JP2021096278A - toner - Google Patents

Abstract

To provide a toner that exhibits excellent low-temperature fixability and electrification maintaining property, and exhibits excellent scratch resistance for a fixed image on thick coat paper.SOLUTION: A toner has toner particles containing a binder resin having a first resin that is a crystalline resin and wax. The content of the first resin in the binder resin is 30.0 mass% or more. The first resin has a specific amount of specific monomer unit. In a temperature differential distribution of an endothermic peak measured by differential scanning calorimetry of the toner, a 1st peak and a 2nd peak derived from the wax are present; the 1st peak has a peak top temperature of 70.0°C to 97.0°C; the 2nd peak is adjacent to the 1st peak; the peak top temperature of the 2nd peak is higher than the peak top temperature of the 1st peak; the height of the valley part between the 1st peak and the 2nd peak is larger than 0 W/(g °C).SELECTED DRAWING: None

Description

The present disclosure relates to toners used in electrophotographic methods, electrostatic recording methods, electrostatic printing methods, and the like.

In recent years, with the widespread use of electrophotographic full-color copiers, not only higher speeds and higher image quality, but also energy saving performance, shorter recovery time from sleep mode, support for a wide variety of media, etc. have been added. Performance improvement is also required.
Specifically, as a toner corresponding to energy saving, a toner having excellent low-temperature fixability that can be fixed at a lower temperature is required in order to reduce power consumption in the fixing process.
Further, as a toner capable of shortening the recovery time from the sleep state, there is a demand for a toner having excellent charge retention and having a small change in the charge amount throughout the sleep state for a long time.
In addition, thick paper coated paper, which is one of a wide variety of media, contains a large amount of inorganic fine particles such as calcium carbonate in order to enhance whiteness, so that the coefficient of friction due to rubbing between papers increases and fixing is performed. The toner in the image is easily peeled off from the paper. Therefore, there is a demand for a toner having excellent scratch resistance so that the toner does not peel off even when the papers are rubbed against each other.
Therefore, a toner using a crystalline polyvinyl resin has been proposed as a toner having excellent low-temperature fixability, charge retention, and scratch resistance (Patent Document 1).
Further, as a toner having excellent scratch resistance, a toner having alkenyl succinic acid as a carboxylic acid component of polyester has been proposed (Patent Document 2).

Japanese Unexamined Patent Publication No. 2018-156074 Japanese Unexamined Patent Publication No. 2016-197207

Since the toner described in Patent Document 1 has a sharp melt property and uses a crystalline polyvinyl resin having high hydrophobicity, it has excellent low temperature fixability and charge retention. Further, by promoting the crystallization of the crystalline resin in the fixed image, a certain effect can be obtained in the pencil scratching test. It is considered that this is because the crystallinity of the crystalline resin restores the elasticity of the toner itself in the fixed image and the toner is not destroyed.
On the other hand, the peeling of toner in a fixed image due to rubbing between papers, which has been required in recent years, is a phenomenon in which toner is peeled from paper rather than being destroyed. Furthermore, since the crystalline polyvinyl resin has a high affinity with wax, the exudation of wax is suppressed, and the wax layer on the surface of the fixed image is less likely to be formed. From the above, it was found that even if the toner described in Patent Document 1 is used, the scratch resistance required in recent years may be inferior.
On the other hand, with respect to the toner described in Patent Document 2, since alkenyl succinic acid has a high affinity with wax, the wax is more likely to be retained in the fixing image than the wax is transferred to the fixing roller at the time of fixing. Therefore, in a paper type such as plain paper, a certain effect on scratch resistance can be obtained. However, it has been found that the scratch resistance may be inferior in the thick coated paper containing a large amount of inorganic fine particles such as calcium carbonate in order to increase the whiteness required in recent years.
From the above, there is an urgent need to develop a toner that satisfies low temperature fixability, charge retention, and scratch resistance.
The present disclosure provides a toner that exhibits excellent low-temperature fixability and charge retention, and also exhibits excellent scratch resistance even in a fixed image such as thick coated paper.

A toner having toner particles containing a binder resin having a first resin and a wax.
The first resin is a crystalline resin and
The content of the first resin in the binder resin is 30.0% by mass or more.
The first resin has a first monomer unit represented by the following formula (1).
The content ratio of the first monomer unit in the first resin is 30.0% by mass to 100.0% by mass.
In the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry of the toner,
There are 1st peak and 2nd peak derived from the wax,
The peak top temperature of the 1st peak is 70.0 ° C. to 97.0 ° C.
The 2nd peak is adjacent to the 1st peak,
The peak top temperature of the 2nd peak is higher than the peak top temperature of the 1st peak.
A toner characterized in that the height of the valley portion of the 1st peak and the 2nd peak is larger than 0 W / (g · ° C.).
[In the following formula (1), R _Z1 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms. ]

According to the present disclosure, it is possible to provide a toner that exhibits excellent low-temperature fixability and charge retention, and also exhibits excellent scratch resistance even in a fixed image such as thick paper coated paper.

Example of temperature derivative distribution of endothermic peak of wax by differential scanning calorimetry

［式（Ｚ）中、Ｒ_Ｚ１は、水素原子、又はアルキル基（好ましくは炭素数１〜３のアルキル基であり、より好ましくはメチル基）を表し、Ｒ_Ｚ２は、任意の置換基を表す。］
結晶性樹脂とは、示差走査熱量計（ＤＳＣ）測定において明確な吸熱ピークを示す樹脂を指す。 In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
The (meth) acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.
When the numerical ranges are described step by step, the upper and lower limits of each numerical range can be arbitrarily combined.
"Monomer unit" refers to the reacted form of a monomeric substance in a polymer. For example, one carbon-carbon bond section in the main chain in which the vinyl-based monomer in the polymer is polymerized is defined as one unit. The vinyl-based monomer can be represented by the following formula (Z).

[In the formula (Z), R _Z1 represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R _Z2 represents an arbitrary substituent. .. ]
Crystalline resin refers to a resin that exhibits a clear endothermic peak in differential scanning calorimetry (DSC) measurements.

The present inventors have proceeded with the study of a toner having excellent low-temperature fixability and charge retention, and also having excellent scratch resistance. As a result, the present inventors obtain a desired toner by containing, in addition to a crystalline resin having a specific structure, a wax showing a specific endothermic peak by differential scanning calorimetry of the toner. I found that I could do it.
The specific endothermic peak includes the 1st peak and the 2nd peak derived from wax in the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry of toner.
The peak top temperature of the 1st peak is 70.0 ° C to 97.0 ° C.
The 2nd peak is adjacent to the 1st peak,
The peak top temperature of the 2nd peak is higher than the peak top temperature of the 1st peak,
The height of the valley of the 1st peak and the 2nd peak is larger than 0 W / (g · ° C.).
Specifically, it is important that the wax that is phase-separated from the crystalline resin, which is the first resin, acts as a nucleating agent for other waxes, and that the other waxes are also phase-separated from the crystalline resin. I found it.

The study leading to the above invention will be described. The reason why the crystalline resin is compatible with the wax is that the absolute value of the polar difference between the crystalline resin having the first monomer unit and the wax is small. On the other hand, by making the crystalline resin highly polar in the dark clouds, the phase separation property with the wax is improved, but the crystallinity of the crystalline resin is disrupted, resulting in a decrease in low temperature fixability. Further, when the crystalline resin is made highly polar, it becomes hydrophilic, so that the hygroscopicity in a high temperature and high humidity environment is also increased, and the charge retention property which is a merit of the crystalline resin is also impaired.
On the other hand, by increasing the molecular weight of the wax, the phase separation with the crystalline resin is improved, but the viscosity of the wax is increased, the exudation of the wax during fixing is suppressed, and a wax layer on the surface of the fixed image is formed. Since it is difficult, the scratch resistance is impaired.

Therefore, the present inventors have investigated a method capable of forming a phase-separated state between the crystalline resin and the wax. As a result, we came up with the idea of using a wax that phase-separates from a crystalline resin as a nucleating agent for low-viscosity wax that aims to function as a wax, rather than having a function as a wax.
Then, as a result of diligently examining the necessary conditions as a nucleating agent for phase-separating the low-viscosity wax with respect to the crystalline resin, between the low-viscosity wax aiming at the function as a wax and the wax acting as a nucleating agent. In, it was found that it is necessary to have an affinity. Since both waxes have an affinity, it has been found that low-viscosity waxes aiming at the function as waxes can be easily phase-separated, starting from the wax nucleating agent that phase-separates from the crystalline resin.
As a result, even in the toner containing the crystalline resin having the first monomer unit, the wax is phase-separated and the exudation of the wax at the time of fixing is guaranteed, so that the surface of the fixed image is covered with the wax. , Excellent scratch resistance can be obtained.

The toner of the present disclosure has a binder resin having a first resin which is a crystalline resin and toner particles containing wax.
The content of the first resin in the binder resin is 30.0% by mass or more.
When the content of the first resin is 30.0% by mass or more, it indicates that the toner contains an appropriate crystalline resin, and excellent low-temperature fixability can be obtained.
On the other hand, when the content of the first resin is less than 30.0% by mass, it indicates that there is little crystalline resin in the toner, and the low temperature fixability is impaired.
The content is more preferably 50.0% by mass or more, still more preferably 55.0% by mass or more.
On the other hand, the upper limit is not particularly limited, but is preferably 90.0% by mass or less, and more preferably 75.0% by mass or less.

The first resin, which is a crystalline resin, has a first monomer unit represented by the formula (1). The first monomer unit is preferably derived from the first polymerizable monomer, which is at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.
When the R of the first monomer unit is an alkyl group having 18 to 36 carbon atoms, the resin can be imparted with crystallinity. Therefore, the toner exhibits sharp meltability, and excellent low-temperature fixability can be obtained. Further, since the alkyl group having 18 to 36 carbon atoms has high hydrophobicity, it has low hygroscopicity in a high temperature and high humidity environment, and excellent charge retention can be obtained.

