, a carboxyl group, a sulfoamide group, a carbomoyl group, a cyano group, a carboxylic acid ester group, and an acyl group.
Examples of the alkyl group and aralkyl group include those exemplified for R ₁ and R ₃ , and examples of the substituent of the substituted amino group include an optionally substituted alkyl group having 1 to 12 carbon atoms.
As a substituted phenyl group, one or more of the hydrogen of the phenyl group is an alkyl group having 1 to 8 carbon atoms, a halogen, a carboxyl group, a cyano group, a nitro group, a halogenated methyl group, a trimethylsilyl group, or a C 1 to 8 carbon group. Examples thereof include an amide group, an acyl group having 1 to 12 carbon atoms, a sulfonyl group having 1 to 12 carbon atoms, an ether group having 1 to 12 carbon atoms, and the like.
Examples of the alicyclic group include a cyclohexyl group and a cyclopentyl group.
Examples of the alkoxyl group include those having 1 to 12 carbon atoms.
Examples of the carboxylic acid ester group include a substituent represented by -COOR ₃₅ , and R ₃₅ represents an optionally substituted alkyl group having 1 to 18 carbon atoms, substituted or unsubstituted phenyl. Group, a substituted or unsubstituted aralkyl group, and the like.

  Preferable specific examples of the compound represented by the formula (1) include pt-butylphenol, pt-octylphenol, p- (α-cumylphenol), p-phenylphenol, 4-hydroxybenzoic acid ester and the like. Is mentioned.

Moreover, there is no restriction | limiting in particular as content of the phenol compound (A) in the said phenols, According to the objective, it can select suitably.
A phenol compound (A) can be used individually by 1 type or in mixture of 2 or more types.

--- Phenol compound (B)-
There is no restriction | limiting in particular as a phenol compound (B), According to the objective, it can select suitably and can be used, It is using at least 1 sort (s) selected from the group which consists of bisphenols, trisphenols, and tetrakisphenols. it can.

As a phenol compound (B), the compound shown by following formula (2) is mentioned, for example.

In the formula (2), R _{9 to} R ₁₂ are each hydrogen, alkyl group, perfluoroalkyl group, alicyclic group, aralkyl group, substituted or unsubstituted phenyl group, alkoxyl group, aryl group, sulfoamide group, carbomoyl group, cyano. Group, carboxylate group, acyl group, vinyl group, or halogen.
As an alkyl group, a C1-C8 thing, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, is preferable.
Preferable specific examples of the compound represented by the formula (2) include 2,2′-bis (hydroxyphenyl) propane.
R ₁₃ represents —SO ₂ —, — (CR ₁₄ R ₁₅ ) _n — (where n = 1 to 12 and R ₁₄ and R ₁₅ may be different from each other. Further, when n ≧ 2 In each of the repeating units, R ₁₄ and R ₁₅ may be different from each other.), —O—, a substituted or unsubstituted cyclohexane having 3 to 8 carbon atoms represented by the following formula (3): A ring, one of those represented by the following formula (4).
However, R ₁₄ and R ₁₅ each represent hydrogen, an alkyl group, a perfluoroalkyl group, or a substituted or unsubstituted phenyl group.
Examples of the alkyl group include those having 1 to 16 carbon atoms, which may or may not be branched.
The perfluoroalkyl group may be branched with carbon 1 to 16.
As the substituted phenyl group, one or more of hydrogens of the phenyl group are alkyl groups having 1 to 8 carbon atoms, halogen, carboxyl group, hydroxy group, cyano group, nitro group, methyl halide group, trimethylsilyl group, carbon number 1 -8 amide groups, C1-C12 acyl groups, C1-C12 sulfonyl groups, C1-C12 ether groups, and the like.

As said trisphenol, what is shown by following formula (5) is mentioned.
Wherein _(5), R 16 _{to R 21} represents the same content as _R 9 _{to R 12} in Formula (2).
R ₂₃ represents the same content as R ₁₃ in formula (2).
Preferable specific examples of the compound represented by the formula (5) include 4-4′-4 ″ -ethylidyltrisphenol.

As said tetrakisphenol, what is shown by following formula (6) is mentioned.
In the formula (6), R _{24 to} R ₃₁ have the same contents as R _{9 to} R ₁₂ in the formula (2).
R ₃₂ and R ₃₃ have the same contents as R ₁₃ in formula (2).

Moreover, there is no restriction | limiting in particular as content of the phenol compound (B) in the said phenols, Although it can select suitably according to the objective, 1 mol%-30 mol% are preferable, and 2 mol%-20 Mole% is more preferable, and 4 mol% to 15 mol% is particularly preferable.
If the molar content of the phenolic compound (B) is less than 1 mol% or exceeds 30 mol%, sufficient negative charging performance may not be obtained, and if it exceeds 30 mol%, dispersibility in the binder resin may be obtained. Tend to get worse. The phenol compound (B) can be used alone or in combination of two or more.

-Aldehydes-
There is no restriction | limiting in particular as said aldehydes, Although it can select suitably according to the objective, Paraformaldehyde, formaldehyde, paraaldehyde, and furfural are preferable.

As said furfural, what is shown by following formula (7) is mentioned.

The upper limit of the number average particle diameter (dispersion diameter) of the polycondensate particles contained in the toner for developing an electrostatic image is preferably 0.8 μm or less, more preferably 0.6 μm or less, and 0.3 μm. The following is still more preferred, with a value of less than 0.1 μm being particularly preferred.
When the number average particle size of the polycondensate particles in the toner for developing an electrostatic charge image exceeds 0.8 μm, the dispersibility of the polycondensate does not reach a sufficient level. Even if a polycondensate having a particle size of is used, the intended transparency cannot be obtained.
Basically, it is considered that a polycondensate having a fine particle diameter having a number average particle diameter of less than 0.1 μm does not adversely affect the light reflection and absorption characteristics.
When the number average particle size of the polycondensate particles in the toner for developing an electrostatic charge image is less than 0.1 μm, good color reproducibility and transparency of an OHP sheet having a fixed image can be obtained.
On the other hand, when there are many polycondensates having a particle diameter exceeding 0.8 μm as their abundance ratio, the brightness and color of the projected image of the OHP sheet tend to be lowered.

  Further, when there are many polycondensates having a particle diameter exceeding 0.8 μm, the polycondensate particles are detached from the surface of the toner particles, and various problems such as fogging, drum contamination, and poor cleaning are liable to occur. Further, when such a color toner is used as a two-component developer, a problem such as carrier contamination is caused, and it is difficult to obtain a stable image in the durability of a large number of sheets. Of course, a good image cannot be expected, and uniform chargeability is hardly obtained.

<Binder resin>
The binder resin is not particularly limited and may be appropriately selected depending on the purpose. For example, a modified polyester resin capable of urea bonding (hereinafter referred to as urea-modified polyester), an unmodified polyester resin, and the like. These resins and their reaction products are included, but it is preferable to contain a urea-modified polyester.

-Urea-modified polyester-
The urea-modified polyester (i) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a reaction product of a polyester prepolymer (A) having an isocyanate group and amines (B). It is done.

--Polyester prepolymer (A) having an isocyanate group--
The polyester prepolymer (A) having an isocyanate group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is a polycondensate of polyol (1) and polycarboxylic acid (2) and active. Examples include those obtained by further reacting a polyester having a hydrogen group (active hydrogen group-containing compound) with polyisocyanate (3).

  There is no restriction | limiting in particular as said polyol (1), According to the objective, it can select suitably, For example, although diol (1-1) and trivalent or more polyol (1-2) are mentioned, diol ( 1-1) A mixture of diol (1-1) and a small amount of polyol (1-2) alone is preferred.

The diol (1-1) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1, 4-butanediol, 1,6-hexanediol, etc .; 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 above alicyclic diols (ethylene oxide, pro Pyrene oxide, butylene oxide, etc.) adducts; alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the bisphenols.
Among these diol (1-1) compounds, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, alkylene oxide adducts of bisphenols, and alkylene glycols having 2 to 12 carbon atoms. Is more preferable.

  The trihydric or higher polyol (1-2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the trihydric or higher polyhydric aliphatic alcohol (glycerin, trimethylol) Ethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, phenol novolac, cresol novolac, etc.); alkylene oxide adducts of trihydric or higher polyphenols.

