JP2014178421A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent low-temperature fixability, excellent hot-offset resistance, excellent heat-resistant storage stability, excellent separability of a recording medium from a fixing member during fixation, and excellent glossiness.SOLUTION: A toner contains at least a binder resin, monoester wax, and colorant. The toner has a melt viscosity (η) at 100°C satisfying the following formula (1); the monoester wax contains at least one monoester compound; and the at least one monoester compound has 30 to 50 carbon atoms. Formula (1): 500 Pa s≤η≤8,000 Pa s.

Description

  The present invention relates to a toner.

  In recent years, there has been a demand in the market to reduce the toner particle size for improving the quality of output images and to improve the low-temperature fixability of toner for energy saving.

  The toner obtained by the conventional kneading and pulverization method has various problems such as difficulty in reducing the particle size, irregular shape, broad particle size distribution, and high fixing energy. . In particular, toner produced by the kneading and pulverization method is cracked at the interface of the release agent (wax) during pulverization, so that a lot of wax is present on the toner surface. For this reason, there is a problem that while the releasing effect is produced, the toner easily adheres to the carrier, the photoconductor and the blade, and the overall performance is not satisfactory.

  On the other hand, in order to overcome the problems caused by the kneading and pulverizing method, a toner manufacturing method by a polymerization method has been proposed. The toner produced by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than the particle size distribution of the toner obtained by the pulverization method, and can also contain wax.

As a method for producing a toner by the polymerization method, for example, an elongation reaction product of a urethane-modified polyester is used for the purpose of improving the fluidity of the toner, improving low-temperature fixability, and improving hot offset resistance. A manufactured toner having a practical sphericity of 0.90 to 1.00 has been proposed (see, for example, Patent Document 1).
In addition, in order to provide a toner that is excellent in powder flowability and transferability in the case of a small-diameter toner, and also excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance, the following technology Has been proposed. For example, a dry toner having a circularity of 0.960 to 1.000 and having a plurality of depressions on the surface has been proposed (see, for example, Patent Document 2). Further, for example, a prepolymer composed of at least a modified polyester resin in an organic solvent, at least one of a compound that extends and crosslinks with the prepolymer, and a material containing a toner component are dissolved or dispersed, and the dissolved or dispersed material There has been proposed a dry toner obtained by carrying out a crosslinking reaction or elongation reaction in an aqueous medium and removing the solvent from the obtained dispersion (for example, see Patent Document 3).
These proposed technologies include a high molecular weight process in which a polyester prepolymer having an isocyanate group is subjected to a polyaddition reaction with an amine in a reaction system in which an organic solvent and an aqueous medium coexist.

  In addition, in order to produce a toner binder having a stable molecular weight distribution and achieve both low-temperature fixability and hot offset resistance, a toner production method having an aging step has been proposed (see, for example, Patent Documents 4 and 5). .

  In addition, for the purpose of improving low-temperature fixability, a technique for introducing a crystalline polyester resin into a polymerization method has been proposed. For example, a method for preparing a dispersion of a crystalline polyester resin using a phase separation solvent has been proposed (see, for example, Patent Document 6).

  In addition, for the purpose of reducing the particle size of the dispersion of the crystalline polyester resin, it has been proposed to reduce the particle size by mixing the crystalline polyester resin alone in a solvent, and raising the temperature and cooling (for example, (See Patent Document 7).

  In order to achieve both low-temperature fixability and heat-resistant storage stability, there has been proposed a toner using a crystalline polyester resin and having a glass transition temperature before and after thermal melting within a certain range (see, for example, Patent Document 8). .

  In order to achieve both low-temperature fixability, heat-resistant storage stability, and offset resistance, a technique using a specific ester wax has been proposed (see, for example, Patent Document 9).

  However, in these previously proposed techniques, excellent low-temperature fixability, excellent hot offset resistance, excellent heat-resistant storage stability, and excellent separation between the fixing member and the recording medium during fixing are required in recent years. It has not yet been possible to obtain a toner having both the properties and excellent glossiness.

  Therefore, it is possible to provide a toner that has both excellent low-temperature fixability, excellent hot offset resistance, excellent heat-resistant storage stability, excellent separation between the fixing member and the recording medium during fixing, and excellent glossiness. Is currently required.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention has excellent low-temperature fixability, excellent hot offset resistance, excellent heat-resistant storage stability, excellent separation between the fixing member and the recording medium during fixing, and excellent glossiness. It is an object to provide a toner possessed together.

Means for solving the problems are as follows. That is,
The toner of the present invention is a toner containing at least a binder resin, a monoester wax, and a colorant,
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1):
The monoester wax contains at least one monoester compound, and the carbon number of the at least one monoester compound is in the range of 30 to 50.
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)

  According to the present invention, the conventional problems can be solved, and excellent low-temperature fixability, excellent hot offset resistance, excellent heat-resistant storage stability, and excellent fixing members and recording media at the time of fixing. Therefore, it is possible to provide a toner having both excellent separation properties and excellent glossiness.

FIG. 1 is a graph showing an example of a flow curve of a flow tester used in the evaluation of thermal characteristics. FIG. 2 is a schematic diagram of an apparatus for measuring the pressing force of the recording medium used for the evaluation of the separability of the example. FIG. 3 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. FIG. 4 is a partially enlarged view of FIG.

(toner)
The toner of the present invention contains at least a binder resin, a monoester wax, and a colorant, and further contains other components as necessary.
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1).
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
The monoester wax contains at least one monoester compound.
The carbon number of the at least one monoester compound is in the range of 30-50.

When the melt viscosity of the toner at the time of fixing is too low, hot offset and cold offset occur, and the separation property between the recording medium and the fixing member is lowered. On the other hand, when the melt viscosity of the toner at the time of fixing is too high, the low-temperature fixability deteriorates.
Further, when the melt viscosity of the wax at the time of fixing is lowered, the hot offset and the friction resistance of the fixed image are improved. However, if the melt viscosity of the wax at the time of fixing is too low, the low-temperature fixability may deteriorate.
Therefore, the inventors have excellent low-temperature fixability, excellent hot offset resistance, excellent heat-resistant storage stability, excellent separation between the fixing member and the recording medium during fixing, and excellent glossiness. In order to provide a toner having the same as the above, it has been intensively studied. As a result, it has been found useful to use certain monoester waxes. However, monoester waxes generally have low resistance, and there is a problem that it is difficult to achieve both hot offset resistance and low-temperature fixing. As a result of further studies, even when a low-resistance monoester wax is used, the melt viscosity (η _T ) at 100 ° C. of the toner satisfies the above formula (1), thereby preventing hot offset resistance and low temperature. It was found that both fixing and fixing can be achieved. As a result, the toner contains at least a binder resin, a monoester wax, and a colorant, and the melt viscosity (η _T ) of the toner at 100 ° C. satisfies the formula (1). And at least one monoester compound, and the carbon number of the at least one monoester compound is in the range of 30 to 50, so that excellent low-temperature fixability and excellent hot offset resistance are obtained. The inventors have found that a toner having both excellent heat-resistant storage stability, excellent separation between a fixing member and a recording medium at the time of fixing, and excellent glossiness can be obtained.

<Binder resin>
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, a polyester resin, a styrene-acryl resin, a polyol resin, a vinyl resin, a polyurethane resin, an epoxy resin, a polyamide resin, a polyimide Examples thereof include resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. These may be used individually by 1 type and may use 2 or more types together. Among these, a polyester resin is preferable.

-Polyester resin-
There is no restriction | limiting in particular as said polyester resin, According to the objective, it can select suitably, For example, a crystalline polyester resin, an amorphous polyester resin, a modified polyester resin etc. are mentioned. Among these, the polyester resin preferably contains a crystalline polyester resin in that excellent low-temperature fixability can be obtained.

  The binder resin preferably contains two or more kinds of binder resins. The two or more binder resins preferably contain a crystalline polyester resin. Examples of the two or more binder resins include a combination of the crystalline polyester resin and the amorphous polyester resin, a combination of the crystalline polyester resin, the amorphous polyester resin, and the modified polyester resin. Is mentioned.

--- Crystalline polyester resin--
There is no restriction | limiting in particular as said crystalline polyester resin, According to the objective, it can select suitably, For example, the crystalline polyester resin etc. which are obtained by making a polyol and polycarboxylic acid react are mentioned.
Examples of the polyol include diols and trihydric or higher alcohols.
Examples of the diol include saturated aliphatic diols having 2 to 12 carbon atoms. Examples of the saturated aliphatic diol having 2 to 12 carbon atoms include ethylene glycol, 1,2-propaneol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,8 -Octanediol, 1,10-decanediol, 1,12-dodecanediol and the like.
Examples of the polycarboxylic acid include dicarboxylic acid and trivalent or higher carboxylic acid. Examples of the dicarboxylic acid include dicarboxylic acids having 2 to 12 carbon atoms having a carbon-carbon double bond, saturated dicarboxylic acids having 4 to 12 carbon atoms, and the like. Examples of the dicarboxylic acid include fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, and 1,12-dodecanedioic acid. Etc. These dicarboxylic acids may be acid anhydrides, acid halides, and alkyl esters having 1 to 4 carbon atoms.
Among these, from the point that the crystallinity of the crystalline polyester resin is high and shows a sudden viscosity change near the melting point, the saturated aliphatic diol having 2 to 12 carbon atoms and the saturated dicarboxylic acid having 4 to 12 carbon atoms A crystalline polyester resin obtained by reacting is preferred.

  Examples of a method for controlling the crystallinity and softening point of the crystalline polyester resin include, for example, a polyol having a trivalent or higher alcohol such as glycerin or a polycarboxylic acid having a trivalent or higher carboxylic acid such as trimellitic anhydride during synthesis. And a method of performing condensation polymerization by adding.

The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. As an example of a crystalline polyester resin, an infrared absorption spectrum having absorption based on δCH (out-of-plane variable angular vibration) of an olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ can be simply mentioned.

A crystalline polyester resin having a sharp molecular weight distribution and a low molecular weight is excellent in low-temperature fixability. However, if there are many components having a low molecular weight, the heat resistant storage stability may be lowered.
The weight-average molecular weight of the crystalline polyester resin-soluble o-dichlorobenzene is not particularly limited and may be appropriately selected depending on the intended purpose. However, with a measured value by GPC (gel permeation chromatography), 3,000 to 50,000 are preferable, and 3,000 to 30,000 are more preferable. When the weight average molecular weight is less than 3,000, the heat-resistant storage stability may be decreased, and when it exceeds 50,000, the low-temperature fixability may be decreased.
There is no restriction | limiting in particular as a number average molecular weight of the said crystalline polyester resin, Although it can select suitably according to the objective, 3,000-5,000 are preferable. When the number average molecular weight is less than 3,000, the heat-resistant storage stability may be decreased, and when it exceeds 5,000, the low-temperature fixability may be decreased.
There is no restriction | limiting in particular as ratio (Mw / Mn) of the weight average molecular weight Mw of the crystalline polyester resin, and a number average molecular weight Mn, Although it can select suitably according to the objective, 1-5 are preferable. When the ratio (Mw / Mn) exceeds 5, the heat resistant storage stability may be lowered.

There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin, Although it can select suitably according to the objective, 40 to 80 degreeC is preferable. When the melting point of the crystalline polyester resin is less than 40 ° C., the heat-resistant storage stability may be lowered, and when it exceeds 80 ° C., the low-temperature fixability may be lowered.
Here, the melting point of the crystalline polyester resin can be measured using, for example, a DSC system (differential scanning calorimeter).

