JP2017156706A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner excellent in suppression of fogging, dot reproducibility, and developability.SOLUTION: The above problem is solved by using the following toner. A toner containing: a polyester resin composition that contains a polyester resin that includes a partial structure represented by R-O- or R-COO- and aliphatic hydrocarbon having 12-102 carbon atoms; and a charge control agent that has a transmissivity after 30 minutes of standing of 10% or less in a test measuring a change over time of the transmissivity of light with a wavelength of 550 nm through a dispersion liquid having 10 mL of hexane dispersed therein.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an image forming method such as electrophotography.

  While an electrophotographic image forming apparatus is required to have high speed, energy saving, and downsizing, the level required in terms of image quality is also increasing. In addition, the appearance of paper information is naturally important, but it is becoming increasingly important to provide functions to images themselves. From such a viewpoint, image quality improvement has become an important proposition. For example, the use of two-dimensional barcodes has increased with the spread of smartphones. The area of the two-dimensional barcode is also becoming smaller, and it is essential to improve the image quality in order to prevent poor reading.

  Security awareness is also improving from the point of paper information management. As a typical example, the demand for copy-forgery-inhibited pattern printing in which small dots that cannot be read by a copier in advance are drawn on the “original” to identify whether the paper information is “original” or “copy” is increasing. Yes. For that purpose, it is important to print small dots appropriately.

  On the other hand, demand for electrophotographic image forming apparatuses is increasing in the tropical region, and at the same time, the demand for image quality as described above is gradually increasing.

  In such an area, even if the temperature is high during the day and the humidity is high, when the temperature falls at night, the water vapor that has been saturated is likely to condense, and thus it is easily exposed to a harsh environment. In particular, since toner is generally used in a space where it is difficult for air to be exchanged, such as in a developing device or a container, the toner performance is greatly affected, and toner performance may be greatly affected.

  As described above, there is a demand for a toner capable of suppressing deterioration in image quality even in a severe situation that was difficult to imagine in the past.

  Patent Document 1 proposes a toner that can obtain good developability and electrostatic offset resistance even when left under heat cycle conditions where humidity is not controlled by controlling the crystal structure of the charge control agent. .

  Patent Document 2 proposes that toner scattering and selective developability can be improved by using a polyester resin obtained by reacting a specific charge control agent and an aliphatic compound.

  In patent document 3, the proposal which can improve low temperature fixability and high temperature offset-proof property is made by making an aliphatic compound react with a polyester resin.

JP 2014-78003 A JP-A-2015-194737 Japanese Patent No. 3015244

  According to these techniques, a certain effect is confirmed with respect to toner fixing properties and image defects. However, these techniques may also be greatly affected by fogging and dot reproducibility depending on the usage environment, for example, in a situation where they are greatly affected by condensation.

  An object of the present invention is to provide a toner capable of suppressing a reduction in fogging and dot reproducibility even under conditions where heat cycles are repeated under high humidity.

The present invention is a toner having toner particles containing a polyester-based resin composition and a charge control agent,
The polyester resin composition is
i) R ¹ —O— or R ² —COO—
[Wherein R ¹ represents a group formed by elimination of one hydrogen atom from an aliphatic hydrocarbon having 12 to 102 carbon atoms, and R ² represents an aliphatic hydrocarbon having 11 to 101 carbon atoms. Represents a group formed by elimination of one hydrogen atom from ]
A polyester resin having a partial structure represented by: and an aliphatic hydrocarbon having 12 to 102 carbon atoms,
ii) Based on the mass of the polyester-based resin composition, the partial structure and the aliphatic hydrocarbon having 12 to 102 carbon atoms are combined to contain 2.5 mass% or more and 10.0 mass% or less. And
iii) In a temperature-endothermic curve obtained by differential scanning calorimetry (DSC), it has an endothermic peak having a peak top at 30 ° C. or higher and 100 ° C. or lower, and the endothermic peak has an endothermic amount of 0.10 J / g or higher. 1.90 J / g or less,
The charge control agent has a transmittance of 30 minutes after standing in a test in which a change in transmittance of light having a wavelength of 550 nm is measured for a dispersion in which 0.01 g of the charge control agent is dispersed in 10 mL of hexane. 10% or less,
This invention relates to a toner.

  According to the present invention, a toner having excellent fog and dot reproducibility can be obtained even when subjected to a heat cycle under high humidity.

  Until now, attempts have been made to control the dispersibility of the charge control agent in the toner, and evaluation after storing the toner under a certain temperature and humidity, or when the toner is stored under a heat cycle where the humidity is not controlled. Performance has been confirmed. However, as described above, the demand for electrophotographic image forming apparatuses is increasing in the tropical region. In such an area, even if the temperature is high during the day and the humidity is high, when the temperature falls at night, the water vapor that has been saturated is likely to condense, and thus it is easily exposed to a harsh environment. In particular, since toner is generally used in a space where it is difficult for air to be exchanged, such as in a developing device or a container, there is a possibility that the toner is greatly affected by condensation. In conventional toners, it can be seen that, when subjected to a heat cycle under high humidity, the charging characteristics of the toner change greatly, and as a result, fog is likely to occur, and dot reproducibility is likely to decrease. It was.

  The present inventors have studied to further control the dispersibility of the charge control agent in order to suppress the occurrence of fogging and the decrease in dot reproducibility in toner that has undergone a heat cycle under high humidity.

  The occurrence of fogging and the reduction in dot reproducibility are common phenomena when the toner charge distribution is broad. If the dispersion of the charge control agent in the toner is already insufficient immediately after the production of the toner, the charging performance tends to change for each toner particle, resulting in a toner having a broad charge distribution.

  On the other hand, even when a toner having a good charge distribution in which the charge control agent is well dispersed in the toner immediately after the toner is produced, moisture generally plasticizes the polyester resin composition when subjected to a heat cycle under high humidity. For this reason, the low-viscosity component in the toner becomes easy to move gradually. For this reason, the distribution of the charge control agent tends to be gradually biased over a long time. The heat cycle is considered to accelerate the movement of the low viscosity component and the charge control agent in the toner because the plasticized polyester resin composition is cured and plasticized again. It is considered that the heat cycle under high humidity promotes broadening of the toner charge distribution.

  As a result of such a heat cycle under high humidity, the dispersion of the charge control agent is in a reduced state, which tends to be a toner with a broad charge distribution, fogging occurs, and dot reproducibility is reduced. It becomes easy.

  Based on these results, the present inventors believe that if the movement of the charge control agent can be suppressed in a heat cycle under high humidity, the occurrence of fogging and the decrease in dot reproducibility can be suppressed. It was.

  As a method, if a component having close affinity with the charge control agent is immobilized in the binder resin, the charge control agent is likely to stay in the site, and the movement of the charge control agent is suppressed even in a heat cycle under high humidity. I thought it was possible.