There is no restriction | limiting in particular as said polycarboxylic acid (2), According to the objective, it can select suitably, For example, dicarboxylic acid (2-1) and trivalent or more polycarboxylic acid (2-2) are mentioned. Dicarboxylic acid (2-1) alone or a mixture of dicarboxylic acid (2-1) and a small amount of trivalent or higher polycarboxylic acid (2-2) is preferable. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid).
Among these polycarboxylic acid (2) compounds, alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms are preferable.

The trivalent or higher polycarboxylic acid (2-2) 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.).
In addition, as polycarboxylic acid (2), what was made to react with the said polyol (1) using the acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.) of what was mentioned above may be used.

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

The polyisocyanate (3) is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate). ); Cycloaliphatic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); Isocyanurates; those obtained by blocking the polyisocyanates with phenol derivatives, oximes, caprolactams, and the like.
These may be used alone or in combination of two or more.

The active hydrogen group-containing compound acts as an elongation agent, a crosslinking agent or the like when the polyester capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like.
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 modified polyester capable of reacting with the active hydrogen group-containing compound is an isocyanate. In the case of the polyester prepolymer (A) having a group, the amines (B) can be made to have a high molecular weight by a reaction such as an elongation reaction or a crosslinking reaction with the polyester prepolymer (A) having an isocyanate group. Is preferred.
There is no restriction | limiting in particular as said active hydrogen group, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, alcoholic hydroxyl groups are particularly preferable.

The ratio of reacting the polyisocyanate (3), which is a polycondensate of the polyol (1) and the polycarboxylic acid (2), with the polyisocyanate (3) is not particularly limited and is appropriately selected depending on the purpose. However, the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group is preferably 5/1 to 1/1. 2/1 is more preferable, and 2.5 / 1 to 1.5 / 1 is particularly preferable.
When [NCO] / [OH] exceeds 5, the low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate.

There is no restriction | limiting in particular as content of the polyisocyanate (3) in the prepolymer (A) which has the said isocyanate group at the terminal, Although it can select suitably according to the objective, 0.5 mass%-40 mass % Is preferable, 1% by mass to 30% by mass is more preferable, and 2% by mass to 20% by mass is particularly preferable.
When the content is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, when the content exceeds 40% by mass, the low-temperature fixability deteriorates.

  There is no restriction | limiting in particular as an isocyanate group contained per molecule in the prepolymer (A) which has the said isocyanate group, Although it can select suitably according to the objective, An average of 1 or more is preferable and an average of 1. 5 to 3 are more preferable, and an average of 1.8 to 2.5 is particularly preferable. If the average number is less than 1 per molecule, the molecular weight of the urea-modified polyester becomes low and the hot offset resistance deteriorates.

--Amines (B)-
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 ( And B4), amino acid (B5), and amino acids B1 to B5 blocked (B6).
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane). , Isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.

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 aminoethyl 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.
The B1 to B5 amino group blocked (B6) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, And ketimine compounds and oxazoline compounds obtained from methyl isobutyl ketone.
Of these amines (B), a diamine (B1) and a small amount of a mixture of a trivalent or higher polyamine (B2) are preferable.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

There is no restriction | limiting in particular as a ratio with which the polyester prepolymer (A) which has the said isocyanate group, and the said amines (B) are made to react, but it can select suitably according to the objective. The equivalent ratio [NCO] / [NHx] of the isocyanate group [NCO] in the polymer (A) and the amino group [NHx] in the amine (B) is preferably 1/2 to 2/1. 5/1 to 1 / 1.5 is more preferable, and 1.2 / 1 to 1 / 1.2 is particularly preferable.
When [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) is lowered, and the hot offset resistance is deteriorated.

The urea-modified polyester (i) may contain a urethane bond as well as a urea bond.
There is no restriction | limiting in particular as molar ratio of urea bond content and urethane bond content, Although it can select suitably according to the objective, 100 / 0-10 / 90 is preferable and 80 / 20-20 / 80 is More preferably, 60/40 to 30/70 is particularly preferable.
When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

The urea-modified polyester (i) is produced by a one-shot method or a prepolymer method.
The mass average molecular weight of the urea-modified polyester (i) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 10,000 or more, more preferably 20,000 to 10 million, and more preferably 30,000 to One million is particularly preferred.
When the mass average molecular weight of the urea-modified polyester (i) is less than 10,000, the hot offset resistance is deteriorated.
The number average molecular weight of the urea-modified polyester may be a number average molecular weight that can be easily obtained to obtain the mass average molecular weight when the unmodified polyester (ii) described later is used.
In the case of the urea-modified polyester (i) alone, the number average molecular weight is not particularly limited and can be appropriately selected according to the purpose, but is preferably 20,000 or less, more preferably 1,000 to 10,000. Preferably, 2,000 to 8,000 are particularly preferable.
In the case of the urea-modified polyester (i) alone, when the number average molecular weight exceeds 20,000, the low-temperature fixability and the gloss when used in a full-color device are deteriorated.

-Unmodified polyester-
As the binder resin, the urea-modified polyester (i) can be used alone, but the urea-modified polyester (i) and the unmodified polyester (ii) can be used in combination.
When the unmodified polyester (ii) is used in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved, which is preferable to the single use.

  The unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, as with the polyester component of the urea-modified polyester (i), the polyol (1) and the poly (polyester) Examples include polycondensates with carboxylic acid (2).

The polycondensate of the polyol (1) and the polycarboxylic acid (2) is not particularly limited and may be appropriately selected depending on the intended purpose. The same polyol (1) as the urea-modified polyester (i) Polycarboxylic acid (2) is preferred.
The unmodified polyester (ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example.

The urea-modified polyester (i) and the unmodified polyester (ii) are preferably at least partially compatible in terms of low-temperature fixability and hot offset resistance.
Accordingly, the polyester component of the urea-modified polyester (i) and the unmodified polyester (ii) preferably have a similar composition.
The mass ratio between the urea-modified polyester (i) and the unmodified polyester (ii) in the case of containing the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the purpose. However, 5 / 95-80 / 20 are preferable, 5 / 95-30 / 70 are more preferable, 5 / 95-25 / 75 are still more preferable, and 7 / 93-20 / 80 are especially preferable.
If the mass ratio of the urea-modified polyester (i) is less than 5%, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

The peak molecular weight of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1,000 to 30,000, and preferably 1,500 to 10,000. More preferred is 2,000 to 8,000.
When the peak molecular weight of the unmodified polyester (ii) is less than 1,000, the heat resistant storage stability is deteriorated, and when it exceeds 30,000, the low temperature fixability is deteriorated.
The hydroxyl value of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, 20 mg KOH / g to 80 mg KOH / g is particularly preferable.
When the hydroxyl value of the unmodified polyester (ii) is less than 5 mgKOH / g, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of the unmodified polyester (ii) is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 1 mgKOH / g to 30 mgKOH / g, and preferably 5 mgKOH / g to 20 mgKOH / g. More preferred.
By having an acid value, it tends to be negatively charged.

The glass transition point (Tg) of the binder resin (toner binder) is preferably 50 ° C to 70 ° C, more preferably 55 ° C to 65 ° C. When the glass transition point (Tg) of the binder resin is less than 50 ° C., blocking of the toner at high temperature storage deteriorates, and when it exceeds 70 ° C., the low-temperature fixability becomes insufficient.
Due to the coexistence of the urea-modified polyester (i), the electrostatic charge image developing toner of the present invention tends to have good heat storage stability even when the glass transition point is low, as compared with known polyester-based toners.

The storage elastic modulus of the binder resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is 100 ° C. or higher at a temperature (TG ′) of 10,000 dyne / cm ^{2 at} a measurement frequency of 20 Hz. Is preferable, and 110 to 200 ° C. is more preferable.
If it is less than 100 ° C., the hot offset resistance deteriorates.
The viscosity of the binder resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, the temperature (Tη) at which the measurement frequency is 20 Hz becomes 1,000 poise, preferably 180 ° C. or less, preferably 90 ° C. to 160 ° C. is more preferable.
If it exceeds 180 ° C., the low-temperature fixability deteriorates.
That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low-temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and particularly preferably 20 ° C. or higher. The upper limit of the difference is not particularly limited.
Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 90 ° C, and particularly preferably 20 ° C to 80 ° C.

