JP2014178420A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent low-temperature fixability, good hot-offset resistance, prevents contamination of fixing means and images, and can form high-quality images with good sharpness for a long period.SOLUTION: A toner contains at least a binder resin, wax, and colorant; and the toner has a melt viscosity (η) at 100°C satisfying the following formula (1), and the wax has a melt viscosity (η) at 100°C satisfying the following formula (2). Formula (1): 500 Pa s≤η≤8,000 Pa s; formula (2): 1 mPa s≤η≤20 mPa 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 the toner by the polymerization method, for example, for the purpose of improving the fluidity of the toner, improving the low-temperature fixability, and improving the hot offset resistance, the toner is produced by using an extension reaction product of urethane-modified polyester. A 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 particle size toner, and that is excellent in all of heat-resistant storage stability, low-temperature fixability, and hot offset resistance, the circularity is 0.960 to 1.000 and a dry toner having a plurality of depressions on the surface (see, for example, Patent Document 2), and a prepolymer comprising at least a modified polyester resin in an organic solvent, the prepolymer and the elongation And at least one of the cross-linking compounds and a material containing the toner composition are dissolved or dispersed, and the dissolved or dispersed material is subjected to a crosslinking reaction or an extension reaction in an aqueous medium, and the solvent is removed from the obtained dispersion. Has been proposed (see, for example, 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). .

  However, in the above-mentioned proposed techniques, high-quality images with high low-temperature fixability, excellent hot offset resistance, excellent antifouling properties of fixing means and images, and high sharpness, which are required in recent years, are obtained. It has not yet been possible to obtain a toner that can be formed over a long period of time.

  Accordingly, it is possible to provide a toner that has excellent low-temperature fixability, good hot offset resistance, and does not contaminate the fixing means and the image, and can form a high-quality image with good sharpness over a long period of time. 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 is excellent in low-temperature fixability, has good hot offset resistance, does not contaminate the fixing means and the image, and can form a high-quality image with good sharpness over a long period of time. An object is to provide a toner that can be used.

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 wax, and a colorant,
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1):
The melt viscosity (η _W ) of the wax at 100 ° C. satisfies the following formula (2).
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
1 mPa · s ≦ η _W ≦ 20 mPa · s (2)

  According to the present invention, the conventional problems can be solved, excellent low-temperature fixability, good hot offset resistance, no fouling of fixing means and images, and high quality with good sharpness. A toner capable of forming an image over a long period of time can be provided.

FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. FIG. 2 is a partially enlarged view of FIG.

(toner)
The toner of the present invention contains at least a binder resin, a wax, and a colorant, preferably contains a wax dispersant, and further contains other components as necessary.
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1).
The melt viscosity (η _W ) of the wax at 100 ° C. satisfies the following formula (2).
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
1 mPa · s ≦ η _W ≦ 20 mPa · s (2)

The η _T preferably satisfies the following formula (3).
The η _W preferably satisfies the following formula (4).
1,000 Pa · s ≦ η _T ≦ 2,000 Pa · s Formula (3)
13 mPa · s ≦ η _W ≦ 17 mPa · s (4)

In the toner, the melt viscosity of the toner at 100 ° C. and the melt viscosity of the wax at 100 ° C. are excellent in low-temperature fixability, good in hot offset resistance, and contaminate fixing means and images. It has been found that this is important for obtaining a toner capable of forming a high-quality image with good sharpness over a long period of time.
As a result of intensive studies, the present inventors have found that the toner contains at least a binder resin, a wax, and a colorant, and the melt viscosity (η _T ) at 100 ° C. of the toner is represented by the following formula ( 1) and the wax has a melt viscosity (η _W ) at 100 ° C. satisfying the following formula (2), it has excellent low-temperature fixability, good hot offset resistance, and contaminates fixing means and images. Thus, the present inventors have found that a toner capable of forming a high-quality image with good sharpness over a long period of time can be obtained, and the present invention has been completed.
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
1 mPa · s ≦ η _W ≦ 20 mPa · s (2)

If the η _T is less than 500 Pa · s, the melt viscosity of the toner at the time of fixing is too low, resulting in a decrease in hot offset resistance and further insufficient separation between the paper and the fixing member. On the other hand, if the η _T exceeds 8,000 Pa · s, the melt viscosity of the toner at the time of fixing is too high, and the low-temperature fixability becomes insufficient.
When the melt viscosity of the wax at the time of fixing is low, the hot offset resistance and the friction resistance of the fixed image tend to be improved. However, if the η _W is less than 1 mPa · s, the low-temperature fixability is insufficient. On the other hand, if the η _W exceeds 20 mPa · s, the melt viscosity of the wax at the time of fixing is too high, and the low-temperature fixability becomes insufficient.

Conventionally, in order to improve the low-temperature fixability, it has been proposed to lower the viscosity of the toner or the viscosity of the wax.
However, as a result of intensive studies by the present inventors, it has been found that good low-temperature fixability cannot be obtained simply by reducing the viscosity of the wax. As a result of further intensive studies, as described above, it has excellent low-temperature fixability, good hot offset resistance, does not contaminate the fixing means and the image, and provides a high-quality image with good sharpness over a long period of time. In order to obtain a toner that can be formed over the range, the melt viscosity (η _T ) of the toner at 100 ° C. satisfies the formula (1), and the melt viscosity (η _W ) of the wax at 100 ° C. It turned out that it is necessary to satisfy | fill said Formula (2).
The reason for this is not clear, but satisfying the above formulas (1) and (2) is considered to be related to adjusting the amount of the wax that exudes from the toner during fixing to an appropriate amount. It is done.
Note that the temperature applied to the toner when fixing the toner on the recording medium is lower than the actual set temperature of the fixing device. From this point, the melt viscosity is measured at 100 ° C.

