JP6611554B2 - toner - Google Patents

Description

  The present invention relates to a toner used in a recording method such as electrophotography.

In recent years, electrophotographic apparatuses have been required to further improve the low-temperature fixing performance of toner in order to achieve energy saving. On the other hand, printing speed has been increased, and both improvement in low-temperature fixing performance and higher printing speed are required.
In order to improve the low-temperature fixing performance, a low melting point wax that exhibits an excellent function is often used. This low melting point wax is a substance having crystallinity having a melting point of 60.0 ° C. or higher and 90.0 ° C. or lower, and examples thereof include aliphatic hydrocarbon waxes and ester waxes.
The low melting point wax itself melts rapidly at the melting point, and improves the low temperature fixing performance by plasticizing the amorphous resin as the main binder.
However, since the low melting point wax has a low molecular weight, it tends to volatilize when heated. Therefore, when the toner containing the low melting point wax is heated in the fixing process, volatile components are likely to be generated. As a result of depositing and depositing, the fouling of the fixing device is likely to occur.
With regard to this fusing unit contamination, the higher the printing speed, the more likely it is that the fouling is more likely. This is because, in a fixing process with a high printing speed, the toner is instantaneously melted in the fixing nip, so that the fixing temperature is set high, so that an excessive amount of heat is easily applied to the toner.

In order to suppress volatile components and suppress fusing unit contamination, Patent Document 1 proposes that the total amount of components generated when hydrocarbon wax is heated at 200 ° C. for 10 minutes. According to this document, it is described that the volatilization of the wax component can be suppressed and the contamination state around the fixing device can be improved.
Similarly, Patent Document 2 proposes to suppress the generation of dust by defining the ratio between the modified wax and the ester wax.

On the other hand, there has also been proposed a technique in which a long-chain alkyl component having an action like a low melting point wax is chemically bonded to an amorphous resin as a main binder.
In this way, by bonding the low melting point component to the main binder, it has the function of a low melting point wax and the apparent molecular weight is increased, so that the generation of volatile components during fixing can be suppressed.
Patent Document 3 proposes an electrostatic charge image developing toner containing a polyester resin at least partially modified with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal. Yes. Patent Document 4 proposes a toner using a polyester unit obtained by reacting a long-chain alcohol having 16 to 102 carbon atoms, a polyhydric alcohol, and a polycarboxylic acid. Further, Patent Document 5 proposes a toner binder resin containing a polyester resin containing a compound having a functional group capable of reacting with an acid or alcohol and a long-chain alkyl group having 30 or more carbon atoms.

JP 2012-78810 A JP 2012-215859 A JP-A-7-175263 JP 2013-97262 A JP 2007-133391 A

As a result of the study by the present inventors, the toners described in Patent Documents 1 and 2 require further improvement for suppressing contamination of the fixing unit at a higher printing speed and in a high fixing temperature environment. There was something.
Moreover, it has been found that Patent Documents 3, 4 and 5 have the following problems. In the examples of the above document, for example, a monovalent long-chain alkyl alcohol monomer having a carbon chain length of 50 is added at the time of polyester polymerization to obtain a modified polyester resin. An alcohol or acid monomer having a long carbon chain length, such as a monovalent long-chain alkyl alcohol monomer having a carbon chain length of 50, used here is obtained through the following process.

For example, in the case of a monovalent long-chain alkyl alcohol having a carbon chain length of 50, an alcohol-modified product is obtained by oxidizing and hydrolyzing an aliphatic hydrocarbon (paraffin wax) having a carbon chain length of about 50.
However, in this modification reaction, conventional modified alcohol products have a modification rate of about 50 to 70%, and a large number of unmodified aliphatic hydrocarbons existed.
The alcohol-modified aliphatic hydrocarbon component reacts with the polyester resin by a polymerization reaction and is incorporated into the polyester resin. On the other hand, unmodified aliphatic hydrocarbon components do not have a reaction point with the main binder, so they exist in the free state in the main binder, and they may be generated as volatile components during fixing. There is. For this reason, the techniques relating to these documents have room for improvement in that the modification rate of the hydrocarbon component is low.
As described above, an object of the present invention is to provide a toner that is excellent in low-temperature fixing performance and less contaminated with a member such as a fixing device even in a high-speed and highly durable use environment.

The present invention is a toner having toner particles containing a polyester resin composition,
The polyester resin composition is
( I) a polyester resin having a terminal structure derived from at least one of a long-chain alkyl monoalcohol having an average value of 27 to 50 carbon atoms and a long-chain alkyl monocarboxylic acid having an average value of 27 to 50 carbon atoms, and,
Containing an aliphatic hydrocarbon having an average carbon number of 27 to 50,
( Ii) The total content of the aliphatic hydrocarbon, the structure derived from the long-chain alkyl monoalcohol, and the structure derived from the long-chain alkyl monocarboxylic acid is based on the mass of the polyester resin composition, 2.5% by mass or more and 10.0% by mass or less,
In the temperature-endothermic curve of the polyester resin composition obtained by differential scanning calorimetry (DSC),
The peak top temperature of the endothermic peak of the polyester resin composition is 60.0 ° C. or higher and 90.0 ° C. or lower,
Endotherm endothermic peak state, and are less 0.10J / g or more 1.90J / g,
The polyester resin composition is a reaction product of a composition (A) containing an alcohol component and a composition (B) containing an acid component,
The composition (A) and the composition (B) are defined in the following (iii) and (iv):
(Iii) The alcohol component contained in the composition (A) contains the long-chain alkyl monoalcohol, the composition (A) contains the aliphatic hydrocarbon, and the composition (A) The content ratio of the long-chain alkyl monoalcohol is from 85% to 99% with respect to the total amount of the long-chain alkyl monoalcohol and the aliphatic hydrocarbon.
(Iv) The acid component contained in the composition (B) contains the long-chain alkyl monocarboxylic acid.
The composition (B) contains the aliphatic hydrocarbon, and the content ratio of the long-chain alkyl monocarboxylic acid in the composition (B) is such that the long-chain alkyl monocarboxylic acid and the aliphatic carbon 85% or more and 99% or less with respect to the total amount of hydrogen,
Of a toner which is characterized that you satisfies at least one.

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixing performance and less contaminated with a member such as a fixing device even in a high-speed and highly durable use environment.

The toner of the present invention is a toner having toner particles containing a polyester resin composition,
The polyester resin composition is
i) A polyester resin having a terminal structure derived from at least one of a long-chain alkyl monoalcohol having an average carbon number of 27 to 50 and a long-chain alkyl monocarboxylic acid having an average carbon number of 27 to 50, and And an aliphatic hydrocarbon having an average carbon number of 27 or more and 50 or less.
ii) a structure derived from an aliphatic hydrocarbon having an average carbon number of 27 to 50, a long-chain alkyl monoalcohol having an average carbon number of 27 to 50, and a long-chain alkyl having an average carbon number of 27 to 50 The total content of the structure derived from the monocarboxylic acid is 2.5% by mass or more and 10.0% by mass or less with respect to the mass of the polyester resin composition.
And in the temperature-endothermic curve of the polyester resin composition obtained by differential scanning calorimetry (DSC), the peak top temperature of the endothermic peak of the polyester resin composition is 60.0 ° C. or higher and 90.0 ° C. or lower. In addition, the endothermic amount of the endothermic peak of the polyester resin composition is 0.10 J / g or more and 1.90 J / g or less.

As the main binder (binder resin) of the toner, a styrene acrylic resin, a polyester resin, or the like is known, but a polyester resin is preferably used in the toner of the present invention because of excellent durability and low-temperature fixability. .
Moreover, in this invention, a polyester resin represents resin in which 50 mass% or more in the structural component of resin is comprised by the polyester resin or the polyester site | part.

  As a result of intensive investigations to provide a toner that is excellent in low-temperature fixing performance and less contaminated with a member such as a fixing device even in a high-speed, high-durability use environment, the present inventors have made the above-described configuration by adopting the following configuration. I found that I could solve the problem. That is, a certain amount of a long-chain alkyl component having an average value of 27 to 50 carbon atoms is contained in the polyester resin composition. Further, in the temperature-endothermic curve of the polyester resin composition obtained by differential scanning calorimetry, the peak top temperature of the endothermic peak is 60.0 ° C. or more and 90.0 ° C. or less, and the endothermic amount of the endothermic peak is 0 .10 J / g or more and 1.90 J / g or less.