When the acid value of the crystalline polyester resin is A and the hydroxyl value of the crystalline polyester resin is B, the acid value and the hydroxyl value of the crystalline polyester resin preferably satisfy the following relational expressions.
10 mgKOH / g <A <40 mgKOH / g
0 mgKOH / g <B <20 mgKOH / g
20 mgKOH / g <A + B <40 mgKOH / g
When the acid value A of the crystalline polyester resin is 10 mgKOH / g or less, the affinity with paper as a recording medium may be lowered, and heat resistant storage stability may be lowered. On the other hand, when the acid value A of the crystalline polyester resin is 40 mgKOH / g or more, or the hydroxyl value is 20 mgKOH / g or more, the charging ability of the toner under high temperature and high humidity may be lowered.
Further, when the total of the acid value and the hydroxyl value is 20 mgKOH / g or less, the compatibility between the crystalline polyester resin and other binder resin (for example, amorphous polyester resin) is lowered, and the low-temperature fixability is reduced. May not be sufficiently obtained. On the other hand, if the total of the acid value and the hydroxyl value is 40 mgKOH / g or more, the compatibility between the crystalline polyester resin and other binder resin (for example, amorphous polyester resin) is excessively increased, so May decrease.
Here, the acid value and the hydroxyl value can be measured by a method defined in JIS K0070.

  The content of the crystalline polyester resin in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 parts by mass to 25 parts by mass with respect to 100 parts by mass of the toner. 5 mass parts-20 mass parts are more preferable. When the content is less than 5 parts by mass, the low-temperature fixability may be deteriorated. When the content is more than 25 parts by mass, the heat resistant storage stability and the toner productivity may be deteriorated.

Here, as the organic solvent, the crystalline polyester resin is completely dissolved at a high temperature to form a uniform solution. On the other hand, when cooled to a low temperature, the crystalline polyester resin phase-separates and becomes an opaque heterogeneous solution. Those that form are preferred.
Examples of the organic solvent include toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used individually by 1 type and may use 2 or more types together.

  Since the crystalline polyester resin has high crystallinity, the crystalline polyester resin exhibits a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. That is, the heat resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, the viscosity is sharply lowered (sharp melt property) to be fixed. Therefore, by using the crystalline polyester resin, it is possible to design a toner having both good heat storage stability and low temperature fixability. Further, the release width (difference between the fixing lower limit temperature and the hot offset occurrence temperature) is also good.

--- Amorphous polyester resin--
There is no restriction | limiting in particular as said amorphous polyester resin, According to the objective, it can select suitably, For example, the amorphous polyester resin etc. which are obtained by making a polyol and polycarboxylic acid react are mentioned.
In the present invention, the non-crystalline polyester resin refers to a product obtained by reacting a polyol and a polycarboxylic acid as described above, and a modified polyester resin, for example, a prepolymer described later, In the present invention, the modified polyester resin obtained by crosslinking and / or extending the prepolymer is not included in the amorphous polyester resin, but is treated as a modified polyester resin.

Examples of the polyol include diols and trihydric or higher alcohols.
Examples of the polyol include ethylene glycol, propylene glycol, neopentyl glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol, or alkylene (2 to 3 carbon atoms) oxide (average added mole number). 1-10) Additives and the like. Moreover, the alkylene (C2-C3) oxide (average addition mole number 1-10) addition product of bisphenol A, etc. are mentioned.
Examples of the alkylene (carbon number 2 to 3) oxide (average addition mole number 1 to 10) adduct of bisphenol A include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane. And polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as said polycarboxylic acid, According to the objective, it can select suitably, For example, C6-C12 saturated aliphatic dicarboxylic acid, C8-C12 aromatic dicarboxylic acid, Fumaric acid Maleic acid, dodecenyl succinic acid, octyl succinic acid, trimellitic acid, pyromellitic acid and the like.
Examples of the saturated aliphatic dicarboxylic acid having 6 to 12 carbon atoms include adipic acid.
Examples of the aromatic dicarboxylic acid having 8 to 12 carbon atoms include phthalic acid, isophthalic acid, terephthalic acid, and the like.
These polycarboxylic acids may be acid anhydrides, acid halides, and alkyl esters having 1 to 4 carbon atoms.
These may be used individually by 1 type and may use 2 or more types together.

  The amorphous polyester resin, the prepolymer described later, and the resin obtained by crosslinking and / or elongation reaction of this prepolymer (that is, a modified polyester resin) are not particularly limited and are appropriately selected depending on the purpose. However, it is preferable that at least a part is compatible. When these are compatible, low-temperature fixability and hot offset resistance can be improved. For this reason, it is preferable that the polyol and polycarboxylic acid which comprise the said amorphous polyester resin, and the polyol and polycarboxylic acid which comprise the said prepolymer are similar compositions.

When the acid value of the crystalline polyester resin is A and the acid value of the amorphous polyester resin is C, it is preferable to satisfy the following formula: −10 mgKOH / g <(A−C) <10 mgKOH / g.
When the acid value difference (AC) between the crystalline polyester resin and the amorphous polyester resin is 10 mgKOH / g or more, the compatibility between the crystalline polyester resin and the amorphous polyester resin is poor, The low temperature fixability may be inferior. In addition, the crystalline polyester resin is likely to be exposed on the toner surface, which may easily cause contamination and filming of the developing portion.

  There is no restriction | limiting in particular as a weight average molecular weight of the said amorphous polyester resin, Although it can select suitably according to the objective, 1,000-10,000 are preferable.

  There is no restriction | limiting in particular as glass transition temperature of the said amorphous polyester resin, Although it can select suitably according to the objective, 35 to 70 degreeC is preferable.

--Modified polyester resin--
There is no restriction | limiting in particular as said modified polyester resin, According to the objective, it can select suitably, For example, polyester resin (this specification which has a site | part which can react with an active hydrogen group containing compound and the said active hydrogen group containing compound) The reaction product with “prepolymer” or “polyester prepolymer”) may be used.

--- Active hydrogen group-containing compound ---
The active hydrogen group-containing compound is a compound that reacts with a polyester resin having a site capable of reacting with the active hydrogen group-containing compound.

  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 and 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.

The active hydrogen group-containing compound is not particularly limited and may be appropriately selected depending on the purpose. The polyester resin having a site capable of reacting with the active hydrogen group-containing compound is a polyester resin containing an isocyanate group. In some cases, amines are preferred in that the polyester resin can be made to have a high molecular weight by an elongation reaction, a crosslinking reaction or the like.
The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher valent amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of a diamine and a small amount of a trivalent or higher amine are preferable.

  There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine etc. are mentioned. There is no restriction | limiting in particular as said aromatic diamine, According to the objective, it can select suitably, For example, phenylenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane etc. are mentioned. The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophorone diamine. It is done. There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine etc. are mentioned.

  The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

  The amino alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.

  The amino mercaptan 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 is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.

  There is no restriction | limiting in particular as what blocked the said amino group, According to the objective, it can select suitably, For example, it is obtained by blocking an amino group with ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketimine compounds and oxazolidone compounds.

--- Polyester resin having a site capable of reacting with active hydrogen group-containing compound ---
There is no restriction | limiting in particular as a polyester resin which has a site | part which can react with the said active hydrogen group containing compound, According to the objective, it can select suitably, For example, polyester resin containing an isocyanate group (henceforth "isocyanate group. And may be referred to as “polyester prepolymer having”). There is no restriction | limiting in particular as the polyester resin containing the said isocyanate group, According to the objective, it can select suitably, For example, the polyester resin which has an active hydrogen group obtained by polycondensing a polyol and polycarboxylic acid, Reaction products with polyisocyanate and the like can be mentioned.

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

The diol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, chain alkylene glycol, diol having an oxyalkylene group, alicyclic diol, bisphenols, alkylene oxide of alicyclic diol Examples include adducts and alkylene oxide adducts of bisphenols.
Examples of the chain alkylene glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, and the like.
Examples of the diol having an oxyalkylene group include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.
Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like.
In addition, there is no restriction | limiting in particular as carbon number of the said chain | strand-shaped alkylene glycol, Although it can select suitably according to the objective, 2-12 are preferable.
Among these, at least one of a chain alkylene glycol having 2 to 12 carbon atoms and an alkylene oxide adduct of bisphenols is preferable, and an alkylene oxide adduct of bisphenols, an alkylene oxide adduct of bisphenols and a carbon number. Is more preferably a mixture with a chain alkylene glycol of 2 to 12.

The trihydric or higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a trihydric or higher aliphatic alcohol, a trihydric or higher polyphenol, or an alkylene of a trihydric or higher polyphenol. Examples include oxide adducts.
The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol.
The trihydric or higher polyphenols are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trisphenol PA, phenol novolac, and cresol novolak.
Examples of the alkylene oxide adducts of trihydric or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trihydric or higher polyphenols.
When the diol and the trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol (trihydric or higher alcohol / diol) is not particularly limited, and is appropriately determined depending on the purpose. Although it can select, 0.01 mass%-10 mass% are preferable, and 0.01 mass%-1 mass% are more preferable.

The polycarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid. It is done. These may be used individually by 1 type and may use 2 or more types together.
Among these, dicarboxylic acid, a mixture of dicarboxylic acid and a small amount of tricarboxylic or higher polycarboxylic acid is preferable.

There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, bivalent alkanoic acid, bivalent alkenoic acid, aromatic dicarboxylic acid etc. are mentioned.
The divalent alkanoic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, and sebacic acid.
There is no restriction | limiting in particular as said bivalent alkenoic acid, Although it can select suitably according to the objective, C4-C20 bivalent alkenoic acid is preferable. There is no restriction | limiting in particular as said C4-C20 bivalent alkenoic acid, According to the objective, it can select suitably, For example, a maleic acid, a fumaric acid, etc. are mentioned.
There is no restriction | limiting in particular as said aromatic dicarboxylic acid, Although it can select suitably according to the objective, C8-C20 aromatic dicarboxylic acid is preferable. There is no restriction | limiting in particular as said C8-C20 aromatic dicarboxylic acid, According to the objective, it can select suitably, For example, a phthalic acid, isophthalic acid, a terephthalic acid, naphthalene dicarboxylic acid etc. are mentioned.

There is no restriction | limiting in particular as said trivalent or more carboxylic acid, According to the objective, it can select suitably, For example, trivalent or more aromatic carboxylic acid etc. are mentioned.
There is no restriction | limiting in particular as said trivalent or more aromatic carboxylic acid, Although it can select suitably according to the objective, C9-C20 trivalent or more aromatic carboxylic acid is preferable. The trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include trimellitic acid and pyromellitic acid.

As the polycarboxylic acid, an acid anhydride or a lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used.
There is no restriction | limiting in particular as said lower alkyl ester, According to the objective, it can select suitably, For example, methyl ester, ethyl ester, isopropyl ester etc. are mentioned.
When the dicarboxylic acid and the trivalent or higher carboxylic acid are used in combination, the mass ratio of the trivalent or higher carboxylic acid to the dicarboxylic acid (trivalent or higher carboxylic acid / dicarboxylic acid) is not particularly limited. However, 0.01 mass% to 10 mass% is preferable, and 0.01 mass% to 1 mass% is more preferable.

  In the polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid (hydroxyl group of the polyol / carboxyl group of the polycarboxylic acid) is not particularly limited. 1 to 2 is preferable, 1 to 1.5 is more preferable, and 1.02 to 1.3 is particularly preferable.

There is no restriction | limiting in particular as content of the structural unit derived from the polyol in the polyester prepolymer which has the said isocyanate group, Although it can select suitably according to the objective, 0.5 mass%-40 mass% are preferable, 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are especially preferable.
When the content is less than 0.5% by mass, the hot offset resistance is lowered, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner. When the content exceeds 40% by mass, Low temperature fixability may be reduced.

The polyisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and phenol derivatives thereof. , Oxime, caprolactam and the like blocked.
The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.
The alicyclic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.
The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanato Examples include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.
The araliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α, α, α ′, α′-tetramethylxylylene diisocyanate.
There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (isocyanatoalkyl) isocyanurate, a tris (isocyanatocycloalkyl) isocyanurate, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.