Specifically, a toner having toner particles containing a polyester resin composition and a charge control agent,
The polyester resin composition is
i) R ¹ —O— or R ² —COO—
[In the formula, R ¹ represents a group formed by removing one hydrogen atom from an aliphatic hydrocarbon having 12 to 102 carbon atoms, and R ² represents an aliphatic carbon having 11 to 101 carbon atoms. A group formed by elimination of one hydrogen atom from hydrogen. ]
Containing a polyester resin having a partial structure represented by: and an aliphatic hydrocarbon having 12 to 102 carbon atoms,
ii) Based on the mass of the polyester-based resin composition, the partial structure and the aliphatic hydrocarbon having 12 to 102 carbon atoms in total are 2.5 mass% to 10.0 mass%. Contains
iii) In the temperature-endothermic curve obtained by differential scanning calorimetry (DSC), it has an endothermic peak at 30 ° C. or more and 100 ° 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,
The charge control agent has a transmittance of 30 minutes after standing in a test in which a change in transmittance of light having a wavelength of 550 nm is measured for a dispersion in which 0.01 g of the charge control agent is dispersed in 10 mL of hexane. Toner that is 10% or less,
It has been found that the use of can maintain the dispersibility of the charge control agent even in a heat cycle under high humidity, and suppress the occurrence of fogging and the deterioration of dot reproducibility.

[Relationship between polyester resin composition and charge control agent]
The relationship between the polyester resin composition and the charge control agent will be described.

The polyester resin composition used in the present invention is
(A) R ¹ —O— or R ² —COO—
[Wherein R ¹ represents a group formed by elimination of one hydrogen atom from an aliphatic hydrocarbon having 12 to 102 carbon atoms, and R ² represents an aliphatic hydrocarbon having 11 to 101 carbon atoms. Represents a functional group formed by elimination of one hydrogen atom from ]
A polyester resin having a partial structure represented by:
(B) an aliphatic hydrocarbon having 12 to 102 carbon atoms;
Containing.

  The polyester resin defined in the above (a) is a polyester resin obtained by reacting an aliphatic monoalcohol having 12 to 102 carbon atoms or an aliphatic monocarboxylic acid having 12 to 102 carbon atoms.

  Further, in the polyester resin composition, the total amount of the partial structure of the polyester resin defined in (a) and the aliphatic hydrocarbon defined in (b) is the same as that of the polyester resin composition. It is 2.5 mass% or more and 10.0 mass% or less on the basis of mass.

  Furthermore, the polyester-based resin composition has an endothermic peak at 30 ° C. or more and 100 ° C. or less in a temperature-endothermic curve obtained by differential scanning calorimetry (DSC), and the endothermic amount of the endothermic peak is 0. It is 10 J / g or more and 1.90 J / g or less. This endothermic peak is derived from the aliphatic hydrocarbon defined in (b) above.

  In order to make the endothermic amount of the endothermic peak within the above range, the amount of the aliphatic hydrocarbon may be adjusted. Specifically, for example, it can be adjusted as follows. First, when obtaining the aliphatic monoalcohol and the aliphatic monocarboxylic acid used in the production of the polyester resin defined in the above (a), the aliphatic hydrocarbon not modified with alcohol or acid is left. And the quantity of the aliphatic hydrocarbon in a polyester-type resin composition can be adjusted by reacting with polyester using the composition containing a modified material and an unmodified material.

In the above partial structure, when the carbon number of R ¹ is 11 or less and when the carbon number of R ² is 10 or less, the number of partial structures in the polyester-based resin composition is required in order to satisfy the regulation relating to the content. Need to be more. In this case, it becomes difficult to control the movement of the charge control agent. When the carbon number of R ¹ is 103 or more and when the carbon number of R ² is 102 or more, the number of partial structures in the polyester-based resin composition is reduced, so that the uneven distribution of the charge control agent becomes remarkable. The interaction between the aliphatic hydrocarbon and the charge control agent will be described in detail in the section on the charge control agent.

  When the total of the partial structure of the polyester resin composition and the aliphatic hydrocarbon having 12 to 102 carbon atoms is less than 2.5% by mass, the partial structure formed in the toner is small. For this reason, there are few places where the charge control agent stays stably, and the fluctuation when the heat cycle is performed under high humidity becomes large. On the other hand, when the total is more than 10.0% by mass, the number of partial structures in the polyester resin composition increases, and the ratio of the charge control agent remaining in the vicinity of the partial structures increases. As a result, the dispersibility of the charge control agent is lowered, fogging is likely to occur, and dot reproducibility is likely to be lowered.

  In the temperature-endothermic curve obtained by differential scanning calorimetry (DSC) of the polyester-based resin composition, when the endothermic amount of the endothermic peak is greater than 1.90 J / g, the aliphatic that does not form a partial structure It shows that there are many hydrocarbons. For this reason, the amount of aliphatic hydrocarbons that easily move in the toner increases, and the fluctuation when subjected to a heat cycle under high humidity becomes large. As a result, fog is likely to occur, and dot reproducibility tends to be reduced. When the endothermic amount of the endothermic peak is less than 0.10 J / g, the dispersion of the charge control agent tends to be inferior, and the triboelectric chargeability tends to be insufficient.

  When the endothermic peak of the polyester-based resin composition is less than 30 ° C., the mobility of the aliphatic hydrocarbon contained is increased, and the charge control agent should be kept at the site of the partial structure in the heat cycle under high humidity. Becomes difficult. As a result, the dispersibility of the charge control agent becomes inferior, fog is likely to occur, and dot reproducibility tends to be lowered. On the other hand, when the endothermic peak is higher than 100 ° C., the mobility of the aliphatic hydrocarbon is low, and the charge control agent stays in the partial structure in a stable state in a heat cycle under high humidity. The dispersibility of is reduced. For this reason, fog is likely to occur, and dot reproducibility is liable to deteriorate.

  Next, the charge control agent will be described.

  Hexane is classified as an aliphatic hydrocarbon and is in a very close relationship with the partial structure and the aliphatic hydrocarbon having 12 to 102 carbon atoms contained in the polyester resin composition. Therefore, the present inventors maintain the dispersibility of the charge control agent even in a heat cycle under high humidity by controlling the affinity between hexane and the charge control agent, thereby reducing fog generation and dot reproducibility. I thought that I could suppress it.

  As a result of studying in accordance with the above idea, in a test in which a change in transmittance of light having a wavelength of 550 nm was measured with respect to a dispersion in which 0.01 g of a charge control agent was dispersed in 10 mL of hexane, the sample was allowed to stand and transmitted after 30 minutes. It was found that it is important that the rate is 10% or less.

  In the test relating to the transmittance described above, the transmittance of 10% or less after standing for 30 minutes indicates that the charge control agent is less likely to settle in hexane. That is, the charge control agent as described above has high affinity with hexane, that is, it has high affinity with the partial structure and aliphatic hydrocarbon of the polyester resin defined in (a) above. Yes.