-Other resins-
There is no restriction | limiting in particular as said other resin, According to the objective, it can select suitably, For example, polymers of styrene, such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and its substituted; styrene-p- Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-acrylic Acid butyl copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate Copolymer, styrene-acrylonitrile copolymer, steel -Vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene copolymer; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified Examples thereof include rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used alone or in combination of two or more.

<Pigment>
The pigment is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), and cadmium yellow. , Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faisa Red, Lachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX , Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y , Alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue (copper phthalocyanine), Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, pyridian, emerald green, pigment green B, naphthol green B, green gold, acid gree Nlake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone Green, Titanium Oxide, Zinc Hana, Litobon, etc.
These may be used individually by 1 type and may use 2 or more types together.

The content of the pigment in the toner for developing an electrostatic charge image is not particularly limited and may be appropriately selected depending on the intended purpose. Is more preferable.
When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed, and when the content exceeds 15% by mass, a poor dispersion of the pigment in the toner occurs. The characteristics may be degraded.

The pigment may be used as a master batch combined with the binder resin.
The masterbatch can be manufactured by using the binder resin as a resin for a masterbatch, and mixing or kneading the binder resin and the pigment under a high shear force. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the pigment and the binder resin.
The so-called flushing method is also preferable in that the wet cake of the pigment can be used as it is and it does not need to be dried.
This flushing method is a method in which an aqueous paste containing a pigment and water is mixed or kneaded with the resin for the masterbatch and an organic solvent, and the pigment is transferred to the resin side to remove moisture and the organic solvent component. .
For the mixing or kneading, for example, a high shear dispersion device such as a three-roll mill is preferably used.

In the case where two types of binder resins are used in combination, the pigment is arbitrarily contained in both the first resin phase and the second resin phase by utilizing the difference in affinity for the two types of resins. Can do.
It is well known that the pigment deteriorates the charging performance of the toner when it is present on the toner surface. Therefore, by selectively incorporating a pigment into the first resin phase present in the inner layer, the charging performance (environmental stability, charge retention ability, charge amount, etc.) of the toner can be improved.

<Other toner composition>
The other toner composition is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a release agent, a charge control agent, resin fine particles, an external additive, a cleaning improver, and a colorant. Is mentioned.

-Release agent-
The release agent is not particularly limited and may be appropriately selected from known waxes according to the purpose. For example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, Sazol wax and the like); carbonyl group-containing wax and the like. Among these, a carbonyl group-containing wax is preferable.

  The carbonyl group-containing wax is not particularly limited and may be appropriately selected from known waxes according to the purpose. Examples thereof include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate). , Pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18-octadecanediol distearate, etc .; polyalkanol ester (tristearyl trimellitic acid, distearyl maleate, etc.) Polyalkanoic acid amides (such as ethylenediamine dibehenyl amide); polyalkylamides (such as trimellitic acid tristearyl amide); and dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred.

The melting point of the wax is preferably 40 ° C to 160 ° C, more preferably 50 ° C to 120 ° C, and particularly preferably 60 ° C to 90 ° C.
When the wax has a melting point of less than 40 ° C., the heat resistant storage stability is adversely affected, and when the wax exceeds 160 ° C., a cold offset tends to occur during fixing at a low temperature.
The melt viscosity of the wax is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point.
If the wax has a melt viscosity exceeding 1,000 cps, the effect of improving hot offset resistance and low-temperature fixability is poor.
The content of the wax in the toner for developing an electrostatic image is not particularly limited and may be appropriately selected depending on the purpose. Although 3 mass%-30 mass% are preferable.

-Charge control agent-
The electrostatic charge image developing toner may contain other charge control agents in addition to a polycondensate obtained by a polycondensation reaction from phenols and aldehydes, if necessary.
The other charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose. For example, triphenylmethane dye, molybdate chelate pigment, rhodamine dye, alkoxy amine, quaternary ammonium salt ( (Including fluorine-modified quaternary ammonium salts), alkylamides, simple substances or compounds of phosphorus, simple substances or compounds of tungsten, fluorine-based activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc., but using colored materials Therefore, a material that is colorless and close to white is preferable.

  Specifically, quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, Orient Chemical Industry) TP-302, TP-415 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, Copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (manufactured by Nippon Kalit Ltd), quinacridone, azo pigment, and others Polymer systems having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts The compound of this is mentioned.

The amount of the charge control agent containing the polycondensate is determined by the toner production method including the type of the binder resin, the presence or absence of additives used as necessary, and the dispersion method. Although it is not uniquely limited, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably in the range of 0.2 to 5 parts by mass with respect to 100 parts by mass of the binder resin. preferable.
When the amount used exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is decreased, The image density is lowered.
The charge control agent containing the polycondensate can be dissolved and dispersed after being melt-kneaded with the binder resin or the masterbatch, or can be added when directly dissolving or dispersing in an organic solvent, or toner The toner particles may be fixed on the surface after preparation.

-Resin fine particles-
Resin fine particles may be added to the electrostatic image developing toner.
As the resin fine particles to be used, any resin can be used as long as it can form an aqueous dispersion, and a thermoplastic resin or a thermosetting resin may be used. For example, a vinyl resin, a polyurethane resin, an epoxy resin, Examples thereof include polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin.
As resin fine particles, these resins may be used alone or in combination of two or more.
Among these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferable because an aqueous dispersion of fine spherical resin particles can be easily obtained.

  The vinyl resin is not particularly limited as long as it is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, and can be appropriately selected according to the purpose. For example, a styrene- (meth) acrylate resin, Examples include styrene-butadiene copolymers, (meth) acrylic acid-acrylic acid ester polymers, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

-External additive-
An external additive may be added to assist the fluidity, developability, and chargeability of the toner for developing an electrostatic image.
There is no restriction | limiting in particular as said external additive, Although it can select suitably according to the objective, An inorganic fine particle can be used preferably.
There is no restriction | limiting in particular as a primary particle diameter of the said inorganic fine particle, Although it can select suitably according to the objective, It is preferable that they are 5 micrometers-2 micrometers, and it is more preferable that they are 5 micrometers-500 micrometers.
As the specific surface area by BET method is not particularly limited and may be appropriately selected depending on the purpose ^and is preferably from 20m ² / g~500m 2 / g.
The proportion of the inorganic fine particles used is preferably 0.01% by mass to 5% by mass and more preferably 0.01% by mass to 2.0% by mass of the toner for developing an electrostatic charge image.

The inorganic fine particles are not particularly limited and may be appropriately selected depending on the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Can be mentioned.
In addition, polymer fine particles, for example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, methacrylic acid ester, acrylate copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting Polymer particles made of a functional resin.

Such an external additive can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity.
The surface treatment agent used for such surface treatment is not particularly limited and may be appropriately selected according to the purpose. However, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, Organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferred.

-Cleaning improver-
The cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium is not particularly limited and can be appropriately selected depending on the purpose. For example, zinc stearate, calcium stearate And fatty acid metal salts such as stearic acid, and polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles.
The polymer fine particles are not particularly limited and may be appropriately selected depending on the intended purpose, but those having a relatively narrow particle size distribution and a volume average particle size of 0.01 μm to 1 μm are preferable.

-Colorant-
In addition to the pigment, a colorant may be added to the toner for developing an electrostatic image.
The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Red, Cadmium Red, Cad Muum Mercury Red, Antimon Zhu, Permanent Red 4R, PA Red, Faise Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oh Lured, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Onge, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid Examples include green lake, malachite green lake, phthalocyanine green, anthraquinone green, (hydrophobized) titanium oxide, zinc white, and ritbon. These may be used individually by 1 type and may use 2 or more types together.
The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content is less than 1% by mass, a reduction in the coloring power of the toner is observed, and when the content exceeds 15% by mass, a poor dispersion of the pigment in the toner occurs. The characteristics may be degraded.