Hereinafter, the configuration of the present invention will be described in detail.
The first feature of the polyester resin composition is i) at least one of a long-chain alkyl monoalcohol having an average value of 27 to 50 carbon atoms and a long-chain alkyl monocarboxylic acid having an average value of 27 to 50 carbon atoms. It is to contain a polyester resin having a derived structure at the terminal and an aliphatic hydrocarbon having an average value of 27 to 50 carbon atoms.
As described above, the terminal polyester resin having a structure derived from at least one of a long-chain alkyl monoalcohol having an average value of 27 to 50 carbon atoms and a long-chain alkyl monocarboxylic acid having an average value of 27 to 50 carbon atoms. By using this, an aliphatic hydrocarbon component that tends to become a volatile component can be bound to the main binder, and contamination of the fixing device or the like can be suppressed.
In addition, by incorporating an aliphatic hydrocarbon component (long chain alkyl component) into the main binder, a plastic effect is rapidly manifested in a configuration in which the long chain alkyl component and the main binder exist separately. Therefore, in a system with a high printing speed, it is important to incorporate a long-chain alkyl component into the main binder with a high reaction rate.

The average value of the carbon number of the long-chain alkyl component for obtaining these effects is 27 or more and 50 or less. The average value of the carbon number and the melting point of the long-chain alkyl component almost correspond to each other. In order to effectively have low-temperature fixing performance, the melting point is preferably 60.0 ° C. or higher and 90.0 ° C. or lower. In the present invention, the average value of the carbon number corresponding to the melting point range is 27 or more and 50 or less.
When the average value of carbon number is less than 27, the melting point of the long-chain alkyl component tends to be less than 60.0 ° C., and the storage stability of the toner tends to deteriorate. On the other hand, when the average value of the number of carbons exceeds 50, the melting point tends to exceed 90.0 ° C., and the effect on low-temperature fixability is hardly obtained.

Further, the polyester resin composition according to the present invention includes a polyester resin having a structure derived from at least one of the above-mentioned long-chain alkyl monoalcohol having the above average carbon number and a long-chain alkyl monocarboxylic acid, and the above-mentioned aliphatic having the above average carbon number. It is characterized by containing a hydrocarbon. Among these, the polyester resin having a terminal structure having a structure derived from at least one of a long-chain alkyl monoalcohol and a long-chain alkyl monocarboxylic acid is incorporated into the polyester resin in which the long-chain alkyl component reacts with the main binder component. Represents resin. On the other hand, the aliphatic hydrocarbon component having the average carbon number represents that it also contains an unmodified component when the long-chain alkyl component is modified with an alcohol or an acid.
That is, it means that the polyester resin composition of the present invention has a polyester resin in which a long-chain alkyl component is incorporated and an aliphatic hydrocarbon component that is an unmodified product of the long-chain alkyl component.

In the present invention, the average carbon number of the long-chain alkyl component is determined by the following method.
The carbon number distribution of the long-chain alkyl component is measured by gas chromatography (GC) as follows. Precisely weigh 10 mg of sample into a sample bottle. To this sample bottle, 10 mg of hexane precisely weighed is added and the lid is capped, and then heated to 150 ° C. with a hot plate and mixed. Thereafter, this sample is quickly injected into the gas chromatography inlet so that no long-chain alkyl component is deposited, and analysis is performed to obtain a chart with the horizontal axis representing the carbon number and the vertical axis representing the signal intensity. Next, in the obtained chart, the ratio of the peak area of each carbon number component to the total area of all detected peaks is calculated, and this is used as the abundance ratio (area%) of each hydrocarbon compound. Then, a carbon number distribution chart is prepared by taking the carbon number on the horizontal axis and the abundance ratio (area%) of the hydrocarbon compound on the vertical axis.
The average carbon number in the present invention indicates the number of carbons at the peak top in the carbon number distribution chart.

The measurement apparatus and measurement conditions are as follows.
GC: HP 6890GC
Column: ULTRA ALLOY-1 P / N: UA1-30m-0.5F (manufactured by Frontier Laboratories)
Carrier gas: He
Oven: (1) Hold for 5 minutes at a temperature of 100 ° C, (2) Increase the temperature to 360 ° C at 30 ° C / min, (3) Hold for 60 minutes at a temperature of 360 ° C Inlet: Temperature 300 ° C
Initial pressure: 10.523 psi
Split ratio: 50: 1
Column flow rate: 1 mL / min

The second feature of the polyester resin composition is ii) a structure derived from an aliphatic hydrocarbon having an average value of 27 to 50 carbon atoms, a long-chain alkyl monoalcohol having an average value of 27 to 50 carbon atoms, and carbon The total content of the structures derived from long chain alkyl monocarboxylic acids having an average number of 27 or more and 50 or less is 2.5% by mass or more and 10.0% by mass or less based on the mass of the polyester resin composition. It is characterized by being.
When the content ratio of the structure derived from the long-chain alkyl component is less than 2.5% by mass based on the mass of the polyester resin composition, it is difficult to obtain an effect on low-temperature fixability. On the other hand, if it exceeds 10.0% by mass, the plasticity effect is too strong and the storage stability tends to deteriorate. Therefore, for resin,
It is necessary to appropriately control the amount of the long-chain alkyl component added. The content is preferably 3.5% by mass or more and 7.5% by mass or less.

The third characteristic of the polyester resin composition is that, in the temperature-endothermic curve obtained by differential scanning calorimetry (DSC), the peak top temperature of the endothermic peak of the polyester resin composition is 60.0 ° C. or more and 90.0. It is at most 0 ° C. (preferably 70 ° C. or more and 85 ° C. or less). In addition, the endothermic amount (ΔH) of the endothermic peak is 0.10 J / g or more and 1.90 J / g or less. ΔH is preferably 0.20 J / g or more and 1.00 J / g or less.

As described above, an object of the present invention is to provide a toner that is excellent in low-temperature fixing performance and less contaminated with a member such as a fixing device. For this purpose, it is necessary to optimize the amount of the free component, that is, the unmodified aliphatic hydrocarbon, which does not bind to the polyester resin component.
This unmodified aliphatic hydrocarbon exhibits an endothermic peak in a temperature-endothermic curve obtained by differential scanning calorimetry (DSC). For this reason, the present inventors can optimize the endothermic amount (ΔH) of this endothermic peak, thereby being excellent in low-temperature fixing performance and suppressing volatilization of unmodified aliphatic hydrocarbons during fixing, It has been found that a toner with less contamination of a member such as a fixing device can be provided.
The endothermic amount ΔH observed by DSC being within the scope of the present application indicates that there are few free long-chain alkyl components, that is, they are incorporated in the polyester resin (main binder).
By incorporating the long-chain alkyl component efficiently into the polyester resin, contamination of the member such as a fixing device is suppressed. On the other hand, by having a certain amount of the unmodified aliphatic hydrocarbon appearing as ΔH, the plastic effect is rapidly expressed starting from the unmodified product site. For this reason, in a system with a high printing speed, it is advantageous in terms of low-temperature fixability.
As a result, it is possible to provide a toner that is excellent in low-temperature fixing performance, can suppress volatilization of unmodified aliphatic hydrocarbons at the time of fixing, and is less contaminated with members such as a fixing device.

The peak top temperature and endothermic amount (ΔH) of the endothermic peak in the present invention are measured by the following methods.
The peak top temperature and endothermic peak amount of the endothermic peak in differential scanning calorimetry (DSC) are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 5 mg of a measurement sample is accurately weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure at room temperature and humidity for min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. In the DSC curve (temperature-endothermic curve) obtained in this temperature raising process, the peak top temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C. is obtained. The endothermic amount ΔH of the endothermic peak is an integral value of the endothermic peak.

Examples of a method for controlling the free amount of the long-chain alkyl component, that is, the endothermic peak amount of DSC, include a method for increasing the alcohol modification rate or acid modification rate of aliphatic hydrocarbons.
That is, the alcohol or acid-modified long-chain alkyl component reacts with the polyester resin by a polymerization reaction and is incorporated into the polyester resin, and no endothermic peak appears in the DSC measurement. On the other hand, since the unmodified aliphatic hydrocarbon component does not have a reaction point with the polyester resin, it is present in a free state in the polyester resin, thereby increasing the endothermic amount of DSC.

As described above, the long-chain alkyl monoalcohol having an average carbon number of 27 to 50 and the long-chain alkyl monocarboxylic acid having an average carbon number of 27 to 50 used in the present invention are industrially used. It can be obtained by modifying an aliphatic hydrocarbon as a raw material with alcohol or acid.
Aliphatic hydrocarbons include saturated hydrocarbons and unsaturated hydrocarbons, and examples thereof include alkanes, alkenes, alkynes, and cyclic hydrocarbons such as cyclohexane, with saturated hydrocarbons (alkanes) being preferred.
For example, for an alcohol-modified product, an aliphatic hydrocarbon having 27 to 50 carbon atoms is subjected to liquid phase oxidation with a molecular oxygen-containing gas in the presence of a catalyst such as boric acid, anhydrous boric acid, or metaboric acid. It is known that it can be converted to alcohol. The amount of the catalyst used is preferably 0.01 to 0.5 mol with respect to 1 mol of the raw material aliphatic hydrocarbon.
As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of gases diluted with an inert gas can be used, but an oxygen concentration of 3 to 20% is preferable. The reaction temperature is preferably 100 ° C. or higher and 200 ° C. or lower.