  In order to achieve low temperature fixability, conventionally known toners have been devised to lower the viscosity of the toner and further reduce the viscosity of the wax. However, when these are implemented, the cold offset deteriorates and the low temperature fixability is reduced. There was a problem that was not enough.

The method for obtaining the toner that simultaneously satisfies the formula (1) and the formula (2) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the melt viscosity (η _T ) Can be controlled by the amount of the high molecular weight material, the presence or absence of the crystalline polyester resin, and the amount thereof, and the melt viscosity (η _W ) can be controlled by the type and molecular weight of the wax.

<Binder resin>
There is no restriction | limiting in particular as said binder resin, Although it can select suitably according to the objective, It is preferable to contain a polyester resin.
The binder resin other than the polyester resin is not particularly limited and can be appropriately selected according to the purpose. For example, styrene-acrylic resin, polyol resin, vinyl resin, polyurethane resin, epoxy resin, polyamide resin, Examples include polyimide 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.

-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 50% by mass or more of the polyester resin, and more preferably 100% by mass.

--- 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 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol. Etc.
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 in o-dichlorobenzene is not particularly limited and may be appropriately selected depending on the intended purpose. 3,000 to 30,000 are preferable, and 5,000 to 20,000 are more preferable. When the weight average molecular weight is less than 3,000, the heat-resistant storage stability may be lowered, and when it exceeds 30,000, the low-temperature fixability may be lowered.
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, 1,000-10,000 are preferable. When the number average molecular weight is less than 1,000, a decrease in heat resistant storage stability may be observed, and when it exceeds 10,000, a decrease in low temperature fixability may be observed.
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, 1-10 are preferable. When the ratio (Mw / Mn) exceeds 10, a decrease in heat resistant storage stability may be observed.

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, 60 to 80 degreeC is preferable. When the melting point of the crystalline polyester resin is less than 60 ° 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.

There is no restriction | limiting in particular as solubility at 70 degreeC with respect to the organic solvent of the said crystalline polyester resin, Although it can select suitably according to the objective, 10 mass parts or more are preferable with respect to 100 mass parts of said organic solvents. If the solubility is less than 10 parts by mass, the affinity between the organic solvent and the crystalline polyester resin is poor, and it is difficult to disperse the crystalline polyester resin to a submicron size in the organic solvent. In some cases, the crystalline polyester resin present in the toner becomes non-uniform, resulting in a decrease in chargeability and a decrease in image quality after long-term use.
There is no restriction | limiting in particular as solubility at 20 degreeC with respect to the organic solvent of the said crystalline polyester resin, Although it can select suitably according to the objective, Less than 3.0 mass parts is with respect to 100 mass parts of said organic solvents. preferable. When the solubility is 3.0 parts by mass or more, the crystalline polyester resin dissolved in the organic solvent is compatible with another binder resin (for example, amorphous polyester resin) before heating. As a result, the heat resistant storage stability may be deteriorated, the developing device may be contaminated, and the image 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.

--- Dissolution and recrystallization method of crystalline polyester resin in organic solvent ---
Examples of the method for dissolving and recrystallizing the crystalline polyester resin in the organic solvent are as follows.
First, 10 g of the crystalline polyester resin and 90 g of the organic solvent are stirred at 70 ° C. for 1 hour.
Next, the stirred solution is cooled at 20 ° C. for 12 hours to recrystallize the crystalline polyester resin.
Next, the recrystallized organic solvent dispersion of the crystalline polyester resin was used as Kiriyama funnel filter paper No. The organic solvent and the crystalline polyester resin are separated by suction filtration using a Kiriyama funnel (made by Kiriyama Seisakusho) 4 (made by Kiriyama Seisakusho) and an aspirator. The crystalline polyester resin obtained by separation is dried at 35 ° C. for 48 hours to obtain a recrystallized product of the crystalline polyester resin.

--- Evaluation of solubility of crystalline polyester resin in organic solvent ---
The solubility of the crystalline polyester resin in the organic solvent can be determined, for example, by the following method.
First, 20 g of the crystalline polyester resin and 80 g of the organic solvent are stirred at a predetermined temperature for 1 hour. The solution after stirring was filtered at a predetermined temperature using filter paper No. 1 for Kiriyama funnel. The organic solvent and the crystalline polyester resin are separated by suction filtration using a Kiriyama funnel (made by Kiriyama Seisakusho) 4 (made by Kiriyama Seisakusho) and an aspirator. Next, the organic solvent obtained by separation is heated at the boiling point of the organic solvent + 50 ° C. for 1 hour to evaporate the organic solvent. From the change in weight before and after the heating, The dissolution amount of the polyester resin is calculated.

--- 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.

--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 5-amino-1,3,3-trimethylcyclohexanemethylamine, 4,4′-diamino-3, 3′-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine and the like can be mentioned. 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.

<Wax>
The wax is not particularly limited as long as the formula (2) is satisfied, and can be appropriately selected depending on the purpose. Examples thereof include waxes and waxes.
Examples of the waxes and waxes include plant waxes, mineral waxes, and petroleum waxes. Examples of the plant wax include carnauba wax, cotton wax, wood wax, and rice wax. Examples of the animal wax include beeswax and lanolin. Examples of the mineral wax include ozokerite and cercin. Examples of the petroleum wax include paraffin, microcrystalline, and petrolatum.