<Organic solvent>
In the present invention, the binder resin, the pigment, and other toner compositions are dissolved or dispersed in an organic medium (oil droplets) to form a dissolved or dispersed material.
As the organic solvent, a general one can be used in consideration of solubility with the binder resin, and in particular, acetone, toluene, butanone and the like are preferable from the viewpoint of dispersibility of the polycondensate.
When this dissolved or dispersed material is used, not only the particle size of the polycondensate particles contained in the resulting color toner is reduced, but also the uniformity of the dispersed state of the particles is increased. The color reproducibility of the projected image is further improved.

Further, when this dissolved or dispersed material is used, since the release agent incompatible with the binder resin is dispersed in the binder resin, the release agent is removed from the toner surface when fixing the toner particles. Even when no oil is applied to the fixing member, it has sufficient offset resistance.
In the case where the release agent is compatible with the binder resin, the exfoliating effect of the release agent at the time of fixing is lost, and offset is likely to occur.

The binder resin and the polycondensate can be kneaded together with the organic solvent in advance and dissolved or dispersed in the organic solvent as a kneaded composite.
A specific method for obtaining the kneaded composite is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a binder resin, a polycondensate, water, and an organic solvent may be used as a Henschel mixer. After mixing with a blender, the resulting mixture may be kneaded at a temperature lower than the melting temperature of the binder resin with a kneader such as a two-roll or three-roll.

<Circularity and circularity distribution>
The electrostatic charge developing toner is preferably spherical and preferably has a good circularity distribution.
The average circularity of the electrostatic charge developing toner is a value obtained by dividing the circumference of an equivalent circle having the same projected area by the circumference of an actual particle by optically detecting the particle. Specifically, the measurement is performed using a flow type particle image analyzer (FPIA-2000; manufactured by Sysmex Corporation). In a predetermined container, 100 to 150 mL of water from which impure solids are removed in advance is added, 0.1 to 0.5 mL of a surfactant is added as a dispersant, and about 0.1 to 9.5 g of a measurement sample is further added. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the concentration and dispersion of the dispersion are set to 3,000 to 10,000 / μL, and the shape and distribution of the toner are measured.
The circularity distribution indicates the ratio of each toner particle having a specific circularity to the total toner particles of the electrostatic charge developing toner.

The average circularity of the electrostatic image developing toner is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of forming a high-definition image with an appropriate density and good reproducibility, it is 0. .960 to 0.980 is preferable, and 0.965 to 0.975 is more preferable.
If the average circularity is less than 0.960, a satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.980, a process such as blade cleaning may occur. In addition, poor cleaning occurs on the photosensitive member and the transfer belt, causing stains on the image.
For example, development / transfer with a low image area ratio results in a small amount of residual toner and poor cleaning does not pose a problem, but images with a high image area ratio such as photographic images, and untransferred images due to poor paper feed, etc. The formed toner may be generated as a transfer residual toner on the photoconductor, and if accumulated, the image may be soiled.
In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited.

As the average circularity and circularity distribution, it is preferable that the average circularity is 0.965 to 0.975, and particles having a circularity distribution of less than 0.94 are 10% or less.
If the toner for developing an electrostatic charge image contains toner particles having an average circularity of less than 0.90, the toner particles have an irregular shape that is too far from a spherical shape. High-quality images without dust cannot be obtained.

The circularity of the electrostatic charge image developing toner can be adjusted to an appropriate region using the polycondensate.
In particular, it is effective to adjust the dispersion diameter of the polycondensate.
In particular, when the number content of the particles having a dispersion diameter of the polycondensate exceeding 0.8 μm in the total polycondensate is 20% or more, the circularity is lowered to a preferable range or less.

<Dv / Dn (ratio of volume average particle diameter / number average particle diameter)>
The volume average particle size (Dv) of the toner for developing an electrostatic image is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm to 8 μm.
When (Dv) is less than 3 μm, when used in a two-component developer, the toner is fused to the surface of the carrier during long-term agitation in the developing device, and the charging ability of the carrier is reduced. When it is used, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner are likely to occur.
Further, when the (Dv) exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and the toner particle size fluctuates greatly when the balance of the toner in the developer is performed. There is.

The ratio (Dv / Dn) between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is not particularly limited and may be appropriately selected depending on the intended purpose. 1.25 is preferred.
When the electrostatic charge image developing toner has a Dv and (Dv / Dn) within the above preferred numerical ranges, it is excellent in heat-resistant storage stability, low-temperature fixability, and hot offset resistance, particularly for full-color copying machines. In the case of two-component developers, even if the toner balance is maintained over a long period of time, fluctuations in the toner particle diameter in the developer are reduced, and even during long-term agitation in the developing device. Good and stable developability can be obtained.

  The electrostatic image developing toner can be used as a one-component magnetic toner or non-magnetic toner that does not use a carrier, and can also be used as a two-component developer.

  In addition, when used as a one-component developer that does not use a carrier, even if the balance of the toner is carried out, the fluctuation of the toner particle diameter is reduced, the filming of the toner on the developing roller, and the thinning of the toner Therefore, the toner is not fused to a member such as a blade, and good and stable developability and images can be obtained even when the developing device is used (stirred) for a long time.

In general, it is said that the smaller the particle size of the toner, the more advantageous it is to obtain a high-resolution and high-quality image, but it is disadvantageous for transferability and cleaning properties. is there.
With the electrostatic charge developing toner, good transferability and cleaning properties can be obtained even if the particle diameter is small.
Further, the phenomenon that is generally observed is the same for a toner that is larger than the number content of the polycondensate.
On the other hand, when the Dv is larger than the preferable range or the (Dv / Dn) is larger than 1.25 with respect to the electrostatic image developing toner, a high-resolution and high-quality image is obtained. It is difficult to obtain the toner, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner often increases, which is disadvantageous.

(Carrier for two components)
When the electrostatic charge developing toner is used in a two-component developer, it may be used by mixing with a magnetic carrier. The content ratio of the carrier and toner in the developer is 1 to 100 parts by mass of the carrier. Part by mass to 10 parts by mass are preferred.
As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 μm to 200 μm can be used.
Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Also, polyvinyl and polyvinylidene resins, for example, acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and polystyrene resins such as styrene acrylic copolymer resins, Halogenated olefin resins such as polyvinyl chloride, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, poly Hexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.

(Method for producing toner for developing electrostatic image)
The electrostatic image developing toner is produced from a system in which oil droplets containing at least a binder resin and a pigment are dispersed in an aqueous phase.
Specifically, from an emulsion or dispersion in which a solution or dispersion in which a toner composition containing at least a binder resin and a pigment is dissolved or dispersed in an organic solvent is emulsified or dispersed in an aqueous medium, Produced by removing the solvent.
More specifically, a solution or dispersion in which a toner composition containing at least a modified polyester resin capable of urea bonding and a pigment is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium to form a crosslinking agent. Or it manufactures by removing a solvent from the dispersion liquid obtained by making it react with an extending | stretching agent.

<Manufacture of binder resin>
The binder resin can be produced by the following method.
The polyol (1) and the polycarboxylic acid (2) are heated to 150-280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate, dibutyltin oxide, etc. To obtain a polyester having a hydroxyl group. Next, the polyisocyanate (3) is reacted with this at 40 to 140 ° C. to obtain the prepolymer (A) having the isocyanate group. Further, the amine (B) is reacted with the prepolymer (A) having an isocyanate group at 0 to 140 ° C. to obtain a urea-modified polyester (i).

When the polyisocyanate (3) is reacted and when the prepolymer (A) having the isocyanate group and the amines (B) are reacted, an organic solvent can be used as necessary. Usable organic solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and Inactive to the polyisocyanate (3) such as ethers (tetrahydrofuran, etc.). When the polyester (ii) that is not modified with a urea bond is used in combination, a polyester (ii) that is not modified with a urea bond is produced in the same manner as the polyester having a hydroxyl group. Dissolve in the solution after completion of the reaction of i) and mix.
The reaction between the prepolymer (A) having an isocyanate group and the amines (B) may be caused in an aqueous medium.

<Production of polycondensate>
The method for incorporating the polycondensate into the toner for developing an electrostatic image is not particularly limited and may be appropriately selected according to the purpose. By a polycondensation reaction of phenols and aldehydes in an organic solvent. Examples include dissolving or dispersing the obtained polycondensate, adding the polycondensate to an aqueous medium, and adding the toner after forming toner particles. The kneaded composite is preferably dissolved or dispersed in an organic solvent.