  When the polyisocyanate and a polyester resin having a hydroxyl group are reacted, the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is not particularly limited and is appropriately selected depending on the purpose. 1 to 5 is preferable, 1.2 to 4 is more preferable, and 1.5 to 2.5 is particularly preferable. When the equivalent ratio is less than 1, hot offset resistance may be deteriorated. When the equivalent ratio is more than 5, low-temperature fixability may be deteriorated.

  There is no restriction | limiting in particular as content of the structural unit derived from polyisocyanate in the polyester prepolymer which has the said isocyanate group, Although it can select suitably according to the objective, 0.5 mass%-40 mass% are preferable. 1 mass%-30 mass% are more preferable, and 2 mass%-20 mass% are especially preferable. When the content is less than 0.5% by mass, the hot offset resistance may be deteriorated, and when it exceeds 40% by mass, the low-temperature fixability may be deteriorated.

  There is no restriction | limiting in particular as an average number of the isocyanate groups which the polyester prepolymer which has the said isocyanate group has per molecule, Although it can select suitably according to the objective, 1 or more are preferable and 1.5-3 are More preferably, 1.8 to 2.5 is particularly preferable. When the average number is less than 1, the molecular weight of the modified polyester resin is lowered, and the hot offset resistance may be lowered.

The modified polyester resin can be produced by a one-shot method or the like. As an example, a method for producing a urea-modified polyester resin will be described.
First, a polyol and a polycarboxylic acid are heated to 150 ° C. to 280 ° C. in the presence of a catalyst such as tetrabutoxy titanate or dibutyl tin oxide. The polyester resin which has is obtained. Next, a polyester resin having a hydroxyl group is reacted with polyisocyanate at 40 ° C. to 140 ° C. to obtain a polyester prepolymer having an isocyanate group. Furthermore, the polyester prepolymer having an isocyanate group is reacted with amines at 0 ° C. to 140 ° C. to obtain a urea-modified polyester resin.

There is no restriction | limiting in particular as number average molecular weight (Mn) of the said modified polyester resin, Although it can select suitably according to the objective, 1,000-10,000 are preferable and 1,500-6,000 are more. preferable.
In addition, when making the polyester resin which has a hydroxyl group and polyisocyanate react, and when making the polyester prepolymer which has an isocyanate group, and amines react, a solvent can also be used as needed.
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include those which are inert with respect to isocyanate groups such as aromatic solvents, ketones, esters, amides and ethers. Can be mentioned. Examples of the aromatic solvent include toluene and xylene. Examples of the ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the esters include ethyl acetate. Examples of the amides include dimethylformamide and dimethylacetamide. Examples of the ethers include tetrahydrofuran.

<Monoester wax>
The monoester wax contains at least one monoester compound.
The carbon number of the at least one monoester compound is in the range of 30-50.

  In general, ester wax is synthesized from a higher alcohol component and a higher carboxylic acid component. These higher alcohol components and higher carboxylic acid components are usually obtained from natural products, and are generally composed of a mixture having an even number of carbon atoms. When these mixtures are esterified as they are, by-products having various similar structures in addition to the target ester compound are produced as a by-product, which tends to adversely affect the properties of the toner. In that case, a monoester wax having a controlled carbon number distribution can be obtained by purifying raw materials and products using solvent extraction or vacuum distillation.

The monoester compound is obtained, for example, by esterifying a monohydric alcohol and a monovalent carboxylic acid, and has one ester bond.
The monoester compound is represented by, for example, the general formula R ¹ —COO—R ² . R ¹ represents a linear alkyl group. R ² represents a linear alkyl group.
Examples of the monoester compound include the following compounds.

The carbon number of the at least one monoester compound is in the range of 30 to 50, and preferably in the range of 32 to 46 carbon atoms.
When the monoester wax contains a monoester compound having less than 30 carbon atoms, the hot offset resistance and gloss become insufficient, and when the monoester wax contains a monoester compound having more than 50 carbon atoms, the low-temperature fixability becomes insufficient. .

There is no restriction | limiting in particular as a method of controlling carbon number of the said monoester compound, According to the objective, it can select suitably, For example, changing the composition of a higher carboxylic acid etc. are mentioned.
The carbon number of the monoester compound can be measured, for example, by thermogravimetry (TGA).

The carbon number between the carbon number (C _max ) of the monoester compound having the maximum carbon number in the monoester wax and the carbon number (C _min ) of the monoester compound having the minimum carbon number in the monoester wax. The range (C _max −C _min +1) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 11 or less, more preferably 9 or less, still more preferably 2 to 9, and 6 to 9 Is particularly preferred. When the carbon number range (C _max −C _min +1) exceeds 11, there is no sharp melt property, and it is difficult to achieve both low-temperature fixing and high-temperature offset resistance, and the heat-resistant storage stability as a toner may deteriorate. .

In addition to the monoester compound, the monoester wax preferably contains a higher alcohol (for example, an alcohol having 5 to 20 carbon atoms) and a higher carboxylic acid (for example, a carboxylic acid having 2 to 20 carbon atoms). .
The sum of the acid value (mgKOH / g) and the hydroxyl value (mgKOH / g) of the monoester wax is not particularly limited and may be appropriately selected depending on the intended purpose, but is 1 mgKOH / g to 20 mgKOH / g. Is preferable, and 3 mgKOH / g to 15 mgKOH / g is more preferable. The acid value (AV) and the hydroxyl value (OHV) represent a carboxyl group and a hydroxy group site showing hydrophilicity in the monoester wax. When the AV and the OHV are large, the monoester wax is hydrophilic. Increase. For this reason, if the AV and the OHV are too large, for example, the affinity with a lipophilic binder resin is lowered, and surface uneven distribution in the binder resin is likely to occur. In this case, for example, when producing in O / W type emulsification, elution from the oil phase to the aqueous phase is likely to occur, resulting in a decrease in yield and quality due to a deterioration in the particle size distribution of the obtained toner. There is. Further, when the toner is used as a two-component developer, filming on the carrier particles and the photoreceptor surface due to the detachment of the monoester wax from the toner surface tends to occur. In addition, the triboelectric charge amount of the toner may decrease, and a sufficient triboelectric charge amount may be continuously obtained. When the sum of the acid value (mgKOH / g) and the hydroxyl value (mgKOH / g) of the monoester wax is in the more preferable range, it is advantageous in that the volatility of the monoester wax can be suppressed. .

  There is no restriction | limiting in particular as melting | fusing point of the said monoester wax, Although it can select suitably according to the objective, 30 to 90 degreeC is preferable, 40 to 80 degreeC is more preferable, 40 to 65 degreeC is especially preferable. preferable. When the melting point is within the more preferable range, it is advantageous in terms of low-temperature fixability and hot offset resistance.

There is no restriction | limiting in particular as melt viscosity ((eta) _W ) in 100 degreeC of the said monoester wax, Although it can select suitably according to the objective, It is preferable to satisfy | fill following formula (2).
1.0 mPa · s ≦ η _W ≦ 20 mPa · s (2)
When the melt viscosity (η _W ) is less than 1.0 mPa · s, hot offset resistance, excellent separation between the fixing member and the recording medium during fixing, and heat resistant storage stability may be deteriorated. When the melt viscosity (η _W ) exceeds 20 mPa · s, the low-temperature fixability and the excellent separation between the fixing member and the recording medium during fixing may be deteriorated.
The melt viscosity (η _W ) can be measured using, for example, a rotary viscometer (for example, DV-E, manufactured by Brookfield).

  There is no restriction | limiting in particular as content of the said monoester wax, Although it can select suitably according to the objective, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts- 16 parts by mass is more preferable, and 3 parts by mass to 10 parts by mass is particularly preferable. When the content is within the more preferable range, it is advantageous in terms of excellent separation between the fixing member and the recording medium at the time of fixing.

  The toner may contain a wax other than the monoester wax, but preferably does not contain a wax other than the monoester wax.

<Colorant>
The colorant 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), 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 Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisa red, para Lortho 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 red, Lazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren 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 Green Lake, Malachite Grits Enlake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon and the like. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 parts. Part by mass is more preferable.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, in addition to the polyester resin, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, or a polymer of its substitution product; styrene-p-chlorostyrene. Copolymer, Styrene-propylene copolymer, Styrene-vinyltoluene copolymer, Styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-butyl acrylate Copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer Coalescence, styrene-acrylonitrile Copolymer, Styrene-vinyl methyl ketone copolymer, Styrene-butadiene copolymer, Styrene-isoprene copolymer, Styrene-acrylonitrile-indene copolymer, Styrene-maleic acid copolymer, Styrene-maleic acid ester copolymer Styrene copolymers such as polymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin Rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used individually by 1 type and may use 2 or more types together.

  The master batch can be obtained, for example, by mixing and kneading the master batch resin and the colorant under high shear. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, a so-called flushing method in which an aqueous paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, the colorant is transferred to the resin side, and moisture and organic solvent components are removed is called a colorant. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

<Other ingredients>
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a charge control agent, an inorganic fine particle, a fluid improvement agent, a cleaning property improvement agent, a magnetic material etc. are mentioned.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose.For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, Alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Can be mentioned.

  Examples of commercially available charge control agents include Nigrosine dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, and oxynaphthoic acid metal complex E-82. , Salicylic acid metal complex E-84, phenol condensate E-89 (above, manufactured by Orient Chemical Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical) Kogyo Co., Ltd.), LRA-901, LR-147 (above, Nippon Carlit Co., Ltd.), which is a boron complex, and the like.

  The content of the charge control agent is uniquely determined by the type of the binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. Although it is not, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of said binder resin, and 0.2 mass part-5 mass parts are more preferable. When the content 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 attraction force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be reduced. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they may be added when dissolved or dispersed directly in an organic solvent, or fixed on the toner surface after preparation of toner particles. You may let them.

-Inorganic fine particles-
The inorganic fine particles can be used as an external additive for imparting fluidity, developability and chargeability to toner particles.
The inorganic fine particles are not particularly limited and can 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, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Is mentioned. These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a primary particle diameter of the said inorganic fine particle, Although it can select suitably according to the objective, 5 nm-2 micrometers are preferable, and 5 nm-500 nm are more preferable.
As the specific surface area by BET method of the inorganic fine particles is not particularly limited and may be appropriately selected depending on the ^purpose, 20m ² / ^g~500m 2 / g are preferred.

  There is no restriction | limiting in particular as content of the said inorganic fine particle, Although it can select suitably according to the objective, 0.01 mass part-5 mass parts are preferable with respect to 100 mass parts of the said toner, 0.01 Mass parts to 2.0 parts by mass are more preferable.

-Fluidity improver-
The fluidity improver means a material that can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity.
Examples of the fluidity improver include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Etc.

-Cleaning improver-
The cleaning property improving agent is added to the toner in order to remove the developer after transfer remaining on the electrostatic latent image carrier or the primary recording medium.
Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, polymethyl methacrylate fine particles, polystyrene fine particles, and the like.

-Magnetic material-
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

  In the toner, the binder resin contains the crystalline polyester resin and the amorphous polyester resin, and at least the crystalline polyester resin, the amorphous polyester resin, the colorant, and the monoester wax It is preferable that the toner material containing a toner material is obtained by dissolving or dispersing an oil phase in an organic solvent in an aqueous medium and removing the organic solvent from the obtained dispersion. More preferably, the aqueous medium contains resin fine particles.

In the toner, the binder resin includes the crystalline polyester resin, the amorphous polyester resin, and a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. A reaction product with the body, at least the active hydrogen group-containing compound, a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound, the crystalline polyester resin, the amorphous polyester resin, An oil phase obtained by dissolving or dispersing the toner material containing the colorant and the monoester wax is dispersed in an aqueous medium to obtain an emulsified dispersion, and the binder resin precursor in the emulsified dispersion. And the active hydrogen group-containing compound are preferably reacted to remove the organic solvent. The aqueous medium preferably contains fine resin particles.
Examples of the binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “binder resin precursor”) are capable of reacting with the active hydrogen group-containing compound. Examples thereof include a polyester resin having a site.