On the other hand, when R of the first monomer unit is an alkyl group having less than 18 carbon atoms, the chain length of the alkyl group is short, so that the crystallinity is lowered and sufficient sharp meltability cannot be obtained. Since the adhesion of the material is reduced, the scratch resistance is inferior.
Further, when R of the first monomer unit is an alkyl group having more than 37 carbon atoms, the melting point becomes high because it has an alkyl group having a long chain length, and the low temperature fixability deteriorates. Furthermore, since it tends to be an alkyl group having a chain length close to that of wax, the affinity with wax is enhanced, sufficient phase separation cannot be obtained, and the exudation of wax at the time of fixing is hindered, so that the surface of the fixed image becomes It is not coated with wax and its scratch resistance is impaired.

[In the formula (1), R _Z1 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms (preferably a linear alkyl group having 18 to 30 carbon atoms). ]
The first monomer unit represented by the formula (1) is preferably a monomer unit derived from at least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms. ..
Examples of the (meth) acrylic acid ester having an alkyl group having 18 to 36 carbon atoms include a (meth) acrylic acid ester having a linear alkyl group having 18 to 36 carbon atoms [(meth) stearyl acrylate, (meth). ) Nonadesyl acrylate, Eikosyl acrylate, Heneikosanyl acrylate, Behenyl acrylate, Lignoceryl acrylate, Ceryl acrylate, Octacosyl acrylate, (meth) Myricyl acrylate, dotriacontyl (meth) acrylate, etc.] and (meth) acrylic acid ester having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth) acrylate, etc.] can be mentioned.
Of these, from the viewpoint of low-temperature fixability, at least one selected from the group consisting of (meth) acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms is preferable, and a linear chain having 18 to 30 carbon atoms is preferable. At least one selected from the group consisting of (meth) acrylic acid esters having an alkyl group of is more preferred, and at least one selected from the group consisting of linear stearyl (meth) acrylate and behenyl (meth) acrylate. More preferred.
As the monomer forming the first monomer unit, one type may be used alone, or two or more types may be used in combination.

The content ratio of the first monomer unit in the first resin is 30.0% by mass to 100.0% by mass.
When the content ratio is in the above range, the toner exhibits sharp meltability due to its crystallinity, and excellent low-temperature fixability can be obtained.
The content ratio of the first monomer unit is preferably 40.0% by mass to 90.0% by mass, more preferably 50.0% by mass to 80.0% by mass, and further preferably 50.0% by mass. % To 60.0% by mass.
On the other hand, when the content ratio of the first monomer unit is less than 30.0% by mass, the ratio of the crystalline portion is small, so that the low temperature fixability is inferior.
When the first resin has a monomer unit derived from (meth) acrylic acid ester having two or more kinds of alkyl groups having 18 to 36 carbon atoms, the content ratio of the first monomer unit is the total of them. Represents the mass ratio of.

Further, in the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry (DSC) of the toner, the 1st peak and the 2nd peak derived from wax are present, and the peak top temperature of the 1st peak is 70.0 ° C. to 97. It is 0.0 ° C, the 2nd peak is adjacent to the 1st peak, the peak top temperature of the 2nd peak is higher than the peak top temperature of the 1st peak, and the height of the valleys of the 1st peak and the 2nd peak is 0 W / (g · ° C). Become larger.
When the 1st peak having a peak top temperature of 70.0 ° C. to 97.0 ° C. is present, it means that a wax having a low viscosity is present in the toner. As a result, the exudation of wax at the time of fixing is guaranteed, and the surface of the fixed image is covered with wax, so that excellent scratch resistance can be obtained.
If there is a 2nd peak adjacent to the 1st peak and the peak top temperature is higher than the 1st peak, and the height of the valley between the 1st peak and the 2nd peak is larger than 0 W / (g · ° C), the wax of the 1st peak is waxed. It is shown that there are waxes having different melting points that have an affinity for. Further, since the peak top temperature of the 2nd peak is higher than the peak top temperature of the 1st peak, it is shown that the wax of the 2nd peak used in combination with the wax of the 1st peak has a high molecular weight, and is a crystalline resin. Phase-separated from one resin.
That is, since the wax of the 2nd peak acts as a wax nucleating agent, the wax of the 1st peak is also guided in the direction of phase separation from the first resin, and the exudation of the wax at the time of fixing is guaranteed. Therefore, since the surface of the fixed image is covered with wax, excellent scratch resistance can be obtained.

On the other hand, in the above temperature differential distribution, when the 1st peak having a peak top temperature of 70.0 ° C. to 97.0 ° C. does not exist, it means that the wax having a low viscosity does not exist in the toner. As a result, the exudation of wax at the time of fixing is not guaranteed, so that the surface of the fixed image is not covered with wax and the scratch resistance is impaired.
Further, even when there is a 2nd peak whose peak top temperature is higher than the 1st peak and the height of the valley portion between the 1st peak and the 2nd peak is 0 or less, the scratch resistance is impaired. In this case, since the peak top temperature of the 2nd peak is higher than the peak top temperature of the 1st peak, the wax of the 2nd peak used in combination has a high molecular weight, so that the wax of the 2nd peak is phase-separated from the first resin. To do.
However, since both waxes do not have an affinity, the 2nd peak wax does not act as a wax nucleating agent. As a result, the wax of the 1st peak does not phase-separate from the first resin, and the exudation of the wax at the time of fixing is not guaranteed. Therefore, the surface of the fixed image is not covered with the wax and the scratch resistance is impaired.
Further, when the 2nd peak higher than the 1st peak does not exist, it means that there is no high molecular weight wax that phase-separates from the first resin. As a result, the wax of the 1st peak does not phase-separate from the first resin, and the exudation of the wax at the time of fixing is not guaranteed. Therefore, the surface of the fixed image is not covered with the wax and the scratch resistance is impaired.

The peak top temperature of the 1st peak is preferably 80.0 ° C. to 95.0 ° C., more preferably 90.0 ° C. to 94.0 ° C. The peak top temperature of the 1st peak can be controlled by the molecular weight and the degree of bifurcation.
In the above temperature derivative distribution, the 1st peak is preferably the highest peak. The height of the 1st peak is preferably higher than the height of the 2nd peak. It is preferable that there is no clear peak other than the 1st peak and the 2nd peak.
The difference between the peak top temperature of the 2nd peak and the peak top temperature of the 1st peak (peak top temperature of the 2nd peak-1st peak peak temperature) is preferably 10 ° C to 20 ° C.
The height of the valley portion of the 1st peak and the 2nd peak is preferably about 0.01 W / (g · ° C) to 0.1 W / (g · ° C). Further, in order to make the height of the valley portion larger than 0 W / (g · ° C.), it is possible by selecting a wax having an overlapping portion in the molecular weight distribution of the wax.

The wax preferably contains a hydrocarbon wax having a weight average molecular weight of Mw 300 to 700 (more preferably 400 to 700) and a hydrocarbon wax having a weight average molecular weight of Mw 1000 to 2000 (more preferably 1000 to 1500).
When the toner contains a hydrocarbon wax having a weight average molecular weight of Mw 300 to 700, it means that a wax having a low viscosity is present in the toner. As a result, the exudation of wax at the time of fixing is promoted, so that the surface of the fixed image is covered with wax, and excellent scratch resistance can be obtained.
Further, when the toner contains a hydrocarbon wax having a weight average molecular weight of Mw 1000 to 2000, it means that the toner contains a wax that is phase-separated from the first resin. As a result, it can be a wax nucleating agent for a hydrocarbon wax having a weight average molecular weight of Mw 300 to 700, which makes it difficult to obtain sufficient phase separation with respect to the first resin. Therefore, the exudation of wax at the time of fixing is promoted, and the surface of the fixed image is covered with wax, and excellent scratch resistance can be obtained.

When the content of toner particles of hydrocarbon waxes having a weight average molecular weight Mw1000~2000 and _{W L} wt%, the content of the toner particles of hydrocarbon waxes having a weight average molecular weight Mw300~700 was _{W S} wt%, It is preferable to satisfy the following formula (2), and it is more preferable to satisfy the following formula (2').
_{0.2 ≦ W L / W S ≦} 0.8 ··· (2)
_{0.3 ≦ W L / W S ≦} 0.6 ··· (2')
If W _L / _{W S} satisfies the above formula (2), than the hydrocarbon wax having a weight average molecular weight Mw1000~2000 acting as a nucleating agent, it hydrocarbon wax having a weight average molecular weight Mw300~700 acting as a wax is often Means. As a result, the exudation of wax at the time of fixing is promoted, so that the surface of the fixed image is covered with wax, and excellent scratch resistance can be obtained.

The content _{W L} in the toner particles of hydrocarbon waxes having a weight average molecular weight Mw1000~2000 is, it is preferable to satisfy the following formula (3), the following formula (3 ') more preferably 1.0 wt% ≦ be met W _L ≤ 5.0% by mass ・ ・ ・ (3)
1.5% by mass ≤ _LL ≤ 4.0% by mass ... (3')
If W _L satisfies the above formula (3), which means that the hydrocarbon wax having a weight average molecular weight Mw1000~2000 acting as a nucleating agent is present in sufficient amount toner. As a result, the exudation of wax at the time of fixing is promoted, so that the surface of the fixed image is covered with wax, and excellent scratch resistance can be obtained.
The _WS is preferably 2.5% by mass to 10.0% by mass, and more preferably 3.0% by mass to 7.0% by mass.

In the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry DSC of the toner, the peak top temperature of an endothermic peak corresponding to a hydrocarbon wax having a weight average molecular weight Mw300~700 and T _S,
Differential scanning calorimetry of hydrocarbon waxes with a weight average molecular weight of Mw 300 to 700 When the peak top temperature in the temperature differential distribution of the endothermic peak measured by DSC is T, it is preferable to satisfy the following formula (4), and the following formula is preferable. It is more preferable to satisfy (4').
In this case, it means that the phase separation property of the hydrocarbon wax having a weight average molecular weight Mw acting as a wax of 300 to 700 with respect to the first resin is sufficiently obtained. As a result, the exudation of wax at the time of fixing is promoted, so that the surface of the fixed image is covered with wax, and excellent scratch resistance can be obtained.
Equation (4) be satisfied, why indicating that the phase separation property is sufficiently obtained, if the wax is easily compatible with the first resin, tend to melting point T _S of the endothermic peak is decreased This is because it is possible to quantify the compatibility-phase isolation in the magnitude relationship of T-T _{S.
0.0 ≦ T-T S ≦ 2.0} ··· (4)
_{0.0 ≦ T-T S ≦ 1.1} ··· (4')
_{T-T S} may be controlled by the quantity ratio and, the degree of overlap 1st peak and 2nd peak with the hydrocarbon wax hydrocarbon wax and a weight average molecular weight Mw1000~2000 of weight average molecular weight Mw300～700.