In order to satisfy the endothermic specification of the DSC of the present invention, the unmodified aliphatic hydrocarbon components are removed by optimizing the reaction conditions and performing a purification operation after the modification reaction, and control within the scope of the present application. be able to.
A preferable range of the modification rate of the aliphatic hydrocarbon component for controlling the endothermic amount of the DSC of the present invention is 85% or more, and more preferably 90% or more. On the other hand, the upper limit is preferably 99% or less.
That is, in the composition (A) containing an alcohol component, the content ratio of the long-chain alkyl monoalcohol is 85% or more with respect to the total amount of the long-chain alkyl monoalcohol and the aliphatic hydrocarbon. It is preferably 90% or more. The composition (C) is the same as the composition (A), and is preferably 85% or more, preferably 90% or more, based on the total amount of the long-chain alkyl monoalcohol and the aliphatic hydrocarbon. Is more preferable.
On the other hand, in the composition (B) containing an acid component, the content ratio of the long-chain alkyl monocarboxylic acid is 85% or more based on the total amount of the long-chain alkyl monocarboxylic acid and the aliphatic hydrocarbon. It is preferable that it is 90% or more. The composition (D) is the same as the composition (B), and the content ratio of the long-chain alkyl monocarboxylic acid is relative to the total amount of the long-chain alkyl monocarboxylic acid and the aliphatic hydrocarbon. It is preferably 85% or more, more preferably 90% or more.

  The long-chain alkyl component used in the present invention preferably has an average value of 30 to 40 carbon atoms, and its melting point (DSC endothermic peak temperature) is preferably 70 to 80 ° C.

The long-chain alkyl monoalcohol of the present invention preferably contains a secondary alcohol as a main component. In addition, having a secondary alcohol as a main component means that 50% by mass or more in the long-chain alkyl monoalcohol is a secondary alcohol.
By using a secondary alcohol as a main component as the long-chain alkyl monoalcohol, the long-chain alkyl component can easily take a folded structure. As a result, steric hindrance and the like are suppressed, and the long-chain alkyl component is more likely to be present more uniformly in the polyester-based resin composition, which is preferable because the storage stability is further improved.
In the case of using a long-chain alkyl monoalcohol, the long-chain alkyl component of the present invention preferably has a hydroxyl value of 80 mgKOH / g or more and 140 mgKOH / g or less, more preferably 90 mgKOH / g or more and 130 mgKOH / g or less. is there.
A preferable acid value when using a long-chain alkyl monocarboxylic acid is 80 mgKOH / g or more and 150 mgKOH / g or less, more preferably 90 mgKOH / g or more and 140 mgK.
OH / g or less.
By controlling to the said range, the reactivity of a polyester resin component and a modification | denaturation site | part increases, As a result, since it becomes possible to reduce the peak area ((DELTA) H) of DSC efficiently, it is preferable.

The acid value and hydroxyl value of the long-chain alkyl monomer (long-chain alkyl monoalcohol, long-chain alkyl monocarboxylic acid) in the present invention can be measured as follows.
<Method for measuring hydroxyl value of long-chain alkyl monomer>
(Devices and instruments)
Measuring cylinder (100ml)
Full pipette (5ml)
Flat bottom flask (200ml)
Glycerin bath (reagent)
Acetylation reagent (25 g of acetic anhydride is taken in a 100-ml volumetric flask and pyridine is added to make a total volume of 100 ml and shaken well.)
Phenolphthalein solution 0.5 kmol / m ³ potassium hydroxide ethanol solution (measurement method)
(A) A long-chain alkyl monomer is precisely weighed into a 0.5 to 6.0 g flat bottom flask, and 5 ml of an acetylating reagent is added to the whole using a pipette.
(B) Place a small funnel at the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. To prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is placed over the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, and after standing to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride.
(D) Further, in order to complete the decomposition, the flask is heated again in a glycerin bath for 10 minutes, and after cooling, the funnel and the wall of the flask are washed with 5 ml of ethanol (95 vol%).
(E) A few drops of phenolphthalein solution is added as an indicator, and titrated with 0.5 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the indicator is light red for about 30 seconds.
(F) In the blank test, (a) to (e) are performed without adding the long-chain alkyl monomer (a).
(G) If the sample is difficult to dissolve, add a small amount of pyridine, or add xylene or toluene to dissolve.
(Calculation)
From the obtained result, the hydroxyl value of the long-chain alkyl monomer is determined by the following formula (1).
A = [{(BC) × 28.05 × f} / S] + D (1)
However,
A: Hydroxyl value of long-chain alkyl monomer (mgKOH / g)
B: Amount (ml) of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test
C: Amount of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution S: Mass of long-chain alkyl monomer (g)
D: Acid value of long-chain alkyl monomer (mgKOH / g)
28.05: Formula weight of potassium hydroxide 56.11 × 1/2

<Method for measuring acid value of long-chain alkyl monomer>
(Devices and instruments)
Erlenmeyer flask (300 ml)
Burette (25ml)
Water bath or hot plate (reagent)
0.1 kmol / m ³ hydrochloric acid 0.1 kmol / m ³ potassium hydroxide ethanol solution (standardization: 25 ml of 0.1 kmol / m ³ hydrochloric acid was taken into an Erlenmeyer flask using all pipettes, phenolphthalein solution was added, Titrate with 1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization.)
Phenolphthalein solution solvent (diethyl ether and ethanol (99.5 vol%) mixed at a volume ratio of 1: 1 or 2: 1. These were added several drops of phenolphthalein solution as an indicator just before use. Neutralize with 1 kmol / m ³ potassium hydroxide ethanol solution.)
(Measurement method)
(A) Weigh accurately 1-20 g of long-chain alkyl monomer in an Erlenmeyer flask.
(B) Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the long-chain alkyl monomer is completely dissolved in a water bath.
(C) Titrate with a 0.1 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the light red color of the indicator lasts for 30 seconds.
(Calculation)
From the obtained results, the acid value of the long-chain alkyl monomer is calculated by the following formula (2).
A = 5.611 × B × f / S (2)
However,
A: Acid value of long chain alkyl monomer (mgKOH / g)
B: Amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml)
f: Factor of 0.1 kmol / m ³ potassium hydroxide ethanol solution S: Mass of long-chain alkyl monomer (g)
5.611: Formula weight of potassium hydroxide 56.11 × 1/10

Moreover, there is no restriction | limiting in particular as a manufacturing method of the polyester resin composition which concerns on this invention, However, It is preferable that it is the following manufacturing method.
That is, the polyester resin composition used in the present invention is preferably a reaction product obtained by reacting a composition (A) containing an alcohol component with a composition (B) containing an acid component. With regard to the composition (A) and the composition (B), the following provisions i) and ii):
i) The alcohol component contains a long-chain alkyl monoalcohol having an average value of 27 to 50 carbon atoms, and the composition (A) contains an aliphatic hydrocarbon having an average value of 27 to 50 carbon atoms.
ii) The acid component contains a long-chain alkyl monocarboxylic acid having an average value of 27 to 50 carbon atoms, and the composition (B) contains an aliphatic hydrocarbon having an average value of 27 to 50 carbon atoms. ,
It is preferable to satisfy at least one of the following.

  Moreover, it is preferable that this polyester resin composition is a reaction material of the polyester resin which has a carboxyl group at the terminal, and a composition (C). The composition (C) contains a long-chain alkyl monoalcohol having an average value of 27 to 50 carbon atoms and an aliphatic hydrocarbon having an average value of 27 to 50 carbon atoms. This reaction product is a polyester resin composition obtained by a method including a step of reacting the carboxyl group of the polyester resin with the long-chain alkyl monoalcohol.

The polyester resin composition is preferably a reaction product of a polyester resin having a hydroxyl group at the terminal and the composition (D). The composition (D) contains a long-chain alkyl monocarboxylic acid having an average value of 27 to 50 carbon atoms and an aliphatic hydrocarbon having an average value of 27 to 50 carbon atoms. This reaction product is a polyester resin composition obtained by a method including a step of reacting the hydroxyl group of the polyester resin with the long-chain alkyl monocarboxylic acid.

More preferably, it is a polyester-based resin composition (reactant) obtained by reacting a composition (A) containing an alcohol component with a composition (B) containing an acid component, and the alcohol component is A long-chain alkyl monoalcohol having an average carbon number of 27 or more and 50 or less is included, and the composition (A) contains an aliphatic hydrocarbon having an average value of carbon number of 27 or more and 50 or less. That is, it is preferable to perform a polyester polymerization reaction in the presence of a long-chain alkyl monoalcohol and an aliphatic hydrocarbon component that is an unmodified component to obtain a polyester resin composition.
By using a long-chain alkyl monoalcohol as the long-chain alkyl component, the modification rate can be increased more stably. Then, it is preferable to introduce the long chain alkyl component into the resin efficiently and uniformly by introducing the long chain alkyl component from the initial stage of the polyester synthesis reaction.