The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1).
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
When the melt viscosity (η _T ) is less than 500 Pa · s or more than 8,000 Pa · s, excellent low-temperature fixability, excellent hot offset resistance, excellent heat-resistant storage stability, and during fixing A toner having both excellent separation property between the fixing member and the recording medium and excellent glossiness cannot be obtained.
The melt viscosity (η _T ) can be measured using, for example, an elevated flow tester (for example, CFT100 type, manufactured by Shimadzu Corporation).

The glass transition temperature (Tg1st) at the first temperature increase in the differential scanning calorimetry (DSC) of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 35 ° C to 100 ° C. 40 ° C to 65 ° C is more preferable, 45 ° C to 65 ° C is even more preferable, and 50 ° C to 60 ° C is particularly preferable. When the glass transition temperature (Tg1st) is within the more preferable range, it is advantageous in terms of low-temperature fixability and hot offset resistance.
There is no restriction | limiting in particular as glass transition temperature (Tg2nd) in the temperature rising 2nd time of the differential scanning calorimetry (DSC) of the said toner, Although it can select suitably according to the objective, 20 to 40 degreeC is preferable. When the glass transition temperature (Tg2nd) is less than 20 ° C., blocking in the developing device and filming on the electrostatic latent image carrier may occur. When the glass transition temperature (Tg2nd) exceeds 40 ° C., the low-temperature fixability may deteriorate.
Here, the glass transition temperature of the toner can be measured using, for example, a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation).
For example, the DSC curve is measured using the differential scanning calorimeter. From the obtained DSC curve, an analysis program is used to select the DSC curve at the first temperature rise, and the endothermic shoulder temperature in the analysis program is used to determine the glass transition temperature Tg1st at the first temperature rise. it can. The DSC curve at the second temperature increase can be selected, and the glass transition temperature Tg2nd at the second temperature increase can be obtained using the endothermic shoulder temperature.

The toner is determined by the total reflection absorption infrared spectroscopy, the peak intensity of the monoester wax and the peak intensity of the crystalline polyester resin from the 2850 cm ^-1 and (P2850), the binder resin from the 828 cm ^-1 The strength ratio (P2850 / P828) to (P828) is preferably 0.10 to 0.20, and more preferably 0.15 to 0.20. When the intensity ratio (P2850 / P828) is within the preferred range, it is advantageous in terms of excellent separation between the fixing member and the recording medium during fixing.
When the intensity ratio (P2850 / P828) is less than 0.10, the monoester wax does not ooze out from the image formed from the toner at the time of fixing, the hot offset resistance is lowered, and the paper and fixing belt , Separation from the roller may be reduced.
When the strength ratio (P2850 / P828) exceeds 0.20, the monoester wax and the crystalline polyester resin are often present on the surface of the toner particles, and the low-temperature fixability may be deteriorated. Further, the adhesion force between the toner and the other member increases, the fluidity of the toner may decrease, and the transfer to the intermediate transfer member or paper may decrease.
Here, the intensity ratio (P2850 / P828) can be determined by, for example, total reflection absorption infrared spectroscopy (FTIR-ATR), and indicates a relative monoester wax amount in the vicinity of the toner particle surface.

The 1/2 outflow temperature measured with the toner flow tester is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 80 ° C. to 150 ° C., more preferably 90 ° C. to 140 ° C. . When the 1/2 outflow temperature is within the more preferable range, it is advantageous in terms of low-temperature fixability, heat-resistant storage stability, and excellent separation between the fixing member and the recording medium during fixing.
The 1/2 outflow temperature can be determined from, for example, a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
Specifically, from the flow curve using a flow tester (see FIG. 1), the temperature at the intermediate value between the outflow end point (Smax) and the minimum value (Smin) is calculated as a 1/2 outflow temperature by the 1/2 method. To do.
The measurement conditions are a load of 30 kg / cm ² , a temperature increase rate of 3.0 ° C./min, a die diameter of 0.50 mm, and a die length of 1.0 mm.

<Toner production method>
There is no restriction | limiting in particular as a manufacturing method of the said toner, According to the objective, it can select suitably, For example, a grinding method, an emulsion polymerization method, etc. are mentioned.
In the toner, the binder resin contains the crystalline polyester resin and the amorphous polyester resin, and at least the crystalline polyester resin, the amorphous polyester resin, the colorant, and the monochromatic polyester resin. It is preferably obtained by dispersing an oil phase obtained by dissolving or dispersing a toner material containing an ester wax in an organic solvent in an aqueous medium and removing the organic solvent from the obtained dispersion. More preferably, the aqueous medium contains resin fine particles.
In the toner, the binder resin includes the crystalline polyester resin, the amorphous polyester resin, and a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound. A reaction product with the body, at least the active hydrogen group-containing compound, a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound, the crystalline polyester resin, the amorphous polyester resin, An oil phase obtained by dissolving or dispersing the toner material containing the colorant and the monoester wax is dispersed in an aqueous medium to obtain an emulsified dispersion, and the binder resin precursor in the emulsified dispersion. And the active hydrogen group-containing compound are preferably reacted to remove the organic solvent. The aqueous medium preferably contains fine resin particles.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of the water-miscible solvent include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Examples of the alcohol include methanol, isopropanol, and ethylene glycol. Examples of the lower ketones include acetone and methyl ethyl ketone.

  The binder resin precursor, the colorant, the monoester wax, and the like may be mixed when forming the dispersion in the aqueous medium. However, after mixing these toner materials in advance, It is more preferable to add the mixture to and disperse the mixture. In the present invention, toner materials such as the binder resin precursor, the colorant, and the monoester wax are not necessarily mixed when forming particles in an aqueous medium. Then, it may be added. For example, after forming particles that do not contain the colorant, the colorant can be added by a known dyeing method.

The dispersion method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. . Among these, the high-speed shearing method is particularly preferable in order to make the particle size of the dispersion 2 μm to 20 μm.
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, but is preferably 1,000 rpm to 30,000 rpm, and is preferably 5,000 rpm to 20,000 rpm. Is more preferable. There is no restriction | limiting in particular in dispersion time, According to the objective, it can select suitably, In the case of a batch system, 0.1 minute-60 minutes are preferable. The temperature during dispersion is preferably 0 ° C. to 80 ° C. (under pressure), more preferably 10 ° C. to 40 ° C.

  There is no restriction | limiting in particular as the usage-amount of the said aqueous medium with respect to 100 mass parts of said toner materials, Although it can select suitably according to the objective, 100 mass parts-1,000 mass parts are preferable. When the amount used is less than 100 parts by mass, the toner material is not well dispersed, and toner particles having a predetermined particle diameter may not be obtained. When the amount exceeds 1,000 parts by mass, it is not economical. Moreover, a dispersing agent can also be used as needed. The use of a dispersant is preferable in that the particle size distribution becomes sharp and the dispersion is stable.

  As a method of reacting the binder resin precursor and the active hydrogen group-containing compound, the active hydrogen group-containing compound may be added and reacted before the toner material is dispersed in an aqueous medium. After dispersion in an aqueous medium, the active hydrogen group-containing compound may be added to cause a reaction from the particle interface. In this case, a polyester resin modified with a polyester prepolymer is produced preferentially on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.

  Examples of the dispersant for emulsifying and dispersing the oil phase in which the toner material is dispersed in a liquid containing water include an anionic surfactant, an amine salt type cationic surfactant, and a quaternary ammonium salt type. And cationic surfactants, nonionic surfactants, and amphoteric surfactants. Examples of the anionic surfactant include alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters. Examples of the amine salt type cationic surfactants include alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, and imidazolines. Examples of the quaternary ammonium salt type cationic surfactant include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride and the like. . Examples of the nonionic surfactant include fatty acid amide derivatives and polyhydric alcohol derivatives. Examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine, and the like.

Furthermore, in order to lower the viscosity of the toner material, for example, an organic solvent in which the modified polyester resin is soluble can be used. The use of an organic solvent is preferable in that the particle size distribution becomes sharp. The organic solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent. Examples of the organic solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, and ethyl acetate. , Methyl ethyl ketone, methyl isobutyl ketone and the like. These may be used individually by 1 type and may use 2 or more types together. Among these, aromatic solvents and halogenated hydrocarbons are preferable. Examples of the aromatic solvent include toluene and xylene. Examples of the halogenated hydrocarbon include methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride.
There is no restriction | limiting in particular as the usage-amount of the said organic solvent with respect to 100 mass parts of said polyester prepolymers, Although it can select suitably according to the objective, 300 mass parts or less are preferable, 100 mass parts or less are more preferable, 25 Part by mass to 70 parts by mass are particularly preferred. When the organic solvent is used, it is preferable to remove the organic solvent by heating under normal pressure or reduced pressure after the elongation reaction and / or the crosslinking reaction.
The elongation reaction and / or cross-linking reaction time is selected depending on the reactivity of the polyester prepolymer and the active hydrogen group-containing compound, but is preferably 10 minutes to 40 hours, more preferably 30 minutes to 24 hours. The reaction temperature is preferably 0 ° C to 100 ° C, more preferably 10 ° C to 50 ° C. Moreover, a well-known catalyst can also be used as needed. Specific examples include tertiary amines such as triethylamine and imidazole.

The organic solvent is removed from the obtained dispersion (emulsified slurry). The organic solvent is removed by (1) a method in which the entire reaction system is gradually heated to completely evaporate and remove the organic solvent in the oil phase, and (2) the emulsion dispersion is sprayed in a dry atmosphere. Examples thereof include a method of completely removing the water-insoluble organic solvent in the oil phase to form toner particles, and evaporating and removing the aqueous dispersant 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.

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

(Developer)
The developer relating to the present invention contains at least the toner of the present invention, and further contains other components such as a carrier, if necessary.
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 life is improved. In view of the above, the two-component developer is preferable.
In the case of the one-component developer using the toner, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, and a blade for thinning the toner The toner is not fused to a member such as the above, and good and stable developability and an image can be obtained even in the long-term use (stirring) of the developing device. In addition, in the case of the two-component developer using the toner of the present invention, even if the toner balance for a long time is performed, the fluctuation of the toner diameter in the developer is small, and it is good even for long-term stirring in the developing device. And stable developability can be obtained.

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

−Core material−
The core material is not particularly limited as long as it has magnetic properties, and can be appropriately selected according to the purpose. Ferrite, magnetite, iron, and nickel are preferable. In addition, considering the adaptability to environmental aspects that are remarkably advanced in recent years, the ferrite is not a conventional copper-zinc ferrite, but manganese ferrite, manganese-magnesium ferrite, manganese-strontium ferrite, manganese-magnesium-strontium ferrite Lithium ferrite is preferable.

-Resin layer-
The material of the resin layer is not particularly limited and may be appropriately selected depending on the purpose. For example, amino resin, polyvinyl resin, polystyrene resin, halogenated olefin resin, polyester resin, polycarbonate resin , Polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride and vinyl fluoride For example, 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.

  There is no restriction | limiting in particular as said silicone resin, According to the objective, it can select suitably, For example, straight silicone resin which consists only of organosilosan bonds; alkyd resin, polyester resin, epoxy resin, acrylic resin, urethane resin, etc. Modified silicone resins modified with

  As content in the said carrier of the component which forms the said resin layer, 0.01 mass%-5.0 mass% are preferable. When the content is less than 0.01% by mass, it may not be possible to form the uniform resin layer on the surface of the core material. When the content exceeds 5.0% by mass, the resin layer becomes thick. It becomes too much and granulation of carriers occurs, and uniform carrier particles may not be obtained.

  The content of the toner when the developer is a two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, but is 2.0 mass relative to 100 mass parts of the carrier. Parts to 12.0 parts by mass are preferable, and 2.5 parts to 10.0 parts by mass are more preferable.