Let the weight average molecular weight of the hydrocarbon wax having a weight average molecular weight of Mw 1000 to 2000 be Mw _L, and let the number average molecular weight be Mn _L. Further, the weight average molecular weight of the hydrocarbon wax having a weight average molecular weight of Mw 300 to 700 is Mw _S , and the number average molecular weight is Mn _S. At this time, the molecular weight distribution Mw _L / Mn _L and the molecular weight distribution Mw _S / Mn _S preferably satisfy the following formula (5), and more preferably the following formula (5').
Mw _S / Mn _S ≤ Mw _L / Mn _L ... (5)
0.0 ≤ Mw _L / Mn _{L- Mw S} / Mn _S ≤ 1.5 ... (5')
When Mw _L / Mn _L and Mw _S / Mn _S satisfy the above formula (5), the molecular weight distribution of the hydrocarbon wax having a weight average molecular weight Mw 1000 to 2000 that can be a nucleating agent is that the hydrocarbon wax having a weight average molecular weight Mw 300 to 700. It means that it is broad with respect to the molecular weight distribution of.
As a result, an affinity is likely to be generated between the two waxes, and the hydrocarbon wax having a weight average molecular weight of Mw 300 to 700 is easily guided in the direction of phase separation from the first resin, so that the wax seeps out during fixing. Cheap. Therefore, the surface of the fixed image is covered with wax, and excellent scratch resistance can be obtained.

The acid value of the first resin, which is a crystalline resin, is preferably 0.1 mgKOH / g to 30.0 mgKOH / g, and more preferably 5.0 mgKOH / g to 20.0 mgKOH / g.
When the acid value is in the above range, hydrogen bonds are formed between the first resin and the paper, and the adhesion between the paper and the toner is enhanced, so that excellent scratch resistance can be obtained. Further, since the wax and the first resin are easily phase-separated, the exudation of the wax at the time of fixing is promoted, and the surface of the fixed image is covered with the wax, so that excellent scratch resistance can be obtained.

The binder resin preferably contains a second resin. The second resin is preferably an amorphous resin. The acid value of the second resin is preferably 0.5 mgKOH / g to 40.0 mgKOH / g, and more preferably 5.0 mgKOH / g to 30.0 mgKOH / g.
When the acid value is in the above range, hydrogen bonds are formed between the second resin and the paper, and the adhesion between the paper and the toner is enhanced, so that excellent scratch resistance can be obtained. Further, since the wax and the second resin are easily phase-separated, the exudation of the wax at the time of fixing is promoted, and the surface of the fixed image is covered with the wax, so that excellent scratch resistance can be obtained.

The mass ratio Y / X of the content Y of the second resin to the content X of the first resin in the binder resin is preferably 0.25 to 2.20, preferably 0.50 to 1.00. Is more preferable.
When Y / X is in the above range, the toner contains a certain amount of the first resin and the sharp melt property is guaranteed, so that excellent low temperature fixability can be obtained.

Further, in the cross-sectional observation of the toner, it is preferable to see a domain matrix structure composed of a matrix containing the first resin and a domain containing the second resin. It is more preferable to see a domain matrix structure composed of a matrix made of the first resin and a domain made of the second resin.
When the first resin, which is a crystalline resin, is contained in the matrix, the sharp melt property is guaranteed, so that excellent low temperature fixability can be obtained.
Such a domain matrix structure can be obtained by the amount ratio or viscosity ratio of the first resin and the second resin.
The average diameter of the number of domains in the cross-sectional observation of the toner is preferably 0.1 μm to 2.0 μm, and more preferably 0.5 μm to 1.5 μm.

The binder resin further contains a third resin, and the third resin preferably contains a resin to which the first resin and the second resin are bonded. When the third resin is contained, the compatibility between the first resin and the wax is lowered, and the phase is separated. As a result, exudation of wax at the time of fixing is promoted, and the surface of the fixed image is covered with wax, so that excellent scratch resistance can be obtained.

The second resin, which is an amorphous resin, preferably contains at least one selected from the group consisting of a hybrid resin in which a vinyl resin and a polyester resin are bonded and a polyester resin.
When the second resin is the above resin, it means that the second resin has a certain ester group, and more phase separability with wax can be obtained. As a result, exudation of wax at the time of fixing is promoted, and the surface of the fixed image is covered with wax, so that excellent scratch resistance can be obtained.

The toner preferably has silica fine particles treated with silicone oil on the surface of the toner particles.
When having silica fine particles treated with silicone oil, the wax existing near the surface of the toner particles and the silicone oil of the silica fine particles adhering to the surface of the toner particles have an affinity, and the exudation of the wax at the time of fixing is promoted. Since the surface of the fixed image is coated with wax, excellent scratch resistance can be obtained.

When the SP value of the first resin is SP _C (J / cm ³ ) ^0.5 and the SP value of the hydrocarbon wax having a weight average molecular weight Mw 1000 to 2000 is SP _W (J / cm ³ ) ^0.5 , It is preferable that SP _C and SP _W satisfy the following formula (6), more preferably the following formula (6 ′), and further preferably the following formula (6 ″).
(SP _C- SP _w ) ≧ 1.0 ・ ・ ・ (6)
2.5 ≧ (SP _C- SP _w ) ≧ 1.5 ・ ・ ・ (6')
2.2 ≧ (SP _C- SP _w ) ≧ 1.9 ・ ・ ・ (6 ″)

<First resin>
The first resin, which is a crystalline resin, preferably has a second monomer unit different from the first monomer unit. When the SP value (J / cm ³ ) ^0.5 of the second monomer unit is SP ₂₁ , it is preferable that the following formula (7) is satisfied. It is more preferable to satisfy the following formula (7').
21.00 ≤ SP ₂₁ ... (7)
21.00 ≤ SP ₂₁ ≤ 40.00 ... (7')
Here, the SP value is an abbreviation for a solubility parameter, and is a value that serves as an index of solubility. The calculation method will be described later.
The unit of the SP value is (J / cm ³ ) ^0.5 , but 1 (cal / cm ³ ) ^0.5 = 2.045 × 10 ^-3 (J / cm ³ ) ^0.5 ( cal / cm ³ ) Can be converted to a unit of ^0.5.

By satisfying the above formula (7), the second monomer unit becomes highly polar, and a polarity difference occurs between the first and second monomer units. Due to this polarity difference, the crystallization of the first monomer unit is promoted, so that excellent low-temperature fixability and charge retention can be obtained. Specifically, the first monomer unit is incorporated into the first resin, which is a crystalline resin, and the first monomer units are aggregated with each other to exhibit crystallinity.
Normally, the crystallization of the first monomer unit is hindered when another monomer unit is incorporated, so that it becomes difficult to develop crystallinity as a crystalline resin. This tendency becomes remarkable when a plurality of types of monomer units are randomly bonded to each other in one molecule of the crystalline resin.
However, by giving a polar difference between the first polymerizable monomer forming the first monomer unit and the second polymerizable monomer forming the second monomer unit, the first polymerization occurs at the time of polymerization. It is considered that the sex monomer and the second polymerizable monomer can be bonded continuously to some extent rather than being bonded randomly. As a result, a block in which the first monomer units are assembled is formed, the crystalline resin becomes a block copolymer, and it is possible to enhance the crystallinity even if other monomer units are incorporated, and excellent low-temperature fixing is possible. Properties and charge retention are obtained.
Furthermore, since it has a highly polar portion, the phase separation between the crystalline resin and the wax is promoted, and the exudation of the wax at the time of fixing is promoted. Scratchability is obtained.
The second monomer unit may be any monomer unit having _{SP 21.}

The first resin preferably contains the second monomer unit in an amount of 0.0% by mass to 70.0% by mass, more preferably 1.0% by mass to 30.0% by mass. It is more preferably contained in an amount of 5% by mass to 5.0% by mass.
When the content ratio of the second monomer unit is in the above range, the polarity of the first resin is appropriately controlled, so that excellent charge retention and scratch resistance can be obtained. Specifically, when the content ratio of the second monomer unit is in the above range, the phase separation between the first resin and the wax is promoted because it has a highly polar moiety. As a result, the exudation of wax at the time of fixing is promoted, so that the surface of the fixed image is covered with wax, and excellent scratch resistance can be obtained.
Furthermore, the fact that the content ratio of the second monomer unit is in the above range indicates that a certain amount of the first monomer unit is present. Therefore, crystallinity is exhibited by assembling the first monomer units, and excellent low-temperature fixability can be obtained.
When there are two or more types of second monomer units satisfying the formula (7) in the first resin, the ratio of the second monomer units represents the total mass ratio of them.

The first resin is at least one selected from the group consisting of a monomer unit represented by the following formula (2) and a monomer unit represented by the following formula (3), which is different from the first monomer unit. It is preferable to have two monomer units.

(In the formula (2), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N),
Amide group (-C (= O) NHR ¹⁰ (R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
Hydroxy group,
-COOR ¹¹ (R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4) or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4)),.
Urea group (-NH-C (= O) -N (R ¹³ ) ₂ (R ¹³ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))) ,
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms), or -COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ ( Each of R ¹⁵ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms).
Is. R ² represents a hydrogen atom or a methyl group. )
(In the formula (3), R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.)

The second polymerizable monomer forming the second monomer unit preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
The second polymerizable monomer is preferably at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula, X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is
Nitrile group (-C≡N),
Amide group (-C (= O) NHR ¹⁰ (R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
Hydroxy group,
-COOR ¹¹ (R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4) or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4)),.
Urea group (-NH-C (= O) -N (R ¹³ ) ₂ (R ¹³ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))) ,
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ represents an alkyl group having 1 to 4 carbon atoms), or -COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ ( Each of R ¹⁵ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms).
Represents.
R ² represents a hydrogen atom or a methyl group. )
(In the formula, R ³ represents an alkyl group having 1 to 4 carbon atoms.
R ⁴ represents a hydrogen atom or a methyl group. )
By using the above-mentioned second polymerizable monomer, excellent low-temperature fixability, charge retention, and scratch resistance can be obtained.