The polyester resin composition of the present invention is preferably a hybrid resin composition containing a hybrid resin in which a polyester moiety and a vinyl polymer moiety are chemically bonded.
It is preferable to use a hybrid resin because the charging property is stable regardless of the environment and the stability of the image density in a high humidity environment is increased.
In this case, it is preferable that the long-chain alkyl component is condensed at the terminal of the polyester portion of the hybrid resin.

In addition, the hybrid resin preferably has a mass ratio of the polyester moiety to the vinyl polymer moiety (polyester moiety / vinyl polymer moiety) of 50/50 to 90/10, more preferably 60/40 to 80. / 20.
By setting it within the above range, it is preferable that stable low-temperature fixability is easily obtained regardless of the environment while obtaining the advantages of the hybrid resin.

The following compounds are mentioned as a polyester-type monomer which comprises the polyester site | part of the polyester resin used for the polyester resin composition concerning this invention, or the said hybrid resin.
The following are mentioned as an alcohol component. Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol 2-ethyl-1,3-hexanediol, bisphenol A hydride, bisphenol derivatives represented by the following formula (3), and diols represented by the following formula (4).

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつ、ｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  When the bisphenol derivative represented by the above formula (3) is used, the ratio EO: PO of the ethylene oxide (EO) adduct to the propylene oxide (PO) adduct is preferably 40:60 to 60:40 in the present invention. . Controlling the ratio of EO: PO within this range is preferable because the long-chain alkyl component is more uniformly dispersed in the resin and the storage stability is improved.

  Examples of the acid component include the following. Benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, or anhydrides thereof; Succinic acid substituted with an alkyl group or alkenyl group of 18 or less or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or an anhydride thereof.

  Further, the polyester resin used in the polyester resin composition according to the present invention or the polyester part of the hybrid resin may use a trivalent or higher polyvalent carboxylic acid or its anhydride and / or a trivalent or higher polyhydric alcohol. . Examples of the trivalent or higher polyvalent carboxylic acid or anhydride thereof include the following. 1,2,4-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid and acid anhydrides or lower alkyl esters thereof. Examples of the trihydric or higher polyhydric alcohol include the following. 1,2,3-propanetriol, trimethylolpropane, hexanetriol, pentaerythritol. In the polyester resin composition of the present invention, an aromatic carboxylic acid having high stability due to environmental fluctuation is particularly preferred, and examples thereof include 1,2,4-benzenetricarboxylic acid and anhydrides thereof.

When the hybrid resin is used in the polyester resin composition according to the present invention, examples of the vinyl monomer constituting the vinyl polymer portion of the hybrid resin include the following compounds.
Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene and its derivatives such as; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride. Vinyl halides such as: vinyl acetate, vinyl propionate, benzoate Vinyl esters such as vinyl; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, Α-methylene aliphatic monocarboxylic esters such as phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, Acrylic acid esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; Vinyl ethers such as til ether, vinyl ethyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N- N-vinyl compounds such as vinyl pyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide.

Furthermore, the following are mentioned. Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, Alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester half ester of unsaturated dibasic acid; dimethyl maleic acid, unsaturated dibasic acid ester such as dimethyl fumaric acid; acrylic acid, Meta Α, β-unsaturated acids such as rillic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, and the α, β-unsaturated acid Anhydrides with lower fatty acids; monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, their anhydrides and their monoesters.
Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy- And monomers having a hydroxy group such as 1-methylhexyl) styrene.

Moreover, when using the said hybrid resin for the polyester resin composition concerning this invention, the vinyl polymer site | part of hybrid resin may have the crosslinked structure bridge | crosslinked with the crosslinking agent which has two or more vinyl groups. The following are mentioned as a crosslinking agent used in this case.
Aromatic divinyl compounds (divinylbenzene, divinylnaphthalene); diacrylate compounds linked by alkyl chains (ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5- Pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentylglycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds linked by an alkyl chain containing an ether bond ( For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diac Acrylate, dipropylene glycol diacrylate, and acrylates of the above compounds replaced with methacrylate); diacrylate compounds entrapped with a chain containing an aromatic group and an ether bond [polyoxyethylene (2) -2, 2-bis (4hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4hydroxyphenyl) propane diacrylate, and acrylates of the above compounds replaced with methacrylate]; polyester-type di Acrylate compounds (“MANDA” manufactured by Nippon Kayaku Co., Ltd.).

Examples of the polyfunctional (having three or more vinyl groups) crosslinking agents include the following. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallyl cyanurate, triallyl trimellitate .
These crosslinking agents are preferably used in an amount of 0.01 to 10.00 parts by mass, more preferably 0.03 to 5.00 parts by mass with respect to 100 parts by mass of the other monomer components. it can.
Among these cross-linking agents, those which are preferably used in the polyester resin composition from the viewpoint of fixability and offset resistance are bonded with an aromatic divinyl compound (particularly divinylbenzene), a chain containing an aromatic group and an ether bond. And diacrylate compounds.

  The following are mentioned as a polymerization initiator used for superposition | polymerization of the said vinyl resin or a vinyl polymer site | part. 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methylpropane), methyl ethyl ketone peroxide , Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide, 2,2-bis (tert- Tilperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide , Α, α'-bis (tert-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide , M-toluoyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2 Ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy 2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert- Butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy 2-ethylhexanoate, di-tert-butyl Over oxy hexahydro terephthalate, di -tert- butyl peroxy azelate.

In the present invention, when the above-described hybrid resin is used for the polyester resin composition, it is preferable that the vinyl resin and / or the polyester resin component contain a monomer component (a bireactive monomer) capable of reacting with both resin components. . Examples of monomers that can react with the vinyl resin among the monomers constituting the polyester resin component include unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl resin component, those that can react with the polyester resin component include those having a carboxyl group or a hydroxy group, acrylic acid or methacrylic acid, or esters thereof.
As a method for obtaining a reaction product of a vinyl resin and a polyester resin, a method obtained by carrying out a polymerization reaction of one or both of the resins in the presence of a polymer containing both reactive monomers is preferable.
In the hybrid resin, these bireactive monomers are monomers constituting the polyester portion when discussing the monomer content. This is because both reactive monomers greatly affect the physical properties of the polycondensation resin (polyester part) regardless of whether the condensation polymerization reaction or the addition polymerization reaction is performed first.

Further, the polyester resin composition as described above may be used alone, but two kinds of high softening point resins (H) and low softening point resins (L) having different softening points are mixed in an arbitrary range. May be used. The high softening point resin (H) preferably has a softening point of 100 ° C or higher and 170 ° C or lower. The softening point resin (L) preferably has a softening point of 70 ° C. or higher and lower than 100 ° C.
When two different types of resins are used, it is preferable that at least 50% by mass or more of the resin is the polyester resin composition of the present invention.
When one type of polyester resin composition is used alone, the softening point Tm is preferably 90 ° C. or higher and 170 ° C. or lower. More preferably, it is 100 degreeC or more and 130 degrees C or less. When Tm is within the above range, the balance between high temperature offset resistance and low temperature fixability is good.

The softening point of the polyester resin composition is determined according to a manual attached to the apparatus using a constant load extrusion type capillary rheometer “flow characteristic evaluation apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation). In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.
In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of piston descent in the flow curve is the sum of X and Smin is the melting temperature Tm in the 1/2 method.

As a measurement sample, about 1.0 g of a sample is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NP System Co., Ltd.) in an environment at 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.
The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

In addition, the glass transition temperature (Tg) of the polyester resin composition is preferably 45.0 ° C. or higher, more preferably 50.0 ° C. or higher, from the viewpoint of storage stability. Further, from the viewpoint of low-temperature fixability, Tg is preferably 75.0 ° C. or less, and more preferably 65.0 ° C. or less.
The glass transition temperature (Tg) of the polyester resin composition for toner is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments).

  As a measurement sample, a precisely weighed about 3 mg of a polyester resin composition is used. This is put in an aluminum pan and an empty aluminum pan is used as a reference. The measurement temperature range is 30 ° C. or more and 200 ° C. or less, once the temperature is increased from 30 ° C. to 200 ° C. at a temperature increase rate of 10 ° C./min, then the temperature is decreased from 200 ° C. to 30 ° C. at a temperature decrease rate of 10 ° C./min. The temperature is raised to 200 ° C. at a temperature rising rate of 10 ° C./min. In the DSC curve obtained in the second temperature raising process, the intersection point between the baseline intermediate line before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg of the resin.