  Since the partial structure in the polyester resin composition exists as a molecular terminal of the polyester resin, it does not move easily in the toner as compared with the case where it exists free. In addition, the charge control agent having a high affinity with the partial structure in the polyester-based resin composition gathers at the site of the partial structure in the polyester-based resin composition. As a result, even when subjected to a heat cycle under high humidity, the charge control agent gathered at the partial structure site can remain in the vicinity thereof and can maintain dispersibility. As a result, the toner charge distribution can be kept sharp even in a heat cycle under high humidity, so that the fog and dot reproducibility can be improved.

  On the other hand, the charge control agent tends to gather around the aliphatic hydrocarbons contained in the polyester resin composition. The aliphatic hydrocarbon is considered to be a component that easily moves through the toner. The charge control agent is difficult to spread throughout the toner if it is only gathered at the site of the partial structure in the polyester resin composition, but there is a component that easily moves, and this and the charge control agent behave together, The charge control agent is dispersed throughout the toner particles. As a result, a toner having more uniform chargeability can be obtained.

  And when the total amount of the partial structure and the aliphatic hydrocarbon is 2.5 to 10.0% by mass, and the content of the aliphatic hydrocarbon is an extent represented by the definition of the endothermic amount, The balance between the staying component and the dispersing component is suitable.

  That is, in the toner particles, both the charge control agent that stays around the component that is difficult to move and the charge control agent that behaves together with the component that easily moves and is dispersed in the toner particle are present in an appropriate ratio. It is considered that the effect of the present invention is obtained.

  In addition, since the transmittance after 30 minutes of standing the hexane dispersion is greatly affected by the structure of the charge control agent, in order to reduce the transmittance to 10% or less, for example, the structure of the charge control agent is changed. Control is sufficient.

  The charge control agent preferably has a number average particle diameter (D1) of primary particles of 0.80 μm or more and 2.00 μm or less. If the number average particle diameter (D1) of the primary particles is within the above range, the primary particles are likely to stay at the site of the partial structure of the polyester resin composition. Therefore, the suppression of fog and the dot reproducibility after the heat cycle under high humidity are further improved. Furthermore, good developability can be obtained even in image formation under high temperature and high humidity after heat cycle under high humidity.

  The charge control agent is preferably a compound represented by the following formula [1], and the initial developability is improved in image formation under high temperature and high humidity after heat cycle under high humidity. The details of this mechanism are presumed as follows. The compound of the formula [1] is an ion-binding compound and easily takes a crystal structure. Therefore, it can be regularly arranged in the part of the partial structure of the polyester-based resin composition, and as a result, the rising of the charge becomes smooth and the initial developability under high temperature and high humidity is considered to be improved.

(In the formula, A ₁ , A ₂ and A ₃ each independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group. M represents an Fe atom, a Cr atom, Alternatively, it represents an Al atom, and X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.
The charge control agent is more preferably a compound represented by the following formula [2]. The initial developability is further improved in image formation under high temperature and high humidity after heat cycle under high humidity. Formula [2] is considered to have a very good rise in charge since it has a plurality of substituents having high electronegativity.

(In the formula, X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.)
When the charge control agent is internally added to the toner particles, the addition amount is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the binder resin. In addition, when externally added to the toner particles, the amount is preferably 0.01 to 5 parts by mass and more preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of the toner particles.

[Other description relating to polyester resin composition]
When an aliphatic hydrocarbon is modified with an aliphatic alcohol having 12 to 102 carbon atoms or an aliphatic carboxylic acid, the modification rate is usually not 100%. Therefore, a mixture of an aliphatic hydrocarbon modified with an alcohol or an acid and an unmodified aliphatic hydrocarbon (hereinafter sometimes referred to as “modified / unmodified mixture”) is obtained. By using this mixture for the synthesis of a polyester resin, a polyester resin composition containing a polyester resin in which a group formed by elimination of one hydrogen atom from an aliphatic hydrocarbon is bonded to an end, and an aliphatic hydrocarbon Can be obtained.

  In order to satisfy the provisions of the present invention for the endothermic peak temperature and endothermic amount of the polyester-based resin composition, the modification rate is controlled by optimizing the reaction conditions, or the purification operation is performed after the modification reaction, and the unmodified The aliphatic hydrocarbon component may be removed. A preferable range of the modification rate of the aliphatic hydrocarbon component is 85% or more, and more preferably 90% or more.

  When the mixture of the modified aliphatic hydrocarbon and the unmodified aliphatic hydrocarbon is alcohol-modified, the hydroxyl value is preferably 80 to 110 mgKOH / g, more preferably 90 to 105 mgKOH / g. In the case of acid modification, the acid value is preferably 90 to 150 mgKOH / g, more preferably 95 to 140 mgKOH / g. By controlling to the said range, since the reactivity of a polyester resin component and a modification | denaturation part increases and as a result, it becomes possible to reduce the endothermic peak area of DSC efficiently, it is preferable.

  Moreover, there is no restriction | limiting in particular as a manufacturing method of the polyester-type resin composition of this invention, However, It is preferable that it is the following manufacturing method.

  The polyester resin composition used in the present invention is preferably produced by a polyester polymerization reaction in the presence of a modified / unmodified mixture. That is, it is preferable to introduce the modified / unmodified mixture from the beginning of the polyester synthesis reaction because the modified / unmodified mixture can be efficiently and uniformly incorporated into the polyester resin composition.

  It is preferable from the viewpoint of the reaction rate that the modified / unmodified mixture contains an aliphatic monoalcohol having 12 to 102 carbon atoms as a main component.

The polyester resin composition contains a polyester resin having R ¹ —O— as a partial structure, and one hydrogen atom is released from the secondary carbon of the aliphatic hydrocarbon having R ^{12 of 12} to 102 carbon atoms. It is preferable that the group is formed. In this case, two hydrocarbon molecular chains exist in one partial structure. The presence of two hydrocarbon molecular chains makes it easier for the charge control agent to remain at the site of the partial structure. Therefore, even in a heat cycle under high humidity, the dispersibility of the charge control agent can be maintained, and deterioration of fogging and dot reproducibility can be suppressed. In order to obtain such a configuration, a modified / unmodified mixture containing an aliphatic secondary monoalcohol having 12 to 102 carbon atoms as a main component may be used.

  Moreover, it is preferable that the polyester resin contained in the polyester-based resin composition is a hybrid resin in which a polyester site and a vinyl polymer site are chemically bonded. In this case, it is preferable that the aliphatic monoalcohol or the aliphatic carboxylic acid is reacted with the terminal of the polyester portion of the hybrid resin.

  By using a hybrid resin, the chargeability is stable regardless of the environment, and the dispersibility of the charge control agent can be maintained even in heat cycles under high humidity, reducing fogging and dot reproducibility. This is preferable because it is possible.

  Examples of the monomer for constituting the polyester portion of the polyester resin or the hybrid resin used in the polyester resin composition include the following compounds.