Specifically, as the second polymerizable monomer, for example, the following polymerizable monomers can be used.
Monomer having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.
A monomer having a hydroxy group; for example, -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate and the like.
A monomer having an amide group; for example, acrylamide, an amine having 1 to 30 carbon atoms and a carboxylic acid having an ethylenically unsaturated bond having 2 to 30 carbon atoms (acrylic acid, methacrylic acid, etc.) are reacted by a known method. Monomer.
Monomers having urea groups: For example, amines having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (dinormal ethylamine, dinormal propylamine, di). Normal butylamine, etc.), aniline, cycloxylamine, etc.] and an isocyanate having an ethylenically unsaturated bond and having 2 to 30 carbon atoms are reacted by a known method.
Monomer having a carboxy group; for example, methacrylic acid, acrylic acid, -2-carboxyethyl (meth) acrylate.
Of these, it is preferable to use a monomer having a nitrile group, an amide group, a hydroxy group, a urea group, and a carboxy group. More preferably, it is a monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxy group, a urea group and a carboxy group and an ethylenically unsaturated bond. More preferably, it is methacrylic acid or acrylic acid.

As the second polymerizable monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caproate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, Vinyl esters such as vinyl pivalate and vinyl octylate are also preferably used. Among them, vinyl esters are non-conjugated monomers, and the reactivity with the first polymerizable monomer is easily maintained appropriately, and the crystallinity of the polymer is easily increased. Therefore, from the viewpoint of low temperature fixability. preferable.

The first resin may contain a third monomer unit different from the first monomer unit and the second monomer unit as long as the mass ratio of the first monomer unit is not impaired.

For example, the following monomers can be used.
Styrene, styrene such as o-methylstyrene and its derivatives, methyl (meth) acrylate, -n-butyl (meth) acrylate, -t-butyl (meth) acrylate, -2-ethylhexyl (meth) acrylate Such (meth) acrylic acid esters.
Among them, the third polymerizable monomer is preferably styrene. That is, the third monomer unit preferably has a structure derived from styrene. When the third polymerizable monomer is styrene, the aromatics of the first resin and the second resin interact with π-π. As a result, the phase separation between the crystalline resin and the wax is promoted, and the exudation of the wax at the time of fixing is ensured. Therefore, the surface layer of the fixed image is covered with the wax, and excellent scratch resistance can be obtained.
The first resin preferably contains the third monomer unit in an amount of 0.0% by mass to 70.0% by mass, more preferably 10.0% by mass to 50.0% by mass, and 30. It is more preferably contained in an amount of 0% by mass to 45.0% by mass.

The first resin, which is a crystalline resin, preferably has a weight average molecular weight (Mw) of tetrahydrofuran (THF) soluble content measured by gel permeation chromatography (GPC) of 10,000 or more and 200,000 or less, preferably 20,000. More preferably, it is 150,000 or less. When Mw is within the above range, elasticity near room temperature can be easily maintained.

The melting point of the first resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 53 ° C. or higher and 70 ° C. or lower. When the melting point of the first resin is within the above range, it exhibits better low-temperature fixability. The melting point of the first resin can be adjusted depending on the type and amount of the polymerizable monomer used.
The first resin is preferably a vinyl polymer. Examples of the vinyl polymer include a polymer of a monomer containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, and examples thereof include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

<Second resin>
The binder resin preferably contains a second resin, and the second resin is an amorphous resin.
Examples of the second resin include the following resins.
Monopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and its substitutions; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene -Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinylmethyl ether copolymer, styrene-vinyl ethyl ether Styrene-based copolymers such as copolymers, styrene-vinylmethylketone copolymers, styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, acrylic Examples thereof include resins, methacrylic resins, polyvinyl acetates, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpen resins, kumaron-inden resins, and petroleum resins.

Among these, it is charged that the second resin contains at least one selected from the group consisting of vinyl resins such as styrene copolymers, polyester resins, and hybrid resins in which vinyl resins and polyester resins are bonded. It is preferable from the viewpoint of start-up property. The bond includes, for example, a covalent bond. The second resin more preferably contains a polyester resin, and more preferably a polyester resin.
The polyester resin is preferably a condensed polymer of an alcohol component and a carboxylic acid component.

Polyhydric alcohol (divalent or trivalent or higher alcohol) and polyvalent carboxylic acid (divalent or trivalent) are used as the monomers used in the polyester resin and the polyester resin of the hybrid resin in which the vinyl resin and the polyester resin are bonded. The above carboxylic acid), its acid anhydride or its lower alkyl ester are used.

The following monomers can be used as the polyhydric alcohol monomer.
As the divalent alcohol component, a bisphenol derivative is preferable.
Examples of the bisphenol derivative include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane. , Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxy) Examples thereof include phenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane.

Other alcohol components include ethylene glycol, diethylene glycol, triolethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1, 5-Pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1 , 4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropantriol, 2-methyl-1,2, Examples thereof include 4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. , 1,2,5-pentantriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned.
Of these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These divalent alcohols and trihydric or higher alcohols can be used alone or in combination of two or more.

The following monomers can be used as the polyvalent carboxylic acid monomer.
Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebatic acid, azelaic acid, and malonic acid. n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and Examples thereof include these lower alkyl esters.
Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

Examples of the trivalent or higher valent carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. , 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimeric acid, acid anhydrides thereof or lower alkyl esters thereof.
Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof is preferably used because it is inexpensive and reaction control is easy. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination of two or more.

The method for producing the polyester is not particularly limited, and a known method can be used. For example, the above-mentioned alcohol monomer and carboxylic acid monomer are charged at the same time and polymerized through an esterification reaction, a transesterification reaction, and a condensation reaction to produce a polyester resin.
The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C. or higher and 290 ° C. or lower. When polymerizing the polyester unit, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used. In particular, the second resin is more preferably polyester polymerized using a tin-based catalyst.
The content of the second resin, which is an amorphous resin, in the binder resin is preferably 3.0% by mass or more, and more preferably 25.0% by mass or more. On the other hand, the upper limit is preferably 70.0% by mass or less, more preferably 50.0% by mass or less, and further preferably 40.0% by mass or less.
The peak molecular weight Mp of the second resin is preferably 3000 to 40,000, more preferably 5000 to 30000, and even more preferably 1000 to 25000.

<Crosslink>
The binder resin preferably contains a third resin. The third resin preferably contains a resin in which a first resin which is a crystalline resin and a second resin which is an amorphous resin are bonded, and a resin in which the first resin and the second resin are bonded. Is more preferable. The third resin preferably has, for example, a structure in which at least a part of the first resin and the second resin is bonded.
As a method of binding the first resin and the second resin, a method of cross-linking a mixture of the first resin and the second resin dissolved or melted with a radical initiator, a method of cross-linking the first resin and the second resin, and the first resin and the second resin. Examples thereof include a method of cross-linking using a cross-linking agent having a functional group that reacts with both of the second resins.
The radical initiator used in the method of cross-linking with a radical initiator is not particularly limited, and examples thereof include inorganic peroxides, organic peroxides, and azo compounds. Moreover, you may use these radical reaction initiators together.

When both the first resin and the second resin have carbon-carbon unsaturated bonds, they are cleaved and the first resin and the second resin are crosslinked. Further, even when one or both of the first resin and the second resin do not have a carbon-carbon unsaturated bond, hydrogen bonded to a carbon atom contained in the first resin and / or the second resin. Both are crosslinked by pulling out the atom. In this case, it is more preferable to use an organic peroxide having a high hydrogen abstraction ability as the radical initiator.
The cross-linking agent having a functional group that reacts with both the first resin and the second resin is not particularly limited, and known ones can be used, for example, a cross-linking agent having an epoxy group and an isocyanate group. Examples thereof include a cross-linking agent, a cross-linking agent having an oxazoline group, a cross-linking agent having a carbodiimide group, a cross-linking agent having a hydrazide group, and a cross-linking agent having an aziridine group.

In the method of cross-linking using a cross-linking agent having a functional group that reacts with both the first resin and the second resin, both the first resin and the second resin need to have a functional group that reacts with the cross-linking agent. There is.
A resin in which at least a part of the first resin and the second resin crosslinked by the above method are bonded (that is, the first resin and the second resin are crosslinked with the third resin, the first resin, and the second resin. A resin composition containing a resin) can be used in the production of toner.
Further, when the toner is produced by the melt-kneading method, the first resin and the first resin are kneaded by melt-kneading the raw material mixture containing the first resin and the second resin in the presence of the radical initiator or the cross-linking agent. It is also possible to produce toner particles containing a resin in which the second resin is bonded.

For example, as the third resin, an amorphous reaction initiator is added while melt-kneading the amorphous polyester resin having a carbon-carbon double bond, which is the second resin, and the crystalline resin, which is the first resin. A resin obtained by carrying out a cross-linking reaction is preferable.
By producing the third resin using the first resin and the second resin, at least a part of the first resin and the second resin is bonded to form the third resin. By doing so, a binder resin containing the first resin, the second resin and the third resin can be obtained.
By binding at least a part of the first resin and the second resin, a binder resin containing the first resin, the second resin and the third resin may be obtained. A third resin may be separately produced and mixed with the first resin and the second resin to obtain a binder resin.
The content of the third resin in the binder resin is preferably 1.0% by mass to 20.0% by mass, and more preferably 5.0% by mass to 15.0% by mass.

The radical reaction initiator used for the above-mentioned cross-linking reaction is not particularly limited, and examples thereof include inorganic peroxides, organic peroxides, and azo compounds. Moreover, you may use these radical reaction initiators together.
The inorganic peroxide is not particularly limited, and examples thereof include hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

The organic peroxide is not particularly limited, and is, for example, benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α-bis (t-butyl peroxy). Diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexylperoxide, 2,5-dimethyl-2,5-di-t-butylperoxy Hexin-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t-butylper Oxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate Examples thereof include noate, t-butylperoxylaurate, t-butylperoxybenzoate, t-butylperoxyisopropyl monocarbonate and t-butylperoxyacetate.
The azo compound and the diazo compound are not particularly limited, and are, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis. (Cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like can be mentioned.