The acid value of the polyester resin composition of the present invention is preferably 15.0 mgKOH / g or more and 30.0 mgKOH / g or less, more preferably 20.0 mgKOH / g or more and 30.0 mgKOH / g or less.
It is preferable to control the acid value within the above-mentioned range, since it is difficult for a decrease in charge due to standing in a high humidity environment. The acid value of the polyester resin composition can be controlled by the monomer composition and molecular weight.
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. Although the acid value of a polyester resin composition is measured according to JIS K 0070-1992, specifically, it measures according to the following procedures.

(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchange water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of a pulverized polyester resin composition sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. To do. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

In the present invention, the method for producing the toner particles is not particularly limited, and a known production method can be used. A melt-kneading step in which a resin component containing a polyester resin composition and, if necessary, toner constituent materials such as a colorant, a release agent and a charge control agent are uniformly mixed and then melt-kneaded, and the obtained melt-kneaded product is cooled A so-called pulverization method in which toner particles are obtained through a pulverization step of pulverization with a pulverizer such as a mechanical pulverizer can be exemplified.
As another method, toner particles can be produced by a so-called polymerization method such as an emulsion polymerization method or a suspension polymerization method.
Among these, the toner particles of the present invention are preferably toner particles obtained through at least a melt-kneading step and a pulverizing step.
Examples of the melt kneader include a biaxial kneading extruder, a heating roll, a kneader, and an extruder.
The melt kneading temperature is preferably controlled so that the temperature of the kneaded product is 70 ° C. or higher and 200 ° C. or lower. By controlling the temperature range, the dispersibility of the polyester resin is improved.

Hereinafter, a method for producing toner particles through at least a melt-kneading process and a pulverizing process will be described in detail, but the present invention is not limited thereto.
The resin component containing the polyester resin composition and, if necessary, the colorant, mold release agent, charge control agent, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill (mixing step). ). The obtained mixture is melt-kneaded using a thermal kneader such as a twin-screw kneading extruder, a heating roll, a kneader, or an extruder (melt kneading step). In that case, a mold release agent, magnetic iron oxide particles, and a metal-containing compound can also be added. After the melt-kneaded product is cooled and solidified, pulverization (pulverization step) and classification (classification step) are performed to obtain toner particles. Further, if necessary, the toner particles and the external additive can be mixed with a mixer such as a Henschel mixer to obtain a toner.

The following are mentioned as a mixer. Henschel mixer (manufactured by Nihon Coke Industries); Super mixer (manufactured by Kawata); Ribocorn (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Taiheiyo Kiko) ); Ladige mixer (made by Matsubo).
Examples of the kneader include the following. KRC Kneader (manufactured by Kurimoto Tekkosho); Bus Co Kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works); Steel mill); three roll mill, mixing roll mill, kneader (Inoue Seisakusho); kneedex (Mitsui Mining Co.); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) (Made by the company).
Examples of the pulverizer include the following. Counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industrial Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works); Urmax (manufactured by Nisso Engineering Co., Ltd.) SK; jet mill (manufactured by Seishin Enterprise Co., Ltd.); kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); turbo mill (manufactured by Turbo Industry Co., Ltd.);

Examples of the classifier include the following. Classifier, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nissin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Elbow Jet (Japan) Iron Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.).
Examples of the sieving apparatus used for sieving coarse particles include the following. Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resona Sieve, Gyroshifter (Tokuju Kosakusha Co., Ltd.)
Vibronic system (Dalton); Soniclean (Shinto Kogyo); Turbo screener (Turbo Kogyo); Micro shifter (Ogino Sangyo); Circular vibrating sieve.

The toner of the present invention can be used as any one of magnetic one-component toner, non-magnetic one-component toner, and non-magnetic two-component toner.
When used as a magnetic one-component toner, magnetic iron oxide particles are preferably used as the colorant. Magnetic iron oxide particles contained in the magnetic one-component toner include magnetic iron oxides such as magnetite, maghemite and ferrite, and magnetic iron oxides including other metal oxides; metals such as Fe, Co and Ni, or Alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and these A mixture is mentioned.
The shape of the magnetic iron oxide particles used in the toner of the present invention is preferably an octahedral shape. Due to the octahedral shape, the dispersibility of the magnetic iron oxide particles is improved.
The addition amount of the magnetic iron oxide particles is preferably 25% by mass or more and 50% by mass or less in the toner, and more preferably 30% by mass or more and 45% by mass or less.

On the other hand, examples of the colorant used as the nonmagnetic one-component toner and the nonmagnetic two-component toner include the following.
As the black pigment, carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black is used, and magnetic powder such as magnetite and ferrite is also used.
As a colorant suitable for the yellow color, a pigment or a dye can be used. Examples of the pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, 191, C.I. I. Bat yellow 1, 3, and 20 are mentioned. Examples of the dye include C.I. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 etc. are mentioned. These are used alone or in combination of two or more.

As a colorant suitable for cyan, a pigment or a dye can be used. Examples of the pigment include C.I. I. Pigment Blue 1, 7, 15, 15; 1, 15; 2, 15; 3, 15; 4, 16, 17, 60, 62, 66, etc., C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 is exemplified. Examples of the dye include C.I. I. Solvent Blue 25, 36, 60, 70, 93, 95 etc. are mentioned. These are used alone or in combination of two or more.
A pigment or dye can be used as a colorant suitable for magenta. Examples of the pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48; 2, 48; 3, 48; 4, 49, 50, 51, 52, 53, 54, 55, 57, 57; 1, 58, 60, 63, 64, 68, 81, 81; 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, etc., C.I. I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35 are mentioned. Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, etc. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27 etc., C.I. I. Oil-soluble dyes such as disperse violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 2
3, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, etc., C.I. I. And basic dyes such as basic violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28. These are used alone or in combination of two or more.
The amount of the colorant added is preferably 0.1 parts by mass or more and 60.0 parts by mass or less, more preferably 0.5 parts by mass or more and 50 parts by mass or less with respect to 100.0 parts by mass of the resin component containing the polyester resin composition. 0.0 parts by mass or less.

  In the toner of the present invention, a release agent (wax) can be used as necessary in order to give the toner releasability. As the wax, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferably used because of easy dispersion in the toner and high releasability. If necessary, one or two or more kinds of waxes may be used together in a small amount. Examples include the following:

  Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanate wax; deoxidation Deoxidized part or all of fatty acid esters such as carnauba wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, and seryl alcohol Saturated alcohols such as melyl alcohol; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; Saturated fatty acid bisamides such as ethylene biscapric amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide; ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N′-diole Unsaturated fatty acid amides such as luadipic acid amide and N, N-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bis-stearic acid amide and N, N-distearyl isophthalic acid amide; calcium stearate , Fatty acid metal salts such as calcium laurate, zinc stearate and magnesium stearate (generally called metal soap); grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid A partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oils and fats.

  Examples of waxes that are particularly preferably used in the present invention include aliphatic hydrocarbon waxes. Examples of such aliphatic hydrocarbon waxes include the following. Low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure; alkylene polymer obtained by thermally decomposing high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen Synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained from the gas by the age method and synthetic hydrocarbon waxes obtained by hydrogenating them; press sweating method, solvent method, vacuum Wax separated by use of distillation or fractional crystallization.

Examples of the hydrocarbon as the base of the aliphatic hydrocarbon wax include the following. Carbonization synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) (for example, the Gintor method, Hydrocol method (using a fluidized catalyst bed)) Hydrogen compounds); hydrocarbons having up to about several hundred carbon atoms obtained by the age method (using an identified catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; hydrocarbons obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst. Specific examples include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industry Co., Ltd.); High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) Sazol H1, H2, C80, C105, C77 (Sazol); HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiwa Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite); wood wax, beeswax, rice wax, candelilla wax, carnauba wax (Co., Ltd.) Celerica NODA).

Among these, it is more preferable to contain a release agent having a peak temperature of the endothermic peak of the release agent of 100 ° C. or more in order to efficiently obtain the release effect.
In addition, when the toner is prepared by a pulverization method, the release agent may be added at the time of melt-kneading or may be at the time of production of a toner resin. These release agents may be used alone or in combination. The release agent is preferably added in an amount of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin component containing the polyester resin composition.

In the toner of the present invention, a charge control agent can be used to stabilize the triboelectric chargeability. Although the charge control agent varies depending on the type and physical properties of other toner particle constituent materials, it is generally contained in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of the resin component including the polyester resin composition. It is more preferable that 0.1 to 5.0 parts by mass is included.
As such charge control agents, there are known ones for controlling the toner to be negatively charged and those for controlling the toner to be positively charged. One or two kinds of various kinds of charge control agents are used depending on the kind and use of the toner. The above can be used.
Examples of toners that are negatively charged include the following. Organometallic complexes (monoazo metal complexes; acetylacetone metal complexes); metal complexes or metal salts of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids. In addition, examples of toners that are negatively charged include aromatic mono- and polycarboxylic acids and metal salts and anhydrides thereof; phenol derivatives such as esters and bisphenol. Among these, in particular, a metal complex or metal salt of an aromatic hydroxycarboxylic acid capable of obtaining stable charging performance is preferably used.

