JP7297503B2 - toner - Google Patents

Description

The present invention relates to a toner for developing an electrostatic charge image (electrostatic latent image) used in image forming methods such as electrophotography and electrostatic printing.

In recent years, the area in which electrophotography is used has expanded to commercial printing represented by package printing and advertisement printing, and there is a need for even higher speeds and higher image quality than when it was used conventionally in offices. Adaptation is required.
In order to adapt to high-speed printing, there is known a technique of lowering the fixing temperature by using a crystalline resin as the binder resin of the toner. Crystalline resins include main-chain crystalline resins in which the main chain crystallizes, typified by crystalline polyesters, and side-chain crystalline resins in which side chains crystallize, typified by long-chain alkyl acrylate polymers. Are known. Among them, side-chain crystalline resins are known to exhibit excellent low-temperature fixability because they tend to increase the degree of crystallinity, and have been extensively studied.

In Patent Document 1, a core containing a side chain crystalline resin is covered with a shell, and the thermal properties of the toner are controlled to achieve not only low-temperature fixability, but also excellent image stackability, sufficient charging performance, and a fixed image. and a wide fixable temperature range.
In Patent Document 2, a core having a sea-island structure in which islands of an amorphous resin are dispersed in a sea of a side-chain crystalline resin is covered with a shell, and the thermal properties of the toner are controlled to improve low-temperature fixability as well as , disclosed toners with enhanced image strength.

JP 2014-130243 A JP 2014-142632 A

On the other hand, in order to achieve high image quality, it is required to faithfully transfer the toner image formed on the drum onto an intermediate transfer member or paper. However, when a large amount of crystalline resin is used as the binder resin of the toner, it is difficult to obtain a toner having excellent transferability due to the influence of the charging property of the binder resin. It has been found that even the toners of the above-mentioned patent documents are inferior in transferability in some cases.
An object of the present invention is to obtain a toner having both excellent low-temperature fixability and transferability by improving the transferability of a toner containing a side-chain crystalline resin in a binder resin.

A first aspect for solving the above problems is a toner having toner particles in which a toner core containing a binder resin is coated with a shell layer,
The binder resin comprises a first monomer unit derived from a first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. Containing a polymer A having a monomer unit,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all monomer units in the polymer A,
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all monomer units in the polymer A,
When the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 , the following formula satisfy (1),
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
In an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM), a shell layer is observed over 90% or more of the outer periphery of the cross section of the toner,
the shell layer is composed of at least one amorphous resin selected from the group consisting of homopolymers, alternating copolymers, and random copolymers;
When the shell layer is composed of two or more amorphous resins,
Resin S1 is a resin having the highest SP value among the resins constituting the shell layer,
Resin S2 is a resin having the lowest SP value among the resins constituting the shell layer,
When the SP value of the resin S1 is SP _S1 (J/cm ³ ) ^0.5 and the SP value of the resin S2 is SP _S2 (J/cm ³ ) ^0.5 , the following formula (2) is satisfied. A toner characterized by
SP _S1 -SP _S2 ≤ 3.0 (2)
A second aspect for solving the above problems is a toner having toner particles in which a toner core containing a binder resin is coated with a shell layer,
a polymer A in which the binder resin is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer; contains,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the composition can be,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition can be,
The SP value of the first polymerizable monomer is SP ₁₂ (J/cm ³ ) ^0.5 , and the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 . When the following formula (3) is satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
In an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM), a shell layer is observed over 90% or more of the outer periphery of the cross section of the toner,
the shell layer is composed of at least one amorphous resin selected from the group consisting of homopolymers, alternating copolymers, and random copolymers;
When the shell layer is composed of two or more amorphous resins,
Resin S1 is a resin having the highest SP value among the resins constituting the shell layer,
Resin S2 is a resin having the lowest SP value among the resins constituting the shell layer,
When the SP value of the resin S1 is SP _S1 (J/cm ³ ) ^0.5 and the SP value of the resin S2 is SP _S2 (J/cm ³ ) ^0.5 , the following formula (2) is satisfied. A toner characterized by
SP _S1 -SP _S2 ≤ 3.0 (2)

According to the present invention, it is possible to provide a toner having both excellent low-temperature fixability and transferability.

［式（Ｃ）中、Ｒ_Ａ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_Ｂ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 invention, the descriptions of "XX or more and YY or less" and "XX to YY" that represent numerical ranges mean numerical ranges including the lower and upper limits, which are endpoints, unless otherwise specified.
In the present invention, (meth)acrylic acid ester means acrylic acid ester and/or methacrylic acid ester.
In the present invention, the term “monomer unit” refers to one unit of a carbon-carbon bond segment in the main chain of the polymer polymerized by the vinyl-based monomer.
A vinyl-based monomer can be represented by the following formula (C).

[In the formula (C), R _A 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 _B represents an arbitrary substituent. . ]
A crystalline resin refers to a resin that exhibits a distinct endothermic peak in differential scanning calorimeter (DSC) measurement.

A first aspect of the present invention is a toner having toner particles in which a toner core containing a binder resin is coated with a shell layer,
The binder resin comprises a first monomer unit derived from a first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. Containing a polymer A having a monomer unit,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all monomer units in the polymer A,
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all monomer units in the polymer A,
When the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 , the following formula satisfy (1),
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
In an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM), a shell layer is observed over 90% or more of the outer periphery of the cross section of the toner,
the shell layer is composed of at least one amorphous resin selected from the group consisting of homopolymers, alternating copolymers, and random copolymers;
When the shell layer is composed of two or more amorphous resins,
Resin S1 is a resin having the highest SP value among the resins constituting the shell layer,
Resin S2 is a resin having the lowest SP value among the resins constituting the shell layer,
When the SP value of the resin S1 is SP _S1 (J/cm ³ ) ^0.5 and the SP value of the resin S2 is SP _S2 (J/cm ³ ) ^0.5 , the following formula (2) is satisfied. A toner characterized by
SP _S1 -SP _S2 ≤ 3.0 (2)

A second aspect of the present invention is a toner having toner particles in which a toner core containing a binder resin is coated with a shell layer,
a polymer A in which the binder resin is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer; contains,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the composition can be,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition can be,
The SP value of the first polymerizable monomer is SP ₁₂ (J/cm ³ ) ^0.5 , and the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 . When the following formula (3) is satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
In an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM), a shell layer is observed over 90% or more of the outer periphery of the cross section of the toner,
the shell layer is composed of at least one amorphous resin selected from the group consisting of homopolymers, alternating copolymers, and random copolymers;
When the shell layer is composed of two or more kinds of amorphous resins,
Resin S1 is a resin having the highest SP value among the resins constituting the shell layer,
Resin S2 is a resin having the lowest SP value among the resins constituting the shell layer,
When the SP value of the resin S1 is SP _S1 (J/cm ³ ) ^0.5 and the SP value of the resin S2 is SP _S2 (J/cm ³ ) ^0.5 , the following formula (2) is satisfied. A toner characterized by
SP _S1 -SP _S2 ≤ 3.0 (2)

The inventors of the present invention presume the following as to the reason why the toner having both excellent low-temperature fixability and transferability can be obtained with the above configuration.
The reason why it is difficult to achieve both low-temperature fixability and transferability in a toner containing a crystalline resin is that the resistance value of the crystalline resin is lower than that of the amorphous resin. Taking a process using an intermediate transfer member as an example, when the resistance value is low, the electric charge of the toner tends to leak due to the influence of the potential difference in the process of transporting the toner using the potential difference such as development and primary transfer. Therefore, in the final secondary transfer process, the toner does not retain sufficient electric charge, and the responsiveness to the transfer current is lowered, which often leads to the deterioration of the transferability.
Also, even in a process that does not have a secondary transfer process, the primary transfer process is affected by charge leakage in the development process, which may similarly lead to deterioration in transferability.