Of these, organic peroxides are preferred because they have high initiator efficiency and do not produce toxic by-products such as cyanides.
Further, since the cross-linking reaction proceeds efficiently and the amount used is small, a reaction initiator having a high hydrogen abstraction ability is more preferable, and t-butylperoxyisopropyl monocarbonate, benzoylper oxide, and di-t-butylper are preferable. Oxide, t-butylcumylper oxide, dicumylperoxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane and A radical reaction initiator having a high hydrogen abstraction ability such as di-t-hexylperoxide is more preferable.
The amount of the radical reaction initiator used is not particularly limited, but is preferably 0.1 part by mass to 50 parts by mass, and more preferably 0.2 part by mass to 5 parts by mass with respect to 100 parts by mass of the binder resin to be crosslinked.

<Wax>
Examples of the wax include the following.
Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystallin wax, paraffin wax, Fishertropch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof. Waxes whose main component is a fatty acid ester such as carnauba wax; deoxidized A part or all of a fatty acid ester such as carnauba wax is deoxidized.
In addition, the following can be mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid, and varinaric acid; , Saturated alcohols such as melisyl alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol , Esters with alcohols such as ceryl alcohol, melisyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislaurin Saturated fatty acid bisamides such as acid amides and hexamethylene bisstearic acid amides; ethylene bisoleic acid amides, hexamethylene bisoleic acid amides, N, N'diorail adipate amides, N, N'diorail sebasic acid amides Unsaturated fatty acid amides such as: m-xylene bisstearic acid amide, aromatic bisamides such as N, N'dystearyl isophthalic acid amide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate. Aliphatic metal salts (generally called metal soap); waxes obtained by grafting aliphatic hydrocarbon wax with vinyl monomer such as styrene or acrylic acid; fatty acids such as behenic acid monoglyceride Partial esterified product of polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable fats and oils.
Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax are preferable from the viewpoint of scratch resistance.
The wax content is preferably 2.0 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

<Colorant>
The toner may contain a colorant, if necessary. Examples of the colorant include the following.
Examples of the black colorant include those that have been toned to black using carbon black; a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, the pigment may be used alone, or the dye and the pigment may be used in combination. From the viewpoint of the image quality of a full-color image, it is preferable to use a dye and a pigment together.
Examples of the magenta toner pigment include the following. C. 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: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112
, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; 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, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following. C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalocyanine groups are substituted in the phthalocyanine skeleton.
Examples of the cyan toner dye include C.I. I. Solvent blue 70 can be mentioned.
Examples of the pigment for yellow toner include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. I. Bat Yellow 1, 3, 20.
Examples of the dye for yellow toner include C.I. I. Solvent Yellow 162 can be mentioned.
These colorants can be used alone or in admixture, and even in the form of a solid solution. The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the colorant is preferably 0.1 part by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

<Charge control agent>
The toner particles may contain a charge control agent, if necessary. By blending a charge control agent, it is possible to stabilize the charge characteristics and control the optimum triboelectric charge amount according to the developing system.
As the charge control agent, known ones can be used, but in particular, a metal compound of an aromatic carboxylic acid, which is colorless, has a high charging speed of toner, and can stably maintain a constant charge amount, is preferable.
The negative charge control agent has a metal salicylate compound, a metal naphthoate compound, a metal dicarboxylic acid compound, a polymer compound having a sulfonic acid or a carboxylic acid in the side chain, a sulfonate or a sulfonic acid esterified product in the side chain. Examples thereof include a high molecular weight compound, a high molecular weight compound having a carboxylate or a carboxylic acid esterified product in a side chain, a boron compound, a urea compound, a silicon compound, and a calix array.
The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 parts by mass to 10.0 parts by mass, and more preferably 0.5 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the binder resin.

<Inorganic fine particles>
The toner may contain inorganic fine particles, if necessary.
The inorganic fine particles may be internally added to the toner particles, or may be mixed with the toner as an external additive. Examples of the inorganic fine particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, and their double oxide fine particles. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable for improving fluidity and homogenizing charge.
The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.
From the viewpoint of improving the fluidity, the inorganic fine particles as an external additive preferably has a specific surface area of ^{50m 2} / ^g~400m 2 / g. Further, from the viewpoint of improving the running stability, inorganic fine particles as an external additive preferably has a specific surface area of ^{10m 2} / ^g~50m 2 / g. Inorganic fine particles having a specific surface area in the above range may be used in combination in order to achieve both improved fluidity and durability stability.
The content of the external additive is preferably 0.1 part by mass to 10.0 parts by mass with respect to 100 parts by mass of the toner particles. A known mixer such as a Henschel mixer can be used for mixing the toner particles and the external additive.

<Developer>
Toner can also be used as a one-component developer, but it is used as a two-component developer by mixing with a magnetic carrier in order to further improve dot reproducibility and to supply a stable image for a long period of time. Is preferable.
Examples of the magnetic carrier include iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth, their alloy particles, and their oxide particles; A generally known material such as a magnetic material such as ferrite; a magnetic material-dispersed resin carrier containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state (so-called resin carrier); can be used.
When the toner is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carriers at that time may be 2% by mass to 15% by mass as the toner concentration in the two-component developer. It is preferably, more preferably 4% by mass to 13% by mass or less.

<Toner manufacturing method>
The method for producing the toner is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion agglutination method, and a dispersion polymerization method can be used.
Hereinafter, the toner manufacturing procedure by the pulverization method will be described.

In the raw material mixing step, other components such as a binder resin, wax, and if necessary, a colorant, a charge control agent, and the like are weighed and mixed in a predetermined amount as materials constituting the toner particles. Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.) and the like.

Next, the mixed materials are melt-kneaded to disperse wax and the like in the binder resin. In the melt-kneading process, batch-type kneaders such as pressure kneaders and Bambary mixers and continuous-type kneaders can be used, and single-screw or twin-screw extruders are the mainstream because of the advantage of continuous production. It has become.
For example, KTK type twin-screw extruder (manufactured by Kobe Steel), TEM type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Iron Works), twin-screw extruder (manufactured by KTK). ), Co-kneader (manufactured by Bus Co., Ltd.), Kneedex (manufactured by Nippon Coke Industries Co., Ltd.), etc. Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

Then, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the crushing process, after coarse crushing with a crusher such as a crusher, a hammer mill, or a feather mill, further, for example, a cryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo Finely crush with a mill (manufactured by Turbo Industries) or an air jet type crusher.

After that, if necessary, inertial classification type elbow jet (manufactured by Nittetsu Mining Co., Ltd.), centrifugal force classification type turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), faculty (manufactured by Hosokawa Micron), etc. Classify using a classifier or sieve.
Further, if necessary, the surface of the toner particles is externally treated with an external additive. As a method of externally adding an external additive, a predetermined amount of classified toner and various known external additives are mixed, and a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano are used. Examples thereof include a method of stirring and mixing using a mixing device such as a hybrid (manufactured by Nippon Coke Industries Co., Ltd.) or Nobilta (manufactured by Hosokawa Micron Co., Ltd.) as an external mixer.

A method for measuring various physical properties of toner particles and raw materials will be described below.
(Method of separating each material from toner)
Each material can be separated from the toner by utilizing the difference in the solubility of each material contained in the toner in a solvent.
First separation: Toner is dissolved in methyl ethyl ketone (MEK) at 23 ° C. to separate soluble (second resin) and insoluble (first resin, wax, colorant, inorganic fine particles, etc.).
Second separation: Insoluble components (first resin, wax, colorant, inorganic fine particles, etc.) obtained by the first separation are dissolved in MEK at 100 ° C. to dissolve soluble components (first resin, wax). Separate insoluble components (colorants, inorganic fine particles, etc.).
Third separation: The soluble component (first resin, wax) obtained by the second separation is dissolved in chloroform at 23 ° C, and the soluble component (first resin) and insoluble component (wax) are separated. ..

(When a third resin is included)
First separation: Toner is dissolved in methyl ethyl ketone (MEK) at 23 ° C, and soluble components (second resin, third resin) and insoluble components (first resin, wax, colorant, inorganic fine particles, etc.) are separated. To separate.
Second separation: The soluble component (second resin, third resin) obtained by the first separation is dissolved in toluene at 23 ° C, and the soluble component (third resin) and insoluble component (second resin) are dissolved. Resin) is separated.
Third separation: Insoluble components (first resin, wax, colorant, inorganic fine particles, etc.) obtained by the first separation are dissolved in MEK at 100 ° C. to dissolve soluble components (first resin, wax). Separate insoluble components (colorants, inorganic fine particles, etc.).
Fourth separation: Dissolve the soluble component (first resin, wax) obtained in the third separation in chloroform at 23 ° C, and separate the soluble component (first resin) and insoluble component (wax). ..

<Measuring method of the content ratio of each monomer unit in the first resin>
The content ratio of each monomer unit in the first resin is measured by ¹ H-NMR under the following conditions.
Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Number of integrations: 64 times Measurement temperature: 30 ° C
Sample: 50 mg of the measurement sample is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare the sample.
From the obtained ¹ H-NMR chart, from the peaks attributed to the components of the first monomer unit, peaks independent of the peaks attributed to the components of the monomer unit derived from other sources were selected. calculating the integral values S ₁ for the peak.
Similarly, among the peaks attributed to the components of the second monomer unit, to select the independent peaks and peak attributable to the components of the monomer units derived from another, the integrated value S ₂ of the peak Is calculated.
Furthermore, when the first resin has a third monomer unit, the peaks attributed to the components of the third monomer unit are independent of the peaks attributed to the components of the monomer unit derived from other sources. select peaks, calculates an integrated value S ₃ of the peak.
The content ratio of the first monomer unit is determined as follows using _{the above integrated values S 1} , S ₂ and S _3. In addition, n ₁ , n ₂ , and n ₃ are the number of hydrogens in the component to which the peak focused on each site is assigned.
Content ratio of the first monomer unit (mol%) =
{(S ₁ / n ₁ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} x 100
Similarly, the content ratios of the second monomer unit and the third monomer unit are determined as follows.
Content ratio of the second monomer unit (mol%) =
{(S ₂ / n ₂ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} × 100
Content ratio of the third monomer unit (mol%) =
{(S ₃ / n ₃ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} x 100
When a polymerizable monomer containing no hydrogen atom is used in the constituent elements other than the vinyl group in the first resin, the measurement nucleus is set to ^{13 C by using 13} C-NMR, and a single pulse is used. Measure in mode ^{and calculate in 1} H-NMR in the same way.