(Image forming apparatus and image forming method)
The image forming apparatus according to the present invention includes at least an electrostatic latent image carrier (hereinafter sometimes referred to as a “photosensitive member”), an electrostatic latent image forming unit, and a developing unit. And have other means.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.
The image forming method can be preferably performed by the image forming apparatus, the electrostatic latent image forming step can be preferably performed by the electrostatic latent image forming unit, and the developing step can be performed by the developing unit. The other steps can be preferably performed by the other means.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

  As the amorphous silicon photoreceptor, for example, a support is heated to 50 ° C. to 400 ° C., and a vacuum deposition method, a sputtering method, an ion plating method, thermal CVD (chemical vapor deposition, Chemical Vapor Deposition) is formed on the support. ), A photo-CVD method, a plasma CVD method, or the like, a photoconductor having a photoconductive layer made of a-Si can be used. Among these, a plasma CVD method, that is, a method in which a source gas is decomposed by direct current, high frequency or microwave glow discharge to form an a-Si deposited film on a support is preferable.

  There is no restriction | limiting in particular as a shape of the said electrostatic latent image carrier, Although it can select suitably according to the objective, A cylindrical shape is preferable. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and more preferably 10 mm to 30 mm. Particularly preferred.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

-Charging member and charging-
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.

The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus.
When the magnetic brush is used as the charging member, as the magnetic brush, for example, various ferrite particles such as Zn-Cu ferrite are used as the charging member, and a non-magnetic conductive sleeve for supporting the ferrite member is included in the charging member. It consists of a magnet roll.
When the fur brush is used as the charging member, as the material of the fur brush, for example, a fur conductively treated with carbon, copper sulfide, metal, or metal oxide is used. A charging member can be obtained by winding or sticking to a cored bar.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

-Exposure member and exposure-
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
There is no restriction | limiting in particular as a light source used for the said exposure member, According to the objective, it can select suitably, For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser General light emitting materials such as (LD) and electroluminescence (EL).
In addition, various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Developing means and development process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image. Can be selected as appropriate.
The development step is not particularly limited as long as it is a step of developing the latent electrostatic image formed on the latent electrostatic image bearing member with toner to form a visible image. For example, it can be carried out by the developing means.
The toner is the toner of the present invention.

The developing means may be of a dry development type or a wet development type. Further, it may be a single color developing means or a multicolor developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrostatically attracted by the static force. It moves to the surface of the electrostatic latent image carrier. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.

-Transfer means and transfer process-
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, an intermediate transfer member is used, and the transfer step can be performed on the intermediate transfer member. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed by, for example, charging the visible image using a transfer charger and the transfer unit.
Here, when the image to be secondarily transferred onto the recording medium is a color image composed of a plurality of colors of toner, the toner of each color is sequentially superimposed on the intermediate transfer member by the transfer means. An image can be formed on the body, and the image on the intermediate transfer body can be collectively transferred onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

-Fixing means and fixing process-
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed every time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state where the toners of the respective colors are stacked.
The fixing step can be performed by the fixing unit.
The heating in the heating and pressing member is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing unit depending on the purpose.

The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, is preferably ^{10N / cm 2 ~80N / cm 2} .

-Cleaning means and cleaning process-
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

-Static elimination means and static elimination process-
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

-Recycling means and recycling process-
The recycling unit is not particularly limited as long as it is a unit that recycles the toner removed in the cleaning step to the developing device, and can be appropriately selected according to the purpose. Can be mentioned.
The recycling process is not particularly limited as long as it is a process for recycling the toner removed in the cleaning process to the developing device, and can be appropriately selected according to the purpose. For example, the recycling unit performs the recycling process. Can do.

-Control means and control process-
The control means is not particularly limited as long as it can control the movement of each means, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.
The control process is not particularly limited as long as it can control the movement of each process, and can be appropriately selected according to the purpose. For example, the control process can be performed by the control means.

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

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

  When a start switch (not shown) is pressed, when the document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 32, and then the document is set on the contact glass 32. Immediately after that, the scanner 300 is driven, and the first traveling body 33 and the second traveling body 34 travel. At this time, light from the light source is irradiated by the first traveling body 33 and reflected light from the document surface is reflected by the mirror in the second traveling body 34 and is received by the reading sensor 36 through the imaging lens 35 to be color. An original (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 18 (black image forming unit, yellow image forming unit, magenta image forming unit, and cyan image) in the tandem developing device 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem type developing device 120 is a static image as shown in FIG. An electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C); The electrostatic latent image bearing member 10 is uniformly charged, and the electrostatic latent image bearing member is exposed in an image corresponding to each color image based on each color image information (FIG. 4). L), and an exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And cyan tona ), A developing device 61 as the developing means for forming a toner image with each color toner, a transfer charger 62 for transferring the toner image onto the intermediate transfer member 50, a cleaning device 63, The static eliminator 64 is provided, and each monochrome image (black image, yellow image, magenta image, and cyan image) can be formed based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to the black electrostatic latent image carrier 10K on the intermediate transfer member 50 that is rotationally moved by the support rollers 14, 15, and 16. Black image formed on top, yellow image formed on electrostatic latent image carrier 10Y for yellow, magenta image formed on electrostatic latent image carrier 10M for magenta, and electrostatic latent image carrier for cyan The cyan image formed on 10C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 50 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. Each sheet is separated and sent to the paper feed path 146, transported by the transport roller 147, guided to the paper feed path 148 in the copying machine main body 150, and abutted against the registration roller 49 and stopped. Alternatively, the sheet feed roller 142 is rotated to feed out sheets (recording paper) on the manual feed tray 54, separated one by one by the separation roller 52, put into the manual feed path 53, and abutted against the registration roller 49 and stopped. . The registration roller 49 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 49 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 50, and a sheet (recording paper) is interposed between the intermediate transfer member 50 and the secondary transfer device 22. The secondary color transfer device 22 transfers the composite color image (color transfer image) onto the sheet (recording paper), thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 50 after image transfer is cleaned by the intermediate transfer member cleaning device 17.

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

(Process cartridge)
The process cartridge according to the present invention has at least an electrostatic latent image carrier and developing means.
The process cartridge is detachable from the image forming apparatus.
The developing unit is a developing unit including the toner of the present invention, which develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. “Part” represents “part by mass” unless otherwise specified. “%” Represents “% by mass” unless otherwise specified.

  In the following examples, each characteristic was measured as follows.

<Measurement of ester wax>
The carbon number of the ester compound in the ester wax was determined by thermogravimetry (TGA).
Then, the carbon number (C _max ) of the ester compound having the maximum carbon number in the two or more kinds of ester compounds in the ester wax and the carbon number (C _min ) of the ester compound having the minimum carbon number in the ester wax are obtained. The carbon number range (C _max −C _min +1) of the ester compound in the ester wax was determined.
Moreover, the acid value (mgKOH / g) and the hydroxyl value (mgKOH / g) in the monoester wax were measured according to the measurement method of acid value (AV) and hydroxyl value (OHV) described later.
The melting point of the monoester wax was measured according to the method for measuring the melting point described later.

<Melt viscosity>
The melt viscosity of the monoester wax was measured under the following conditions.
First, 60 g of the sample was put in a 100 mL test tube, set in a drive lock bath EB-303 (manufactured by ASONE Co., Ltd.), and the temperature was raised until the temperature reached 100 ° C. After reaching 100 ° C., the viscosity was measured at 100 rpm using a rotary viscometer DV-E (manufactured by Brookfield) and rotor LV # 1. The viscosity after 3 minutes from the start of rotation was measured, and the melt viscosity (η _W ) of the monoester wax at 100 ° C. was measured.

The melt viscosity of the toner was measured under the following conditions.
First, as a sample, 1 g of toner was pressed with a molding machine to produce pellets for a flow tester. The prepared pellet is set in an elevated flow tester CFT100 type (manufactured by Shimadzu Corporation), and the viscosity at 100 ° C. when measured under the following conditions is measured to measure the melt viscosity (η _T ) of the toner at 100 ° C. did.
〔Measurement condition〕
Die diameter: 0.50 mm, Die length: 1.0 mm
Measurement temperature: 40 ° C to 200 ° C
Temperature increase rate: 3.0 ° C / min
Test weight: 30kgf
Stroke: 8.0mm

<Measurement of acid value>
Measurement was performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
First, 0.5 g of a sample (0.3 g in the case of ethyl acetate-soluble component) was added to 120 mL of toluene, and dissolved by stirring at room temperature (23 ° C.) for about 10 hours.
Furthermore, 30 mL of ethanol was added to prepare a sample solution.
The acid value was measured at 23 ° C. using an automatic potentiometric titrator (DL-53 Titrator, manufactured by METTLER TOLEDO) and electrode DG113-SC (manufactured by METTLER TOLEDO), and analysis software LabX Light Version 1.00. 000 was used for analysis.
Note that a mixed solvent of 120 mL of toluene and 30 mL of ethanol was used for the apparatus.
The hydroxyl value was also measured under the same conditions.
The measurement can be performed by the measurement method described above, but specifically, the calculation was performed as follows.
Titration with a standardized 0.1N potassium hydroxide / alcohol solution in advance,
Formula: Acid value [KOHmg / g] = Titration [mL] × N × 56.1 [mg / mL] / Sample weight [g] (where N is a factor of 0.1N potassium hydroxide / alcohol solution) To determine the acid value.

<Measurement of hydroxyl value>
Measurement was performed under the following conditions in accordance with the measurement method described in JIS K0070-1966.
First, 0.5 g of a sample was precisely weighed into a 100 mL volumetric flask, and 5 mL of an acetylating reagent was accurately added thereto.
Then, it was heated by being immersed in a bath at 100 ° C. ± 5 ° C.
After 1 to 2 hours, the flask was taken out of the bath, allowed to cool, then added with water and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask was again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask was thoroughly washed with an organic solvent.
This solution was subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the automatic potentiometric titrator to determine the hydroxyl value.

<1/2 outflow temperature>
The 1/2 outflow temperature was determined from a flow curve measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
Specifically, from the flow curve using a flow tester (see FIG. 1), the temperature at the intermediate value between the outflow end point (Smax) and the minimum value (Smin) is calculated as a 1/2 outflow temperature by the 1/2 method. did.
The measurement conditions were a load of 10 kg / cm ² , a temperature increase rate of 3.0 ° C./min, a die diameter of 0.50 mm, and a die length of 10.0 mm.

<Measurement of melting point and glass transition temperature>
The melting point and glass transition temperature were measured as follows using a DSC system (differential scanning calorimeter) (DSC-60, manufactured by Shimadzu Corporation).
First, about 5.0 mg of a sample was placed in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace.
Then, it heated from 0 degreeC to 150 degreeC with the temperature increase rate of 10 degree-C / min in nitrogen atmosphere. Thereafter, the sample is cooled from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min, and a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation) Was used to measure the DSC curve.
From the obtained DSC curve, using the analysis program in the DSC-60 system, the DSC curve at the first temperature rise was selected, and using the “endothermic shoulder temperature” in the analysis program, at the first temperature rise. Obtain the glass transition temperature (Tg1st) of the sample, then select the DSC curve at the second temperature rise and use the “endothermic shoulder temperature” to determine the glass transition temperature (Tg2nd) of the sample at the second temperature rise. Asked.
From the obtained DSC curve, using the analysis program in the DSC-60 system, using the “endothermic peak temperature” in the analysis program, the DSC curve at the time of the first temperature increase is selected, and at the first temperature increase For the melting point of the sample, a DSC curve at the time of the second temperature increase was selected, and the melting point of the sample at the second temperature increase was determined using “endothermic peak temperature” in the analysis program.

<Measurement of weight average molecular weight>
-Crystalline polyester resin-
The weight average molecular weight and the number average molecular weight of the crystalline polyester resin were measured as follows.
The column was stabilized in a heat chamber at 145 ° C., and o-dichlorobenzene containing 0.3% BHT (dibutylhydroxytoluene) was allowed to flow as an eluent at a flow rate of 1 mL / min. Measurement was performed by injecting 50 μL to 200 μL of 140 ° C. o-dichlorobenzene solution of the resin prepared to 3%.
Waters 150CV type was used as a measuring machine, and Shodex AT-G + AT-806MS (two) was used as a column.
In measuring the molecular weight of the sample (toner), the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. The slice width was 0.05 seconds.
As a standard polystyrene sample for preparing a calibration curve, TSK-GEL standard material “PS-polymer kit” manufactured by Tosoh Corporation was used.
An RI (refractive index) detector was used as the detector.