The polycondensation reaction method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, phenols and aldehydes are added to an organic solvent such as xylene, and alkali metals or alkaline earths are added. In the presence of a strong base such as a metal hydroxide, the polycondensation reaction is carried out for 3 to 20 hours while distilling off water at a temperature from 80 ° C. to the boiling point of the solvent, preferably from 100 ° C. to the boiling point of the solvent. And a method of recrystallization using a poor solvent such as alcohol, and a method of drying an organic solvent under reduced pressure and then washing with an alcohol such as methanol, ethanol and isopropanol.
As the strong base, sodium hydroxide, rubidium hydroxide, potassium hydroxide and the like can be preferably used.

The ratio of the mass of the organic solvent used here and the mass of the phenols and aldehydes is not particularly limited and can be appropriately selected according to the purpose. It is preferably used in the range of 0.5 to 100 times the total amount, and more preferably in the range of 1 to 10 times.
Moreover, the molar ratio of phenols and aldehydes used here is preferably phenols: aldehydes = 1: 0.5 to 5, more preferably phenols: aldehydes = 1: 1 to 2.
The molar ratio of the phenols and strong base used here is not particularly limited and can be appropriately selected according to the purpose. Phenols: strong base = 1: 10 to 0.00001 is preferable, Phenols: Strong base = 1: 0.01-0.001 is more preferable.

Concerning the reaction between a phenolic compound and an aldehyde compound in the presence of a strong base such as an alkali metal or alkaline earth metal hydroxide, the aldehyde undergoes an electrophilic substitution reaction at the ortho-position or para-position of the hydroxyl group of the phenolic compound. To repeat the reaction, the Organic Chemistry Handbook (Technology Hall, issued July 10, 1968, described on page 532), RIKEN Dictionary (Iwanami Shoten, 5th edition, issued February 20, 1998, No. 1) Pp. 198-199).
When a phenol compound (B) is used for phenols, the molecular weight increases due to an increase in the reaction point with the aldehyde, the molecular weight distribution becomes wide, and the molecular entanglement with the binder resin increases. The dispersion state becomes more uniform, and higher chargeability as a toner can be obtained.

When the polycondensate has poor solubility in the organic solvent, the electrostatic image developing toner comprising at least a binder resin, a release agent incompatible with the binder resin, and a pigment. The mixture of the binder resin and the polycondensate is previously kneaded by adding water to an organic solvent.
In this case, initially, the binder resin and the polycondensate are sufficiently adhered to each other so that the dispersion is effectively performed. Therefore, the polycondensate is dispersed in the binder resin. Is good, the dispersion diameter of the polycondensate is small, and good chargeability and transparency are obtained.

<Production of dissolved or dispersed product>
The binder resin and the pigment are dissolved or dispersed in an organic solvent to form a dissolved product or dispersion.
As the organic solvent, a general one can be used in consideration of solubility with the binder resin, and in particular, acetone, toluene, butanone and the like are preferable from the viewpoint of dispersibility of the polycondensate.

The polycondensate, the master batch, and the other toner composition such as the release agent and the colorant (for example, hydrophobized titanium oxide) are used to form a solution or dispersion in an aqueous medium. However, after mixing in an organic solvent and dissolving or dispersing in advance, it can be added as a dissolved or dispersed material in an aqueous medium and dispersed.
However, the other toner compositions such as the polycondensate, the release agent, and the colorant do not necessarily have to be mixed when forming particles in an aqueous medium, and formed particles. It may be added later.
For example, after forming particles not containing a colorant, the colorant can be added by a known dyeing method.

<Manufacture of toner for developing electrostatic image in aqueous medium>
Next, the solution or dispersion is dispersed in an aqueous medium to form a dispersion (emulsified dispersion) that is reacted with a crosslinking agent or an extender.
The method for producing the toner for developing an electrostatic image in an aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably produced by the following method.
As an aqueous medium, water alone may be used, but an organic solvent miscible with water may be used in combination. Examples of miscible organic solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.

The toner particles may be formed by reacting a solution or dispersion made of the prepolymer (A) having an isocyanate group in an aqueous medium with the amines (B), or the urea-modified product prepared in advance. Polyester (i) may be used.
As a method for stably forming a solution or dispersion comprising the urea-modified polyester (i) or the prepolymer (A) having an isocyanate group in an aqueous medium, the urea-modified polyester (i) or Examples thereof include a method of adding a toner raw material composition comprising the isocyanate group-containing prepolymer (A) and dissolving or dispersing the composition by shearing force.

  In the exemplary embodiment, the polycondensate and the other toner composition are not necessarily mixed when forming particles in an aqueous medium, and may be added after the particles are formed. Good.

The specific method for dissolution or dispersion is not particularly limited and may be appropriately selected according to the purpose. However, the high-speed shearing method is preferable from the viewpoint of setting the particle size of the dissolved or dispersed material to 2 to 20 μm, which is advantageous for subsequent processing.
The number of rotations when the high-speed shearing disperser is used is not particularly limited and may be appropriately selected depending on the intended purpose. Is more preferable.
The dispersion time is not particularly limited, and is not particularly limited and can be appropriately selected according to the purpose. However, in the case of a batch method, 0.1 minute to 5 minutes is preferable.
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 150 degreeC (under pressurization) is preferable, and 40 to 98 degreeC is more preferable.
A higher temperature is preferable in that the dispersion of the urea-modified polyester (i) or the prepolymer (A) having an isocyanate group has a low viscosity and is easily dispersed.

In the step of synthesizing the urea-modified polyester (i) from the prepolymer (A) having an isocyanate group, the amine (B) may be added and reacted before the toner composition is dispersed in the aqueous medium. After dispersing in the medium, amines (B) may be added to cause a reaction from the particle interface.
In this case, urea-modified polyester is preferentially produced on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.

  The amount of the aqueous medium used with respect to 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) having an isocyanate group is not particularly limited and may be appropriately selected depending on the purpose. 50 parts by mass to 2,000 parts by mass, and more preferably 100 parts by mass to 1,000 parts by mass.

When the amount is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2,000 parts by mass, the economy will deteriorate.
Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  A dispersant for emulsifying or dispersing the oily phase in which the toner composition is dispersed in an aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, alkylbenzene sulfonate, α -Anionic surfactants such as olefin sulfonates and phosphate esters, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyls Quaternary ammonium salt type cationic surfactants such as dimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride, nonionic surfactants such as fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, Dodecyldi (aminoe ) Glycine, di (octyl aminoethyl) glycine and N- alkyl -N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

Further, by using an anionic or cationic surfactant having a fluoroalkyl group, the dispersion effect can be increased in a very small amount.
The anionic surfactant having a fluoroalkyl group is not particularly limited and may be appropriately selected depending on the intended purpose. However, the fluoroalkylcarboxylic acid having 2 to 10 carbon atoms and its metal salt, perfluorooctanesulfonyl Disodium glutamate, sodium 3- [omega-fluoroalkyl (C6-C11) oxy] -1-alkyl (C3-C4) sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino]- 1-propanesulfonic acid sodium, fluoroalkyl (C11 to C20) carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, Perfluorooctane sulfonic acid diethanolamide N-propyl-N- (2hydroxyethyl) perfluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoper Fluoroalkyl (C6-C16) ethyl phosphate is preferred.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (Daikin Kogyo Co., Ltd.), Megaface F-l0, F-l20, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), F-Top EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).

  The cationic surfactant having a fluoroalkyl group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, an aliphatic primary, secondary or secondary amic acid having a fluoroalkyl group, Aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts, and trade name Surflon S-121 (Asahi Glass Co., Ltd.) ), FLORARD FC-135 (manufactured by Sumitomo 3M), Unidyne DS-202 (manufactured by Daikin Industries), Megaface F-150, F-824 (manufactured by Dainippon Ink & Co.), F-top EF-132 (Tochem) Products, manufactured by), aftergent F-300, 310 (manufactured by Neos) And the like.

  Moreover, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite, etc. can be used as an inorganic compound dispersant that is hardly soluble in water.