<Calculation method of SP value>
The SP value such as SP _{21 is obtained} as follows according to the calculation method proposed by Fedors.
For each polymerizable monomer or wax, for atoms or atomic groups in the molecular structure, the evaporation energy from the table described in "Polym. Eng. Sci., 14 (2), 147-154 (1974)". Obtain (Δei) (cal / mol) and molar volume (Δvi) (cm ³ / mol), and set (4.184 × ΣΔei / ΣΔvi) ^0.5 as the SP value (J / cm ³ ) ^0.5 .
SP ₂₁ is calculated by the same calculation method as above for an atom or an atomic group having a molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization.
SP _C is determined evaporation energy (.DELTA.ei) and molar volume of the monomer unit derived from a polymerizable monomer constituting the ([Delta] Vi) per monomer unit, the mole ratio of the first resin in each monomer unit and (j) The product is calculated by dividing the total evaporation energy of each monomer unit by the total molar volume, and is calculated by the following formula.
_{SP C = {4.184 × (Σj} × ΣΔei) / (Σj × ΣΔvi)} 0.5

<Measurement of resin weight average molecular weight by GPC>
The peak molecular weight and weight average molecular weight (Mw) of the THF-soluble components of the first resin and the second resin and other resins are measured by gel permeation chromatography (GPC) as follows.
First, the sample is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Columns: Shodex KF-801, 802, 803, 804, 805, 806,
7 stations of 807 (manufactured by Showa Denko)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) is used.

<Measurement of number average molecular weight Mn and weight average molecular weight Mw of wax by GPC>
The number average molecular weight and the weight average molecular weight of the wax are measured by gel permeation chromatography (GPC) as follows. Special grade 2,6-di-t-butyl-4-methylphenol (BHT) is added to o-dichlorobenzene for gel chromatograph so as to have a concentration of 0.10% by mass / volume, and the mixture is dissolved at room temperature.
Wax and o-dichlorobenzene to which the above BHT is added are placed in a sample bottle and heated on a hot plate set at 150 ° C. to dissolve the release agent. When the release agent has melted, put it in a preheated filter unit and install it in the main body. A GPC sample that has passed through the filter unit is used. The sample solution is adjusted so that the concentration is 0.15% by mass. This sample solution is used for measurement under the following conditions.
・ Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
・ Detector: RI for high temperature
-Column: TSKgel GMHHR-HHT 2 stations (manufactured by Tosoh)
・ Temperature: 135.0 ℃
-Solvent: o-dichlorobenzene for gel chromatograph (BHT 0.10 mass / volume% added)
-Flow velocity: 1.0 ml / min
・ Injection amount: 0.4 ml
In calculating the molecular weight of the wax, standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-" 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) is used.
(When measuring from toner)
Wax is separated from the insoluble matter (wax) obtained by the above separation method by utilizing the difference in melting point. Specifically, by melting the insoluble matter at the temperature of the valley of the 1st peak and the 2nd peak, only the wax derived from the 1st peak is melted, so that the wax derived from the 2nd peak can be separated.

<Measurement method of acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.
(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it 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 that 25 mL of 0.1 mol / L hydrochloric acid was placed in a triangular flask, several drops of the phenolphthaline solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS K 8001-1998 are used.
(2) Operation (A) Main test 2.0 g of the crushed sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that a sample is not used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: mass (g) of sample.

<Method of measuring peak top temperature of heat absorption peak measured by differential scanning calorimetry (DSC) of crystalline resin, method of measuring peak top temperature in temperature differential distribution of heat absorption peak measured by DSC of wax, and toner Method for measuring peak top temperature of 1st peak and 2nd peak derived from wax in the temperature differential distribution of heat absorption peak measured by DSC>
These peak top temperatures are measured according to ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments).
The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, about 3 mg of a sample (crystalline resin, wax or toner) is precisely weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference.
Temperature rise rate: 10 ° C / min
Measurement start temperature: 30 ° C
Measurement end temperature: 180 ° C
The measurement is performed at a heating rate of 10 ° C./min in the measurement range of 30 to 180 ° C. The temperature is once raised to 180 ° C. and held for 10 minutes, then lowered to 30 ° C., and then the temperature is raised again.
When a crystalline resin is used as a sample, the peak top temperature of the crystalline resin is calculated from the temperature-heat absorption curve in the temperature range of 30 ° C. to 80 ° C. in the second temperature raising process.
When wax is used as a sample, the peak top temperature is calculated from a curve obtained by differentiating the temperature-heat absorption curve in the temperature range of 30 ° C. to 140 ° C. with respect to temperature.
When toner is used as the sample, the peak top temperature of the 1st peak and the 2nd peak derived from the wax is calculated from the curve obtained by differentiating the temperature-heat absorption curve in the temperature range of 30 ° C. to 140 ° C. with respect to temperature. In addition, the heights of the valleys of the 1st peak and the 2nd peak are also calculated.
(Confirmation of whether the 1st peak and 2nd peak are derived from wax)
By confirming the peak top temperature in the temperature differential distribution of the endothermic peak measured by DSC of the insoluble matter (wax) obtained by the above separation method, it can be determined whether or not the wax is wax.

(Toner cross-section observation and matrix / domain analysis method)
First, a flakes that serve as a reference sample for abundance are prepared.
After the first resin, which is a crystalline resin, is sufficiently dispersed in a visible light curable resin (Aronix LCR series D800), it is cured by irradiating it with short wavelength light. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a flaky sample of 250 nm. Similarly, a flaky sample is prepared for the second resin, which is an amorphous resin.
Further, the first resin and the second resin are mixed at 0/100, 30/70, 70/30, and 0/100 on a mass basis to prepare a kneaded product by melting and kneading. Similarly, these are also dispersed in a visible light-curable resin, cured, and then cut out to prepare a flaky sample.
Next, the cut-out samples are observed in cross sections of these reference samples using a transmission electron microscope (electron microscope JEM-2800 manufactured by JEOL Ltd.) (TEM-EDX), and element mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen.
The mapping conditions are as follows.
Acceleration voltage: 200kV
Electron beam irradiation size: 1.5 nm
Live time limit: 600sec
Dead time: 20-30
Mapping resolution: 256 x 256

Calculate (oxygen element intensity / carbon element intensity) and (nitrogen element intensity / carbon element intensity) based on the spectral intensity (average in an area of 10 nm square) of each element, and calculate the first resin and the second resin. Create a calibration line for the mass ratio of. If the monomer unit of the first resin contains nitrogen atoms, the calibration curve of (nitrogen element strength / carbon element strength) will be used for future quantification.
Next, the toner sample is analyzed.
After the toner is sufficiently dispersed in the visible light curable resin (Aronix LCR series D800), it is cured by irradiating it with short wavelength light. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a flaky sample of 250 nm. Next, the cut-out sample is observed using a transmission electron microscope (electron microscope JEM-2800 manufactured by JEOL Ltd.) (TEM-EDX). A cross-sectional image of the toner particles is acquired, and element mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen.
The toner cross section to be observed is selected as follows. First, the cross-sectional area of the toner is obtained from the toner cross-sectional image, and the diameter of a circle having an area equal to the cross-sectional area (circle equivalent diameter) is obtained. Only the toner cross-sectional image in which the absolute value of the difference between the equivalent circle diameter and the weight average particle size (D4) of the toner is within 1.0 μm is observed.
For the domain confirmed by the observation image, (oxygen element intensity / carbon element intensity) and / or (nitrogen element intensity / carbon element intensity) are calculated based on the (10 nm square average) spectral intensity of each element. The ratio of the first resin to the second resin is calculated by comparing with the calibration line. The domain in which the ratio of the second resin is 80% or more is defined as the domain of the present disclosure.
After identifying the domain confirmed by the observation image, the particle size of the domain existing in the toner cross section is determined by the binarization process. The particle size is the major axis of the domain. This is measured at 10 points per toner, and the arithmetic mean value of the domains of 10 toners is defined as the number average diameter of the domains. Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) is used for the binarization process.

(Measurement of the contents of the first resin and the second resin in the binder resin in the toner)
In each separation step obtained by the above separation, the contents of the first resin and the second resin in the binder resin in the toner are calculated by measuring the masses of the soluble component and the insoluble component.

(Measurement of wax content in toner)
By measuring the mass of soluble and insoluble matter in each separation step obtained by the above separation,
Calculate the wax content in the toner.

Hereinafter, the present invention will be specifically described with reference to Examples, but these are not intended to limit the present invention in any way. In the following formulations, parts are based on mass unless otherwise specified.

<Production example of crystalline resin A1>
-Solvent: 100.0 parts of toluene-100.0 parts of monomer composition (The monomer composition shall be a mixture of behenyl acrylate, acrylonitrile, and styrene in the following proportions).
(Behenyl acrylate (first polymerizable monomer): 55.00 parts (24.51 mol%))
(Acrylic acid (second polymerizable monomer): 3.00 parts (7.06 mol%))
(Styrene (third polymerizable monomer): 42.00 parts (68.42 mol%))
-Initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV): 0.5 part In a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube, under a nitrogen atmosphere, the above The material was put in. The inside of the reaction vessel was stirred at 200 rpm and heated to 70 ° C. for 12 hours to carry out a polymerization reaction to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the temperature of the solution was lowered to 25 ° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the insoluble methanol. The obtained methanol-insoluble matter was filtered off, washed with methanol, and vacuum dried at 40 ° C. for 24 hours to obtain a crystalline resin A1. The weight average molecular weight Mw of the crystalline resin A1 was 30,000, the peak top temperature of the temperature-heat absorption curve was 61 ° C., and the acid value Av was 23.4 mgKOH / g.
When the above crystalline resin A1 was analyzed by NMR, it contained 24.51 mol% of a monomer unit derived from behenyl acrylate, 7.06 mol% of a monomer unit of acrylic acid, and 68.42 mol% of a monomer unit derived from styrene. It was. _{The SP value (SP c} ) of the unit derived from the polymerizable monomer was calculated by the above method.

<Production example of crystalline resins A2 to A12>
In the production example of the crystalline resin A1, the reaction was carried out in the same manner except that the respective polymerizable monomers and the number of copies were changed so as to be shown in Table 1, to obtain crystalline resins A2 to A12. The physical characteristics are shown in Tables 2 and 3.
The crystalline resins A2 to A12 also contained each monomer unit having the same ratio as that used, similarly to the crystalline resin A1.