-Other resins-
The weight average molecular weight and number average molecular weight of other resins were measured as follows.
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation)
Temperature: 40 ° C
Solvent: tetrahydrofuran (THF)
Flow rate: 0.35 mL / min
Sample: 0.4 mL injection of 0.15% sample Sample pretreatment: After dissolving the sample in tetrahydrofuran (THF, containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) to a concentration of 0.15%, Filtration with a 0.2 μm filter In measuring the weight average molecular weight Mw and the number average molecular weight Mn of the resin, the molecular weight distribution of the sample is expressed as follows: Calculated from the relationship.
As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used.
An RI (refractive index) detector was used as the detector.

<Toner intensity ratio (P2850 / P828)>
The intensity ratio (P2850 / P828) between the peak intensity (P2850) of 2850 cm ⁻¹ derived from the monoester wax and the crystalline polyester resin and the peak intensity (P828) of 828 cm ⁻¹ derived from the binder resin is as follows: It was measured.
First, 3 g of toner was pressed for 1 minute under a load of 6 tons (t) using an automatic pellet molding machine (Type-M No. 50 BRP-E, manufactured by Maekawa Test Instruments Co., Ltd.). A pellet having a thickness of about 2 mm was produced.
The surface of the obtained toner pellet was measured by total reflection absorption infrared spectroscopy (FTIR-ATR).
The microscopic FTIR apparatus used was a Spectrum One manufactured by PERKIN ELMER with a MultiScope FTIR unit, and measurement was performed with a germanium (Ge) crystal micro ATR having a diameter of 100 μm.
In addition, four places were measured on the conditions of infrared incident angle 41.5 degrees, resolution 4cm <^-1> , and integration 20 times, and it calculated | required from the average value.

(Production Example 1-1)
<Production of monoester wax A>
In a four-necked flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 1,740 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent special grade, manufactured by Kishida Chemical Co., Ltd.) 1,300 1,200 parts of a long-chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 120 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax A.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-2)
<Production of monoester wax B>
In a four-neck flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 1,800 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent grade, manufactured by Kishida Chemical Co., Ltd.) 1,500 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 100 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax B.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-3)
<Production of monoester wax C>
In a four-neck flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 1,700 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent special grade, manufactured by Kishida Chemical Co., Ltd.) 1,300 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 100 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax C.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-4)
<Manufacture of monoester wax D>
In a four-neck flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 2,000 parts of benzene, 1,000 parts of a long-chain alkylcarboxylic acid component (palmitic acid, manufactured by Kanto Chemical Co., Ltd.), long 1,000 parts of a chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 110 parts of p-toluenesulfonic acid were added and sufficiently stirred and dissolved. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax D.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-5)
<Manufacture of monoester wax E>
In a four-necked flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 2,100 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent grade, manufactured by Kishida Chemical Co., Ltd.) 1,500 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 120 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax E.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-6)
<Manufacture of monoester wax F>
In a four-necked flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 2,000 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent special grade, manufactured by Kishida Chemical Co., Ltd.) 1,300 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 70 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax F.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-7)
<Manufacture of monoester wax G>
In a four-necked flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 1,000 parts of benzene, 1,000 parts of a long-chain alkylcarboxylic acid component (palmitic acid, manufactured by Kanto Chemical Co., Ltd.), long 1,000 parts of a chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 70 parts of p-toluenesulfonic acid were added and sufficiently stirred and dissolved. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax G.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-8)
<Production of monoester wax H>
In a four-necked flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 1,500 parts of benzene, 1,000 parts of a long-chain alkylcarboxylic acid component (palmitic acid, manufactured by Kanto Chemical Co., Ltd.), long 1,000 parts of a chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 80 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax H.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-9)
<Production of monoester wax I>
In a four-necked flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 1,000 parts of benzene, 1,000 parts of a long-chain alkylcarboxylic acid component (palmitic acid, manufactured by Kanto Chemical Co., Ltd.), long 1,000 parts of a chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 70 parts of p-toluenesulfonic acid were added and sufficiently stirred and dissolved. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax I.
The properties of the obtained monoester wax are shown in Table 1.

(Production 1-10)
<Manufacture of monoester wax J>
In a four-neck flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 1,700 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent special grade, manufactured by Kishida Chemical Co., Ltd.) 1,300 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 100 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax J.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-11)
<Manufacture of monoester wax K>
In a four-necked flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 1,650 parts of benzene, 800 parts of a long-chain alkylcarboxylic acid component (stearic acid, reagent special grade, manufactured by Kishida Chemical Co., Ltd.), 1,000 parts of a long-chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 80 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax K.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-12)
<Manufacture of monoester wax L>
In a four-necked flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 1,550 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent special grade, manufactured by Kishida Chemical Co., Ltd.) 1,300 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 120 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax L.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-13)
<Production of monoester wax M>
In a four-necked flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 1,600 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent grade, manufactured by Kishida Chemical Co., Ltd.) 1,000 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 100 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax M.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-14)
<Manufacture of monoester wax N>
In a four-necked flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 1,460 parts of benzene, a long-chain alkylcarboxylic acid component (behenic acid, reagent EP grade, manufactured by Tokyo Chemical Industry Co., Ltd.) 900 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 70 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax N.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-15)
<Manufacture of monoester wax O>
In a four-necked flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 1,800 parts of benzene, a long-chain alkylcarboxylic acid component (stearic acid, reagent grade, manufactured by Kishida Chemical Co., Ltd.) 1,000 1,000 parts of a long chain alkyl alcohol component (stearyl alcohol, reagent grade, manufactured by Kishida Chemical Co., Ltd.) and 120 parts of p-toluenesulfonic acid were added and sufficiently stirred to dissolve. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax O.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 1-16)
<Manufacture of monoester wax P>
In a four-necked flask reactor equipped with a Dimroth reflux apparatus and a Dean-Stark water separator, 900 parts of benzene, 900 parts of a long-chain alkylcarboxylic acid component (palmitic acid, manufactured by Kanto Chemical Co., Ltd.), a long-chain alkyl alcohol component (Stearyl alcohol, reagent special grade, manufactured by Kishida Chemical Co., Ltd.) 1,000 parts and 70 parts of p-toluenesulfonic acid were added and sufficiently stirred and dissolved. And after refluxing for 5 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain monoester wax P.
The properties of the obtained monoester wax are shown in Table 1.

(Production Example 2)
<Manufacture of crystalline polyester resin>
1,5-butanediol 2,010 parts, adipic acid 2,520 parts, trimellitic anhydride 285 parts, and a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, After putting 4.9 parts of hydroquinone and reacting at 160 ° C. for 6 hours, the temperature was raised to 200 ° C. and reacted for 2 hours, and further reacted at 8.3 kPa for 1 hour to synthesize a crystalline polyester resin. The obtained crystalline polyester resin had a weight average molecular weight Mw = 13,000.

(Production Example 3)
<Preparation of crystalline polyester resin dispersion>
100 g of crystalline polyester resin and 400 g of ethyl acetate were put into a metal 2 L container, dissolved by heating at 70 ° C., and then rapidly cooled in an ice water bath at a rate of 15 ° C./min. To this, 500 mL of glass beads (diameter 3 mm) was added, and pulverized for 10 hours with a batch type sand mill apparatus (manufactured by Campehapio Co., Ltd.) to obtain [crystalline polyester resin dispersion].

(Production Example 4)
<Production of resin fine particle dispersion>
In a reaction vessel equipped with a stirrer and a thermometer, 680 parts of water, 12 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 84 parts of styrene, 82 parts of methacrylic acid Part, 100 parts of butyl acrylate, and 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours.
30 parts of 1% aqueous ammonium persulfate solution was added to the reaction solution after the reaction, and the mixture was aged at 75 ° C. for 5 hours. Vinyl resin (styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt) A [resin fine particle dispersion] which is an aqueous dispersion of a copolymer was obtained.

(Production Example 5)
<Prepolymer production>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10 mmHg-15 mmHg for 5 hours, and the intermediate polyester was synthesize | combined.
The obtained intermediate polyester had a weight average molecular weight Mw = 9,500, an acid value AV = 0.5 mgKOH / g, and a hydroxyl value OHV = 51 mgKOH / g.
Next, 410 parts of the intermediate polyester, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. [Prepolymer] (polyester resin containing an isocyanate group) was synthesized.
The free isocyanate content of the obtained [prepolymer] was 1.53% by mass.

(Production Example 6)
<Synthesis of ketimine compound (active hydrogen group-containing compound)>
170 parts of isophorone diamine and 75 parts of methyl ethyl ketone were charged into a reaction vessel equipped with a stir bar and a thermometer, and reacted at 50 ° C. for 5 hours to synthesize [ketimine compound (active hydrogen group-containing compound)].
The amine value of the obtained [ketimine compound] was 418.

(Production Example 7)
<Preparation of ethylene oxide adduct>
1 mol of bisphenol A and 2 g of potassium hydroxide are placed in an autoclave equipped with stirring and temperature control, 6 mol of ethylene oxide is introduced at 135 ° C. under a pressure in the range of 0.1 MPa to 0.4 MPa, and then added for 3 hours. I let you. 16 g of an adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd., 2MgO · 6SiO ₂ · XH ₂ O) was added to the reaction product, and the mixture was aged by stirring at 90 ° C. for 30 minutes. Thereafter, filtration was performed to obtain an ethylene oxide adduct of bisphenol A having an average addition molar amount of ethylene oxide of 2.2 mol.

<Production of propylene oxide adduct>
1 mol of bisphenol A and 2 g of potassium hydroxide are introduced into an autoclave equipped with stirring and temperature control, 5 mol of propylene oxide is introduced at 135 ° C. under a pressure in the range of 0.1 MPa to 0.4 MPa, and then subjected to addition reaction for 3 hours. It was. 16 g of an adsorbent “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd., 2MgO · 6SiO ₂ · XH ₂ O) was added to the reaction product, and the mixture was aged by stirring at 90 ° C. for 30 minutes. Thereafter, filtration was performed to obtain a propylene oxide adduct of bisphenol A having an average addition molar amount of propylene oxide of 2.2.

<Manufacture of amorphous polyester resin>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of the bisphenol A ethylene oxide 2-mole adduct, 84 parts of the bisphenol A propylene oxide 3-mole adduct, 270 parts of terephthalic acid, 120 of isophthalic acid And 2 parts of dibutyltin oxide were added and reacted at 270 ° C. for 8 hours under normal pressure. Next, reaction was performed for 7 hours under reduced pressure of 10 mmHg to 15 mmHg to synthesize [amorphous polyester resin]. The obtained [amorphous polyester resin] had a weight average molecular weight Mw = 4,500, an acid value = 17 mgKOH / g, and AV + OHV = 80 mgKOH / g.

(Production Example 8)
<Manufacture of master batch>
1,200 parts of water, carbon black (manufactured by Printe35 / Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5] 540 parts, [amorphous polyester resin] 1,200 parts, Henschel mixer (Japan) Coke Kogyo Co., Ltd.) and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain master batch A.

Example 1
<Production of oil phase>
In a container equipped with a stirrer and a thermometer, 378 parts of [amorphous polyester resin], 50 parts of monoester wax A, 20 parts by weight of [crystalline polyester resin dispersion], CCA (salicylic acid metal complex E-84: Orient Chemistry) 20 parts of Kogyo Co., Ltd.) and 950 parts of ethyl acetate were charged. And it heated up at 80 degreeC with stirring, and hold | maintained at 80 degreeC for 5 hours, Then, it cooled to 30 degreeC in 1 hour, and obtained [wax dispersion liquid A]. Next, 500 parts of [Masterbatch] and 500 parts of ethyl acetate were charged in a container and mixed for 1 hour to obtain [Raw material solution].