  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).

(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 adduct (EO) 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 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 an alkenyl group or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid or itaconic acid, or an anhydride thereof.

  Further, the polyester resin used in the polyester resin composition or the polyester portion of the hybrid resin may use a trivalent or higher polyvalent carboxylic acid or anhydride thereof 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, aromatic alcohols that are highly stable due to environmental fluctuations are 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, a known monomer may be used as the vinyl monomer for constituting the vinyl polymer portion of the hybrid resin, and examples thereof include the following compounds.

  Unsaturated monoolefins; Unsaturated polyenes; Halogenated vinyls; Vinyl esters; Acrylic esters; Methacrylic esters; Unsaturated dibasic acids; Unsaturated dibasic acid anhydrides; Saturated dibasic acid ester.

  Moreover, when using the said hybrid resin for the polyester-type resin composition of this invention, the vinyl polymer site | part of a hybrid resin may have the crosslinked structure bridge | crosslinked with the crosslinking agent which has two or more vinyl groups. As the crosslinking agent used in this case, known ones can be used, and examples thereof include the following. Aromatic divinyl compounds (divinylbenzene, divinylnaphthalene); diacrylate compounds. These crosslinking agents can be used in an amount of 0.01 to 10.00 parts by mass, and more preferably 0.03 to 5.00 parts by mass with respect to 100 parts by mass of other monomer components.

  As the polymerization initiator used for the polymerization of the vinyl polymer portion, a known one may be used, and examples thereof include an azo initiator and a peroxide initiator.

  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 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 capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  In addition, the above polyester-based resin composition 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 to 170 ° C. The low 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 as the binder resin, at least 50% by mass or more of the binder resin needs to be a polyester resin composition.

  When the polyester resin composition is used alone as a binder resin, the softening point Tm is preferably 90 to 170 ° C. More preferably, it is 100-130 degreeC. If Tm is within the above range, the balance between high temperature offset resistance and low temperature fixability is good.

  In addition, the glass transition temperature (Tg) of the polyester resin composition is preferably 45.0 ° C. or higher, and particularly 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 particularly preferably 65.0 ° C. or less.

  Moreover, the acid value of a polyester-type resin composition is 15.0-30.0 mgKOH / g, More preferably, it is 20.0-30.0 mgKOH / g. By controlling the acid value within the above range, the effects of the present invention can be easily obtained.

  The toner of the present invention preferably has a positive component ratio of 4.0% by number or less based on the total number of toners after leaving the heat cycle under high humidity. Even if the toner is subjected to a heat cycle under high humidity, if the dispersibility of the charge control agent is maintained and an increase in the positive component can be suppressed, fogging hardly occurs.

[Other ingredients]
The toner of the present invention can be used as a magnetic toner containing a magnetic material. In this case, the magnetic material can also serve as a colorant.

  Magnetic materials include iron oxides such as magnetite, hematite and ferrite, metals such as iron, cobalt and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, bismuth, calcium, Mention may be made of alloys of metals such as manganese, titanium, tungsten, vanadium and mixtures thereof. These magnetic materials have an average particle diameter of 2 μm or less, preferably 0.05 to 0.5 μm. The amount to be contained in the toner is preferably 20 to 200 parts by mass with respect to 100 parts by mass of the resin component.

  The colorant that can be used in the present invention will be described.

  Carbon black and grafted carbon can be used as the black colorant. Further, it may be used by adjusting the color to black using a yellow / magenta / cyan colorant.

  Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like.

  The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The addition amount of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner according to the present invention may contain a wax in order to impart releasability at the time of fixing. Known waxes can be used as the wax.

  In addition, an external additive may be added to the toner according to the present invention in order to improve fluidity and chargeability.

  As an external additive, a well-known thing can be used, for example, the following can be used. Fluorine resin powder such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fine powder silica such as wet process silica and dry process silica, fine powder titanium oxide, fine powder alumina, silicon and other metals Complex oxides; oxides such as zinc oxide and tin oxide; double oxides such as strontium titanate, barium titanate, calcium titanate, strontium zirconate and calcium zirconate; carbonate compounds such as calcium carbonate and magnesium carbonate etc. These external additives may be surface-treated with a silane compound, a titanium coupling agent, or silicone oil.

  It is preferable to use 0.01 to 3 parts by mass of the external additive in a total amount with respect to 100 parts by mass of the toner particles.

[Toner Production Method]
The method for producing toner particles according to the present invention is not particularly limited. For example, a so-called polymerization method such as a pulverization method, an emulsion polymerization method, a suspension polymerization method, or a dissolution suspension method can be used.

  In the pulverization method, first, the binder resin, the colorant, the wax, the charge control agent and the like constituting the toner particles are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Subsequently, the obtained mixture is melt-kneaded using a heat kneader such as a twin-screw kneading extruder, a heating roll, a kneader, or an extruder, and after cooling and solidification, pulverization and classification are performed. Thereby, the toner particles according to the present invention can be obtained.

  Furthermore, the toner according to the present invention can be obtained by sufficiently mixing a desired external additive with a mixer such as a Henschel mixer, if necessary.

  Next, it describes regarding the measuring method of each physical property which concerns on this invention.

<Modification rate in modified / unmodified mixture, aliphatic hydrocarbon modified with acid or alcohol, carbon number of unmodified aliphatic hydrocarbon>
The carbon number of the modified / unmodified mixture is measured by a gas chromatography mass spectrometer (GC / MS) as follows. Precisely weigh 10 mg of the denatured / denatured mixture into a sample bottle. To this sample bottle, precisely weighed 10 g of hexane is added, the lid is capped, and then heated to 150 ° C. with a hot plate and mixed. Then, in order to prevent the precipitation of aliphatic hydrocarbons, quickly inject this sample into the gas chromatography inlet for analysis, and display a carbon number distribution chart with the horizontal axis representing the carbon number and the vertical axis representing the signal intensity. obtain. Next, in the obtained chart, all detected peaks are assigned to a modified product and an unmodified product by mass spectrum.

  In the carbon number distribution chart, the total area for each component is calculated for the peaks attributed to the modified product and the unmodified product. The ratio of each component was calculated by dividing the total peak area of each component by the total area of all detected peaks, and the ratio of the modified product was taken as the modification rate. Moreover, the carbon number in the present invention indicates the carbon number that is the peak top in the carbon number distribution chart.

The measurement apparatus and measurement conditions are as follows.
GC: Agilent Technologies 7890A GC
MS: Agilent Technologies 5975C
Column: ULTRA ALLOY-1 P / N: UA1-30m-0.5F (manufactured by Frontier Laboratories)
Carrier gas: He
Oven: (1) Hold at a temperature of 100 ° C. for 5 minutes, (2) Raise the temperature to 360 ° C. at 30 ° C./min, (3) Hold at a temperature of 360 ° C. for 60 minutes Inlet: Temperature 300 ° C.
Initial pressure: 10.523 psi
Split ratio: 50: 1
Column flow rate: 1 mL / min
MS mass range: 46-800 Ionization: EI Ion source: 250 ° C. Quadrupole temperature: 150 ° C.