表１〜表３中の略号は以下の通り。
ＢＥＡ：ベヘニルアクリレート
ＳＴＡ：ステアリルアクリレート
ＭＹＡ：ミリシルアクリレート
ＨＡ：ヘキサデシルアクリレート
ＡＡ：アクリル酸
Ｓｔ：スチレン

The abbreviations in Tables 1 to 3 are as follows.
BEA: Behenyl Acrylate STA: Stearyl Acrylate MYA: Millicyl Acrylate HA: Hexadecyl Acrylate AA: Acrylic Acid St: Styrene

<Production example of amorphous polyester resin P1>
-Bisphenol A / propylene oxide adduct (average number of moles added 2.0):
78.00 copies (47.19 mol%)
Fumaric acid: 22.00 parts (52.81 mol%)
-Titanium tetrabutoxide (esterification catalyst): 0.5 parts The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was carried out for 5 hours while maintaining the temperature at 200 ° C., and after confirming that the softening point measured according to ASTM D36-86 reached the temperature of 140 ° C. The temperature was lowered to stop the reaction, and an amorphous polyester resin P1 was obtained. The obtained amorphous polyester resin P1 had a peak molecular weight Mp of 20000, a softening point Tm of 140 ° C., and an acid value Av of 11.3 mgKOH / g.
When the amorphous polyester resin P1 was analyzed by NMR, the monomer unit derived from polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane was 47.19 mol%, and the monomer derived from fumaric acid was obtained. The unit contained 52.81 mol%.

<Production example of amorphous polyester resins P2 to P5>
In the production example of the amorphous polyester resin P1, the reaction was carried out in the same manner except that the respective polymerizable monomers and the number of copies were changed as shown in Table 4, to obtain amorphous polyester resins P2 to P5. The physical characteristics are shown in Table 4.
Amorphous polyester resins P2 to P5 also contained each monomer unit in the same proportion as used, similar to amorphous polyester resin P1.

表４中の略号は以下の通り。
ＰＯ２：ビスフェノールＡ・プロピレンオキシド付加物（平均付加モル数２．０）
ＦＡ：フマル酸

The abbreviations in Table 4 are as follows.
PO2: Bisphenol A / propylene oxide adduct (average number of moles added 2.0)
FA: Fumaric acid

<Production example of amorphous hybrid resin>
(Polyester resin prescription)
-Bisphenol A / propylene oxide adduct (average number of moles added 2.0):
52.00 parts (50.20 mol%)
Fumaric acid: 13.00 parts (49.80 mol%)
-Titanium tetrabutoxide (esterification catalyst): 0.5 part The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple. Next, the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.
-Styrene: 33.70 parts (94.72 mol%)
-Acrylic acid: 1.30 parts (5.28 mol%)
-Polymerization initiator t-Butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 0.5 part The vinyl-based monomer was added dropwise from the dropping funnel over 4 hours and reacted at 160 ° C. for 5 hours. .. After that, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was carried out for 1 hour while maintaining the temperature at 200 ° C., and after confirming that the softening point measured according to ASTM D36-86 reached the temperature of 140 ° C. The temperature was lowered to stop the reaction, and an amorphous hybrid resin was obtained.
The obtained amorphous hybrid resin had a peak molecular weight of 20000, a softening point of 140 ° C., and an acid value of 10.1 mgKOH / g.

<Production example of amorphous vinyl resin>
-Solvent: 100.0 parts of xylene-Styrene: 61.00 parts (65.23 mol%)
-N-Butyl acrylate: 37.70 parts (32.76 mol%)
-Acrylic acid: 1.30 parts (2.01 mol%)
-Initiator of polymerization t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 0.5 part In a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube, the above materials are placed in a nitrogen atmosphere. Was put in. The inside of the reaction vessel was heated to 185 ° C. while stirring at 200 rpm, and the polymerization reaction was carried out for 10 hours. Subsequently, the solvent was removed and vacuum dried at 40 ° C. for 24 hours to obtain an amorphous vinyl resin.
The obtained amorphous vinyl resin had a peak molecular weight of 20000, a softening point of 140 ° C., and an acid value of 10.1 mgKOH / g.

<Production example of binder resin 1>
・ Crystalline resin A1: 60.0 parts ・ Amorphous polyester resin P1: 40.0 parts Weigh and mix the above materials and supply them to a biaxial kneader (manufactured by Kurimoto Iron Works, S5KRC kneader) at 1 kg / H. At the same time, 4.0 parts of t-butylperoxyisopropyl monocarbonate was supplied as a radical reaction initiator at 0.1 kg / H and kneaded and extruded at 160 ° C. for 5 minutes at 100 rpm to carry out the reaction. Further, nitrogen was flowed from the bentro, and the mixture was mixed while removing the organic solvent. The binder resin 1 was obtained by cooling what was obtained by mixing. By GPC measurement, it was confirmed that the crystalline resin A1 and the amorphous polyester resin P1 partially reacted to increase the molecular weight.

<Production example of binder resin 2-22>
In the production example of the binder resin 1, the reaction was carried out in the same manner except that the type and number of copies of each crystalline resin, the type and number of copies of the amorphous polyester resin, and the presence or absence of the radical reaction initiator were changed as shown in Table 5. , And the binder resin 2 to 22 was obtained.
For the binder resins 2, 3, 5 to 22, it was confirmed by GPC measurement that the crystalline resin and the amorphous resin partially reacted and the molecular weight increased.

表５中の略号は以下の通り。
Ｈｙｂ：非晶性ハイブリッド樹脂
Ｖｉｎｙｌ：非晶性ビニル系樹脂

The abbreviations in Table 5 are as follows.
Hybrid: Amorphous hybrid resin Vinyl: Amorphous vinyl resin

<Production example of wax 1>
Hydrocarbons were synthesized using synthetic gas as a raw material using an iron catalyst. 50 ml of n-hexadecane as a solvent and 3 g of the above iron-based catalyst were charged into a continuous stirring slurry bed reactor having a capacity of 100 ml. First, a reduction treatment was performed. The reduction conditions are as follows.
Reduction gas: Syngas (H ₂ / CO = 1)
Iron catalyst: 3g
Gas flow velocity: 150 cc / min
Temperature: 300 ° C
Pressure: 0.5 MPa
Next, wax 1 was obtained by purifying the hydrocarbon compound obtained by carrying out the Fischer-Tropsch reaction. The reaction conditions are as follows.
Reaction gas: Syngas (H ₂ / CO = 1)
Iron catalyst: 3g
Gas flow velocity: 150 cc / min
Temperature: 260 ° C
Pressure: 2.0 MPa
The weight average molecular weight Mw of the obtained wax 1 was 600, Mw / Mn was 1.3, and the peak top temperature of the curve obtained by differentiating the temperature-heat absorption curve with temperature was 92.0 ° C.

<Production example of waxes 2 to 12>
In the production example of wax 1, the reaction was carried out in the same manner except that the purification conditions were changed so as to have the physical characteristics shown in Table 5, to obtain waxes 2 to 12.

<Manufacturing example of toner 1>
-Bundling resin 1: 83.0 parts-Wax 1: 5.0 parts-Wax 6: 2.0 parts-Colorant (Cyan pigment Dainichiseika: Pigment Blue 15: 3):
10.0 parts A biaxial kneader (PCM) set at a temperature of 150 ° C. after mixing the above materials with a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 1500 rpm and a rotation time of 3 min. Kneaded with -30 type, manufactured by Ikekai Co., Ltd.). The obtained kneaded product was cooled and roughly pulverized to 1 mm or less with a hammer mill.
The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, using Faculti (F-300, manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 1. The operating conditions were a classification rotor rotation speed of 11000 rpm and a distributed rotor rotation speed of 7200 rpm.
-Toner particles 1: 100.0 parts-Silica fine particles A: Fumed silica surface-treated with silicone oil (Median diameter (D50) on a number basis is 120 nm) 4.0 parts The above material is a Henschel mixer (FM-75 type, FM-75 type, Toner 1 exhibiting negative chargeability was obtained by mixing with Mitsui Miike Machinery Co., Ltd. at a rotation speed of 1900 rpm and a rotation time of 10 min.
In toner 1, there was a 2nd peak adjacent to the 1st peak and having a peak top temperature higher than the 1st peak in the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry (DSC). The height of the valleys of the 1st peak and the 2nd peak was larger than 0 W / (g · ° C). Peak top temperature of 2nd peak was 107 ° C., a peak top temperature of the 1st peak is 92.0 ° C., the change _{T-T S} peak top temperature was 0.0 ° C..

<Manufacturing example of toners 2 to 44>
In the production example of toner 1, the same as the production example of toner 1 except that the type and addition amount of the binder resin, the type and addition amount of wax, and the type of the treatment agent for silica fine particles are changed as shown in Table 7. Toners 2 to 44 were obtained. Table 7 shows the physical characteristics of the obtained toner.
When the cross-section of the obtained toner was observed, in the toners 1 to 40 and 42 to 44, in the matrix containing the first resin which is a crystalline resin and the domain containing the second resin which is an amorphous resin. A structured domain matrix structure was seen.
On the other hand, in the toner 41, a domain matrix structure composed of a matrix containing the second resin and a domain containing the first resin was observed.

表中、Ｓｉｏｉｌはシリコーンオイルを示し、ＨＭＤＳはヘキサメチルジシラザンを示す。

In the table, Sioil indicates silicone oil, and HMDS indicates hexamethyldisilazane.

<Manufacturing example of magnetic carrier 1>
-Magnetite 1 with a number average particle size of 0.30 μm and (magnetization strength of 65 Am ^{2 / kg under a magnetic field of 1000 / 4π (kA / m))
-Magnetite 2 with a} number average particle size of 0.50 μm and (magnetization strength of 65 Am 2 / kg under a magnetic field of 1000 / 4π (kA / m))
4.0 parts of a silane compound (3- (2-aminoethylaminopropyl) trimethoxysilane) was added to 100 parts of each of the above materials, and the mixture was mixed and stirred at 100 ° C. or higher in a container at high speed, and each fine particle was mixed. Was processed.
・ Phenol: 10% by mass
・ Formaldehyde solution: 6% by mass
(40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water)
-Magnetite treated with the above silane compound: 58% by mass
-Magnetite treated with the above silane compound: 26% by mass
100 parts of the above material, 5 parts of a 28 mass% aqueous ammonia solution, and 20 parts of water are placed in a flask, and the temperature is raised to 85 ° C. in 30 minutes while stirring and mixing, and the mixture is held for 3 hours to carry out a polymerization reaction to produce the product. The phenolic resin was cured.
Then, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60 ° C. to obtain a magnetic material-dispersed spherical magnetic carrier 1. The volume-based 50% particle size (D50) was 34.21 μm.