Further, the dispersed droplets may be stabilized by a polymer protective colloid.
The polymeric protective colloid is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid , Fumaric acid, maleic acid or maleic anhydride or other (meth) acrylic monomers containing hydroxyl groups such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, Β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol mono METAKU Rylic acid ester, glycerin monoacrylic acid ester, glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl Esters of compounds containing vinyl alcohol and carboxyl groups such as propyl ether, such as vinyl acetate, vinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acrylic chloride, methacrylic acid Acid chlorides such as chloride, nitrogen atoms such as vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine, or heterocyclic rings thereof Homopolymers or copolymers such as polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Polyoxyethylenes such as polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, and polyoxyethylene nonyl phenyl ester, and celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

Further, a dispersion stabilizer can also be used.
The dispersion stabilizer is not particularly limited and may be appropriately selected depending on the intended purpose. However, when an acid such as calcium phosphate or a substance that is soluble in alkali is used, the calcium phosphate salt may be converted with an acid such as hydrochloric acid. After dissolving, the calcium phosphate salt is removed from the fine particles by a method such as washing with water. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant can be left on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or the prepolymer (A) having an isocyanate group is soluble can be used.
The use of the solvent is preferable in that the particle size distribution becomes sharp.
In addition, the solvent preferably has a boiling point of less than 100 ° C. and is volatile from the viewpoint of easy removal.

Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more.
In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred.
As a usage-amount of the solvent with respect to 100 parts of said prepolymer (A) which has an isocyanate group, 0 mass part-300 mass parts are preferable, 0 mass part-100 mass parts are more preferable, and 25 mass parts-70 mass parts are especially. preferable.
When the solvent is used, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.

The elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure having the isocyanate group-containing prepolymer (A) and the amines (B), but preferably 10 minutes to 40 hours, 2 hours to 24 hours are more preferable.
The reaction temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C.
Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

<Removal of solvent>
Finally, the solvent is removed from the emulsified dispersion (dispersion).
The method for removing the organic solvent from the obtained emulsified dispersion is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire system is gradually raised, and the organic solvent in the droplets is removed. A method of completely evaporating and removing can be employed.
Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together.
As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

In order to fix the polycondensate obtained by the polycondensation reaction from phenols and aldehydes so as not to desorb on the toner surface, an aqueous dispersion of toner particles after removing the organic solvent in the above step Can be fixed by heating at a temperature higher than the softening temperature of the binder resin.
Thereafter, impurities remaining in the aqueous medium such as a surfactant may be washed and removed.

When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, fine particles or coarse particles which are not preferable as toner particles can be removed by a cyclone, a decanter, centrifugation, or the like in the liquid.
Of course, the classification operation may be performed after the powder is obtained as a powder after drying, but is preferably performed in a liquid in terms of efficiency.
The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation.

  The resulting dried toner powder is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or mechanical impact force is applied to the mixed powder. By fixing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the toner particles as the resulting composite.

The specific means is not particularly limited and can be appropriately selected according to the purpose.For example, a method of applying an impact force to the mixture with blades rotating at high speed, the mixture is charged into a high-speed air stream, and accelerated. There is a method in which particles or composite particles collide with an appropriate collision plate.
As an apparatus having the above-mentioned means, an ong mill (manufactured by Hosokawa Micron Co.), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.), and a pulverization air pressure reducer, a hybridization system (manufactured by Nara Machinery Co., Ltd.) ), Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

  Hereinafter, a developer, an image forming apparatus, and an image forming method using the toner for developing an electrostatic image will be described.

(Developer)
The developer of this embodiment contains at least the toner for developing an electrostatic image. Further, it contains other appropriately selected components such as a carrier. The developer may be a one-component developer or a two-component developer. However, when the developer is used in a high-speed printer or the like corresponding to the recent improvement in information processing speed, the service life is improved. In this respect, a two-component developer is preferable.

  In the case of a one-component developer using the toner for developing an electrostatic charge image, the toner particle diameter hardly fluctuates even if the balance of the toner is performed, so that the filming of the toner on the developing roller and the toner thinning are performed. The toner is not fused to a member such as a blade, and good and stable developability and an image can be obtained even in the long-term use (stirring) of the developing device.

  Further, in the case of a two-component developer using the toner for developing an electrostatic image, there is little fluctuation in the toner particle diameter in the developer even if the balance of the toner is performed over a long period of time. Good and stable developability can be realized.

  There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.

There is no restriction | limiting in particular as a material of a core material, It can select suitably from well-known things, For example, a manganese-strontium (Mn-Sr) type material of 50 emu / g-90 emu / g, manganese-magnesium (Mn -Mg) type material etc. can be used. From the viewpoint of securing the image density, a highly magnetized material such as iron powder (100 emu / g or more), magnetite (75 emu / g to 120 emu / g) is preferable. Further, in terms of being able to weaken the contact of the toner with the toner being in a spiked state and advantageous in improving the image quality, a copper-zinc (Cu—Zn) type (30 emu / g to 80 emu / g) or the like is used. Weakly magnetized materials are preferred.
These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably 10 μm to 150 μm, more preferably 40 μm to 100 μm in terms of volume average particle diameter. This is because if the average particle size (volume average particle size (D50)) is less than 10 μm, the number of fine powder systems increases in the distribution of carrier particles, and the magnetization per particle is lowered, which may cause carrier scattering. If the thickness exceeds 150 μm, the specific surface area may decrease and toner scattering may occur, and the reproducibility of the solid portion may be deteriorated particularly in a full color having a large solid portion.

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

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

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide.
In addition, the average particle diameter of the conductive powder is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.

As the resin layer, for example, after preparing a coating solution by dissolving a silicone resin or the like in a solvent, the coating solution is uniformly applied to the surface of the core material by a known coating method, dried, and then baked. Can be formed.
Examples of the application method include an immersion method, a spray method, and a brush coating method.

The solvent is not particularly limited and may be appropriately selected depending on the intended purpose.
Toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cersol butyl acetate, and the like can be used.

  The baking method is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. Techniques such as a method to be used and a method to use a microwave can be employed.

The amount of the resin layer in the carrier is preferably 0.01% by mass to 5.0% by mass.
If the amount is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. If the amount exceeds 5.0% by mass, the resin layer becomes too thick and the Granulation may occur and uniform carrier particles may not be obtained.

  When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90% by mass to 98% by mass Preferably, 93 mass%-97 mass% is more preferable.

  Since the developer of the present embodiment contains the toner for developing an electrostatic image, the developer is excellent in various properties such as aggregation resistance, chargeability, fluidity, transferability, fixability, and heat storage stability, and pigment. Has good dispersibility, has a wide color reproduction range, can sufficiently improve coloration, transparency, and clarity, and forms a high-quality image comparable to a full-color image formed by silver salt photography or printing. be able to.

  The developer can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method, and in particular, image formation described below. It can be suitably used for an apparatus and an image forming method.

(Image forming apparatus and image forming method)
The image forming apparatus (not shown) is not particularly limited as long as it uses the toner for developing an electrostatic image, and can be appropriately selected depending on the purpose. The electrostatic latent image forming unit, the developing unit, the transfer unit, and the fixing unit, preferably a cleaning unit, and other units appropriately selected as necessary, for example, a neutralizing unit, Recycling means, control means, etc.
In addition, these steps are not particularly limited and can be appropriately selected depending on the purpose.

The image forming step (image forming method) is not particularly limited as long as it uses the toner for developing an electrostatic image, and can be appropriately selected according to the purpose. A development process, a transfer process, and a fixing process, preferably including a cleaning process, and further including other processes appropriately selected as necessary, for example, a static elimination process, a recycling process, a control process, and the like.
In addition, these steps are not particularly limited and can be appropriately selected depending on the purpose.

Examples of the present invention will be described below, but the idea of the present invention is not limited to these examples.
In the following, “part” means “part by mass”.

—Polycondensate Synthesis Example 1—
0.45 mol of pt-butylphenol, 0.032 mol of 2,2′-bis (4-hydroxyphenyl) propane, 18.5 g of paraformaldehyde (0.6 mol as formaldehyde), and 3 g of 5N aqueous potassium hydroxide solution And refluxing reaction was carried out for 8 hours while distilling off water in 300 mL of xylene. The reaction solution was recrystallized using methanol, filtered, the filtrate was further washed with methanol, and the resulting solid was dried to obtain product A.