As the wax, ester wax is particularly preferable in that it has a small amount of volatile components derived from the wax at the time of fixing, is less likely to cause an offset at the time of fixing, is resistant to hot offset, and has a low temperature fixing property.
The ester wax is an ester of a fatty acid and an alcohol. There is no restriction | limiting in particular as said ester wax, Although it can select suitably according to the objective, C26-46 ester wax is preferable.

  From the viewpoint of low-temperature fixability, the ester wax preferably has a small carbon number. On the other hand, from the viewpoint of hot offset resistance, the ester wax preferably has a large carbon number. Therefore, the wax is preferably a mixture of ester waxes having different carbon numbers. Since such a wax can effectively act as a wax between the fixing roller and the toner interface, hot offset resistance can be improved without applying wax such as oil to the fixing roller.

  There is no restriction | limiting in particular as melting | fusing point of the said wax, Although it can select suitably according to the objective, 50 to 120 degreeC is preferable.

  There is no restriction | limiting in particular as content of the said wax, Although it can select suitably according to the objective, 1 mass part-10 mass parts are preferable with respect to 100 mass parts of said toners. When the content is less than 1 part by mass, the hot offset resistance may be deteriorated, and when it exceeds 10 parts by mass, the heat resistant storage stability and the charging characteristics may be deteriorated.

<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.

<Wax dispersant>
The toner preferably contains the wax dispersant. By containing the wax dispersant, the dispersibility of the wax in the binder resin is improved, and the dispersion state of the wax can be easily controlled by the contents of the wax and the wax dispersant. Further, the toner preferably contains 50% by mass to 100% by mass of the polyester resin, but when the polyester resin and the wax are almost incompatible, when the wax dispersant is not used, When the toner is manufactured, the wax may not enter the toner but may escape to the aqueous medium, and the wax may be liberated on the toner surface, or the wax on the toner surface may increase and may be applied to other members. May cause contamination. From these aspects, it is preferable to use the wax dispersant.

The wax dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. The graft polymer of the resin (D) described below and a resin (E) different from the resin (D) is described below. A graft polymer having a structure in which the resin (D) is a main chain and the resin (E) is a side chain is preferable.
There is no restriction | limiting in particular as said resin (D), According to the objective, it can select suitably, For example, a wax etc. are mentioned. Examples of the wax include polyolefin resins and heat-reduced polyolefin resins. Of these, heat-reduced polyolefin resin is preferable.
Examples of the olefins constituting the polyolefin resin include ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene and the like.
Examples of the polyolefin resin include olefin polymers, olefin polymer oxides, modified olefin polymers, and copolymers with other monomers copolymerizable with olefins. Is mentioned.
Examples of the olefin polymers include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, propylene / 1-hexene copolymer, and the like.
Examples of modified products of the olefin polymers include adducts of maleic acid derivatives of the olefin polymers. Examples of the maleic acid derivative include maleic anhydride, monomethyl maleate, monobutyl maleate, dimethyl maleate and the like.
Examples of the copolymer with other monomers copolymerizable with the olefins include copolymers of monomers and olefins such as unsaturated carboxylic acids and unsaturated carboxylic acid alkyl esters. It is done. Examples of the unsaturated carboxylic acid include (meth) acrylic acid, itaconic acid, maleic anhydride, and the like. Examples of the unsaturated carboxylic acid alkyl ester include (meth) acrylic acid alkyl (C1 to C18) ester, maleic acid alkyl (C1 to C18) ester, and the like.

  Moreover, the polymer of the said olefins should just have a polymer structure in a polymer structure, and the monomer does not necessarily need to have an olefin structure. For example, polymethylene (such as sazol wax) can be used.

  The polyolefin resin is preferably an olefin polymer, an olefin polymer oxide, an olefin polymer modified product, polyethylene, polymethylene, polypropylene, ethylene / propylene polymer, oxidized polyethylene, oxidized type. Polypropylene and maleated polypropylene are more preferred, and polyethylene and polypropylene are particularly preferred.

As said resin (E), an acrylic resin etc. are mentioned, for example.
As a monomer which comprises the said acrylic resin, the alkyl (C1-C5) ester of unsaturated carboxylic acid, a vinyl ester monomer, etc. are mentioned, for example. Examples of the alkyl (carbon number 1 to 5) ester of the unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Examples of the vinyl ester monomer include vinyl acetate. Among these, alkyl (meth) acrylate is preferable, and alkyl (meth) acrylate having an alkyl chain having 1 to 5 carbon atoms is more preferable.
As a monomer which comprises the said acrylic resin, as an aromatic vinyl monomer used together with the alkyl (meth) acrylate whose carbon number of the said alkyl chain is 1-5, a styrene-type monomer etc. are mentioned, for example. Examples of the styrenic monomer include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, Examples include benzylstyrene. Among these, styrene is particularly preferable.

  The mass ratio (D) / (E) between the resin (D) of the wax dispersant and the resin (E) in the toner is not particularly limited and can be appropriately selected according to the purpose. However, 1-50 are preferable. When the mass ratio (D / E) exceeds 50, the compatibility between the wax dispersant and the binder resin may be deteriorated. When the mass ratio (D / E) is less than 1, the wax dispersant is added to the added wax. May not be sufficiently compatible with each other, and dispersion of the wax may decrease.