<Method of measuring endothermic peak temperature and endothermic amount (ΔH)>
The endothermic peak temperature and endothermic amount of the polyester resin composition in differential scanning calorimetry (DSC) are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (TA Instruments). The The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat quantity uses the heat of fusion of indium.

  Specifically, about 2 mg of a measurement sample is accurately weighed, put 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 10 ° C., and then the temperature is raised again. In the DSC curve obtained in this temperature raising process, the temperature at the peak top of the maximum endothermic peak in the temperature range of 10 to 200 ° C. is obtained. The endothermic peak endothermic amount (ΔH) is an integral value of the endothermic peak.

<Measurement method of hydroxyl value of sample>
(Devices and instruments)
Measuring cylinder (100 mL)
Full pipette (5 mL)
Flat bottom flask (200 mL)
Glycerin bath

(reagent)
Acetylation reagent (take 25 g of acetic anhydride in a 100-mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake well)
・ Phenolphthalein solution ・ 0.5 kmol / m ³ potassium hydroxide ethanol solution

(Measurement method)
(A) A sample is accurately weighed in 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 on the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order 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 put on the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, and after cooling, 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 putting a sample.
(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 sample is obtained by the following formula (1).
A = [{(BC) × 28.05 × f} / S] + D (1)
A: Hydroxyl value (mgKOH / g)
B: Amount (mL) of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test
C: Amount (mL) of 0.5 kmol / m ³ potassium hydroxide ethanol solution used for titration
f: Factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution S: Mass of sample (g)
D: Acid value of sample (mgKOH / g)
28.05: Formula weight of potassium hydroxide 56.11 × 1/2

<Method for measuring acid value of sample>
(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 is taken into an Erlenmeyer flask using all pipettes, and a phenolphthalein solution is added, Titrate with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization.)
Phenolphthalein solution (diethyl ether and ethanol (99.5 vol%) mixed at a volume ratio of 1: 1 or 2: 1. These were added just a few drops of phenolphthalein solution as an indicator immediately before use. Neutralize with 1 kmol / m ³ potassium hydroxide ethanol solution.)

(Measurement method)
(A) A sample 1 to 20 g is accurately weighed 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 sample is completely dissolved on 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 result, the acid value of the sample is calculated by the following formula (2).
A = 5.611 × B × f / S (2)
A: Acid value (mgKOH / g)
B: Amount (mL) of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration
f: Factor of 0.1 kmol / m ³ potassium hydroxide ethanol solution S: Mass of sample (g)
5.611: Formula weight of potassium hydroxide 56.11 × 1/10

<Measurement method of Tg>
For the glass transition temperature (Tg) of the polyester resin composition, the endothermic peak temperature and endothermic peak amount in differential scanning calorimetry (DSC) are measured using a differential scanning calorimetric analyzer “Q2000” (manufactured by TA Instruments). Measured according to ASTM D3418-82.

  As a measurement sample, a sample obtained by accurately weighing about 2 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 of the midpoint line of the baseline before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg.

<Measurement method of softening point>
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 melted 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 NPA System) in an environment of 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

<Measurement method of transmittance of hexane dispersion of charge control agent>
Into a glass 100 mL flat bottom beaker, add 10 mL of hexane. In this, 0.01g of charge control agents are added.

  Then, dispersion is performed for 5 minutes using an ultrasonic disperser. In addition, as an ultrasonic disperser, two oscillators having an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispensing System Tetora 150” having an electrical output of 120 W (manufactured by Nikka Bios) Is used.

  The transmittance is measured with a spectrophotometer (Shimadzu Corporation UV-3100PC). The dispersion is put into a spectrophotometer cell (manufactured by GL Sciences Inc., quartz cell, model: S10-UV-10E) and transmittance measurement is started, and transmittance data after 30 minutes is adopted. At this time, hexane is put in the control cell.

  The transmittance measurement conditions are as follows.

(Measurement condition)
Measurement mode: Time course measurement value: Transmittance wavelength: 550 nm
Slit width: 3.0nm
Measurement time: 60 minutes Sampling pitch: 0.1
Number of data: 601

<Measurement of triboelectric charge amount of toner>
The measurement of the triboelectric charge amount of the toner was measured using E-SPART Analyzer MODEL EST-III ver. 9.03 (manufactured by Hosokawa Micron) is used.

  A toner and a carrier (F81-2535, manufactured by Powder Tech Co., Ltd.) are placed on a two-component feeder (developer holding base having a rotating disk with a built-in magnet) attached to E-SPART Analyzer (manufactured by Hosokawa Micron). The sample is mixed so that the toner concentration becomes 5% by mass and further mixed for 1 minute by a turbula mixer. Next, nitrogen gas is sprayed from the air nozzle to the sample held by the magnetic force in the two-component feeder to blow off only the toner, and only the toner is sucked into the E-SPART Analyzer measuring section through the sample introduction tube at the bottom of the two-component feeder. To do. The toner sucked into the measuring unit is measured for a charge amount q / d (femto-C / μm) corresponding to the particle diameter d (μm). Then, the average triboelectric charge quantity q / m of all particle diameters was obtained based on this data with the attached software, and the ratio of the number of positive components to the total number standard was calculated as the positive component ratio.

The measurement conditions for E-SPART Analyzer are as follows.
Nitrogen gas blow pressure: 20 kPa
Nitrogen gas blow time: 1 second Nitrogen gas blow interval: 4 seconds Applied voltage: 100V
Count number: 3000

<Measurement method of number average particle diameter (D1) of primary particles of charge control agent>
The number average particle diameter (D1) of the primary particles of the charge control agent was measured with a flow particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation).

  A specific measurement method is as follows. First, about 20 mL of ion-exchanged water from which impure solids and the like are previously removed is placed in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 mL of a diluted solution obtained by diluting 3) with ion-exchanged water is added. Further, about 0.05 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is put, and about 2 mL of the above-mentioned Contaminone N is added to this water tank.

  For the measurement, the flow type particle image analyzer equipped with a high-magnification imaging unit (objective lens (20 ×)) was used, and the particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure was introduced into the flow particle image analyzer, and 3000 charge control agent particles were measured in the HPF measurement mode and in the total count mode. The average value of the circle-equivalent diameters based on the number was defined as the number average particle diameter (D1) of the primary particles.