In the toner disclosed in the above patent document, a core made of a crystalline resin or a core made of a sea-island structure of a crystalline resin and an amorphous resin is covered with a shell in order to improve chargeability. As a result, the charge retentivity when left standing after charging is improved. However, it has been found that it is not sufficient for charge retention in processes such as development and primary transfer. The reason for this is that the low-resistance crystalline portion forms a simple continuous phase, so that the charge of the shell layer leaks through the crystalline portion.
Patent Document 1 also discloses a toner having a resin obtained by copolymerizing a long-chain alkyl acrylate, which is a monomer that forms a crystalline site, and acrylic acid, which is a highly polar monomer. However, since the amount of the highly polar monomer is small in the above toner, phase separation between the crystalline portion and the highly polar portion is insufficient. As a result, the resistance of the resin as a whole is lowered, and similarly, it has been found that leaks in processes such as development and primary transfer cannot be suppressed.
Therefore, in order to suppress charge leakage in processes such as development and primary transfer, it is necessary to use a resin in which the crystalline portion and the amorphous portion are phase-separated and the crystalline portion does not form a simple continuous phase. It is considered effective to use

Therefore, as a result of intensive studies, the present inventors have found that a monomer unit derived from a (meth)acrylic acid ester having an alkyl group having 18 to 36 carbon atoms and a monomer unit whose SP value is sufficiently separated from the monomer unit. It has been found that a toner using a polymer A having a specific ratio of
In the polymer A, the SP values between the two monomer units are sufficiently separated, and both the monomer units are present in a sufficient amount, so that the two monomer units are not compatible with each other and are phase-separated. be able to. On the other hand, in order to have both monomer units in the same molecule, a crystalline containing 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 The moieties cannot form a simple continuous phase.
For this reason, it is expected that a micro-phase-separated structure in which the crystalline portion and the amorphous portion are phase-separated is likely to be intricately intertwined. The present inventors presume that the polymer A has a microphase-separated structure in which a low-resistance crystalline portion and a high-resistance amorphous portion are intricately intertwined, thereby suppressing leakage.
That is, the polymer A preferably has a crystalline portion containing a first monomer unit derived from the first polymerizable monomer. Moreover, the polymer A preferably has an amorphous portion containing a second monomer unit derived from the second polymerizable monomer.

Further, in order to obtain polymer A, a (meth)acrylic acid ester having an alkyl group having 18 to 36 carbon atoms and a monomer having an SP value sufficiently separated from the (meth)acrylic acid ester are copolymerized. is preferred. As a result, the monomers are not uniformly mixed during polymerization, and a block copolymer-like structure in which the crystalline portion and the amorphous portion are separated can be easily obtained. By adopting a structure similar to that of a block copolymer, the crystallinity of the crystalline portion is enhanced, and the microphase separation structure described above can be easily obtained.
As described above, the toner containing the polymer A has excellent transferability, but as a result of examination, it was confirmed that the mere use of the polymer A as the binder resin is not sufficient to improve the transferability after long-term use. was done. Therefore, the present inventors conducted studies for further improvement.

Among them, the present inventors paid attention to the adhesion force of the toner. Although the toner containing the polymer A is excellent in suppressing electric charge leakage, it is considered that the toner particle surface is uneven because the toner particle surface has a microphase-separated structure. In general, the toner is obtained by adding an inorganic fine powder or the like as an external additive to the surface of the toner particles, and the charging property of the toner surface is made uniform by this function. However, after long-term use, the state of attachment of the external additive changes, so that the resin on the surface of the toner particles is more exposed, and the charging uniformity of the surface of the toner particles is greatly affected.
When the toner particle surface has a non-uniform structure in which the crystalline portion and the amorphous portion are phase-separated, the charge is concentrated on the highly polar amorphous portion during charging, thereby increasing the electrostatic adhesion force of the toner. . In addition, since the crystalline portion is closer to the viscous body than the amorphous portion, the non-electrostatic adhesion force is increased by the exposure of the crystalline portion. A toner with high adhesion tends to adhere to members such as a latent image bearing member and an intermediate transfer member in a transfer process, resulting in a decrease in transferability.
Accordingly, the present inventors have found that the above problems can be solved by coating a toner core having a non-uniform surface containing the polymer A with a shell composed of an amorphous resin having a uniform composition and structure. perfected the invention.

The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic esters having alkyl groups of 18 to 36 carbon atoms.
Examples of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, (meth) ) nonadecyl acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosa (meth)acrylate, (meth)acrylate myricyl acrylate, dotriacontane (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].
Among these, at least one selected from the group consisting of (meth)acrylic acid esters having a straight-chain alkyl group having 18 to 36 carbon atoms is preferable from the viewpoint of toner transferability and low-temperature fixability, More preferred is at least one selected from the group consisting of (meth)acrylic acid esters having a straight-chain alkyl group having 18 to 30 carbon atoms, and more preferred is straight-chain stearyl (meth)acrylate and It is at least one selected from the group consisting of behenyl (meth)acrylate.

In the first embodiment, the content of the first monomer units in polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all monomer units in polymer A. .
Further, in the second embodiment, the polymer A is the weight of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. It is a coalescence. The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the composition. be.
When the content is within the above range, the crystallinity of the crystalline portion of the polymer A is enhanced and the phase separation from the amorphous portion is promoted. Therefore, a toner having excellent transferability and low-temperature fixability can be obtained. The content is preferably 10.0 mol % to 60.0 mol %, more preferably 20.0 mol % to 40.0 mol %.
On the other hand, if the content is less than 5.0 mol %, the amount of crystalline sites is small, and thus toner having sufficient low-temperature fixability may not be obtained. In addition, since the crystallinity of the resin is small, the degree of crystallinity of the resin is difficult to increase, and phase separation from the amorphous portion may become unclear. Conversely, when the content exceeds 60.0 mol %, the amount of crystalline sites is large, so that it is difficult to inhibit charge leakage, and a toner having sufficient transfer properties may not be obtained.

In the present invention, when there are multiple types of monomer units that satisfy the requirements of the first monomer unit in the polymer A, the value of SP ₁₁ in formula (1) is the weighted average of the SP values of each monomer unit. value. For example, the monomer unit A with an SP value of SP ₁₁₁ contains A mol% based on the number of moles of the entire monomer units that satisfy the requirements for the first monomer unit, and the monomer unit B with an SP value of SP ₁₁₂ is included in the first monomer unit. The SP value (SP ₁₁ ) when containing (100-A) mol% based on the number of moles of the entire monomer unit that satisfies the requirements of
SP ₁₁ = (SP ₁₁₁ ×A+SP ₁₁₂ ×(100−A))/100
is. The same calculation is performed when three or more monomer units satisfying the requirements of the first monomer unit are included. On the other hand, SP ₁₂ also represents an average value calculated based on the molar ratio of each first polymerizable monomer.
Moreover, when a plurality of first monomer units are present, the content ratio of the first monomer units is the sum of the contents of the respective monomer units. The same applies when there are a plurality of first polymerizable monomers.

In the first embodiment, the content of the second monomer unit in polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all monomer units in polymer A. .
In the second aspect, the content of the second polymerizable monomer in the composition is 20.0 mol% based on the total number of moles of all polymerizable monomers in the composition. ~95.0 mol%.
When the content is within the above range, the crystalline portion and the amorphous portion can be sufficiently phase-separated, and a toner having excellent transferability can be obtained.
The content is preferably 40.0 mol % to 95.0 mol %, more preferably 40.0 mol % to 70.0 mol %.
On the other hand, when the content is less than 20.0%, the crystalline portion and the amorphous portion are likely to be compatible with each other, so that charge leakage is less likely to be inhibited. Therefore, a toner having sufficient transferability may not be obtained. On the other hand, if the content exceeds 95.0 mol %, the crystalline portion becomes relatively small, and a toner having sufficient low-temperature fixability may not be obtained. In addition, since the crystalline sites are relatively reduced, the degree of crystallinity of the resin is difficult to increase, and the melting point may be lowered.