  There is no restriction | limiting in particular as glass transition temperature of the said wax dispersing agent, Although it can select suitably according to the objective, 55 to 80 degreeC is preferable and 55 to 70 degreeC is more preferable. When the glass transition temperature of the wax dispersant exceeds 80 ° C, the low-temperature fixability may be impaired, and when it is less than 55 ° C, the hot offset resistance may be deteriorated.

  There is no restriction | limiting in particular as content of the said wax dispersing agent, Although it can select suitably according to the objective, 0.01 mass part-8 mass parts are preferable with respect to 100 mass parts of the said toner. 5 mass parts-6 mass parts are more preferable. When the content is within the more preferable range, the amount of the wax present on the toner surface is appropriately maintained, and particularly, the releasability from the fixing roller and the belt is improved, and the smear resistance is excellent. The effect can be demonstrated.

  Moreover, the content of the wax dispersant is preferably 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the wax.

<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.

  The toner contains the wax dispersant, and the binder resin contains the crystalline polyester resin and the amorphous polyester resin, and includes at least the crystalline polyester resin, the amorphous polyester resin, An oil phase obtained by dissolving or dispersing a colorant, the wax, and a toner material containing the wax dispersant in an organic solvent is dispersed in an aqueous medium, and the organic solvent is removed from the obtained dispersion. It is preferable that it is obtained by doing.

The toner contains the wax dispersant, and the binder resin can react with the crystalline polyester resin, the amorphous polyester resin, and the active hydrogen group-containing compound and the active hydrogen group-containing compound. Containing a reaction product with a binder resin precursor having a specific site, and containing 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, and the crystalline polyester resin An emulsion obtained by dissolving or dispersing a toner material containing the amorphous polyester resin, the colorant, the wax, and the wax dispersant in an aqueous medium to obtain an emulsified dispersion, It is preferably obtained by reacting the binder resin precursor with the active hydrogen group-containing compound in an emulsified dispersion and removing the organic solvent.
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 toner has a peak intensity of 2850 cm ⁻¹ derived from the wax and the crystalline polyester resin (P2850) and a peak intensity of 828 cm ⁻¹ derived from the binder resin (P828) determined by total reflection absorption infrared spectroscopy. ) (P2850 / P828) is preferably 0.10 to 0.20.
When the intensity ratio (P2850 / P828) is less than 0.10, wax exudes less from an image formed from toner at the time of fixing, hot offset resistance decreases, and paper and fixing belt, roller The separability may be reduced.
When the strength ratio (P2850 / P828) exceeds 0.20, the 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 obtained, for example, by total reflection absorption infrared spectroscopy (FTIR-ATR), and indicates a relative amount of wax near the toner particle surface.

  Next, the volume average particle size and number average particle size, acid value, and glass transition temperature in the toner of the present invention will be described.

<Volume average particle diameter and number average particle diameter of toner>
The volume average particle diameter Dv of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm to 8 μm. When the volume average particle diameter Dv is less than 3 μm, transferability may be deteriorated. When the volume average particle diameter Dv is more than 8 μm, image resolution may be deteriorated.
The ratio (Dv / Dn) between the volume average particle diameter Dv and the number average particle diameter Dn of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is 1.00 to 1.25. preferable. When the ratio (Dv / Dn) exceeds 1.25, the resolution of the image may be lowered.
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner can be measured by, for example, a Coulter counter method. Examples of the measuring device include Coulter Counter TA-II (manufactured by Beckman Coulter), Coulter Multisizer II (manufactured by Beckman Coulter), and the like.

<Toner acid value>
The acid value of the toner is an important index for low-temperature fixability and hot offset resistance. The acid value of the toner is derived from the terminal carboxyl group of the polyester resin, and is preferably 0.5 mgKOH / g to 40 mgKOH / g in order to control the low-temperature fixability and the hot offset resistance.
When the acid value exceeds 40 mgKOH / g, the elongation reaction and / or crosslinking reaction of the binder resin precursor is insufficient in the production of the toner, and the hot offset resistance may be lowered. On the other hand, if the acid value is less than 0.5 mg KOH / g, the effect of improving the dispersion stability by the base cannot be obtained during the production of the toner, or the elongation reaction of the binder resin precursor and / or The cross-linking reaction may easily proceed, and the production stability may decrease.
Here, the acid value of the toner can be measured according to a measuring method described in JIS K0070-1992, for example.

<Glass transition temperature of toner>
The glass transition temperature of the toner is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoints of low-temperature fixability, heat-resistant storage stability, and high durability, the glass transition temperature at the first temperature rise. The Tg1st is 45 ° C. to 65 ° C., more preferably 50 ° C. to 60 ° C.
When the glass transition temperature Tg1st at the first temperature increase is less than 45 ° C., blocking in the developing device or filming to the electrostatic latent image carrier may occur. Fixability may be reduced.
There is no restriction | limiting in particular as Tg2nd which is a glass transition temperature in the 2nd temperature rise, Although it can select suitably according to the objective, 20 to 40 degreeC is preferable.
When the glass transition temperature Tg2nd at the second temperature increase is less than 20 ° C., blocking in the developing device or filming to the electrostatic latent image carrier may occur. Fixability may be reduced.
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, and the DSC curve at the first temperature rise is selected from the obtained DSC curve using the analysis program, and the endothermic shoulder temperature in the analysis program is determined. To determine the glass transition temperature Tg1st at the first temperature increase, then select the DSC curve at the second temperature increase, and use the endothermic shoulder temperature to determine the glass transition temperature Tg2nd at the second temperature increase. Can do.