<Production example of two-component developer 1>
92.0 parts of the magnetic carrier 1 and 8.0 parts of the toner 1 were mixed by a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a two-component developer 1.

<Production example of two-component developer 2-44>
In the production example of the two-component developer 1, the same operation was performed except that the toner was changed as shown in Table 8, to obtain the two-component developer 2-44.

<Example 1>
Evaluation was performed using the above-mentioned two-component developer 1.
As an image forming apparatus, a Canon digital commercial printing printer imageRUNNER ADVANCE C5560 remodeling machine was used, and the two-component developer 1 was put into a cyan-position developer.
The modification points of the device were changed so that the fixing temperature, process speed, DC voltage V _{DC of the developer carrier, charging voltage V D} of the electrostatic latent image carrier, and laser power could be set freely. Image output evaluation outputs FFh image (solid image) of a desired image ratio, V _DC as the toner amount on the FFh image in paper is _desired, by adjusting the _V D and laser _power, The evaluation described later was performed.
FFh is a value obtained by displaying 256 gradations in hexadecimal, 00h is the first gradation of 256 gradations (white background portion), and FFh is the 256th gradation of 256 gradations (solid portion). ..
Evaluation is based on the following evaluation methods, and the results are shown in Table 9.

[Scratch resistance]
Paper: Image Coat Gloss 158 (158.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.05 mg / cm ² (2Fh image)
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 3 m x 15 cm is placed in the center of the above A4 paper. Fixing test environment: Room temperature and humidity environment (temperature 23 ° C / humidity 50% RH (hereinafter N / N))
Fixing temperature: 180 ° C
Process speed: 377 mm / sec
The above evaluation image was output and the scratch resistance was evaluated. The value of the difference in reflectance was used as an evaluation index for scratch resistance.
First, a Gakushin type friction fastness tester (AB-301: manufactured by Tester Sangyo Co., Ltd.) was used to apply a load of 0.5 kgf to the image part of the evaluation image, and friction (10 reciprocations) with a new evaluation paper. ). After that, using a reflect meter (REFLECTOMTER MODEL TC-6DS: manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the rubbed portion and the reflectance of the non-friction portion are measured.
Then, the difference in reflectance before and after friction was calculated using the following formula. The difference in the obtained reflectance was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was judged to be good.
Reflectance difference = Reflectance of non-friction part-Reflectance of friction part (evaluation standard)
A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 3.0% D: 3.0% or more

[Charge retention rate in high temperature and high humidity environment]
Paper: GFC-081 (81.0 g / m ² ) (Canon Marketing Japan Inc.) Amount of toner on paper: 0.35 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 2 cm x 5 cm is placed in the center of the above A4 paper. Fixing test environment: High temperature and high humidity environment: Temperature 30 ° C / Humidity 80% RH (hereinafter "H / H")
Process speed: 377 mm / sec
The triboelectric charge of the toner was calculated by suction-collecting the toner on the electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter. Specifically, the triboelectric charge of the toner on the electrostatic latent image carrier was measured by a Faraday-Cage.
A Faraday cage is a coaxial double cylinder, and the inner cylinder and outer cylinder are insulated. If a charged body having a charge amount of Q is placed in this inner cylinder, it is as if a metal cylinder having a charge amount Q exists due to electrostatic induction. This induced charge amount is measured with an electrometer (Kesley 6517A, manufactured by Kessley Co., Ltd.), and the toner mass (kg) in the inner cylinder divided by the charge amount Q (mC) (Q / M) is the triboelectric charge of the toner. The amount was taken.
Triboelectric charge of toner (mC / kg) = Q / M
First, the evaluation image is formed on the electrostatic latent image carrier, the rotation of the electrostatic latent image carrier is stopped before the image is transferred to the intermediate transfer body, and the toner on the electrostatic latent image carrier is applied to the metal. [Initial Q / M] was measured by suction and collection with a cylindrical tube and a cylindrical filter.
Subsequently, in an H / H environment, the developer was left in the evaluator for 2 weeks, and then the same operation as before the leaving was performed. / M (mC / kg) was measured. The Q / M per unit mass on the initial electrostatic latent image carrier is set to 100%, and the maintenance rate of Q / M per unit mass on the electrostatic latent image carrier after leaving is set to [[After leaving. Q / M] / [Initial Q / M] × 100) was calculated and judged according to the following criteria. If the evaluation was A to C, it was judged to be good.
(Evaluation criteria)
A: Maintenance rate is 95% or more B: Maintenance rate is 90% or more and less than 95% C: Maintenance rate is 85% or more and less than 90% D: Maintenance rate is less than 85%

[Low temperature fixability]
Paper: GFC-081 (81.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
Amount of toner on paper: 0.70 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
Evaluation image: An image of 2 cm x 5 cm is placed in the center of the above A4 paper Test environment: Low temperature and low humidity environment: Temperature 15 ° C / Humidity 10% RH (hereinafter "L / L")
Fixing temperature: 150 ° C
Process speed: 377 mm / sec
The above evaluation image was output and the low temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index of low temperature fixability.
The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). ^{Next, a load of 4.9 kPa (50 g / cm 2} ) is applied to the portion where the image density is measured, and the fixed image is rubbed (5 reciprocations) with Sylbon paper, and the image density is measured again.
Then, the rate of decrease in image density before and after rubbing was calculated using the following formula. The rate of decrease in the obtained image density was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was judged to be good.
Image density reduction rate = (image density before rubbing-image density after rubbing) / image density before rubbing x 100
(Evaluation criteria)
A: Image density reduction rate less than 3% B: Image density reduction rate 3% or more and less than 5% C: Image density reduction rate 5% or more and less than 8% D: Image density reduction rate 8% or more

<Examples 2 to 38 and Comparative Examples 1 to 6>
The evaluation was carried out in the same manner as in Example 1 except that the two-component developing agents 2 to 44 were used. The evaluation results are shown in Table 9.

Claims (14)

A toner having toner particles containing a binder resin having a first resin and a wax.
The first resin is a crystalline resin and
The content of the first resin in the binder resin is 30.0% by mass or more.
The first resin has a first monomer unit represented by the following formula (1).
The content ratio of the first monomer unit in the first resin is 30.0% by mass to 100.0% by mass.
In the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry of the toner,
There are 1st peak and 2nd peak derived from the wax,
The peak top temperature of the 1st peak is 70.0 ° C. to 97.0 ° C.
The 2nd peak is adjacent to the 1st peak,
The peak top temperature of the 2nd peak is higher than the peak top temperature of the 1st peak.
A toner characterized in that the height of the valley portion of the 1st peak and the 2nd peak is larger than 0 W / (g · ° C.).

[In the formula (1), R _Z1 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms. ] The toner according to claim 1, wherein the wax contains a hydrocarbon wax having a weight average molecular weight of Mw 300 to 700 and a hydrocarbon wax having a weight average molecular weight of Mw 1000 to 2000. The content of the toner particles of hydrocarbon waxes of the weight average molecular weight Mw1000~2000 and _{W L} wt%, the content of the toner particles of hydrocarbon waxes of the weight average molecular weight Mw300~700 _{W S} wt% The toner according to claim 2, which satisfies the following formula (2).
_{0.2 ≦ W L / W S ≦} 0.8 ··· (2) The content _{W L} of the toner particles of hydrocarbon waxes of the weight average molecular weight Mw1000~2000 The toner according to claim 2 or 3 satisfying the following formula (3).
1.0 mass% ≤ _LL ≤ 5.0 mass% ... (3) In the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry of the toner, the peak top temperature of an endothermic peak corresponding to a hydrocarbon wax in the weight average molecular weight Mw300~700 and T _S,
Claims 2 to 4 satisfy the following formula (4), where T is the peak top temperature in the temperature differential distribution of the endothermic peak measured by differential scanning calorimetry of hydrocarbon wax having a weight average molecular weight of Mw 300 to 700. The toner according to any one item.
_{0.0 ≦ T-T S ≦ 2.0} ··· (4) The weight average molecular weight of the hydrocarbon wax having a weight average molecular weight of Mw 1000 to 2000 is Mw _L , and the number average molecular weight is Mn _L.
When the weight average molecular weight of the hydrocarbon wax having a weight average molecular weight Mw 300 to 700 is Mw _S and the number average molecular weight is Mn _S ,
The toner according to any one of claims 2 to 5, wherein the molecular weight distribution Mw _L / Mn _L and the molecular weight distribution Mw _S / Mn _{S satisfy the following formula (5).}
Mw _S / Mn _S ≤ Mw _L / Mn _L ... (5) When the SP value (J / cm ³ ) ^0.5 of the first resin is SP _C and the SP value of the hydrocarbon wax having a weight average molecular weight Mw 1000 to 2000 is SP _W , the SP _C and SP _W are as follows. The toner according to any one of claims 2 to 6, which satisfies the formula (6).
(SP _C- SP _w ) ≧ 1.00 ・ ・ ・ (6) The toner according to any one of claims 1 to 7, wherein the acid value of the first resin is 0.1 mgKOH / g to 30.0 mgKOH / g. The binding resin contains a second resin and
The second resin is an amorphous resin,
The toner according to any one of claims 1 to 8, wherein the acid value of the second resin is 0.5 mgKOH / g to 40.0 mgKOH / g. The toner according to claim 9, wherein the mass ratio Y / X of the content Y of the second resin to the content X of the first resin in the binder resin is 0.20 to 2.20. The toner according to claim 9 or 10, wherein a domain matrix structure composed of a matrix containing the first resin and a domain containing the second resin can be seen in a cross-sectional observation of the toner. The binding resin further contains a third resin and contains
The toner according to any one of claims 9 to 11, wherein the third resin contains a resin to which the first resin and the second resin are bonded. The toner according to any one of claims 9 to 12, wherein the second resin comprises at least one selected from the group consisting of a hybrid resin in which a vinyl resin and a polyester resin are bonded and a polyester resin. The toner according to any one of claims 1 to 13, wherein the toner has silica fine particles treated with silicone oil on the surface of the toner particles.

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