  Transfer 1,324 parts of the above-mentioned [raw material solution] to a container and use a bead mill to fill a liquid feed rate of 1 kg / hour, a disk peripheral speed of 6 m / second, 80% by volume of 0.5 mm zirconia beads, and three-pass conditions. Then, carbon black and monoester wax were dispersed. Next, 1042 parts of a 65% ethyl acetate solution of [amorphous polyester resin] was added thereto. One pass was performed with the bead mill under the above conditions to obtain [toner material liquid (oil phase)] having a solid content concentration (130 ° C., 30 minutes) of 50%.

<Preparation of aqueous phase>
990 parts of water, 83 parts of [resin fine particle dispersion], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate, and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid. This is referred to as [aqueous phase].

<Emulsification and solvent removal>
[Toner material solution] 665 parts, [Prepolymer] 110 parts, [Crystalline polyester resin dispersion] 74 parts, and [Ketimine compound] 5 parts were put in a container. Then, after mixing for 1 minute at 5,000 rpm using a TK homomixer (manufactured by Primix Co., Ltd.), add 1,200 parts of [aqueous phase] to the container, and using a TK homomixer for 20 minutes at a rotational speed of 13,000 rpm. By mixing, an [emulsified slurry] was obtained.
[Emulsion slurry] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [dispersed slurry].

<Washing and drying>
(1): After 100 parts of [dispersed slurry] were filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the obtained filter cake, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the obtained filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(4): 300 parts of ion-exchanged water was added to the obtained filter cake, mixed with a TK homomixer (10 minutes at a rotation speed of 12,000 rpm), and then filtered.
The operations (1) to (4) were performed twice to obtain a filter cake.
Finally, the filter cake was dried at 45 ° C. for 48 hours in a circulating dryer, and sieved toner base particles were obtained with a mesh having an opening of 75 μm.

<Mixed>
To 100 parts of the obtained toner base particles, 3.8 parts of hydrophobic silica (HDK H 2000, manufactured by Clariant Co., Ltd.) was added, and the peripheral speed was 33 m / s using a Henschel mixer (manufactured by Nippon Coke Industries, Ltd.). Under the conditions, the mixture was mixed for 3 minutes, and 0.59 parts of titanium oxide (MT-150A, manufactured by Teika Co., Ltd.) was further mixed for 3 minutes under the condition of a peripheral speed of 33 m / s. The mixed powder was passed through a mesh having a mesh size of 38 μm to remove a coarse powder and to prepare a toner to which a hydrophobic fine powder was externally added.

<Manufacture of carriers>
Acrylic resin solution (solid content 50%) 21.0 parts, guanamine solution (solid content 70%) 6.4 parts, alumina particles [diameter 0.3 μm, specific resistance 10 ¹⁴ (Ω · cm)] 7.6 parts, Silicone resin solution 65.0 parts [solid content 23% (SR2410: manufactured by Toray Dow Corning Silicone)], aminosilane 1.0 part [solid content 100% (SH6020: manufactured by Toray Dow Corning Silicone)], 60 parts of toluene and 60 parts of butyl cellosolve were dispersed with a homomixer for 10 minutes to obtain a coating film forming solution of an acrylic resin and a silicone resin containing alumina particles. Firing ferrite powder [(MgO) _1.8 (MnO) _49.5 (Fe ₂ O ₃ ) _48.0 : average particle size; 25 μm] as a core material is coated with the coating film forming solution on the surface of the core material. The coated ferrite powder was obtained by applying with a Spira coater (Okada Seiko Co., Ltd.) to a thickness of 0.15 μm and drying. The obtained coated ferrite powder was fired in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed. Thus, a carrier having a weight average particle diameter of 35 μm was obtained.

<Preparation of two-component developer>
Using the toner and the carrier, 7 parts of toner were uniformly mixed and charged using a type of tumbler mixer in which a container was rolled and stirred with respect to 100 parts of the carrier to prepare a two-component developer.

(Example 2)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax B in Example 1.

(Example 3)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax C in Example 1.

Example 4
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax D in Example 1.

(Example 5)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax E in Example 1.

(Example 6)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax F in Example 1.

(Example 7)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax G in Example 1.

(Example 8)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax H in Example 1.

Example 9
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax I in Example 1.

(Example 10)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax J in Example 1.

(Example 11)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax K in Example 1.

(Example 12)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax L in Example 1.

(Example 13)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax M in Example 1.

(Example 14)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax N in Example 1.

(Example 15)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax O in Example 1.

(Example 16)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax P in Example 1.

(Example 17)
A toner was obtained in the same manner as in Example 1 except that 50 parts of monoester wax A was changed to 18 parts in the preparation of the oil phase of Example 1.

(Example 18)
A toner was obtained in the same manner as in Example 1 except that 50 parts of the monoester wax A was changed to 2 parts in the preparation of the oil phase of Example 1.

(Example 19)
In the preparation of the oil phase and the preparation of the emulsified slurry in Example 1, the [crystalline polyester resin dispersion] was changed to 0 part, and in the preparation of the emulsified slurry, the [prepolymer] was changed to 110 parts to 60 parts. In the same manner as in Example 1, a toner was obtained.

(Example 20)
A toner was obtained in the same manner as in Example 1 except that 110 parts of [Prepolymer] were changed to 79 parts in the preparation of the emulsified slurry of Example 1.

(Example 21)
In the preparation of the oil phase and the preparation of the emulsified slurry in Example 1, the [crystalline polyester resin dispersion] was changed to 0 part, and in the preparation of the emulsified slurry, 110 parts of the [prepolymer] were changed to 50 parts. In the same manner as in Example 1, a toner was obtained.

(Example 22)
A toner was obtained in the same manner as in Example 1 except that 110 parts of [Prepolymer] were changed to 75 parts in the preparation of the emulsified slurry of Example 1.

(Example 23)
A toner was obtained in the same manner as in Example 1 except that in the preparation of the oil phase of Example 1, the amount of [crystalline polyester resin] added was changed to 400 parts.

(Example 24)
<Preparation of polyester solution>
1100 parts of [amorphous polyester resin] and 400 parts of ethyl acetate were placed in a metal 2 L container and heated and dissolved at 75 ° C. to prepare a [polyester resin solution].

<Production of toner>
A toner was obtained in the same manner as in Example 1, except that [Crystalline Polyester Dispersion] was replaced with [Polyester Resin Solution].

(Example 25)
[Prepolymer] 100 parts [Amorphous polyester resin] 20 parts, [Crystalline polyester resin] 7 parts, Monoester wax A 8.43 parts (6% of the toner base particles produced) In the case where the obtained toner base particles are 100 parts, 6 parts are internally added.) Copper phthalocyanine pigment (Pig. 15-3) (trade name: cyanine blue 4920, 4 parts by Daiichi Seika Kogyo Co., Ltd.) and 1 part of zirconium salt of salicylic acid as a charge control agent were mixed in a Henschel mixer, then kneaded in a kneader, and classified in a fluid bed grinder and a rotor classifier. Thereafter, mixing was performed to obtain a toner.

(Example 26)
<Preparation of oil phase>
In a beaker, 32 parts of [Prepolymer], 102 parts of [Amorphous polyester resin], 44 parts of [Crystalline polyester resin] and 80 parts of ethyl acetate were placed and dissolved by stirring to obtain a solution.
Further, 10 parts of monoester wax A, 12 parts of carbon black, and 120 parts of ethyl acetate were placed in a bead mill and dispersed for 30 minutes to obtain a dispersion.
The solution and the dispersion were mixed, stirred for 5 minutes at 12,000 rpm using a TK homomixer, and then subjected to dispersion treatment for 10 minutes using a bead mill.
Next, 3 parts of isophorone diamine was added and stirred for 5 minutes at 12,000 rpm using a TK homomixer to obtain an oil phase.

<Preparation of dispersion slurry>
In a beaker, 526.5 parts of ion-exchanged water, 70 parts of [resin fine particle dispersion] and 0.5 part of sodium dodecylbenzenesulfonate were added and stirred at 12,000 rpm using a TK homomixer. 403 parts of the oil phase was added and stirred for 30 minutes to obtain a dispersed slurry.

Next, ethyl acetate was removed from the dispersion slurry until the mass ratio of ethyl acetate to solids was 10%. Further, after aging at 50 ° C. for 2 hours, ethyl acetate was removed from the dispersion slurry. Thereafter, filtration, washing, drying, and air classification were performed to obtain base particles.
Next, 100 parts of base particles and 0.25 part of Bontron E-84 (manufactured by Orient Chemical Co., Ltd.) as a charge control agent were placed in a Q-type mixer (manufactured by Nihon Coke Industries Co., Ltd.) and mixed. . At this time, the mixing process was carried out for 5 cycles, with the peripheral speed of the turbine blades set to 50 m / sec, the 2-minute operation and the 1-minute pause as one cycle.
Further, 0.5 part of hydrophobic silica H2000 (manufactured by Clariant Japan) was added and mixed to obtain a toner. At this time, the mixing process was performed for 5 cycles, with the peripheral speed of the turbine blades set to 15 m / sec, mixing for 30 seconds and pause for 1 minute as one cycle.

(Example 27)
450 parts of 0.1 mol / L-Na ₃ PO ₄ aqueous solution was added to 720 parts of ion-exchanged water, heated to 60 ° C., and then 67.7 parts of 1.0 mol / L-CaCl ₂ aqueous solution was added to stabilize the dispersion. An aqueous medium containing the agent was obtained.
75 parts of styrene, 25 parts of n-butyl acrylate, 0.5 part of divinylbenzene, 15 parts of amorphous polyester resin synthesized in Production Example 7, 1 part of negative charge control agent T-77 (manufactured by Hodogaya Chemical Co., Ltd.), And 190 parts of magnetic iron oxide were uniformly dispersed and mixed using an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to a temperature of 60 ° C., and 15 parts of monoester wax A and 4 parts of di (sec-butyl) peroxydicarbonate (10-hour half-life temperature 51 ° C.) as a polymerization initiator. The mixture was dissolved and a polymerizable monomer composition was obtained.
The polymerizable monomer composition was charged into the aqueous medium, and stirred at 10,000 rpm for 15 minutes with a TK homomixer (manufactured by Primics Co., Ltd.) at a temperature of 60 ° C. and in an N ₂ atmosphere. Thereafter, the mixture was stirred with a paddle stirring blade and polymerized at a reaction temperature of 70 ° C. for 360 minutes. Thereafter, the suspension was cooled to room temperature at 3 ° C. per minute, and hydrochloric acid was added to dissolve the dispersant, followed by filtration, washing with water and drying to obtain toner particles.
100 parts of the toner particles obtained and a hydrophobic silica fine powder (silica having an average primary particle size of 12 nm was treated with hexamethyldisilazane and then treated with silicone oil, and the BET specific surface area after treatment was 120 m ² / g. 1.0 part of the hydrophobic silica fine powder) was mixed using a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain a toner.

(Comparative Example 1)
<Preparation of diester wax Q>
A four-neck flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator was charged with 1,740 parts of benzene, 1,300 parts of docosane dipalmitic acid, 1,200 parts of docosanediol, and p-toluenesulfone. 120 parts of acid was added and sufficiently stirred to dissolve. And after refluxing for 7 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain diester wax Q having a melting point of 60 ° C.

<Production of toner>
In Example 1, a toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the diester wax Q prepared above.

(Comparative Example 2)
<Preparation of triester wax R>
A four-neck flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator was charged with 1,740 parts of benzene, 1,300 parts of docosan tripalmitic acid, 1,200 parts of docosantriol, and p-toluenesulfone. 120 parts of acid was added and sufficiently stirred to dissolve. And after recirculating | refluxing for 9 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain triester wax R having a melting point of 77 ° C.