<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.
The toner includes an oil phase obtained by dissolving or dispersing a toner material containing at least the crystalline polyester resin, the amorphous polyester resin, the colorant, the wax, and the wax dispersant in an organic solvent. It is preferably obtained by dispersing in an aqueous medium and removing the organic solvent from the resulting dispersion.
The toner includes 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, the colorant, An oil phase obtained by dissolving or dispersing the wax and a toner material containing the wax dispersant is dispersed in an aqueous medium to obtain an emulsified dispersion, and the binder resin precursor in the emulsified dispersion is obtained. It is preferably obtained by reacting with the active hydrogen group-containing compound and removing the organic solvent.

There is no restriction | limiting in particular as content in the said oil phase of the said wax dispersing agent, Although it can select suitably according to the objective, 30 mass parts-100 mass parts are preferable with respect to 100 mass parts of said waxes. 35 parts by mass to 90 parts by mass are more preferable. When the content is less than 30 parts by mass, the amount of wax on the toner surface increases, which may cause contamination of other members. When the content exceeds 100 parts by mass, hot offset resistance may be reduced.
It is preferable to add 5 to 40 parts by mass of water with respect to 100 parts by mass of the emulsified dispersion (emulsified slurry).

  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 wax, the wax dispersant and the like may be mixed when forming the dispersion in an aqueous medium, but after mixing these toner materials in advance, More preferably, the mixture is added and dispersed in an aqueous medium. In the present invention, toner materials such as the binder resin precursor, the colorant, the wax, and the wax dispersant do not necessarily need to be mixed when forming particles in an aqueous medium. You may add, after forming particle | grains. 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 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 an image forming apparatus according to the present invention will be described with reference to the drawings.
The image forming apparatus shown in FIG. 1 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. 1. 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 charging device 160, which is the charging member for uniformly charging the electrostatic latent image carrier 10, and the electrostatic latent image carrier are exposed in an image corresponding to each color image based on each color image information (FIG. 2). 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.

  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, the melt viscosity of the wax and toner was measured as follows. Further, the acid value, hydroxyl value, melting point, glass transition temperature, weight average molecular weight and number average molecular weight in resins such as crystalline polyester resin, amorphous polyester resin, and polyester prepolymer were measured as follows.

<Melt viscosity>
The melt viscosity of the 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 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.
In the case of a hydroxyl group, the measurement was performed 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.

<Measurement of melting point and glass transition temperature>
The melting point and glass transition temperature of the resin 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. The glass transition temperature Tg1st of the sample was determined, and then the DSC curve at the second temperature increase was selected, and the glass transition temperature Tg2nd of the sample at the second temperature increase was determined using the “endothermic shoulder temperature”.
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 and number 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: Injection of 10 μL of 0.15% sample Sample pretreatment: After dissolving the sample in tetrahydrofuran (THF, containing stabilizer, Wako Pure Chemical Industries, Ltd.) to a concentration of 0.15%, Filtration with a 2 μm filter 10 μL of a tetrahydrofuran sample solution was injected and measured.
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 was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts.
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 of 2850 cm ⁻¹ derived from the wax and the crystalline polyester resin (P2850) and the peak intensity of 828 cm ⁻¹ derived from the binder resin (P828) was measured as follows. .
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.

<Volume Average Particle Size Dv, Number Average Particle Size Dn, and Ratio (Dv / Dn)>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analysis software (Beckman Coulter Multisizer) is used. 3 Version 3.51). Specifically, 0.5 mL of 10% surfactant (alkylbenzene sulfonate Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 mL glass beaker, and 0.5 g of each toner is added. Stir and then add 80 mL of ion exchange water. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter) as the measurement solution. In the measurement, the dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

(Production Example 1)
<Crystalline polyester resin>
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 2,500 g of 1,12-decanediol, 2,330 g of 1,8-octanedioic acid, and hydroquinone 9 g was added, reacted at 180 ° C. for 20 hours, heated to 200 ° C., reacted for 6 hours, and further reacted at 8.3 kPa for 10 hours to synthesize [crystalline polyester resin].
The obtained [crystalline polyester resin] had a melting point of 64 ° C., a weight average molecular weight of 5,720, an acid value of 28 mgKOH / g, and a hydroxyl value of 3.5 mgKOH / g.

(Production Example 2)
<Wax dispersant>
In an autoclave reaction vessel equipped with a thermometer and a stirrer, 600 parts of xylene and 300 parts of low molecular weight polyethylene (Sunwax LEL-400, softening point 128 ° C., manufactured by Sanyo Chemical Industries, Ltd.) were dissolved sufficiently. After nitrogen substitution, a mixed solution of 2,310 parts of styrene, 270 parts of acrylonitrile, 150 parts of butyl acrylate, 78 parts of di-t-butylperoxyhexahydroterephthalate, and 455 parts of xylene was added dropwise at 175 ° C. over 3 hours. The polymer was polymerized and held at this temperature for 30 minutes.
Next, the solvent was removed to synthesize [Wax Dispersant].

(Production Example 3)
<Amorphous polyester resin (low molecular polyester resin)>
In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propylene oxide 3 mol adduct, isophthalate 100 parts of acid, 108 parts of terephthalic acid, 46 parts of adipic acid and 2 parts by weight of dibutyltin oxide were added and reacted at 230 ° C. for 10 hours under normal pressure. Furthermore, after reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours, 30 parts of trimellitic anhydride was put into a reaction vessel and reacted at 180 ° C. under normal pressure for 3 hours to synthesize [amorphous polyester resin].
The obtained [Amorphous polyester resin] had a number average molecular weight Mn of 1,800, a weight average molecular weight Mw of 5,500, a glass transition temperature of 50 ° C., and an acid value of 20 mgKOH / g.