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) About 200 mL of the electrolytic solution is placed in a glass 250 mL round-bottom beaker dedicated to Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 mL of the electrolytic solution is placed in a glass 100 mL flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 mL of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 L of ion exchange water is placed in the water tank of the ultrasonic disperser, and about 2 mL of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

<Example of production of charge control agent (C-1)>
To a mixed solution of 76.5 parts of water and 15.2 parts of 35% hydrochloric acid, 10 parts of 4-chloro-2-aminophenol was added and stirred under cooling. The mixture was cooled with ice, and the temperature of the solution was maintained at 0 ° C to 5 ° C. 13.6 parts of sodium nitrite dissolved in 24.6 parts of water was added dropwise to the aqueous hydrochloric acid solution and stirred for 2 hours for diazotization. . To this, excess nitrous acid was eliminated with sulfamic acid, followed by filtration to obtain a diazo solution.

  Next, 12.0 parts of 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone was added to 87 parts of water, 12.1 parts of 25% sodium hydroxide, 4.9 parts of sodium carbonate, and n- The solution was added to and dissolved in 104.6 parts of butanol. The said diazo solution was added there, and it stirred at the temperature of 20 to 22 degreeC for 4 hours, and performed the coupling reaction. Thereafter, 92.8 parts of water and 43.5 parts of 25% aqueous sodium hydroxide solution were added and washed with stirring, and the lower aqueous layer was separated and removed.

  Next, 42.2 parts of water, 5.9 parts of salicylic acid, 24.6 parts of butanol, and 48.5 parts of 15% sodium carbonate were added to the reaction solution and stirred. Furthermore, 15.1 parts of 38% ferric chloride aqueous solution and 18.0 parts of 15% sodium carbonate were added, and the pH of the reaction solution was adjusted to 4.5 with acetic acid. After raising the liquid temperature to 30 ° C., the solution was stirred for 8 hours to carry out a complexing reaction. After the stirring was stopped, the mixture was allowed to stand to separate the lower aqueous layer. Further, 189.9 parts of water was added and washed with stirring, and the lower aqueous layer was separated. After filtration, the cake was washed with 253 parts of water. After vacuum drying at a temperature of 60 ° C. for 24 hours, a charge control agent (C-1) which is a monoazo metal complex compound was obtained.

  The structure of the charge control agent (C-1) was identified from the infrared absorption spectrum, visible part absorption spectrum, elemental analysis (C, H, N), atomic absorption analysis, and mass spectrum. confirmed. The number average particle size (D1) of the primary particles of the charge control agent (C-1) was 1.41 μm, and the transmittance after 30 minutes of standing in the hexane dispersion test was 6.7%.

<Production Example of Charge Control Agents (C-2) to (C-4)>
In the production example of the charge control agent (C-1), the charge control agents (C-2) to (C-4) were obtained by changing the time of the complexing reaction. When the structures of the charge control agents (C-2) to (C-4) were identified, it was confirmed that they had the same structure as the charge control agent (C-1). Table 1 shows the physical properties of the charge control agents (C-2) to (C-4).

<Example of production of charge control agent (C-5)>
In the production example of the charge control agent (C-1), 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone was changed to 3-methyl-1-phenyl-5-pyrazolone. Other than that was carried out similarly to the manufacture example of charge control agent (C-1), and obtained charge control agent (C-5).

  When the structure of the charge control agent (C-5) was identified, it was confirmed that the structure was as follows. Table 1 shows the physical properties of the charge control agent (C-5).

<Charge control agent (C-6)>
S-34 manufactured by Orient Chemical Co., Ltd. was used as the charge control agent (C-6). The structure of the charge control agent (C-6) is shown below, and the physical properties are shown in Table 1.

<Charge control agent (C-7)>
As the charge control agent (C-7), T-77 manufactured by Hodogaya Chemical Co., Ltd. was used. The structure of the charge control agent (C-7) is shown below. Note that a + b + c is 1. The physical properties are shown in Table 1.

<Production Example of Mixture (A-1) Containing Modified / Unmodified Aliphatic Hydrocarbon>
1200 g of aliphatic hydrocarbon (peak carbon number 35) was placed in a glass cylindrical reaction vessel, and 38.5 g of boric acid was added at a temperature of 140 ° C. Immediately thereafter, a mixed gas of 50 volume% air and 50 volume% nitrogen with an oxygen concentration of about 10 volume% 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, a reaction product containing a modified product of the upper layer was obtained. 20 parts by mass of the modified product was added to 100 parts by mass of n-hexane, and the unmodified component was dissolved and removed to obtain a mixture (A-1). Table 2 shows the physical properties of the obtained mixture (A-1).

<Production Example of Mixture (A-2) Containing Modified / Unmodified Aliphatic Hydrocarbon>
20 parts by mass of a linear aliphatic primary monoalcohol (peak carbon number 50) was added to 100 parts by mass of n-hexane to obtain a mixture (A-2) in which unmodified components were dissolved and removed. Table 2 shows the physical properties of the obtained mixture (A-2).

<Production Example of Mixture (A-3) Containing Modified / Unmodified Aliphatic Hydrocarbon>
Except having used aliphatic hydrocarbon (peak carbon number 22), it carried out similarly to the manufacture example of the mixture (A-1), and obtained the mixture (A-3). Table 2 shows the physical properties of the obtained mixture (A-3).

<Production Example of Mixture (A-4) Containing Modified / Unmodified Aliphatic Hydrocarbon>
A mixture (A-4) was obtained in the same manner as in the production example of the mixture (A-1) except that an aliphatic hydrocarbon having an average carbon number of 50 (peak carbon number: 50) was used. Table 2 shows the physical properties of the obtained mixture (A-4).

<Production Example of Mixture (A-5) Containing Modified / Unmodified Aliphatic Hydrocarbon>
A mixture (A-5) was obtained in the same manner as in the production example of the mixture (A-1) except that the conditions for dissolving and removing the unmodified component with n-hexane were changed. Table 2 shows the physical properties of the obtained mixture (A-5).

<Production Example of Mixture (A-6) Containing Modified / Unmodified Aliphatic Hydrocarbon>
Except having used the linear aliphatic primary monoalcohol (peak carbon number 33), it carried out similarly to the manufacture example of the mixture (A-2), and obtained the mixture (A-6). Table 2 shows the physical properties of the obtained mixture (A-6).

<Production Example of Mixture (A-7) Containing Modified / Unmodified Aliphatic Hydrocarbon>
20 parts by mass of a linear aliphatic primary monocarboxylic acid (peak carbon number 32) was added to 100 parts by mass of n-hexane, and the unmodified component was dissolved and removed to obtain a mixture (A-7). Table 2 shows the physical properties of the obtained mixture (A-7).

<Production Example of Mixture (A-8) Containing Modified / Unmodified Aliphatic Hydrocarbon>
A mixture (A-8) was obtained in the same manner as in Production Example of the mixture (A-2) except that the unmodified component was not dissolved and removed with n-hexane. Table 2 shows the physical properties of the obtained mixture (A-8).

<Production Example of Mixture (A-9) Containing Modified / Unmodified Aliphatic Hydrocarbon>
Except having used the aliphatic hydrocarbon (peak carbon number 105), it carried out similarly to the manufacture example of the mixture (A-1), and obtained the mixture (A-9). Table 2 shows the physical properties of the obtained mixture (A-9).