-Polycondensate synthesis example 2-
0.25 mol of pt-butylphenol, 0.225 mol of pt-octylphenol, 0.032 mol of 2,2′-bis (4-hydroxyphenyl) propane, and 18.5 g of paraformaldehyde (0.6 mol as formaldehyde) And 3 g of 5N aqueous potassium hydroxide solution, a reflux reaction was carried out for 8 hours while distilling off water in 300 mL of xylene. The reaction solution was recrystallized using methanol, filtered, the filtrate was further washed with methanol, and the resulting solid was dried to obtain product B.

-Polycondensate synthesis example 3-
0.45 mol of pt-butylphenol, 0.030 mol of 2,2′-bis (4-hydroxyphenyl) propane, 0.005 mol of 4-4′-4 ″ -ethylidinetrisphenol, 18.5 g of paraformaldehyde Using 0.6 mol of formaldehyde and 3 g of 5N aqueous potassium hydroxide, refluxing reaction was carried out for 8 hours while distilling off water in 300 mL of xylene. The reaction solution was recrystallized using methanol, filtered, the filtrate was further washed with methanol, and the obtained solid was dried to obtain a product C.

Example 1
<Synthesis of binder resin>
724 parts of bisphenol A ethylene oxide 2-mole adduct, 276 parts of isophthalic acid and 2 parts of dibutyltin oxide are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe and reacted at 230 ° C. for 8 hours at normal pressure. Further, after reacting at a reduced pressure of 10 mmHg to 15 mmHg for 5 hours, the mixture was cooled to 160 ° C., 32 parts of phthalic anhydride was added thereto, and the mixture was reacted for 2 hours.

  Subsequently, it cooled to 80 degreeC and made it react with 188 parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the polyester prepolymer which has an isocyanate group was obtained. Next, 267 parts of a polyester prepolymer having an isocyanate group and 14 parts of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester (i) having a mass average molecular weight of 64,000.

  In the same manner as above, 724 parts of bisphenol A ethylene oxide 2 mol adduct and 276 parts of terephthalic acid were polycondensed at 230 ° C. for 8 hours under normal pressure, and then reacted for 5 hours at a reduced pressure of 10 mmHg to 15 mmHg to obtain a peak molecular weight of 5,000. Of unmodified polyester (ii) was obtained.

  200 parts of urea-modified polyester (i) and 800 parts of unmodified polyester (ii) are dissolved and mixed in 2,000 parts of an ethyl acetate / MEK (1/1) mixed solvent, and ethyl acetate of binder resin (1) is mixed. / MEK solution was obtained. A part was dried under reduced pressure, and the binder resin (1) was isolated. As a result of analysis, Tg was 62 ° C.

(Preparation of toner for developing electrostatic image)
In a beaker, 240 parts of the binder resin (1) in ethyl acetate / MEK solution, 20 parts of pentaerythritol tetrabehenate (melting point 81 ° C., melt viscosity 25 cps), 4 parts of copper phthalocyanine pigment, 2 parts of product A The mixture was stirred at 12,000 rpm using a TK homomixer at 60 ° C. and uniformly dissolved and dispersed to obtain an electrostatic charge image developing toner material solution.

  In a beaker, 706 parts of ion-exchanged water, 294 parts of hydroxyapatite 10% suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.2 part of sodium dodecylbenzenesulfonate were placed uniformly. Dissolved. Next, the temperature was raised to 60 ° C., and the toner material solution was added and stirred for 10 minutes while stirring at 12,000 rpm with a TK homomixer. Then, this mixed solution was transferred to a flask equipped with a stir bar and a thermometer, heated to 30 ° C., the solvent was removed under reduced pressure, filtered, washed and dried, followed by air classification to obtain toner particles.

The volume average particle diameter (Dv) was 4.3 μm, the number average particle diameter (Dn) was 3.6 μm, and Dv / Dn was 1.19.
Further, the average dispersed particle diameter of the product A in the toner was 0.75 μm, and the number% in which the particle diameter exceeded 0.8 μm was 25%.
Next, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner for developing an electrostatic charge image of Example 1.
The evaluation results are shown in Tables 2 and 3.

(Example 2)
<Synthesis of polyester resin A>
The composition shown in Table 1 was put into a 1 L four-necked round bottom flask equipped with a thermometer, a stirrer, a condenser, and a nitrogen gas introduction tube. The flask was set in a mantle heater, and a nitrogen gas introduction tube Nitrogen gas was further introduced to raise the temperature while keeping the inside of the flask in an inert atmosphere, and then 0.05 g of dibutyltin oxide was added and reacted at a temperature of 200 ° C. to obtain polyester resin A.
This polyester resin A had a peak molecular weight of 4,200 and a glass transition point of 59.4 ° C.

<Manufacture of master batch (1)>
Product A: 50 parts Binder resin: Polyester resin A: 50 parts Water: 30 parts

  The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the product A aggregate of the polycondensate. 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 mmφ with a pulverizer to obtain a master batch (1).

<Preparation of toner for developing electrostatic image>
A toner was formed in the same manner as in Example 1 except that the addition of the polycondensate was changed to 4 parts of the master batch (1). At that time, after removing the solvent under reduced pressure, the dispersion was stirred at 60 ° C. for 1 hour to immobilize the polycondensate. Subsequent washing and drying treatment was performed in the same manner as in Example 1. The obtained toner had a volume average particle diameter (Dv) of 4.1 μm, a number average particle diameter (Dn) of 3.6 μm, and Dv / Dn of 1.14.
Further, the number average particle diameter of the product A in the toner was 0.58 μm, and the number% in which the particle diameter exceeded 0.8 μm was 7%.
Next, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain an electrostatic charge image developing toner of Example 2.
The evaluation results are shown in Tables 2 and 3.

(Example 3)
<Manufacture of master batch (2)>
Product B: 50 parts Binder resin: Polyester resin A: 50 parts Water: 30 parts

  The raw materials were mixed with a Henschel mixer to obtain a mixture in which water was infiltrated into the product B aggregate of the polycondensate. 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 mmφ with a pulverizer to obtain a master batch (2).

<Preparation of toner for developing electrostatic image>
A toner was formed in the same manner as in Example 2 except that the addition of the polycondensate was changed to 4 parts of the master batch (2). The volume average particle diameter (Dv) of the toner is 4.3 μm, the number average particle diameter (Dn) is 3.7 μm, and Dv / Dn is 1.16. Further, the number average particle diameter of the product B in the toner was 0.52 μm, and the number% in which the particle diameter exceeded 0.8 μm was 4%. Next, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain an electrostatic charge image developing toner of Example 3.
The evaluation results are shown in Tables 2 and 3.

Example 4
<Manufacture of master batch>
Product C: 50 parts Binder resin: Polyester resin A: 50 parts Water: 30 parts

  The raw materials were mixed in a Henschel mixer to obtain a mixture in which water was infiltrated into the product C aggregate of the polycondensate. 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 mmφ with a pulverizer to obtain a master batch (3).

<Preparation of toner for developing electrostatic image>
A toner was formed in the same manner as in Example 2 except that the addition of the polycondensate was changed to 4 parts of the master batch (3). The volume average particle diameter (Dv) of the toner was 4.0 μm, the number average particle diameter (Dn) was 3.5 μm, and Dv / Dn was 1.14. Further, the number average particle diameter of the product C in the toner was 0.43 μm, and the number% in which the particle diameter exceeded 0.8 μm was 2%. Next, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain an electrostatic charge image developing toner of Example 4.
The evaluation results are shown in Tables 2 and 3.

(Comparative Example 1)
<Preparation of toner for developing electrostatic image>
The binder resin (1) is converted into a toner in the same manner as in Example 1 except that the product A is not used, and the volume average particle diameter (Dv) is 4.2 μm and the number average particle diameter (Dn) is 3.5 μm. Dv / Dn was 1.19. Subsequently, 100 parts of toner particles were mixed with 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner for developing an electrostatic charge image of Comparative Example 1.
The evaluation results are shown in Tables 2 and 3.