In the first embodiment, the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 , and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 . Then, SP ₁₁ and SP ₂₁ satisfy the following formula (1).
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
In the second embodiment, the polymer A has an SP value of the first polymerizable monomer of SP ₁₂ (J/cm ³ ) of ^0.5 , and an SP value of the second polymerizable monomer of When SP ₂₂ (J/cm ³ ) is ^0.5 , the following formula (3) is satisfied.
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
When the SP value difference is within the above range, the crystalline portion and the amorphous portion can be sufficiently phase-separated, and a toner having excellent transferability can be obtained. The above SP ₂₁ -SP ₁₁ is preferably 4.00 or more, more preferably 5.00 or more. When SP ₂₁ -SP ₁₁ is within the above range, the phase separation between the crystalline portion and the amorphous portion becomes clearer, improving the transferability. Also, the above SP ₂₁ −SP ₁₁ is preferably 20.00 or less, more preferably 15.00 or less. When SP ₂₁ -SP ₁₁ is within the above range, compatibility between the crystalline portion and the amorphous portion during fixing is likely to proceed, and a toner having sufficient low-temperature fixability even in a higher-speed fixing process can be obtained. can be done.
Similarly, SP ₂₂ −SP ₁₂ is preferably 2.00 or more, more preferably 3.00 or more. Also, SP ₂₂ −SP ₁₂ is preferably 10.00 or less, more preferably 7.00 or less.
On the other hand, if the SP value difference is less than the lower limit, the phase separation between the crystalline portion and the amorphous portion may be insufficient, and a toner having sufficient transfer properties may not be obtained. Further, when the above SP value difference exceeds the upper limit, the crystalline portion is not compatible with the amorphous portion even during fixing, so that a toner having sufficient low-temperature fixability may not be obtained.
A method of calculating the SP value will be described later. In the present invention, the second monomer unit corresponds to all monomer units that satisfy SP ₂₁ that satisfies formula (1) with respect to SP ₁₁ calculated by the above method. Similarly, the second polymerizable monomer corresponds to all polymerizable monomers having an SP _{of 22} that satisfies the formula (3) with respect to the SP of ₁₂ calculated by the above method.
That is, when the second polymerizable monomer is two or more polymerizable monomers, SP ₂₁ represents the SP value of the monomer unit derived from each polymerizable monomer, SP ₂₁ −SP ₁₁ is determined for each monomer unit derived from the second polymerizable monomer. Similarly, SP ₂₂ represents the SP value of each polymerizable monomer, and SP ₂₂ -SP ₁₂ are determined for each second polymerizable monomer.
The content ratio of the second monomer unit is the sum of the contents of all the monomer units satisfying the above conditions. The same applies when there are a plurality of second polymerizable monomers.

As the second polymerizable monomer, for example, among the polymerizable monomers listed below, a polymerizable monomer that satisfies formula (1) or formula (3) can be used.
The second polymerizable monomer may be used singly or in combination of two or more.
monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, and the like;
Monomers 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 2 to 30 carbon atoms having an ethylenically unsaturated bond (acrylic acid, methacrylic acid, etc.) are reacted by a known method. monomers, etc.

A monomer having a urethane group; for example, an alcohol having 2 to 22 carbon atoms having an ethylenically unsaturated bond (2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and an isocyanate having 1 to 30 carbon atoms [monoisocyanate compound (benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate and 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1 , 3-butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, etc.), alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate, etc.), and aromatic diisocyanate compounds (phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6 -tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate and xylylene diisocyanate, etc.)] by a known method, and alcohols having 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecyl alcohol, heneicosanol, behenyl alcohol, erucyl alcohol, etc.) and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond [2-isocyanatoethyl (meth) Acrylates, 2-(0-[1′-methylpropylideneamino]carboxyamino)ethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate and 1,1- (Bis(meth)acryloyloxymethyl)ethyl isocyanate, etc.] by a known method.

Monomers having a urea group: for example, amines having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di- n-butylamine, etc.), aniline and cycloxylamine, etc.] and a monomer having an ethylenically unsaturated bond and an isocyanate having 2 to 30 carbon atoms reacted by a known method.
A monomer having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate, and the like.
Among them, it is preferable to use a monomer having a nitrile group, an amide group, a urethane group, a hydroxy group, or a urea group. More preferred are monomers having at least one functional group selected from the group consisting of a nitrile group, an amide group, a urethane group, a hydroxy group, and a urea group, and an ethylenically unsaturated bond. By using these monomers, it is easy to keep the resistance of the polymer low even under high humidity. Therefore, it becomes easy to obtain a toner having excellent transferability even under high humidity, which is preferable.

As the second polymerizable monomer, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, pivalic acid Vinyl esters such as vinyl and vinyl octylate are also preferably used. Vinyl esters are non-conjugated monomers and have relatively low reactivity with the first polymerizable monomer, which is a conjugated monomer. phase separation is likely to be promoted. Therefore, it becomes easier to obtain a toner having excellent transferability.
Moreover, when vinyl esters are used as the second polymerizable monomer, reactivity contributes to phase separation in addition to SP value difference. Therefore, as long as the contents of SP ₂₁ -SP ₁₁ , SP ₂₂ -SP ₁₂ and the first polymerizable monomer are within the scope of the present invention, It becomes possible to obtain the same phase separation property as in the case, and it becomes easy to obtain a toner having excellent transferability.
The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
Moreover, it is preferable that the second polymerizable monomer is 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 a nitrile group (-C≡N),
amide group (-C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
hydroxy group,
—COOR ¹¹ (R ¹¹ is 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)),
urethane group (-NHCOOR ¹² (R ¹² is an alkyl group having 1 to 4 carbon atoms)),
a urea group (--NH--C(=O)--N(R ¹³ ) ₂ (each R ¹³ is independently 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 is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(=O)—N(R ¹⁵ ) ₂ (R ¹⁵ is each independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
is.
Preferably, R ¹ is a nitrile group (-C≡N),
amide group (-C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms)),
hydroxy group,
—COOR ¹¹ (R ¹¹ is 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)),
a urea group (--NH--C(=O)--N(R ¹³ ) ₂ (each R ¹³ is independently 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 is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(=O)—N(R ¹⁵ ) ₂ (R ¹⁵ is each independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
is.
R ² is an alkyl group having 1 to 4 carbon atoms, and each R ³ is independently a hydrogen atom or a methyl group. )

Polymer A is preferably a vinyl polymer. Examples of vinyl polymers include polymers of monomers containing ethylenically unsaturated bonds. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of undergoing radical polymerization, and includes, for example, vinyl group, propenyl group, acryloyl group, methacryloyl group and the like.
The acid value of polymer A is preferably 30 mgKOH/g or less, more preferably 20 mgKOH/g or less. Within the above range, it is easy to keep the resistance value of the polymer low even under high humidity. Therefore, it becomes easier to obtain a toner having excellent transferability even under high humidity. Although the lower limit of the acid value is not particularly limited, it is preferably 0 mgKOH/g or more. The acid value can be controlled by the type and amount of polymerizable monomer added.