<Production Example of Mixture (A-10) Containing Modified / Unmodified Aliphatic Hydrocarbon>
A mixture (A-10) was obtained in the same manner as in Production Example of the mixture (A-1) except that the unmodified component was not dissolved and removed with n-hexane. Table 2 shows the physical properties of the obtained mixture (A-10).

<Production Example of Polyester Resin Composition (B-1)>
・ Bisfer A ethylene oxide adduct (2.0 mol adduct) 50.0 mol parts ・ Bisfer A propylene oxide adduct (2.3 mol adduct) 50.0 mol parts ・ Terephthalic acid 60.0 mol parts ・ Tri anhydride Mellitic acid 20.0 mol parts / acrylic acid 10.0 mol parts The polyester monomer and a mixture (A-1) in an amount of 5.0 mass% in the finally obtained resin composition were added ( In addition, the addition amount of the mixture (A-1) may be a little added with respect to the target ratio in consideration of the amount of water generated during the synthesis of the polyester. 60 parts by mass of the mixture was 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, and stirred at 160 ° C. in a nitrogen atmosphere. There, 40 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 reaction mixture was taken out from the container, cooled and pulverized to obtain a polyester resin composition (B-1) which is a hybrid resin. Table 3 shows the physical properties of the obtained polyester resin composition (B-1).

<Production Example of Polyester Resin Composition (B-2)>
・ Bisfer A propylene oxide adduct (2.2 mol adduct) 60.0 mol part ・ Bisfer A ethylene oxide adduct (2.2 mol adduct) 40.0 mol part ・ Terephthalic acid 77.0 mol part The above polyester monomer And a 5 liter autoclave containing a mixture (A-1) in an amount of 5.0% by mass in the resin composition finally obtained and dibutyltin oxide in an amount of 0.2% by mass. Was charged. The autoclave was equipped with a reflux condenser, a water separator, an N ₂ gas introduction pipe, a thermometer, and a stirring device. A polycondensation reaction was carried out at 230 ° C. while introducing N ₂ gas into the autoclave. The reaction time was adjusted so that the desired softening point was obtained, and after completion of the reaction, the reaction time was taken out from the container, cooled and pulverized to obtain a polyester resin composition (B-2). Table 3 shows the physical properties of the polyester resin composition (B-2).

<Production Example of Polyester Resin Composition (B-3)>
Bisphenol A ethylene oxide (2.2 mol adduct): 45.0 mol parts Bisphenol A propylene oxide (2.2 mol adduct): 40.0 mol parts Ethylene glycol: 15.0 mol parts Terephthalic acid: 100. 0 mol part The polyester monomer, a mixture (A-2) in an amount of 5.0 mass% in the resin composition finally obtained, and titanium tetrabutoxide in an amount of 0.05 mass% A 5 liter autoclave was charged. The autoclave was equipped with a reflux condenser, a water separator, an N ₂ gas introduction pipe, a thermometer, and a stirring device. A polycondensation reaction was carried out at 230 ° C. while introducing N ₂ gas into the autoclave. The reaction time was adjusted so that the desired softening point was obtained, and after completion of the reaction, the reaction time was taken out from the container, cooled and pulverized to obtain a polyester resin composition (B-3). Table 3 shows the physical properties of the polyester resin composition (B-3).

<Production Example of Polyester Resin Composition (B-4)>
Bisphenol A ethylene oxide (2.2 mol adduct): 100.0 mol parts Terephthalic acid: 65.0 mol parts Trimellitic anhydride: 25.0 mol parts Acrylic acid: 10.0 mol parts Mixture 60 of the above polyester monomers 60 Mass part and the mixture (A-2) of the quantity from which the content in the resin composition finally obtained will be 4.8 mass% were put into the 4 necked flask. There, a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device were attached and stirred at 160 ° C. in an N ₂ atmosphere. 40 parts by mass of vinyl-based polymerization monomer (90.0 mol parts of styrene and 10.0 mol parts of 2-ethylhexyl acrylate) constituting the vinyl polymer portion and 1 part by mass of benzoyl peroxide as a polymerization initiator are added from the dropping funnel. It was dripped over 4 hours. And reaction was performed at 160 degreeC for 5 hours. Thereafter, the temperature is raised to 230 ° C., 0.2 part by mass of titanium tetrabutoxide is added to the total amount of monomers for constituting the polyester unit, and the softening point of the resulting resin reaches a predetermined value. A polymerization reaction was performed. After completion of the reaction, the reaction product was taken out of the container, cooled and pulverized to obtain a polyester resin composition (B-4) which is a hybrid resin. Table 3 shows the physical properties of the polyester resin composition (B-4).

<Production Example of Polyester Resin Compositions (B-5) to (B-11)>
Except having changed the kind and content rate of a mixture as shown in Table 3, it is the same as that of the manufacture example of a polyester-type resin composition (B-1), and polyester-type resin composition (B-5)-(B-). 11) was obtained. Table 3 shows the physical properties of the obtained polyester resin compositions (B-5) to (B-11).

<Production Example of Polyester Resin Composition (B-12)>
Except having changed the kind of mixture as shown in Table 3, it carried out similarly to the manufacture example of the polyester-type resin composition (B-3), and obtained the polyester-type resin composition (B-12). Table 3 shows the physical properties of the obtained polyester resin composition (B-12).

<Production Example of Polyester Resin Composition (B-13)>
Except having changed the kind of mixture as shown in Table 3, it carried out similarly to the manufacture example of the polyester-type resin composition (B-4), and obtained the polyester-type resin composition (B-13). Table 3 shows the physical properties of the obtained polyester resin composition (B-13).

<Examples of production of polyester resin compositions (B-14) to (B-17)>
Except having changed the kind and addition amount of a mixture as shown in Table 3, it is the same as that of the manufacture example of a polyester-type resin composition (B-1), and polyester-type resin composition (B-17)-(B-). 17) was obtained. Table 3 shows the physical properties of the obtained polyester resin compositions (B-14) to (B-17).

In any polyester resin composition,
(I) The carbon number of the modified product contained in the “mixture containing modified / unmodified aliphatic hydrocarbon” used is the carbon number of the partial structure of the polyester resin,
(Ii) The carbon number of the unmodified product contained in the “mixture containing the modified / unmodified aliphatic hydrocarbon” used was the carbon number of the aliphatic hydrocarbon.

<Example 1>
Polyester resin composition (B-1): 100 parts by mass Magnetic particles (average particle size 0.12 μm, octahedral shape): 45 parts by mass Fischer-Tropsch wax (C105 manufactured by Sasol, melting point: 105 ° C.) :
2 parts by mass / charge control agent (C-1): 2 parts by mass After the above materials were premixed with a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.), a twin-screw extruder (trade name: PCM-30, Ikekai Iron Works) The temperature was set and melt kneaded so that the melt temperature at the discharge port was 130 ° C.