Examples of toners that are positively charged include the following. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like; onium salts such as phosphonium salts And these lake pigments; triphenylmethane dyes and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanide) Compounds); metal salts of higher fatty acids. In the present invention, these can be used alone or in combination. Among these, charge control agents such as nigrosine compounds and quaternary ammonium salts are particularly preferably used for controlling the toner to be positively charged.
Specific examples include the following. Spiron Black TRH, T-77, T-95, TN-105 (Hodogaya Chemical Co., Ltd.); BONTRON (registered trademark) S-34, S-44, E-84, E-88 (Orient Chemical Co., Ltd.) ); TP-302, TP-415 (Hodogaya Chemical Co., Ltd.); BONTRON (registered trademark) N-01, N-04, N-07, P-51 (Orient Chemical Co., Ltd.); Copy Blue PR ( Clariant).

Moreover, charge control resin can also be used and can also be used together with the above-mentioned charge control agent.
The toner of the present invention may be mixed with a carrier and used as a two-component developer. As the carrier, a normal carrier such as ferrite or magnetite or a resin-coated carrier can be used. A binder type carrier in which magnetic powder is dispersed in a resin can also be used.
The resin-coated carrier is composed of carrier core particles and a coating material that is a resin that coats (coats) the surface of the carrier core particles. Examples of the resin used for the coating material include styrene-acrylic resins such as styrene-acrylic acid ester copolymer and styrene-methacrylic acid ester copolymer; acrylic resins such as acrylic acid ester copolymer and methacrylic acid ester copolymer. Fluorine-containing resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; aminoacrylate resins. Other examples include ionomer resins and polyphenylene sulfide resins. These resins can be used alone or in combination.

In the toner of the present invention, in order to improve charging stability, durable developability, fluidity and durability, it is one of preferred embodiments that silica fine powder is added to the toner particles as an external additive.
The silica fine powder preferably has a specific surface area of 30 m ² / g or more, more preferably 50 m ² / g or more and 400 m ² / g or less by the BET method by nitrogen adsorption. The silica fine powder is preferably used in an amount of 0.01 to 8.00 parts by mass, and more preferably 0.10 to 5.00 parts by mass with respect to 100 parts by mass of the toner particles. The BET specific surface area of the silica fine powder is, for example, a silica fine powder using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), GEMINI 2360/2375 (manufactured by Micrometric), Tristar 3000 (manufactured by Micrometric). Nitrogen gas is adsorbed on the surface of the body and can be calculated using the BET multipoint method.
Silica fine powder has unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane coupling agents, and functional groups as necessary for the purpose of hydrophobization and triboelectric charge control. It is also preferable that it is treated with a treatment agent such as a silane compound or other organosilicon compound, or in combination with various treatment agents.

  Furthermore, you may add another external additive to the toner of this invention as needed. Examples of such external additives include charging aids, conductivity imparting agents, fluidity imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, abrasives, and the like. An inorganic fine powder is mentioned. Examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. Of these, strontium titanate powder is preferable.

In the present invention, the modification rate of the long-chain alkyl monomer was calculated by measuring the hydroxyl value (or acid value). Specifically, the ratio (based on the number of moles) of hydroxyl groups (or carboxyl groups) reacting per molecule of the long-chain alkyl monomer was calculated using the hydroxyl value (or acid value).
For one molecule of the long-chain alkyl monomer, the average carbon chain length determined by measurement was calculated as one molecule.

  Hereinafter, the present invention will be specifically described with reference to examples. However, this does not limit the embodiment of the present invention. In addition, all the parts and% of an Example and a comparative example are mass references | standards unless there is particular notice.

<Example of production of long-chain alkyl monomer (A-1)>
1200 g of a chain saturated hydrocarbon having an average carbon number of 35 is put into a glass cylindrical reaction vessel, and 38.5 g of boric acid is added at a temperature of 140 ° C., and immediately an oxygen concentration of about 10 vol. % Gas mixture was blown at a rate of 20 liters per minute and reacted at 200 ° C. for 3.0 hours. Then, warm water was added to the reaction solution, hydrolysis was performed at 95 ° C. for 2 hours, and after standing, an upper layer reaction product (modified product) was obtained. 20 parts by mass of the modified product was added to 100 parts by mass of n-hexane to obtain a long-chain alkyl monomer (A-1) in which unmodified components were dissolved and removed. Various physical properties of the obtained long-chain alkyl monomer (A-1) are shown in Table 1.

<Example of production of long-chain alkyl monomer (A-2)>
In the production example (A-1) of the long-chain alkyl monomer, the long-chain alkyl monomer was produced in the same manner as in the production example (A-1) of the long-chain alkyl monomer except that the purification conditions (extraction time, etc.) with n-hexane were changed. An alkyl monomer (A-2) was obtained. Various physical properties of the obtained long-chain alkyl monomer (A-2) are shown in Table 1.

<Example of production of long-chain alkyl monomer (A-3)>
20 parts by mass of primary long-chain alkyl monoalcohol having an average carbon number of 30 was added to 100 parts by mass of n-hexane to obtain a long-chain alkyl monomer (A-3) from which unmodified components were dissolved and removed. Various physical properties of the obtained long-chain alkyl monomer (A-3) are shown in Table 1.

<Example of production of long-chain alkyl monomer (A-4)>
In the production example (A-3) of the long chain alkyl monomer, the long chain alkyl monomer (A-3) was produced in the same manner as in the production example of the long chain alkyl monomer (A-3) except that a long chain alkyl monoalcohol having an average carbon number of 27 was used. Monomer (A-4) was obtained. Various physical properties of the obtained long-chain alkyl monomer (A-4) are shown in Table 1.

<Example of production of long-chain alkyl monomer (A-5)>
20 parts by mass of a long-chain alkyl monocarboxylic acid having an average carbon number of 40 was added to 100 parts by mass of n-hexane to obtain a long-chain alkyl monomer (A-5) from which unmodified components were dissolved and removed. Table 1 shows properties of the obtained long-chain alkyl monomer (A-5).

<Example of production of long-chain alkyl monomer (A-6)>
20 parts by mass of a long-chain alkyl monocarboxylic acid having an average carbon number of 50 was added to 100 parts by mass of n-hexane to obtain a long-chain alkyl monomer (A-6) from which unmodified components were dissolved and removed. Table 1 shows properties of the obtained long-chain alkyl monomer (A-6).

<Example of production of long-chain alkyl monomer (A-7)>
1200 g of a chain saturated hydrocarbon having an average carbon number of 35 is put into a glass cylindrical reaction vessel, and 38.5 g of boric acid is added at a temperature of 140 ° C., and immediately, an oxygen concentration of about 10 vol. % Of the mixed gas was blown at a rate of 20 liters per minute and reacted at 170 ° C. for 2.5 hours. Then, warm water was added to the reaction solution, followed by hydrolysis at 95 ° C. for 2 hours. 7) was obtained. Table 1 shows properties of the obtained long-chain alkyl monomer (A-7).

<Example of production of long-chain alkyl monomer (A-8)>
1200 g of a chain saturated hydrocarbon having an average carbon number of 35 is put into a glass cylindrical reaction vessel, and 38.5 g of boric acid is added at a temperature of 140 ° C., and immediately, an oxygen concentration of about 10 vol. % Of the mixed gas was blown at a rate of 20 liters per minute, reacted at 175 ° C. for 2.5 hours, warm water was added to the reaction solution, and the mixture was hydrolyzed at 95 ° C. for 2 hours. 8) was obtained. Table 1 shows properties of the obtained long-chain alkyl monomer (A-8).

<Example of production of long-chain alkyl monomer (A-9)>
20 parts by mass of a secondary long-chain alkyl monoalcohol having an average carbon number of 25 was added to 100 parts by mass of n-hexane to obtain a long-chain alkyl monomer (A-9) from which unmodified components were dissolved and removed. Table 1 shows properties of the obtained long-chain alkyl monomer (A-9).

<Example of production of long-chain alkyl monomer (A-10)>
20 parts by mass of a secondary long-chain alkyl monoalcohol having an average carbon number of 55 was added to 100 parts by mass of n-hexane to obtain a long-chain alkyl monomer (A-10) from which unmodified components were dissolved and removed. Table 1 shows properties of the obtained long-chain alkyl monomer (A-10).