In addition, the polymer A is a range that does not impair the molar ratio of the first monomer unit derived from the first polymerizable monomer and the second monomer unit derived from the second polymerizable monomer. , a third polymerizable monomer that is not within the scope of the above formula (1) or formula (3) (i.e., different from the first polymerizable monomer and the second polymerizable monomer) may contain a third monomer unit derived from.
As the third polymerizable monomer, among the monomers listed in the second polymerizable monomer section, a monomer that does not satisfy the formula (1) or formula (3) can be used. can.
In addition, the following monomers having no nitrile group, amide group, urethane group, hydroxy group, urea group, or carboxy group can also be used.
For example, styrene, styrene such as o-methylstyrene and derivatives thereof, methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-(meth)acrylate (meth)acrylic acid esters such as ethylhexyl; Among them, at least one selected from the group consisting of styrene, methyl methacrylate, and methyl acrylate is preferable.
In addition, since the above monomer does not have a polar group, the SP value is low, and it is difficult to satisfy the formula (1) or the formula (3). However, when the formula (1) or formula (3) is satisfied, it can be used as the second polymerizable monomer.
By satisfying the above conditions, a polymer with low resistance can be obtained while maintaining crystallinity. Therefore, it is possible to obtain a toner having both excellent low-temperature fixability and transferability.

A charge decay constant can be used as an index of the resistance value. The charge decay constant of polymer A is preferably 100 or less. Within this range, the charge is less likely to leak. Therefore, it becomes easier to obtain a toner having excellent transferability. The charge decay constant of polymer A is more preferably 1 or more and 50 or less. This range is more preferable because overcharging can be suppressed by transfer of charges between toners while leakage of charges is further suppressed. The charge decay constant of polymer A can be controlled by the type and amount of polymerizable monomer added.

An endothermic amount at an endothermic peak can be used as an index of crystallinity. From the viewpoint of low-temperature fixability, the endothermic amount of the endothermic peak derived from the melting of the polymer A is 20 (J/g) to 100 (J/g) when the toner is measured with a differential scanning calorimeter. is preferred. More preferably, the endothermic amount is 30 (J/g) to 80 (J/g). The endothermic amount can be controlled by the amount of the first monomer unit or the first polymerizable monomer added.

In an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM), a shell layer is observed over 90% or more of the outer periphery of the cross section of the toner (hereinafter, the rate at which the shell layer is observed on the outer periphery is also referred to as a coverage rate. ). In this case, in addition to satisfying the requirements described later, the toner particle surfaces are sufficiently uniform, and a toner having excellent transferability can be obtained. The shell layer is preferably observed over 95% or more of the outer circumference of the cross section of the toner. On the other hand, when the shell layer is observed in less than 90% of the outer circumference of the toner cross section, the uniformity of the toner particle surface may be insufficient, and a toner having sufficient transferability may not be obtained.
Although the upper limit is not particularly limited, the coverage is preferably 100% or less, more preferably 99.5% or less.
The coverage can be controlled by the amount and method of addition of the material forming the shell layer.

The shell layer is composed of at least one amorphous resin selected from the group consisting of homopolymers, alternating copolymers and random copolymers. In this case, the toner particle surface becomes sufficiently uniform, and a toner having excellent transferability can be obtained. Among them, a homopolymer or an alternating copolymer is preferable because of its excellent uniformity.
In the present invention, regardless of the type of polymer, a homopolymer is a polymer composed only of monomer units derived from a single monomer, and monomer units derived from two types of monomers are alternately arranged. The resulting polymer is referred to as an alternating copolymer, and a polymer in which monomer units derived from two or more types of monomers are arranged without regularity is referred to as a random copolymer.
For example, a polymer obtained by condensation polymerization of one kind of hydroxy acid is a homopolymer, and a resin obtained by condensation polymerization of one kind of diol and one kind of dicarboxylic acid is an alternating copolymer. A resin obtained by simultaneously polycondensing two kinds of diols and two kinds of dicarboxylic acids is a random copolymer when there is no great difference in reactivity between the monomers.

Thermosetting resins having a network-like crosslinked structure are also classified in the same way if they satisfy the above conditions. For example, a silicone resin obtained by condensation polymerization of one type of alkylsilane is a homopolymer, and a melamine resin obtained by condensation polymerization of melamine and formaldehyde is an alternating copolymer.
On the other hand, when the shell layer is composed of a block copolymer or a graft copolymer other than the above, phase separation of each monomer unit easily occurs on the toner particle surface, resulting in insufficient uniformity of the toner particle surface. , it may not be possible to obtain a toner having sufficient transferability. Further, when the shell layer is composed of a crystalline resin, the shell layer leaks electric charge, and thus the toner having sufficient transferability may not be obtained.

As the amorphous resin used for the shell layer, conventionally known amorphous resins can be used without particular limitation as long as they are homopolymers, alternating copolymers or random copolymers.
Specifically, thermoplastic resins include polyester resins, polyurethane resins, polyamide resins, vinyl resins, and the like; and thermosetting resins include melamine resins, urea resins, and the like. Among them, from the group consisting of polyester resins, polyurethane resins, melamine resins, vinyl resins, and urea resins, because they are excellent in phase separation from the toner core, they are easy to obtain alternating copolymers, and they are easy to make toner particle surfaces uniform. At least one selected is preferred.

A polyester resin can be obtained by reacting a polyhydric carboxylic acid having a valence of 2 or more and a polyhydric alcohol.
Examples of polyvalent carboxylic acids include the following compounds. Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenylsuccinic acid, and their anhydrides or their lower alkyl esters, as well as maleic acid, fumaric acid, Aliphatic unsaturated dicarboxylic acids such as itaconic acid and citraconic acid. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or their lower alkyl esters. These may be used individually by 1 type, and may use 2 or more types together.

Examples of polyhydric alcohols include the following compounds.
Alkylene glycol (ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol); alkylene ether glycol (polyethylene glycol and polypropylene glycol); alicyclic diol (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); Alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols or bisphenols.
The alkyl portion of alkylene glycols and alkylene ether glycols may be linear or branched. Furthermore, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol and the like. These may be used individually by 1 type, and may use 2 or more types together.
For the purpose of adjusting the acid value and hydroxyl value, monohydric acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol can be used as necessary.
The method for producing the polyester resin is not particularly limited, but for example, transesterification or direct polycondensation can be used alone or in combination.

The polyester resin is preferably produced at a polymerization temperature of 180° C. or higher and 230° C. or lower, and if necessary, the pressure in the reaction system is reduced, and the reaction is preferably carried out while removing water and alcohol generated during condensation. If the monomers do not dissolve or are compatible with each other at the reaction temperature, it is recommended to dissolve them by adding a high-boiling solvent as a dissolution aid. The polycondensation reaction is carried out while distilling off the solubilizing solvent. When a monomer having poor compatibility is present in the copolymerization reaction, it is preferable to first condense the monomer having poor compatibility, the monomer and the acid or alcohol to be polycondensed, and then polycondensate together with the main component.
Examples of catalysts that can be used in the production of polyester include the following. Titanium catalysts of titanium tetraethoxide, titanium tetrapropoxide, titanium tetraisopropoxide, titanium tetrabutoxide. Dibutyltin dichloride, dibutyltin oxide, diphenyltin oxide tin catalysts.

Next, the polyurethane resin will be described. A polyurethane resin is a reaction product of a diol and a substance containing a diisocyanate group, and a resin having various functions can be obtained by adjusting the diol and the diisocyanate.
Examples of the diisocyanate component include the following. Aromatic diisocyanates having 6 to 20 carbon atoms (excluding carbon atoms in the NCO group, hereinafter the same), aliphatic diisocyanates having 2 to 18 carbon atoms, alicyclic diisocyanates having 4 to 15 carbon atoms, and these diisocyanates Modified products of (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretimine group, isocyanurate group or oxazolidone group-containing modified product; hereinafter also referred to as "modified diisocyanate"), and these A mixture of two or more of
Aromatic diisocyanates include the following. m- and/or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate.
Moreover, the following are mentioned as an aliphatic diisocyanate. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and dodecamethylene diisocyanate.
Moreover, the following are mentioned as an alicyclic diisocyanate. isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate and methylcyclohexylene diisocyanate.

Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred is XDI. , IPDI and HDI.
In addition to the diisocyanate component, a tri- or higher functional isocyanate compound can also be used.
As the diol component that can be used in the polyurethane resin, the dihydric alcohol that can be used in the polyester resin described above can be used.

Melamine resins are polycondensates of melamine and formaldehyde, and the monomer used to form melamine resins is melamine. The urea resin is a polycondensate of urea and formaldehyde and the monomer used to form the urea resin is urea. Melamine and urea may undergo known modifications.

A preferable range in the case of using a thermoplastic resin as the amorphous resin will be described below, but the range is not limited to this.
The glass transition temperature (Tg) of the amorphous resin is preferably 50°C or higher and 150°C or lower. Within the above range, the transferability can be enhanced without impairing the low-temperature fixability. It is more preferably 60° C. or higher and 130° C. or lower, and still more preferably 65° C. or higher and 120° C. or lower.
The weight average molecular weight of the amorphous resin is preferably 5000 or more and 500000 or less. Within the above range, the transferability can be enhanced without impairing the low-temperature fixability. It is more preferably 6,000 or more and 200,000 or less, and still more preferably 7,000 or more and 100,000 or less.

The content of the amorphous resin in the shell layer is preferably 0.1 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the binder resin. It is more preferably 0.2 parts by mass or more and 30.0 parts by mass or less, and still more preferably 0.4 parts by mass or more and 25.0 parts by mass or less.

When the shell layer is composed of two or more kinds of amorphous resins, the resin having the highest SP value among the resins constituting the shell layer is designated as the resin S1, and the resin having the lowest SP value among the resins constituting the shell layer. is resin S2, the SP value of resin S1 is SP _S1 (J/cm ³ ) ^0.5 , and the SP value of resin S2 is SP _S2 (J/cm ³ ) ^0.5 , SP _S1 and SP _S2 satisfies the following formula (2).
SP _S1 -SP _S2 ≤ 3.0 (2)
In this case, the toner particle surface becomes sufficiently uniform, and a toner having excellent transferability can be obtained. SP _S1 -SP _S2 is preferably 2.0 or less. Although the lower limit is not particularly limited, it is preferably 0 or more. More preferably, the shell layer is composed of one type of amorphous resin.
Also, the thickness of the shell layer is preferably 2 nm to 100 nm. When the thickness of the shell layer is within the above range, charge leakage can be effectively suppressed without impairing low-temperature fixability. More preferably, the thickness of the shell layer is 5 nm to 50 nm.

Further, in the present invention, the polymer A satisfies the contents of the first polymerizable monomer and the second polymerizable monomer in the composition and satisfies the formula (3), This makes it easier for the polymer A to have a block copolymer-like structure in which the crystalline portion and the amorphous portion are separated. Therefore, the binder resin tends to have a structure in which the crystalline portion and the amorphous portion are microphase-separated. Therefore, a toner having both excellent low-temperature fixability and transferability can be obtained.

Subsequently, other materials used in the present invention will be described in detail below.
<Binder resin>
In addition to the polymer A, the toner particles may contain known resins such as vinyl resins, polyester resins, polyurethane resins, and epoxy resins as binder resins.
As the polyester resin and the polyurethane resin, those listed in the section of the amorphous resin can be used. In addition, the polymerizable monomer that can be used for the vinyl-based resin can be used for the above-mentioned first polymerizable monomer, the above-mentioned second polymerizable monomer, and the above-mentioned third polymerizable monomer. and other polymerizable monomers. You may use it in combination of 2 or more types as needed.
The content of the polymer A in the binder resin is preferably 50.0% by mass or more. When the amount is 50.0% by mass or more, the sharp melt property of the toner is likely to be maintained, and the low-temperature fixability is improved. More preferably, it is 80.0% by mass to 100% by mass, and polymer A is even more preferable as the binder resin.

<Wax>
The toner particles may contain wax.
Examples of wax include the following.
esters of monohydric alcohols and monocarboxylic acids such as behenyl behenate, stearyl stearate, and palmityl palmitate;
Divalent carboxylic acid and monoalcohol esters such as dibehenyl sebacate;
Esters of dihydric alcohols and monocarboxylic acids such as ethylene glycol distearate and hexanediol dibehenate;
Esters of trihydric alcohols and monocarboxylic acids such as glycerin tribehenate;
Esters of tetrahydric alcohols and monocarboxylic acids such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate;
Esters of hexahydric alcohol and monocarboxylic acid such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate;
Synthetic ester waxes such as esters of polyfunctional alcohols such as polyglycerin behenate and monocarboxylic acids;
Natural ester waxes such as carnauba wax and rice wax;
petroleum-based hydrocarbon waxes such as paraffin wax, microcrystalline wax, petrolatum, and derivatives thereof;
Fischer-Tropsch process hydrocarbon waxes and derivatives thereof;
Polyolefin hydrocarbon waxes such as polyethylene wax and polypropylene wax and derivatives thereof; higher aliphatic alcohols;
fatty acids such as stearic acid and palmitic acid; acid amide waxes;
When the content of the wax is W parts by mass and the content of the first monomer unit is A parts by mass, the content of the polymer A in the toner is 100 parts by mass. It is preferable to satisfy the following formula (4).
0.2×A≦W≦A (4)

Since the polymer A has high crystallinity and is coated with a shell, the toner of the present invention exhibits high storage stability. However, in an environment where high and low temperatures are repeated, for example, during storage in areas where there is a large temperature difference between day and night, the crystallinity collapses, and the phase separation between the crystalline and amorphous regions becomes unclear, and the polymer The resistance value of A may decrease. In addition, the uniformity of the surface of the toner particles may deteriorate due to compatibility of the crystalline portion with the shell layer. These factors may reduce transcription after storage.
Here, when the wax amount W satisfies the above formula (4), the wax exists in a state in which a portion of the wax is compatible with the crystalline portion of the toner and a portion of the wax is precipitated in the crystalline portion. After storage in an environment with a large temperature difference, the precipitated wax acts as a nucleating agent for the crystalline portion, and the recrystallization of the crystalline portion is promoted along with the crystallization of the compatible wax. However, high crystallinity can be maintained. Therefore, deterioration of transcription after storage can be suppressed.
In addition, when a large amount of wax is added to a toner containing an amorphous binder resin as a main component, the SP value difference between the wax and the binder resin is large. Separated wax may seep to the surface. Then, under the influence of exuded wax, the non-electrostatic adhesion force of the toner increases, and transferability may deteriorate.
However, in the toner of the present invention, since the crystalline portion with a low SP value and the amorphous portion with a high SP value of the polymer A are phase-separated, the wax with a low SP value cannot be trapped in the crystalline portion. , the exudation of the wax to the toner particle surface can be suppressed. Therefore, even when a large amount of wax is added, transferability is less likely to deteriorate.
More preferably, the wax amount W satisfies the following formula (5).
0.2×A≦W≦0.8×A (5)
When the wax amount W satisfies the above formula (5), the exudation of the wax is further suppressed, making it easier to obtain a toner with even better transferability. In addition, the crystalline portion can effectively plasticize the amorphous portion during fixation, thereby improving the low-temperature fixability.
Further, when W is 10.0 to 40.0, deposition of wax on the toner surface is suppressed, which is more preferable.
In addition, it is preferable to use a hydrocarbon wax or an ester wax, more preferably a hydrocarbon wax, because of their excellent action as the nucleating agent.