(Comparative Example 2)
<Preparation of toner for developing electrostatic image>
Toner was prepared in the same manner as in Example 2 except that 2 parts of polyester resin A was used instead of 4 parts of master batch (1). The volume average particle diameter (Dv) was 4.5 μm, the number average particle diameter (Dn) was 3.8 μm, and Dv / Dn was 1.18. Subsequently, 0.5 part of hydrophobic silica and 0.5 part of hydrophobic titanium oxide were mixed with 100 parts of toner particles using a Henschel mixer to obtain a toner for developing an electrostatic charge image of Comparative Example 2.
The evaluation results are shown in Tables 2 and 3.

(Evaluation item)
(A) Dispersion diameter of the polycondensate in the electrostatic image developing toner The pigment and release agent (wax) in the electrostatic image developing toner are difficult to distinguish from the polycondensate in observation. A toner is prepared with a prescription without a mold agent (wax), an ultrathin section of the toner is prepared, and a cross-sectional photograph of the toner (magnification × 100, using a transmission electron microscope (H-9000H manufactured by Hitachi, Ltd.)). 000). From this photograph, an average value was obtained from the dispersion diameter of 100 randomly selected polycondensate portions. Here, the dispersion diameter of one particle is the average of the longest diameter and the shortest diameter, and the aggregate itself is one particle in the aggregated state.

(B) Particle size The average particle size and particle size distribution of the toner for developing an electrostatic charge image were measured by a car Coulter counter method. Specifically, using Coulter Multisizer III type, measurement was performed by connecting to a personal computer (manufactured by NEC) and an interface (Coulter Electronics Co., Ltd.) that outputs number distribution and volume distribution.

The measurement method is described below.
First, 0.1 mL to 5 mL of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 mL to 150 mL of the electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 mg to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles or toner are measured using the 100 μm aperture as the aperture by the measuring device. Calculate volume distribution and number distribution.
The channels include: 2.00 μm to less than 2.52 μm; 2.52 μm to less than 3.17 μm; 3.17 μm to less than 4.00 μm; 4.00 μm to less than 5.04 μm; 5.04 μm to less than 6.35 μm; .35 μm to less than 8.00 μm; 8.00 μm to less than 10.08 μm; 10.08 μm to less than 12.70 μm; 12.70 μm to less than 16.00 μm; 16.00 μm to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 μm to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm. The volume-based volume average particle diameter (Dv) obtained from the volume distribution according to the present invention, the number average particle diameter (Dn) obtained from the number distribution, and the ratio (Dv / Dn) were obtained.

(C) Average circularity The circularity of the toner of the present invention was measured by a flow type particle image analyzer FPIA-2000 (manufactured by Toa Medical Electronics Co., Ltd.). As a specific measurement method, 0.1 mL to 0.5 mL of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 mL to 150 mL of water from which impure solids have been previously removed, and further measurement is performed. Add about 0.1 to 0.5 g of sample. The suspension in which the sample is dispersed is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and the shape and distribution of the toner are adjusted by the above apparatus with a dispersion concentration of 3,000 / μL to 10,000 / μL. This was done by measuring.

(E) Haze Degree Using the ROHOR OHP sheet (type PPC-DX) as the transfer paper for the monochromatic image sample, the haze degree of the sample at a fixing belt surface temperature of 160 ° C. was measured by Suga Test Instruments Co., Ltd. Direct reading haze degree It measured by computer HGM-2DP type.
This haze degree is also referred to as haze, and is measured as a measure of the transparency of the toner. The lower the value, the higher the transparency and the better the color developability when an OHP sheet is used. The haze value indicating good color developability is preferably 30% or less, and more preferably 20% or less.

(G) Image density After outputting a solid image, the image density was measured by X-Rite (manufactured by X-Rite). This was measured at five points for each color alone, and the average was obtained for each color. 1.4 or higher is a practical level.

(H) Image granularity A photographic image was output in a single color, and the degree of granularity was visually evaluated.
(◎: Fine lines can be clearly distinguished, ○: Some parts cannot be separated, △: Some can be separated, ×: Not separated)

(I) Cleaning property The transfer residual toner on the photosensitive member that has passed the cleaning process is transferred to a white paper with a scotch tape (manufactured by Sumitomo 3M Co., Ltd.) and measured with a Macbeth reflection densitometer RD514. A value of 0.01 or less was evaluated as ◯ (good), and a value exceeding it was evaluated as x (defect).

(J), (k) Charge Amount 6 g of developer was weighed, charged into a metal cylinder that could be sealed and blown, and then the charge amount was determined. The toner concentration was adjusted to 4.5 mass% to 5.5 mass%.

(L) Fog The degree of toner contamination on the transfer paper upper surface was visually evaluated.
(◎: None, ○: Almost none, level that does not matter, Δ: Partially dirty, ×: Fully visible.)

(M) Toner scattering The toner contamination state in the copying machine was visually evaluated.
(◎: None, ○: Although it is seen near the developing unit, the machine exhaust port is not dirty, Δ: Machine exhaust port is contaminated, X: Machine exhaust port is contaminated, and scattered toner adheres to the image.)

Using an electrostatic charge image developing toner of Examples 1 to 4 and Comparative Examples 1 and 2 using a modified imgio MP C4500 machine manufactured by Ricoh, an image area ratio 5% chart continuous 50,000 sheet output durability test was performed.
The evaluation item (j) was confirmed before the output durability test, and the evaluation items (j), (l), and (m) were confirmed after the output durability test.

  As apparent from Tables 2 and 3, the electrostatic charge image developing toners of Examples 1 to 4 were superior in all evaluation items as compared with the electrostatic charge image developing toners of Comparative Examples 1 and 2. Has an effect.

Claims (12)

  It is produced from a system in which at least oil droplets containing a binder resin and a pigment are dispersed in an aqueous phase, and contains a polycondensate obtained by a polycondensation reaction of phenols and aldehydes. Toner for charge image development.   The solvent is removed from the emulsified liquid or dispersion obtained by emulsifying or dispersing the dissolved or dispersed material in which the toner composition containing at least the binder resin and the pigment is dissolved in the organic solvent in the aqueous medium. A toner for developing an electrostatic image, comprising a polycondensate produced by a polycondensation reaction of a phenol and an aldehyde.   A solution or dispersion obtained by dissolving or dispersing a toner composition containing at least a modified polyester resin capable of urea bonding and a pigment in an organic solvent is dispersed in an aqueous medium, and a crosslinking agent or an extender. For electrostatic image development, comprising a polycondensate produced by polycondensation reaction of phenols and aldehydes, produced by removing the solvent from the dispersion obtained by the reaction toner.   4. The kneaded complex obtained by kneading a polycondensate obtained by polycondensation reaction of phenols and aldehydes with a binder resin in an organic solvent is dissolved or dispersed. The toner for developing an electrostatic charge image according to 1. Phenols have one phenolic hydroxyl group, and hydrogen is bonded to the ortho position of the phenolic hydroxyl group, from p-alkylphenol, p-aralkylphenol, p-phenylphenol, p-hydroxybenzoic acid ester Bisphenols and trisphenols having at least one phenolic compound (A) selected from the group consisting of two or more phenolic hydroxyl groups, and hydrogen bonded to the ortho position of the phenolic hydroxyl group And at least one phenol compound (B) selected from the group consisting of tetrakisphenols,
The toner for developing an electrostatic charge image according to any one of claims 1 to 4, wherein the aldehyde contains at least one of paraformaldehyde and formaldehyde.   6. The toner for developing an electrostatic charge image according to claim 5, wherein the phenol compound (B) is a bisphenol.   The volume average particle diameter (Dv) of the toner particles is 3 μm to 8 μm, and the ratio Dv / Dn between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is 1.25 or less. The toner for developing an electrostatic charge image according to any one of 6.   The electrostatic image developing toner according to claim 1, wherein the toner particles have an average circularity of 0.960 to 0.980.   9. A method for producing a toner for developing an electrostatic charge image, wherein the toner for developing an electrostatic charge image according to claim 1 is produced.   A developer comprising the electrostatic image developing toner according to claim 1 and a carrier.   An image forming apparatus using the electrostatic image developing toner according to claim 1.   An image forming method using the electrostatic charge developing toner according to claim 1.