<Example of production of polyester resin composition (B-1)>
-Bisfer A ethylene oxide adduct (2.0 mol addition) 50.0 mol parts-Bisfer A propylene oxide adduct (2.3 mol addition) 50.0 mol parts-Terephthalic acid 60.0 mol parts-Trimellitic anhydride 20. 0 mol part / acrylic acid 10.0 mol part In addition to 70 parts by mass of the polyester monomer, a mixture in which the long-chain alkyl monomer (A-1) was added so as to be 5.0% by mass with respect to the entire polyester resin composition was prepared. A four-necked flask is charged and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and stirred at 160 ° C. in a nitrogen atmosphere. There, 30 parts by mass of a vinyl-based polymerization monomer (styrene: 60.0 mol parts, acrylic acid-2-ethylhexyl: 40.0 mol parts) constituting the vinyl polymer portion and 2.0 mol parts of benzoyl peroxide as a polymerization initiator were added. What was mixed was dripped over 4 hours from the dropping funnel. Then, after reacting at 160 ° C. for 5 hours, the temperature was raised to 230 ° C., 0.05% by mass of tetraisobutyl titanate was added, and the reaction time was adjusted so as to obtain a desired viscosity.
After completion of the reaction, the product was taken out from the container, cooled and pulverized to obtain a polyester resin composition (B-1). Table 3 shows properties of the obtained polyester resin composition (B-1).

<Examples of production of polyester resin compositions (B-2) to (B-7)>
Except having changed into monomer prescription as described in Table 2, it carried out similarly to the manufacture example of the polyester resin composition (B-1), and obtained the polyester resin composition (B-2)-(B-7). . Table 3 shows properties of the obtained polyester resin compositions (B-2) to (B-7).

<Example of production of polyester resin composition (B-8)>
-Bisfer A ethylene oxide adduct (2.0 mol addition) 40.0 mol parts-Bisfer A propylene oxide adduct (2.3 mol addition) 60.0 mol parts-Terephthalic acid 60.0 mol parts-Trimellitic anhydride 20. 0 mol part / acrylic acid 10.0 mol part The above-mentioned polyester monomer mixture 50 parts by mass is charged into a four-necked flask and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, under a nitrogen atmosphere. And stir at 160 ° C. There, 50 parts by mass of a vinyl-based polymerization monomer (styrene: 60.0 mol parts, acrylic acid-2-ethylhexyl: 40.0 mol parts) constituting the vinyl polymer portion and 2.0 mol parts of benzoyl peroxide as a polymerization initiator were added. What was mixed was dripped over 4 hours from the dropping funnel. Then, after reacting at 160 ° C. for 5 hours, the temperature was raised to 230 ° C., 0.05% by mass of tetraisobutyl titanate was added, and the reaction time was adjusted so as to obtain a desired viscosity.
Thereafter, the long-chain alkyl monomer (A-3) is added so as to be 10.0% by mass with respect to the entire polyester resin composition, and the temperature is raised to 200 ° C. under reduced pressure to react to obtain a desired viscosity. Adjusted the time.
After completion of the reaction, the product was taken out from the container, cooled and pulverized to obtain a polyester resin composition (B-8). Table 3 shows properties of the obtained polyester resin composition (B-8).

<Example of production of polyester resin composition (B-9)>
A polyester resin composition (B-9) was obtained in the same manner as in the production example of the polyester resin composition (B-8) except that the monomer formulation was changed as shown in Table 2. Table 3 shows properties of the obtained polyester resin composition (B-9).

<Polyester resin composition (B-10)>
As shown in Table 2, the monomer was charged into a 5 liter autoclave together with 0.05% by mass of tetraisobutyl titanate with respect to the total amount of monomers, and a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer were installed. A polycondensation reaction was performed at 230 ° C. while introducing nitrogen gas into the autoclave. The reaction time was adjusted to achieve the desired softening point. Thereafter, the long-chain alkyl monomer (A-5) is added so as to be 2.5% by mass with respect to the entire polyester resin composition, and the temperature is raised to 200 ° C. under reduced pressure to react so as to obtain a desired viscosity. Adjusted the time. After completion of the reaction, the product was taken out from the container, cooled and pulverized to obtain a polyester resin composition (B-10). Table 3 shows properties of the obtained polyester resin composition (B-10).

<Example of production of polyester resin composition (B-11)>
A polyester resin composition (B-11) was obtained in the same manner as in the production example of the polyester resin composition (B-10) except that the monomer formulation was changed as shown in Table 2. Table 3 shows properties of the obtained polyester resin composition (B-11).

<Production Example of Polyester Resin Compositions (B-12) to (B-17)>
Except having changed into monomer prescription as shown in Table 2, it carried out similarly to the manufacture example of the polyester resin composition (B-1), and obtained the polyester resin composition (B-12)-(B-17). . Table 3 shows properties of the obtained polyester resin compositions (B-12) to (B-17).

<Example of production of polyester resin composition (B-18)>
・ Bisfer A ethylene oxide adduct (2.0 mol addition) 10.0 mol parts ・ Bisfer A propylene oxide adduct (2.3 mol addition) 32.5 mol parts ・ Ethylene glycol 25.0 mol parts ・ Terephthalic acid 40.5 mol parts -0.5 mol part of isophthalic acid-9.0 mol part of trimellitic anhydride 9.0 mol part "Unilin 700" with respect to the total amount of the polyester resin composition with respect to the acid component and alcohol component of the above charged composition (Toyo Petrolite Co., Ltd.) "was added, and 1500 ppm of antimony trioxide with respect to the total acid component was put into a reaction vessel equipped with a distillation tower. Next, the number of revolutions of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction. Subsequently, the temperature in the reaction system was lowered and maintained at 235 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was set to 133 Pa, and a condensation reaction was performed while distilling the diol component from the reaction system. The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase in viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. And stirring was stopped when the predetermined torque was shown, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reaction product was taken out over about 40 minutes to obtain a polyester resin composition (B-18). .
Table 3 shows properties of the obtained polyester resin composition (B-18).

<Production Example of Polyester Resin Composition (B-19)>
Except having changed into the prescription of Table 2, it carried out similarly to the manufacture example of the polyester resin composition (B-10), and obtained the polyester resin composition (B-19). Table 3 shows properties of the obtained polyester resin composition (B-19).

<Example of production of polyester resin composition (B-20)>
Except having changed into the monomer prescription of Table 2, it carried out similarly to the manufacture example of the polyester resin composition (B-1), and obtained the polyester resin composition (B-20). Table 3 shows properties of the obtained polyester resin composition (B-20).

<Example 1>
Polyester resin composition (B-1) 100.0 parts by mass Magnetic iron oxide particles (octahedral shape) 60.0 parts by mass (number average particle size 0.13 μm, Hc = 11.5 kA / m, σs = 88 Am ² / kg, σr = 14 Am ² / kg)
Release agent Fischer-Tropsch wax 2.0 parts by mass (manufactured by Sasol, C105, melting point 105 ° C.)
Charge control agent (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 2.0 parts by mass After the above materials were premixed using a Henschel mixer, a twin-screw kneading extruder (PCM-30 manufactured by Ikekai Tekko Co., Ltd.)) Was melt kneaded.
The obtained kneaded product was cooled, coarsely pulverized with a hammer mill, and then pulverized with a mechanical pulverizer (T-250 manufactured by Turbo Kogyo Co., Ltd.). The finely pulverized powder thus obtained was classified using a multi-division classifier utilizing the Coanda effect to obtain negatively chargeable toner particles having a weight average particle diameter (D4) of 7.0 μm. Hydrophobic silica fine powder 1 [BET specific surface area 150 m ² / g with respect to 100 parts by mass of toner particles, 30 parts by mass of hexamethyldisilazane (HMDS) and 10 parts by mass of dimethyl silicone oil with respect to 100 parts by mass of silica fine powder 1.0 part by mass and 0.6 part by mass of strontium titanate fine powder (median diameter: 1.0 μm) were externally mixed using a Henschel mixer (FM-75 type manufactured by Nippon Coke Industries, Ltd.). Then, the mixture was sieved with a mesh having an opening of 150 μm to obtain toner (T-1).
The following evaluation was performed on the obtained toner (T-1).

<Low temperature fixability test>
Low-temperature fixability was modified so that the temperature of the fixing device can be arbitrarily set and the process speed can be set to 500 mm / sec. An external fixing device was used.
Using the above apparatus, the amount of toner applied per unit area is 0.5 mg in a normal temperature and humidity environment (temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (temperature 15 ° C., humidity 10% RH). The unfixed image set to / cm ² was passed through a fixing device whose temperature was adjusted to 160 ° C. As the recording medium, “Prober bond paper” (105 g / m ² , manufactured by Fox River) was used. The obtained fixed image was rubbed with sylbon paper to which a load of 4.9 kPa (50 g / cm ² ) was applied, and evaluated by a reduction rate (%) of the image density before and after rubbing. The image density was measured with a Macbeth densitometer (manufactured by Macbeth), which is a reflection densitometer, using an SPI filter.
A (very good): The reduction rate of the image density is less than 5.0%.
B (good): The reduction rate of the image density is 5.0% or more and less than 10.0%.
C (Normal): The reduction rate of the image density is 10.0% or more and less than 15.0%.
D (poor): The reduction rate of the image density is 15.0% or more.
The results are shown in Table 5.