<Polymerization initiator>
As the polymerization initiator for obtaining the polymer A, a known polymerization initiator can be used without particular limitation.
Specific examples are as follows. hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, Sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-hydroperoxide, tert-butyl performate, peracetic acid- tert-butyl, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, per-N-(3-toluyl)palmitate-tert-butylbenzoyl peroxide, t-butyl per Oxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydro Peroxide-based polymerization initiators typified by peroxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and the like;
2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis -azo or diazo polymerization initiators typified by 4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and the like;

<Colorant>
The toner may contain a colorant.
As the coloring agent, conventionally known black, yellow, magenta, and cyan colors, pigments and dyes of other colors, magnetic substances, and the like can be used without particular limitation.
As the black colorant, specifically, a black pigment such as carbon black is used.
Examples of yellow colorants include the following monoazo compounds; disazo compounds; condensed azo compounds; isoindolinone compounds; benzimidazolone compounds; anthraquinone compounds; and yellow pigments and yellow dyes. More specifically, the following C.I. I. Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185, C.I. I. solvent yellow 162 and the like.

Specific examples of magenta colorants include the following monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; basic dye lake compounds; magenta pigments and magenta dyes typified by More specifically, the following C.I. I. Pigment Red 2,3,5,6,7,23,48:2,48:3,48:4,57:1,81:1,122,144,146,150,166,169,177,184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Violet 19 and the like.
Specific examples of cyan colorants include the following copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, cyan pigments and cyan dyes represented by basic dye lake compounds and the like. More specifically, the following C.I. I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66 and the like.
The content of the coloring agent is preferably 1.0 parts by mass to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

The toner may contain a magnetic material to be a magnetic toner. In this case, the magnetic substance can also serve as a coloring agent.
As magnetic substances, the following iron oxides represented by magnetite, hematite, ferrite, etc.; metals represented by iron, cobalt, nickel, etc., or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc , antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and other metal alloys and mixtures thereof.
When a magnetic material is used, its content is preferably 40.0 parts by mass to 150.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

<Charge control agent>
The toner may contain a charge control agent.
As the charge control agent, conventionally known charge control agents can be used without any particular limitation. Specifically, as the negative charge control agent, the following metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid and dicarboxylic acid, or polymers or polymers containing metal compounds of the above aromatic carboxylic acids copolymer;
Polymers or copolymers having sulfonic acid groups, sulfonate groups or sulfonate ester groups;
Metal salts or metal complexes of azo dyes or azo pigments;
Boron compounds, silicon compounds, calixarene and the like can be mentioned.
Examples of the positive charge control agent include the following quaternary ammonium salts, polymeric compounds having quaternary ammonium salts in side chains; guanidine compounds; nigrosine compounds; imidazole compounds.
The polymer or copolymer having a sulfonate group or sulfonate ester group includes styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, and vinyl sulfone. A homopolymer of a sulfonic acid group-containing vinyl monomer such as acid or methacrylsulfonic acid, or a copolymer of a vinyl monomer shown in the section of the binder resin and the above sulfonic acid group-containing vinyl monomer. can be done.
The content of the charge control agent is preferably 0.01 to 5.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

<External Additives>
The toner may contain external additives.
As the external additive, conventionally known external additives can be used without any particular limitation. Specifically, raw silica fine particles such as wet-process silica and dry-process silica, or silica fine particles obtained by surface-treating the raw silica fine particles with a treatment agent such as a silane coupling agent, a titanium coupling agent, or silicone oil, Vinylidene fluoride fine particles, resin fine particles such as polytetrafluoroethylene fine particles, and the like are included.
When the external additive is contained, the content thereof is preferably 0.1 to 5.0 parts by mass with respect to 100.0 parts by mass of the toner particles.

Next, a method for manufacturing toner will be described in detail.
Conventionally known methods such as a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a pulverization method can be used as the method for producing the toner, but the method is not limited to these. The above methods are broadly classified into a suspension polymerization method in which a toner is produced simultaneously with polymer production, and a dissolution suspension method, an emulsion aggregation method, and a pulverization method in which a toner is produced using a separately produced polymer.
As an example, a method of obtaining a toner by a suspension polymerization method and an emulsion aggregation method will be described below.

<Method for Producing Toner by Suspension Polymerization>
(Dispersion process)
(meth)acrylic ester having an alkyl group having 18 to 36 carbon atoms as the first polymerizable monomer, one or more second polymerizable monomers, and, if necessary, a third A raw material dispersion liquid is prepared by adding a polymerizable monomer composition comprising the polymerizable monomer of (1) and various materials as necessary and melting, dissolving or dispersing them using a dispersing machine. At this time, an appropriate amount of a highly hydrophilic amorphous resin that forms a shell by migrating to the surface layer of the toner particles during polymerization may be added to the raw material dispersion according to the desired thickness of the shell layer.
Further, if necessary, the colorant, wax, charge control agent, solvent for viscosity adjustment, and other additives listed in the section on materials can be added as appropriate. As the solvent for adjusting the viscosity, any known solvent can be used without particular limitation as long as it can dissolve and disperse the above materials well and has low solubility in water. Examples include toluene, xylene, ethyl acetate and the like. Dispersers include, for example, homogenizers, ball mills, colloid mills, and ultrasonic dispersers.

(Granulation process)
A raw material dispersion is put into an aqueous medium prepared in advance, and a suspension is prepared using a dispersing machine such as a high-speed stirrer or an ultrasonic dispersing machine. The aqueous medium preferably contains a dispersion stabilizer for particle size adjustment and aggregation suppression. As the dispersion stabilizer, conventionally known dispersion stabilizers can be used without particular limitation.
For example, as inorganic dispersion stabilizers, phosphates represented by hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, etc.; carbonates represented by calcium carbonate, magnesium carbonate, etc. salts; metal hydroxides represented by calcium hydroxide, magnesium hydroxide, aluminum hydroxide; sulfates represented by calcium sulfate, barium sulfate, calcium metasilicate, bentonite, silica, alumina and the like.
Examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salts of carboxymethyl cellulose, polyacrylic acid and its salts, and starch.
Among them, an inorganic dispersion stabilizer is preferable because it has a large charge polarization and a strong adsorptive power to the oil phase, and therefore has a strong anti-agglomeration effect. Further, hydroxyapatite, tricalcium phosphate, and dicalcium phosphate are more preferable because they can be easily removed by pH adjustment.

(Polymerization process)
The polymerizable monomer in the suspension is polymerized to obtain toner particles having polymer A.
The polymerization initiator may be mixed with other additives when preparing the raw material dispersion, or may be mixed into the raw material dispersion immediately before suspending it in the aqueous medium. Moreover, it can be added in a state of being dissolved in a polymerizable monomer or another solvent, if necessary, during the granulation process or after the completion of the granulation process, that is, immediately before starting the polymerization process. After polymerizing the polymerizable monomer to obtain a polymer, solvent removal treatment is performed by heating or reducing pressure as necessary to obtain an aqueous dispersion of toner particles.
When a highly hydrophilic amorphous resin is added to the raw material dispersion, the amorphous resin migrates to the surface layer of the toner particles and forms a shell layer from the granulation process to the polymerization process.

(Filtration process, washing process, drying process, classification process, external addition process)
Toner particles are obtained by carrying out a filtering step of obtaining a solid content from an aqueous dispersion of toner particles by solid-liquid separation, and optionally a washing step, a drying step, and a classification step for adjusting the particle size. The toner particles may be used as toner as they are. If necessary, toner particles and an external additive such as inorganic fine powder can be mixed and adhered using a mixer to obtain a toner.