(Production Example 4)
<Polyester prepolymer>
In a reaction vessel equipped with a condenser, 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, trimellitic anhydride 22 Part and 2 parts of dibutyltin oxide were allowed to react at 230 ° C. for 8 hours under normal pressure. Further, an intermediate polyester was synthesized by reacting under reduced pressure of 10 mmHg to 15 mmHg for 5 hours.
The obtained intermediate polyester had a number average molecular weight Mn of 2,100, a weight average molecular weight Mw of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. It was.
Next, 410 parts of the synthesized intermediate polyester, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, a [polyester prepolymer] was synthesized.
The free isocyanate content of the obtained [polyester prepolymer] was 1.53%.

(Production Example 5)
<Master batch (MB)>
1,200 parts of water, 540 parts of carbon black (Printex 35, manufactured by Dexa Corporation, DBP oil absorption 42 mL / 100 mg, pH 9.5) and 1,200 parts of [amorphous polyester resin] synthesized in Production Example 3 Mixing was performed using a mixer (Mitsui Mining Co., Ltd.). Next, the obtained mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then cooled by rolling, and pulverized with a pulverizer (manufactured by Hosokawa Micron Co., Ltd.) to prepare [Masterbatch].

Example 1
<Production of toner>
-Preparation of pigment / wax dispersion-
378 parts of [Amorphous polyester resin] synthesized in Production Example 3, 110 parts of paraffin (HNP-11, manufactured by Nippon Seiwa Co., Ltd.), Production Example 2 [Wax dispersant] 77 parts (the content of the wax dispersant is 70% with respect to the wax), 22 parts of a charge control agent (CCA, salicylic acid metal complex E-84, manufactured by Orient Chemical Co., Ltd.), and 947 parts of ethyl acetate Was heated to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour.
Next, 500 parts of [Masterbatch] produced in Production Example 5 and 500 parts of ethyl acetate were charged into the container and mixed for 1 hour to obtain a raw material solution.
Transfer 1,324 parts of the resulting raw material solution to a container, and use a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.) to feed 1 kg / hr of liquid feeding speed, 6 m / sec of disk peripheral speed, and 0.5 mm diameter zirconia beads. Carbon black and wax were dispersed under the conditions of 80% by volume filling and 3 passes.
Next, 1,042.3 parts of a 65% ethyl acetate solution of [amorphous polyester resin] synthesized in Production Example 3 was added, followed by one pass with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion]. .
The obtained [pigment / wax dispersion] had a solid content of 50%.

-Preparation of crystalline polyester resin dispersion-
100 g of [crystalline polyester resin] obtained in Production Example 1 and 400 g of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 75 ° C., and then rapidly cooled in an ice-water bath at a rate of 27 ° C./min. .
500 mL of glass beads (3 mm in diameter) were added thereto, and pulverized and dispersed for 10 hours using a batch type sand mill (manufactured by Campehapio Co., Ltd.) to prepare [Crystalline polyester resin dispersion].

-Synthesis of organic fine particle emulsion-
In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of a sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, methacrylic acid When 138 parts of acid and 1 part of ammonium persulfate were added and stirred for 15 minutes at 400 rpm, a white emulsion was obtained.
The obtained emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours.
Further, 30 parts by mass of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to disperse an aqueous dispersion of vinyl resin (styrene salt copolymer of styrene-methacrylic acid-ethylene methacrylate ethylene adduct sulfate). A [fine particle dispersion] was obtained as a liquid.

-Preparation of aqueous phase-
Mix 990 parts of water, 83 parts of [fine particle dispersion], 37 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.) and 90 parts of ethyl acetate. A liquid was obtained. This is referred to as [aqueous phase].

-Preparation of oil phase-
[Pigment / Wax Dispersion] 664 parts (amount in which the wax content in the toner is 4%), 73 parts of [Polyester Prepolymer] synthesized in Production Example 4, 150 parts of [Crystalline Polyester Resin Dispersion] (Crystals) 7.8 parts of a conductive polyester resin in the toner) and 7.8 parts of 5-amino-1,3,3-trimethylcyclohexanemethylamine (manufactured by Sigma Aldrich Japan Co., Ltd.) are put in a container, and TK is added. Using a homomixer (manufactured by PRIMIX Co., Ltd.), mixing at 5,000 rpm for 1 minute gave [oil phase].

-Emulsification and desolvation-
Next, 850 parts of [oil phase] and 1,200 parts of [aqueous phase] were placed in the container, and mixed for 20 minutes at 13,000 rpm using a TK homomixer to obtain [emulsified slurry].
A solution obtained by adding 410 parts of ion-exchanged water to 2,050 parts of the obtained [emulsified slurry] was put into a container equipped with a stirrer and a thermometer, and after desolvation at 30 ° C. for 8 hours, 45 ° C. The mixture was aged for 4 hours to obtain [Dispersion Slurry].