<Fixing device contamination assessment>
Contamination evaluation of the fixing device is performed by a laser beam printer (HP L) manufactured by Hewlett-Packard Company.
(asJet Enterprise 600 M603) was used so that the printing speed was 75 sheets / min and the fixing temperature was 220 ° C.
Using the evaluation machine, 250,000 test charts having a printing rate of 12% were printed in a normal temperature and humidity environment (temperature 23.5 ° C., humidity 60% RH). Each time the toner runs out, the cartridge was replaced and printing continued.
The state of contamination around the fixing device after printing was visually evaluated according to the following criteria.
A (very good): There is no noticeable contamination around the fixing device.
B (good): A small amount of contamination is observed around the fixing device.
C (Normal): The spread of contamination is clearly observed in the fixing guide portion.
D (Poor): A considerable amount of contamination is noticeable around the fixing device.
The results are shown in Table 5.

<Preservation evaluation test>
10 g of toner was weighed into a 50 cc polycup and left in a constant temperature bath at 55 ° C. for 3 days. The toner after standing was visually observed, and the storage stability was evaluated according to the following criteria.
A (very good): As soon as the cup is turned, it is loosened.
B (good): There is a lump, but it gets smaller and loosens as you turn the cup.
C (Normal): Even if the cup is loosened, a lump remains.
D (poor): There is a big lump, and it does not loosen even if you turn the cup.
The results are shown in Table 5.

<Evaluation of developability and storage stability under high temperature and high humidity>
Using a laser beam printer (HP LaserJet Enterprise 600 M603) manufactured by Hewlett-Packard Co., in a high-temperature and high-humidity environment (temperature 32.5 ° C., humidity 80% RH), after passing 500 test charts, the test chart image was solid. The reflection density of the black part was measured, calculated with an average of 5 points, and evaluated according to the following criteria.
A (very good): The average value of image density is 1.45 or more B (good): The average value of image density is 1.35 or more and less than 1.45 C (normal): The average value of image density is 1.25 Above 1.35 D (Poor): Average image density is less than 1.25

Thereafter, the sample is left in the same environment for 72 hours, the test chart is again passed through, the reflection density of the solid black portion is measured, and the reduction rate of the image density after being left with respect to the image density before being left is obtained. It was evaluated with.
A (very good): The image density reduction rate is less than 3.0%.
B (good): The image density reduction rate is 3.0% or more and less than 6.0%.
C (Normal): The image density reduction rate is 6.0% or more and less than 10.0%.
D (Poor): Image density reduction rate is 10.0% or more.

<Examples 2 to 11>
Toners (T-2) to (T-11) were prepared in the same manner as in Example 1 with the formulation shown in Table 4. Evaluation similar to Example 1 was implemented with respect to the obtained toner. The results are shown in Table 5.

<Example 12>
Polyester resin composition (B-2) 100 parts by mass Carbon black 5 parts by weight Release agent Fischer-Tropsch wax 2 parts by mass (Sazol, C105, melting point 105 ° C)
Charge control agent (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 2 parts by mass The above materials were premixed with a Henschel mixer and then melt kneaded with a biaxial kneading extruder.
The obtained kneaded product was cooled, coarsely pulverized with a hammer mill, and then pulverized with a jet mill. The finely pulverized powder thus obtained was classified using a multi-division classifier utilizing the Coanda effect to obtain negatively chargeable toner particles having a weight average particle diameter (D4) of 7.0 μm.
To 100 parts by mass of the obtained toner particles, 1.0 part by mass of titanium oxide fine particles having a number average particle diameter of 50 nm of primary particles surface-treated with 15% by mass of isobutyltrimethoxysilane and surface treatment with 20% by mass of hexamethyldisilazane. 0.8 mass parts of hydrophobic silica fine particles having a number average particle diameter of 16 nm of the primary particles were added, and externally added and mixed with a Henschel mixer (FM-75 type manufactured by Nippon Coke Industries Co., Ltd.). Sieve and toner (T-12) was obtained.
Regarding the evaluation of the toner (T-12), the same evaluation as in Example 1 was performed except that the conditions were changed as follows.

<Low temperature fixability test>
Evaluation was performed in the same manner as in Example 1 except that the fixing device temperature was changed to 140 ° C. in the evaluation method of Example 1. The results are shown in Table 5.
<Fixing device contamination assessment>
With respect to the durability development evaluation, it was the same as in Example 1 except that an evaluation machine modified to 75 sheets / min of a laser beam printer (HP Color LaserJet CP6015xh) manufactured by Hewlett-Packard Co. and a fixing temperature of 220 ° C. was used. Was evaluated. The results are shown in Table 5.
<Preservation evaluation test>
The storage stability was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 5.
<Changes in image density before and after standing in a high temperature and high humidity environment>
Evaluation was performed in the same manner as in Example 1 except that the evaluation machine in the evaluation method of Example 1 was changed to a laser beam printer (HP Color LaserJet CP6015xh) manufactured by Hewlett-Packard Company. The results are shown in Table 5.

<Comparative Examples 1-6>
Toners (T-13) to (T-18) were prepared in the same manner as in Example 1 with the formulation shown in Table 4. Evaluation similar to Example 1 was implemented with respect to the obtained toner. The results are shown in Table 6.

<Comparative Example 7>
A toner (T-19) was produced in the same manner as in Example 12 with the formulation shown in Table 4. Evaluation similar to Example 12 was implemented with respect to the obtained toner. The results are shown in Table 6.

Claims (7)

A toner having toner particles containing a polyester resin composition,
The polyester resin composition is
( I) a polyester resin having a terminal structure derived from at least one of a long-chain alkyl monoalcohol having an average value of 27 to 50 carbon atoms and a long-chain alkyl monocarboxylic acid having an average value of 27 to 50 carbon atoms, and,
Containing an aliphatic hydrocarbon having an average carbon number of 27 to 50,
( Ii) The total content of the aliphatic hydrocarbon, the structure derived from the long-chain alkyl monoalcohol, and the structure derived from the long-chain alkyl monocarboxylic acid is based on the mass of the polyester resin composition. 2.5% by mass or more and 10.0% by mass or less,
In the temperature-endothermic curve of the polyester resin composition obtained by differential scanning calorimetry (DSC),
The peak top temperature of the endothermic peak of the polyester resin composition is 60.0 ° C. or higher and 90.0 ° C. or lower,
Endotherm endothermic peak state, and are less 0.10J / g or more 1.90J / g,
The polyester resin composition is a reaction product of a composition (A) containing an alcohol component and a composition (B) containing an acid component,
The composition (A) and the composition (B) are defined in the following (iii) and (iv):
(Iii) The alcohol component contained in the composition (A) contains the long-chain alkyl monoalcohol, the composition (A) contains the aliphatic hydrocarbon, and the composition (A) The content ratio of the long-chain alkyl monoalcohol is from 85% to 99% with respect to the total amount of the long-chain alkyl monoalcohol and the aliphatic hydrocarbon.
(Iv) The acid component contained in the composition (B) contains the long-chain alkyl monocarboxylic acid, the composition (B) contains the aliphatic hydrocarbon, and the composition (B The content ratio of the long-chain alkyl monocarboxylic acid in) is 85% or more and 99% or less with respect to the total amount of the long-chain alkyl monocarboxylic acid and the aliphatic hydrocarbon.
Toner characterized that you satisfies at least one of. The polyester resin composition is
It is a reaction product of a polyester resin having a carboxyl group at the terminal and the composition (C)
The toner according to claim 1, wherein the composition (C) contains the long-chain alkyl monoalcohol and the aliphatic hydrocarbon. The polyester resin composition is
It is a reaction product of a polyester resin having a hydroxyl group at the terminal and the composition (D),
The toner according to claim 1, wherein the composition (D) contains the long-chain alkyl monocarboxylic acid and the aliphatic hydrocarbon. The polyester resin composition is
The toner according to any one of claims 1-3 polyester moiety and a vinyl polymer sites is a hybrid resin composition containing a chemically bound hybrid resin. The toner according to claim 4 , wherein a mass ratio of the polyester portion to the vinyl polymer portion (polyester portion / vinyl polymer portion) of the hybrid resin is 50:50 to 90:10. Long chain alkyl mono-alcohol, the toner according to any one of claims 1 to 5 containing a secondary alcohol as the main component. The polyester the acid value of the resin composition, toner according to any one of claims 1 to 6 or less 15.0 mg KOH / g or more 30.0 mg KOH / g.