<Method for Producing Toner by Emulsion Aggregation Method>
(Manufacturing process of polymer A)
As the method for producing the polymer A, conventionally known production methods such as a solution polymerization method, a suspension polymerization method, an emulsion polymerization method, a bulk polymerization method, and a dispersion polymerization method can be used, but are not limited thereto. .
As an example, a method for obtaining polymer A by a solution polymerization method will be described below.
(meth)acrylic ester having an alkyl group having 18 to 36 carbon atoms as the first polymerizable monomer, one or more second polymerizable monomers, and, if necessary, a third (1) is dissolved in a solvent such as toluene to prepare a monomer solution. A polymerization initiator is added thereto and the polymerizable monomer is polymerized to obtain a polymer solution in which the polymer A is dissolved in a solvent such as toluene. The polymer solution is mixed with a solvent in which polymer A is insoluble (for example, methanol or the like) to precipitate polymer A. The precipitated polymer A is filtered and washed to obtain polymer A.

(Step of preparing resin fine particle dispersion)
The fine resin particle dispersion can be prepared by a known method, but is not limited to these methods. For example, an emulsion polymerization method, a self-emulsification method, a phase inversion emulsification method in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in an organic solvent, or a high temperature in an aqueous medium without using an organic solvent. There is a forced emulsification method in which the resin is forcibly emulsified by treatment.
As an example, a method for preparing a fine resin particle dispersion by a phase inversion emulsification method will be described below.
A resin component containing the polymer A is dissolved in an organic solvent in which these are soluble, and a surfactant and a basic compound are added. At that time, if the resin component is a crystalline resin having a melting point, it may be dissolved by heating to the melting point or higher. Subsequently, while stirring with a homogenizer or the like, the aqueous medium is slowly added to precipitate the fine resin particles. After that, the solvent is removed by heating or reducing pressure to prepare an aqueous dispersion of resin fine particles.
Here, the organic solvent used for dissolving the resin component containing the polymer A may be any one capable of dissolving them. Specific examples include toluene and xylene.

The surfactant used in the preparation process is not particularly limited, but examples include anionic surfactants such as sulfate ester salt-based, sulfonate-based, carboxylate-based, phosphate ester-based, and soap-based surfactants. cationic surfactants such as amine salt type and quaternary ammonium salt type; nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type and polyhydric alcohol type; Surfactants may be used singly or in combination of two or more.
Basic compounds used in the preparation step include inorganic bases such as sodium hydroxide and potassium hydroxide; organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. A basic compound may be used individually by 1 type, and may use 2 or more types together.

(Preparation of colorant dispersion)
A known dispersing method can be used to prepare the colorant dispersion, and general dispersing means such as a homogenizer, ball mill, colloid mill, and ultrasonic disperser can be used, and there is no limitation. Moreover, the above-mentioned surfactant is mentioned as surfactant used at the time of dispersion|distribution.

(Preparation of wax dispersion)
In preparing the wax dispersion, the wax is dispersed in water together with a surfactant, a basic compound, etc., then heated to a temperature above the melting point of the wax, and a homogenizer or disperser that imparts a strong shearing force is used. Distributed processing. Through such treatment, a wax dispersion is obtained. The surfactants used in dispersing include the surfactants described above. Moreover, the above-mentioned basic compound is mentioned as a basic compound used at the time of dispersion|distribution.

(Agglomerated particle forming step)
In the aggregated particle forming step, first, a resin fine particle dispersion, a colorant dispersion, a wax dispersion, and the like are mixed to form a mixture. Next, while heating at a temperature below the melting point of the fine resin particles, the pH is made acidic to cause aggregation to form aggregated particles containing resin fine particles, colorant particles, and release agent particles, thereby obtaining an aggregated particle dispersion liquid. .

(First fusion step)
In the first fusion step, the pH of the aggregated particle dispersion is raised under stirring conditions similar to those in the aggregated particle formation step to stop the progress of aggregation, and heating is performed at a temperature equal to or higher than the melting point of the polymer. A coalesced particle dispersion is obtained.

(Step of adhering amorphous resin fine particles)
In the amorphous resin particle adhering step, the amorphous resin particle dispersion is added to the fused particle dispersion, and the pH is lowered to adhere the amorphous resin particles to the surface of the fused particles to obtain resin adhered particles. to obtain a dispersion of Here, this coating layer corresponds to a shell layer formed through a shell layer forming step to be described later. Incidentally, the amorphous resin fine particle dispersion can be produced according to the preparation process of the resin fine particle dispersion described above.

(Second fusion step)
In the second fusion step, in the same manner as in the first fusion step, the progress of aggregation is stopped by raising the pH of the resin-adhered particle dispersion, and the adhered resin is aggregated by heating at a temperature equal to or higher than the melting point of polymer A. The particles are fused to obtain toner particles having a shell layer formed thereon.

(Filtration process, washing process, drying process, classification process, external addition process)
After that, a filtering process for filtering out the solid content of the toner particles, and optionally a washing process, a drying process, and a classification process for adjusting the particle size are carried out to obtain toner particles. The toner particles may be used as toner as they are. If necessary, toner particles and an external additive such as inorganic fine powder can be mixed and adhered using a mixer to obtain a toner.

<Other Shell Layer Forming Methods>
In the suspension polymerization method and the emulsion aggregation method, as described above, a method of forming a shell layer simultaneously with the production of toner particles can be used. In addition, the dissolution suspension method can also form a shell layer in the same manner as the suspension polymerization method.
Alternatively, the shell layer may be formed after forming the toner core. As an example, a method of forming a shell layer on an aqueous toner core dispersion (hereinafter referred to as a toner core dispersion) by an emulsification aggregation method and a method of forming a shell layer using a thermosetting resin precursor will be described below. is not limited to

<Formation of shell layer by emulsion aggregation method>
A shell layer can be formed by subjecting the toner core dispersion liquid to the same operations as the amorphous resin fine particle adhesion step and the second fusing step in the toner production method by the emulsification aggregation method described above.
After that, a filtering process for filtering out the solid content of the toner particles, and optionally a washing process, a drying process, and a classification process for adjusting the particle size are carried out to obtain toner particles.

<Formation of Shell Layer Using Thermosetting Resin Precursor>
After adjusting the pH of the toner core dispersion to around 4, a material for forming a shell layer is dissolved in the aqueous dispersion containing the toner cores. Thereafter, a reaction between materials for forming a shell layer is allowed to proceed in the dispersion to form a shell layer covering the surface of the toner core, thereby obtaining a toner particle dispersion.
Here, the shell layer is formed, for example, by reacting melamine, urea, reaction products of glyoxal and urea, and precursors (methylol compounds) produced by the addition reaction of these with formaldehyde.
After that, a filtering process for filtering out the solid content of the toner particles, and optionally a washing process, a drying process, and a classification process for adjusting the particle size are performed to obtain toner particles.