<Production of toner>
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the triester wax R prepared above in Example 1.

(Comparative Example 3)
<Preparation of monoester wax S>
In a four-neck flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 1,740 parts of benzene, 1,300 parts of lauric acid, 1,200 parts of lauryl alcohol, and 120 parts of p-toluenesulfonic acid Was sufficiently stirred and dissolved. And after recirculating | refluxing for 9 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain a monoester wax S having a melting point of 77 ° C.

<Production of toner>
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax S and 110 parts of [Prepolymer] were changed to 150 parts.

(Comparative Example 4)
<Preparation of monoester wax T>
A four-neck flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator was charged with 1,740 parts of benzene, 1,300 parts of lignoceric acid, 1,200 parts of lignoceryl alcohol, and p-toluenesulfonic acid 120. Part was added and sufficiently stirred to dissolve. And after recirculating | refluxing for 9 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain a monoester wax T having a melting point of 77 ° C.

<Production of toner>
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax T in Example 1.

(Comparative Example 5)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the monoester wax S in Example 1.

(Comparative Example 6)
In Example 1, a toner was obtained in the same manner as in Example 1 except that the monoester wax A was changed to the monoester wax T, and 110 parts of the [prepolymer] were changed to 50 parts.

(Comparative Example 7)
A toner was obtained in the same manner as in Example 1 except that 110 parts of [Prepolymer] was changed to 50 parts in Example 1.

(Comparative Example 8)
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was changed to the monoester wax S and 110 parts of [Prepolymer] were changed to 50 parts in Example 1.

(Comparative Example 9)
<Preparation of diester wax U>
In a four-neck flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator, 1,740 parts of benzene, 1,300 parts of docosane distearic acid, 1,200 parts of docosanediol, and p-toluenesulfone 120 parts of acid was added and sufficiently stirred to dissolve. And after refluxing for 7 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain a diester wax U having a melting point of 60 ° C.

<Production of toner>
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the diester wax U in Example 1.

(Comparative Example 10)
<Preparation of triester wax V>
A four-necked flask reactor equipped with a Dimroth reflux and a Dean-Stark water separator was charged with 1,740 parts of benzene, 1,300 parts of docosan tristearic acid, 1,200 parts of docosan triol, and p-toluenesulfone. 120 parts of acid was added and sufficiently stirred to dissolve. And after recirculating | refluxing for 9 hours, the valve | bulb of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and subsequently dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain triester wax V having a melting point of 77 ° C.

<Production of toner>
A toner was obtained in the same manner as in Example 1 except that the monoester wax A was replaced with the triester wax V in Example 1.

(Comparative Example 11)
A toner was obtained in the same manner as in Example 1 except that 110 parts of [Prepolymer] was changed to 200 parts in Example 1.

  The characteristics of the toners of the examples and comparative examples are summarized in Tables 2-1 and 2-2.

<Evaluation method and evaluation results>
According to the following evaluation method, each toner of the examples and comparative examples was evaluated, and the evaluation results are shown in Table 3.
<< Fixability >>
Using imago Neo Neo 450 manufactured by Ricoh Co., Ltd., a plain image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) with a solid image of 1.0 ± 0.1 mg / cm ² Adjustments were made so that the toner was developed, and the temperature of the fixing belt was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the fixing lower limit temperature on thick paper were measured.
The lower limit fixing temperature was determined as the fixing lower limit temperature at the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more.
A toner satisfying a temperature range of 135 ° C. to 200 ° C. that can be fixed by this test method can obtain a stable fixed image without being affected by the deterioration of the fixing device and the use state of the user.
Also, the temperature at which the offset occurs was measured.
The evaluation conditions for the minimum fixing temperature were a paper feed linear velocity of 120 mm / second to 150 mm / second, a surface pressure of 1.2 kgf / cm ² , and a nip width of 3 mm.
The evaluation conditions for the upper limit fixing temperature were a feed linear velocity of 50 mm / sec, a surface pressure of 2.0 kgf / cm ² , and a nip width of 4.5 mm.
The minimum fixing temperature of the conventional low-temperature fixing toner is about 140 ° C.
The evaluation criteria are as follows.
[Evaluation criteria for low-temperature fixability]
A: Lower limit fixing temperature is less than 120 ° C. O: Lower limit fixing temperature is 120 ° C. or higher and lower than 125 ° C. Δ: Lower limit fixing temperature is 125 ° C. or higher and lower than 140 ° C. Maximum fixing temperature (evaluation criteria for high-temperature offset resistance and hot offset resistance)
A: Fixing upper limit temperature is 200 ° C. or more. ○: Fixing upper limit temperature is 190 ° C. or more and less than 200 ° C. Δ: Fixing upper limit temperature is 180 ° C. or more and less than 190 ° C. ×: Fixing upper limit temperature is less than 180 ° C.

<< Separability >>
The force required for peeling the recording medium from the fixing belt (that is, the separation resistance force) was measured using a measuring apparatus for measuring the pressing force of the recording medium shown in FIG. And separability was evaluated based on the obtained result.
In FIG. 2, the recording medium S is conveyed while being pressed against the measurement claw 528. The pressing force at this time is read by a load cell 527 provided at the other end of the measurement claw 528 via a fulcrum 529. As shown in FIG. 2, the measurement claw 528 is provided on the fixing roller 525 side immediately after the nip portion 530 between the fixing roller 525 and the pressure roller 526.
The value read by the load cell 527 is the force (separation resistance) required to peel the recording medium S from the fixing roller 525, and the smaller the separation resistance, the better the separation. Whether or not the recording medium can be separated from the fixing roller is determined based on the magnitude of the separation resistance measured based on the predetermined condition.
In this evaluation, the separation resistance at a fixing temperature of 160 ° C. was defined as the separation resistance of the toner, and the separation performance was evaluated based on the following evaluation criteria. The toner adhesion amount at the time of measurement was 0.9 g / cm ² .
〔Evaluation criteria〕
A: 251 gf to 300 gf
○: 201 gf to 250 gf
Δ: 200 gf or less ×: 301 gf or more

<< Glossiness >>
The solid image is evaluated at a temperature between 170 ° C. and 210 ° C. in the same manner as the fixing property, and the glossiness at each temperature is set at 10 locations with a gloss of 60 ° using a gloss meter VGS-1D manufactured by Nippon Denshoku Industries Co., Ltd. Images were evaluated according to the following evaluation criteria.
[Evaluation criteria]
A: Maximum glossiness is 40 to 50
○: Maximum glossiness is 30 to 39
Δ: Maximum glossiness is 20 to 29
X: Maximum glossiness is 19 or less

<< Heat resistant storage stability >>
After the toner was stored at 50 ° C. for 8 hours, it was sieved with a 42 mesh sieve for 2 minutes, and the residual rate on the wire mesh was measured according to the following evaluation criteria.
At this time, the toner having better heat-resistant storage stability has a smaller remaining rate.
[Evaluation criteria]
○: Residual rate is less than 1% △: Residual rate is 1% or more and less than 5% ×: Residual rate is 5% or more

<< Comprehensive evaluation >>
As a comprehensive evaluation, the above evaluation was evaluated according to the following evaluation criteria.
[Evaluation criteria]
◎: There is no △ and ×, and one or more ◎ is included. ○: All are ◯. △: There is △ and there is no ×. ×: At least one × is included. Things can be used.

Aspects of the present invention are as follows, for example.
<1> A toner containing at least a binder resin, a monoester wax, and a colorant,
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1):
The toner according to claim 1, wherein the monoester wax contains at least one monoester compound, and the carbon number of the at least one monoester compound is in the range of 30 to 50.
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
<2> The toner according to <1>, wherein the melt viscosity (η _W ) of the monoester wax at 100 ° C. satisfies the following formula (2).
1.0 mPa · s ≦ η _W ≦ 20 mPa · s (2)
<3> carbon between the maximum number of carbon atoms of the mono-ester compound having the carbon number (C _max) and the number of carbon atoms of the mono-ester compound having the smallest number of carbons in the monoester wax and (C _min) in the monoester wax The toner according to any one of <1> to <2>, wherein a number range (C _max −C _min +1) is 9 or less.
<4> The monoester wax according to any one of <1> to <3>, wherein the sum of the acid value (mgKOH / g) and the hydroxyl value (mgKOH / g) is 3 mgKOH / g to 15 mgKOH / g. Toner.
<5> The toner according to any one of <1> to <4>, wherein the monoester wax has a melting point of 40 ° C to 80 ° C.
<6> The toner according to any one of <1> to <5>, wherein the content of the monoester wax is 3 parts by mass to 16 parts by mass with respect to 100 parts by mass of the toner.
<7> The glass transition temperature (Tg1st) at the first temperature increase in differential scanning calorimetry is 40 ° C. to 65 ° C., and the glass transition temperature (Tg2nd) at the second temperature increase is 20 ° C. to 40 ° C. The toner according to any one of <1> to <6>.
<8> The toner according to any one of <1> to <7>, wherein a 1/2 outflow temperature measured by a flow tester is 90 ° C to 140 ° C.
<9> The binder resin according to any one of <1> to <8>, wherein the binder resin contains two or more binder resins and the two or more binder resins contain a crystalline polyester resin. Toner.
<10> 2850 cm ⁻¹ peak intensity derived from monoester wax and crystalline polyester resin (P2850) and 828 cm ⁻¹ peak intensity derived from binder resin (P828), as determined by total reflection absorption infrared spectroscopy. The toner according to <9>, wherein the intensity ratio (P2850 / P828) is 0.10 to 0.20.

Japanese Patent Laid-Open No. 11-133665 JP 2002-287400 A JP 2002-351143 A Japanese Patent No. 2579150 JP 2001-158819 A JP-A-8-176310 Japanese Patent Laid-Open No. 2005-15589 Japanese Patent No. 4347174 Japanese Patent No. 3287733

Claims (10)

A toner containing at least a binder resin, a monoester wax, and a colorant,
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1):
The toner, wherein the monoester wax contains at least one monoester compound, and the carbon number of the at least one monoester compound is in the range of 30 to 50.
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1) The toner according to claim 1, wherein the melt viscosity (η _W ) of the monoester wax at 100 ° C. satisfies the following formula (2).
1.0 mPa · s ≦ η _W ≦ 20 mPa · s (2) The carbon number range between the carbon number (C _max ) of the monoester compound having the maximum carbon number in the monoester wax and the carbon number (C _min ) of the monoester compound having the minimum carbon number in the monoester wax. The toner according to claim 1, wherein (C _max −C _min +1) is 9 or less.   The toner according to claim 1, wherein the sum of the acid value (mgKOH / g) and the hydroxyl value (mgKOH / g) of the monoester wax is 3 mgKOH / g to 15 mgKOH / g.   The toner according to claim 1, wherein the melting point of the monoester wax is 40 ° C. to 80 ° C.   The toner according to claim 1, wherein the content of the monoester wax is 3 parts by mass to 16 parts by mass with respect to 100 parts by mass of the toner.   The glass transition temperature (Tg1st) at the first temperature increase in differential scanning calorimetry is 40 ° C to 65 ° C, and the glass transition temperature (Tg2nd) at the second temperature increase is 20 ° C to 40 ° C. The toner according to any one of 6 to 6.   The toner according to any one of claims 1 to 7, wherein a 1/2 outflow temperature measured by a flow tester is 90 ° C to 140 ° C.   The toner according to claim 1, wherein the binder resin contains two or more kinds of binder resins, and the two or more kinds of binder resins contain a crystalline polyester resin. Determined by the total reflection absorption infrared spectroscopy, the intensity ratio of the monoester wax and crystalline polyester resins derived peak intensity of 2850 cm ^-1 of the (P2850), and peak intensity of 828 cm ^-1 derived from the binder resin (P828) The toner according to claim 9, wherein (P2850 / P828) is 0.10 to 0.20.