-Cleaning and drying-
After filtering 100 parts of the obtained [dispersed slurry] under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer (manufactured by Primix Co., Ltd.) Filtered.
Next, 100 parts of a 10% aqueous sodium hydroxide solution was added, mixed at 12,000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure.
Next, 100 parts of 10% hydrochloric acid was added, mixed for 10 minutes at 12,000 rpm using a TK homomixer, and then filtered.
Next, 300 parts of ion-exchanged water was added, and after mixing for 10 minutes at 12,000 rpm using a TK homomixer, an operation of filtering was performed twice to obtain [filter cake].
The obtained [filter cake] was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having an opening of 75 μm to produce toner base particles 1 of Example 1.

(Example 2)
-Preparation of toner-
In Example 1, toner base particles 2 of Example 2 were prepared in the same manner as in Example 1, except that 73 parts of [Polyester Prepolymer] used in the preparation of [Oil Phase] was changed to 109.4 parts. did.

(Example 3)
-Preparation of toner-
In Example 1, except that paraffin (HNP-11, Nippon Seiwa Co., Ltd.) used in the production of [Pigment / Wax Dispersion] was changed to microcrystalline (Hi-mic-1090, Nippon Seiwa Co., Ltd.). In the same manner as in Example 1, toner base particles 3 of Example 3 were produced.

Example 4
-Preparation of toner-
In Example 2, except that the paraffin (HNP-11, Nippon Seiwa Co., Ltd.) used in the production of [Pigment / Wax Dispersion] was changed to microcrystalline (Hi-mic-1090, Nippon Seiwa Co., Ltd.). In the same manner as in Example 2, toner base particles 4 of Example 4 were produced.

(Example 5)
-Synthesis of wax-
To four flasks equipped with a thermometer, a nitrogen inlet tube, a stirrer, and a condenser tube were added 279.1 g of behenyl alcohol (22 carbon atoms) and 809.1 g of behenyl myristate (14 carbon atoms). Reaction water was distilled off at a temperature of 15 ° C. for 15 hours to obtain [ester wax].

-Preparation of toner-
[Polyester prepolymer used in the production of [oil phase] instead of [Ester wax] in Example 1 except that the paraffin (HNP-11, Nippon Seiwa Co., Ltd.) used in the production of [Pigment / Wax Dispersion] The toner base particles 5 of Example 5 were produced in the same manner as in Example 1 except that 73 parts were changed to 87.6 parts.

(Example 6)
-Preparation of polyester resin solution-
100 g of [amorphous polyester resin] synthesized in Production Example 3 and 400 g of ethyl acetate were placed in a metal 2 L container and heated and dissolved at 75 ° C. to prepare a [polyester resin solution].

-Preparation of toner-
Toner base particles 6 of Example 6 were produced in the same manner as in Example 1 except that [Crystalline Polyester Resin Dispersion] was replaced with [Polyester Resin Solution] in Example 1.

(Example 7)
-Preparation of toner-
In Example 6, toner base particles 7 of Example 7 were produced in the same manner as in Example 6, except that 73 parts of [Polyester Prepolymer] used in the production of [Oil Phase] was changed to 36.5 parts. did.

(Comparative Example 1)
-Preparation of toner-
In Example 6, toner base particles 8 of Comparative Example 1 were prepared in the same manner as in Example 6 except that 73 parts of [Polyester Prepolymer] used in preparation of [Oil Phase] was changed to 21.9 parts. did.

(Comparative Example 2)
-Preparation of toner-
In Example 6, toner base particles 9 of Comparative Example 2 were produced in the same manner as in Example 6 except that 73 parts of [Polyester Prepolymer] used in the production of [Oil Phase] was changed to 109.4 parts. did.

(Comparative Example 3)
-Preparation of toner-
The toner of Comparative Example 3 was prepared in the same manner as in Example 7 except that paraffin (HNP-11, Nippon Seiwa Co., Ltd.) was replaced with carnauba wax (WA-05, manufactured by Celerica NODA) in Example 7. Base particles 10 were produced.

(Comparative Example 4)
-Preparation of toner-
In Comparative Example 3, the toner base particles 11 of Comparative Example 4 were the same as Comparative Example 3 except that 36.5 parts of [Polyester Prepolymer] used in the production of [Oil Phase] were changed to 109.4 parts. Was made.

-External treatment-
To 100 parts of the toner base particles 1 to 11 obtained in Examples 1 to 7 and Comparative Examples 1 to 4, 0.7 part of hydrophobic silica (HDK H2000, manufactured by Clariant Japan) as an external additive and hydrophobized Toner was prepared by mixing 0.3 part of titanium oxide with a Henschel mixer (manufactured by Nihon Coke Kogyo Co., Ltd.) and externally adding it.

<Production of developer>
A developer comprising 5% of each toner subjected to external additive treatment and 95% of a copper-zinc ferrite carrier having an average particle diameter of 40 μm coated with a silicone resin was prepared.

<Evaluation>
Next, using the toners and developers of Examples 1 to 7 and Comparative Examples 1 to 4 that were produced, various characteristics were evaluated as follows. The results are shown in Table 1.