  The obtained kneaded material was cooled, coarsely pulverized with a hammer mill, and then finely pulverized using a pulverizer (trade name: Turbo Mill T250, manufactured by Turbo Kogyo Co., Ltd.). The obtained finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain toner particles 1 having a weight average particle diameter (D4) of 6.8 μm.

  To 100 parts by mass of the toner particles 1, 1.2 parts by mass of negatively chargeable hydrophobic silica were externally added and mixed using a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.) to obtain toner 1. This toner was evaluated for the following items.

[Evaluation]
The obtained toner 1 was aged under the following standing conditions 1 to 3.
・ Leaving condition 1
24 hours at 25 ° C, 60% RH
Left in the following heat cycle environment (humidity is constant at 25% H)
<1> Hold at 25 ° C for 1 hour <2> Increase temperature linearly to 45 ° C over 11 hours <3> Hold at 45 ° C for 1 hour <4> Reduce temperature linearly to 25 ° C over 11 hours The above <1> to <4> were taken as one cycle, and a total of 20 cycles were performed.
・ Leaving condition 3
Leaving in the following heat cycle environment under high humidity (humidity is constant at 95% H)
<1> Hold at 25 ° C for 1 hour <2> Increase temperature linearly to 45 ° C over 11 hours <3> Hold at 45 ° C for 1 hour <4> Reduce temperature linearly to 25 ° C over 11 hours The above <1> to <4> were taken as one cycle, and a total of 20 cycles were performed.

  Evaluation was performed on the toner 1 left under the leaving conditions 1 to 3.

  For the evaluation, a commercially available magnetic one-component developing printer HP LaserJet Enterprise 600 M603dn (manufactured by Hewlett-Packard Company: process speed 350 mm / s) was used. The developing sleeve was replaced with one having a sleeve diameter of 14 mm and the magnetic flux density on the sleeve surface was changed to 80 mT. The evaluation results are shown in Table 5.

<Evaluation of fogging>
A horizontal line pattern with a printing rate of 2% is assumed to be 1 sheet / 1 job, and a mode is set so that the next job starts after the machine stops between jobs. The fog density was measured after the first sheet and 12,000 sheets.

  Using a reflectometer (manufactured by Tokyo Denshoku), measure the reflectance (%) of the white portion of the fixed image and the reflectance (%) of the transfer material, and calculate the difference as the fog density (%). did.

  The evaluation of the fog was performed under low temperature and low humidity (15 ° C., 10% RH), where the toner charge distribution tends to be broad and is assumed to be more severe with respect to the fog. The toner left under each condition was aged at low temperature and low humidity (15 ° C., 10% RH) for 24 hours, and then the evaluation was started.

<Evaluation of dot reproducibility>
The dot reproducibility was evaluated in a normal temperature and humidity environment (25 ° C., 60% RH). A horizontal line pattern with a print rate of 2% is set to 2 sheets / job, and a total of 1000 images are printed in a mode in which the machine is temporarily stopped between jobs and the next job starts. It was. Subsequently, a halftone image (image density is set to 0.5 to 0.6) in which isolated dots are printed on Xerox 4200 (Xerox Co., Ltd., 75 g / m ² paper) is output, and 100 isolated 1 dots are obtained using an optical microscope. The number of defects in was measured. Evaluation was started after the toner left under each condition was aged for 24 hours in a normal temperature and humidity environment (25 ° C., 60% RH).
A: 5 or less defects in 100 isolated dots B: 6 or more and 10 or less defects in 100 isolated dots C: 11 or more and 20 or less defects in 100 isolated dots D: Isolated More than 21 defects in 100 dots

<Development evaluation>
Evaluation of developability was carried out in a high temperature and high humidity environment (32 ° C., 80% RH). After a total of 1000 images of a horizontal line pattern having an initial printing rate of 1% and a total of 1000 images were printed, a 5 mm round solid image was output and the image density was measured. The image density was measured by measuring the reflection density of a 5 mm round solid image using an SPI filter with a Macbeth densitometer (Macbeth Co., Ltd.) which is a reflection densitometer. A larger number indicates better.

  The reason why the evaluation was performed in a high-temperature and high-humidity environment (32 ° C., 80% RH) is that the chargeability of the toner is likely to be lowered, and is a severe condition for evaluating the developability. The toner left under each condition was aged for 24 hours in a high temperature and high humidity environment (32 ° C., 80% RH), and then the evaluation was started.

<Examples 2 to 15 and Comparative Examples 1 to 6>
Toners 2 to 15 and comparative toners 1 to 6 were obtained in the same manner as in Example 1 except that the types and amounts of the polyester resin composition and the charge control agent were changed as shown in Table 4. Further, the same evaluation as in Example 1 was performed, and the evaluation results are shown in Table 5.

Claims (5)

A toner having toner particles containing a polyester resin composition and a charge control agent,
The polyester resin composition is
i) R ¹ —O— or R ² —COO—
[Wherein R ¹ represents a group formed by elimination of one hydrogen atom from an aliphatic hydrocarbon having 12 to 102 carbon atoms, and R ² represents an aliphatic hydrocarbon having 11 to 101 carbon atoms. Represents a group formed by elimination of one hydrogen atom from ]
Containing a polyester resin having a partial structure represented by: and an aliphatic hydrocarbon having 12 to 102 carbon atoms,
ii) Based on the mass of the polyester-based resin composition, the partial structure and the aliphatic hydrocarbon having 12 to 102 carbon atoms in total are contained in an amount of 2.5% by mass or more and 10.0% by mass or less. And
iii) In a temperature-endothermic curve obtained by differential scanning calorimetry (DSC), it has an endothermic peak having a peak top at 30 ° C. or higher and 100 ° C. or lower, and the endothermic peak has an endothermic amount of 0.10 J / g or higher. 1.90 J / g or less,
The charge control agent has a transmittance of 30 minutes after standing in a test in which a change in transmittance of light having a wavelength of 550 nm is measured for a dispersion in which 0.01 g of the charge control agent is dispersed in 10 mL of hexane. 10% or less,
Toner characterized by the above.   The toner according to claim 1, wherein the number average particle diameter (D1) of primary particles of the charge control agent is 0.80 μm or more and 2.00 μm or less. The toner according to claim 1, wherein the charge control agent is a compound represented by the following formula [1].

(In the formula, A ₁ , A ₂ and A ₃ each independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group. M represents an Fe atom, a Cr atom, Alternatively, it represents an Al atom, and X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof. The toner according to claim 1, wherein the charge control agent is a compound represented by the following formula [2].

(In the formula, X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.) R ¹ to form an R ¹ -O- of the polyester resin composition, is a functional group having a carbon number of hydrogen atoms formed by one desorbed from secondary carbon aliphatic hydrocarbons 12-102 The toner according to any one of claims 1 to 4.