<Low temperature fixability and hot offset property>
For low-temperature fixability and hot-offset properties, a copy machine (made by Ricoh Co., Ltd., imagio MP C4500) is used with a modified fixing unit. Evaluated by doing.
The cold offset temperature (fixing lower limit temperature) and the hot offset temperature (hot offset temperature) were determined by changing the fixing temperature, and the low temperature fixability and the hot offset property were evaluated according to the following criteria.
The lower limit fixing temperature of the conventional low-temperature fixing toner is about 140 ° C. to 150 ° C.
[Evaluation criteria for low-temperature fixability]
◎: Cold offset occurs at 120 ° C or less ○: Cold offset occurs at 121 ° C to 130 ° C △: Cold offset occurs at 131 ° C to 140 ° C ×: Cold offset occurs at 141 ° C or higher

[Evaluation criteria for hot offset properties]
◎: Hot offset occurs at 170 ° C or higher ○: Hot offset occurs at 165 ° C to 169 ° C △: Hot offset occurs at 160 ° C to 164 ° C ×: Hot offset occurs at 159 ° C or lower

<Long-term stability evaluation>
For long-term stability, the fixing temperature at low temperature of the evaluation toner is determined by evaluation of “low temperature fixing property and hot offset property”. Evaluation was made by visually confirming the contamination of the wax.
Using a device in which the fixing unit of a copying machine (manufactured by Ricoh Co., Ltd., imgio MP C4500) was modified, paper (Ricoh Co., Ltd., type 6200) was set thereon, and a copying test was performed.
Evaluation was performed according to the following evaluation criteria.
[Evaluation criteria for long-term stability]
◎: No contamination of toner or wax on paper ○: Some contamination of toner or wax on paper is observed ×: Contamination of toner or wax on paper is observed

Aspects of the present invention are as follows, for example.
<1> A toner containing at least a binder resin, a wax, and a colorant,
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1):
The toner is characterized in that the melt viscosity (η _W ) of the wax at 100 ° C. satisfies the following formula (2).
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
1 mPa · s ≦ η _W ≦ 20 mPa · s (2)
<2> The toner according to <1>, wherein the binder resin contains a polyester resin, and the polyester resin contains a crystalline polyester resin.
<3> is determined by the total reflection absorption infrared spectroscopy, a wax and a crystalline polyester resin derived peak intensity of 2850 cm ^-1 of the (P2850), the peak intensity of the binder resin from the 828cm ^-1 (P828) and the The toner according to <2>, wherein the intensity ratio (P2850 / P828) is 0.10 to 0.20.
<4> The toner according to any one of <1> to <3>, wherein the wax is an ester wax.
<5> A wax dispersant is contained, and the content of the wax dispersant is 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the wax. Toner.
<6> The toner according to any one of <4> to <5>, wherein the ester wax is an ester wax having 26 to 46 carbon atoms.
<7> Contains a wax dispersant,
The binder resin contains a crystalline polyester resin and an amorphous polyester resin,
An oil phase obtained by dissolving or dispersing at least the crystalline polyester resin, the amorphous polyester resin, a colorant, a wax, and a toner material containing the wax dispersant in an organic solvent is dispersed in an aqueous medium. The toner according to any one of <1> to <6>, which is obtained by removing the organic solvent from the obtained dispersion.
<8> Contains a wax dispersant,
The binder resin contains a reaction product of a crystalline polyester resin, an amorphous polyester resin, and an active hydrogen group-containing compound and a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound,
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, a colorant, a wax, and the wax dispersant An oily phase obtained by dissolving or dispersing a toner material containing benzene is dispersed in an aqueous medium to obtain an emulsified dispersion, and the binder resin precursor and the active hydrogen group-containing compound are reacted in the emulsified dispersion. And the toner according to any one of <1> to <6> obtained by removing the organic solvent.
<9> The toner according to any one of <5> to <8>, wherein the wax dispersant is a graft polymer of a polyolefin resin and an acrylic resin.

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

Claims (9)

A toner containing at least a binder resin, a wax, and a colorant,
The melt viscosity (η _T ) of the toner at 100 ° C. satisfies the following formula (1):
A toner wherein the wax has a melt viscosity (η _W ) at 100 ° C. that satisfies the following formula (2):
500 Pa · s ≦ η _T ≦ 8,000 Pa · s Formula (1)
1 mPa · s ≦ η _W ≦ 20 mPa · s (2)   The toner according to claim 1, wherein the binder resin contains a polyester resin, and the polyester resin contains a crystalline polyester resin. Determined by the total reflection absorption infrared spectroscopy, the intensity ratio of the 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) (P2850 The toner according to claim 2, wherein / P828) is 0.10 to 0.20.   The toner according to claim 1, wherein the wax is an ester wax.   The toner according to claim 1, comprising a wax dispersant, wherein the content of the wax dispersant is 20 parts by mass to 100 parts by mass with respect to 100 parts by mass of the wax.   The toner according to claim 4, wherein the ester wax is an ester wax having 26 to 46 carbon atoms. Contains a wax dispersant,
The binder resin contains a crystalline polyester resin and an amorphous polyester resin,
An oil phase obtained by dissolving or dispersing at least the crystalline polyester resin, the amorphous polyester resin, a colorant, a wax, and a toner material containing the wax dispersant in an organic solvent is dispersed in an aqueous medium. The toner according to claim 1, wherein the toner is obtained by removing the organic solvent from the obtained dispersion. Contains a wax dispersant,
The binder resin contains a reaction product of a crystalline polyester resin, an amorphous polyester resin, and an active hydrogen group-containing compound and a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound,
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, a colorant, a wax, and the wax dispersant An oily phase obtained by dissolving or dispersing a toner material containing benzene is dispersed in an aqueous medium to obtain an emulsified dispersion, and the binder resin precursor and the active hydrogen group-containing compound are reacted in the emulsified dispersion. The toner according to claim 1, wherein the toner is obtained by removing the organic solvent.   The toner according to claim 5, wherein the wax dispersant is a graft polymer of a polyolefin resin and an acrylic resin.

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