Next, the method for measuring the toner of the present invention will be described below.
<Method for calculating the rate at which the shell layer is observed and the thickness of the shell layer>
The ratio (coverage) at which the shell layer of the toner is observed and the thickness of the shell layer can be determined by measuring the shape of the cross section of a single toner grain. A specific method for measuring the shape of the cross section of a single toner particle is as follows.
First, after sufficiently dispersing the toner in a photocurable epoxy resin, the epoxy resin is cured by irradiating ultraviolet rays. The obtained cured product is cut using a microtome equipped with a diamond blade to prepare a flaky sample with a thickness of 100 nm. After the sample was dyed with ruthenium tetroxide, the cross section of the toner was observed using a transmission electron microscope (TEM) (trade name: electron microscope Tecnai TF20XT, manufactured by FEI) at an acceleration voltage of 120 kV. A TEM image is obtained. At this time, the cross section of the toner particles is 0.9 to 1.1 times the number average particle diameter (D1) of the toner particles measured according to the method for measuring the number average particle diameter (D1) of the toner particles described later. Select one with twice the major axis diameter.
In the observation method described above, ruthenium tetroxide strongly stains the amorphous resin in the toner particles. As a result, the shell portion containing the amorphous resin as the main component is dyed, and the undyed core portion containing the crystalline resin as the main component can be observed as a contrast. Note that the observation magnification is 20000 times.
Based on the obtained TEM image, in the cross section of one toner particle, the length C1 (nm) of the portion where the shell layer is observed in the peripheral length of one toner particle and the peripheral length C2 (nm) of one toner particle is calculated, and C1/C2×100 (%) is defined as the coverage of the shell layer (percentage at which the shell layer is observed).
The longest line segment passing through the center of gravity of the cross section of one toner particle is defined as the major axis of the toner particle, and the length is defined as the major axis diameter R (nm). Let (R−r)/2 (nm) be the thickness of the shell layer, where r (nm) is the length between the two core/shell interfaces on the major axis.
With regard to the ratio at which the shell layer is observed and the thickness of the shell layer, this measurement is carried out for 100 toner particles, and the arithmetic average value is adopted.

<Method for measuring content ratio of monomer units derived from various polymerizable monomers in polymer A>
The content of monomer units derived from various polymerizable monomers in the polymer A 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
Accumulated times: 64 times Measurement temperature: 30°C
Sample: Prepared by putting 50 mg of a sample to be measured into a sample tube with an inner diameter of 5 mm, adding deuterated chloroform (CDCl ₃ ) as a solvent, and dissolving it in a constant temperature bath at 40°C.
From the obtained ¹ H-NMR chart, among the peaks attributed to the constituent elements of the monomer units derived from the first polymerizable monomer, the peaks attributed to the constituent elements of the monomer units derived from other selects an independent peak and calculates the integrated value S1 of this peak. Similarly, from among the peaks attributed to the constituent elements of the monomer units derived from the second polymerizable monomer, select peaks that are independent of the peaks attributed to the constituent elements of the monomer units derived from other monomers. , the integrated value S2 of this peak is calculated.
Furthermore, when a third polymerizable monomer is used, from the peak attributed to the component of the monomer unit derived from the third polymerizable monomer, the component of the monomer unit derived from other A peak independent of the peak attributed to is selected, and the integrated value S3 of this peak is calculated.
The content ratio of the monomer units derived from the first polymerizable monomer is determined as follows using the integral values S1, S2, and S3. Note that n1, n2, and n3 are the numbers of hydrogen atoms in the constituent elements to which the focused peaks are assigned for each site.
Proportion of monomer units derived from the first polymerizable monomer (mol%) =
{(S1/n1)/((S1/n1)+(S2/n2)+(S3/n3))}×100
Similarly, the ratio of monomer units derived from the second polymerizable monomer and the third polymerizable monomer is obtained as follows.
Proportion (mol%) of monomer units derived from the second polymerizable monomer =
{(S2/n2)/((S1/n1)+(S2/n2)+(S3/n3))}×100
Percentage of monomer units derived from the third polymerizable monomer (mol%) =
{(S3/n3)/((S1/n1)+(S2/n2)+(S3/n3))}×100
In addition, when a polymerizable monomer containing no hydrogen atom is used in the polymer A as a constituent element other than the vinyl group, ¹³ C-NMR is used with ¹³ C as the atomic nucleus to be measured, and the single pulse mode is used. , and similarly calculated by ¹ H-NMR.
In addition, when the toner is produced by suspension polymerization, the peaks of the release agent and other resins may overlap and independent peaks may not be observed. As a result, the content ratio of the monomer units derived from various polymerizable monomers in the polymer A may not be calculated. In that case, the polymer A′ can be produced by performing the same suspension polymerization without using a release agent or other resin, and the polymer A′ can be regarded as the polymer A for analysis.

<Method for calculating SP value>
SP ₁₂ and SP ₂₂ are obtained as follows according to the calculation method proposed by Fedors.
For each polymerizable monomer, the vaporization energy (Δei ) (cal/mol) and molar volume (Δvi) (cm ³ /mol), and (4.184×ΣΔei/ΣΔvi) ^0.5 is defined as SP value (J/cm ³ ) ^0.5 .
SP ₁₁ and SP ₂₁ are calculated by the same calculation method as above for the atoms or atomic groups in the molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization.
Also, SP _S1 and SP _S2 are obtained as follows.
The SP value (SP _S ) of the resin constituting the shell layer, the evaporation energy (Δei) and molar volume (Δvi) of the repeating unit constituting the resin are obtained for each repeating unit, and the molar ratio of each repeating unit in the resin (j) is calculated, and the sum of the evaporation energies of each repeating unit is divided by the sum of the molar volumes.
Formula (S1): SP _S = {(Σj×ΣΔei)/(Σj×ΣΔvi)} ^1/2
As described above, _SPS is calculated for each resin constituting the shell layer. Let SP _S1 be the maximum value among them, and SP _S2 be the minimum value.
The unit of the SP value in the present invention is (J/m ³ ) ^0.5 , and 1 (cal/cm ³ ) ^0.5 = 2.045×10 ³ (J/m ³ ) ^0.5 ( cal/cm ³ ) can be converted to units of ^0.5 .

<Method for measuring weight average molecular weight Mw of polymer A>
The weight average molecular weight (Mw) of the THF-soluble portion of polymer A is measured by gel permeation chromatography (GPC) as follows.
First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisc" (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 THF-soluble components is 0.8% by mass. This sample solution is used for measurement under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0ml/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).

<Method for Measuring Endothermic Amount of Endothermic Peak of Toner>
The endothermic amount of the endothermic peak derived from the melting of the polymer A of the toner is determined by DSC Q1000 (TA
(manufactured by Instruments, Inc.) under the following conditions.
Heating rate: 10°C/min
Measurement start temperature: 20°C
Measurement end temperature: 180°C
The melting points of indium and zinc are used to correct the temperature of the device detector, and the heat of fusion of indium is used to correct the amount of heat.
Specifically, 5 mg of toner is precisely weighed, placed in an aluminum pan, and subjected to differential scanning calorimetry. An empty silver pan is used as a reference.
The endothermic amount of the endothermic peak resulting from the melting of the polymer A in the first temperature rising process is defined as the endothermic amount of the endothermic peak of the toner. In addition, in the toner containing the polymer A and the wax, when the endothermic peak derived from the melting of the polymer A and the endothermic peak derived from the melting of the wax are observed to overlap, the above measurement is performed separately for the wax. , determines the endotherm of the endothermic peak resulting from the melting of the wax. Then, the endothermic amount of the endothermic peak derived from the melting of the polymer A is obtained by subtracting the endothermic amount of the endothermic peak derived from the melting of the wax from the endothermic amount of the endothermic peaks observed together.

<Method for Measuring the Melting Points of Polymer A and Wax>
The melting points of polymer A and wax in the present invention are measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Heating rate: 10°C/min
Measurement start temperature: 20°C
Measurement end temperature: 180°C
The melting points of indium and zinc are used to correct the temperature of the device detector, and the heat of fusion of indium is used to correct the amount of heat.
Specifically, 5 mg of a sample is precisely weighed, placed in an aluminum pan, and subjected to differential scanning calorimetry. An empty silver pan is used as a reference.
Let the peak temperature of the maximum endothermic peak in the first heating process be the melting point.
Note that the maximum endothermic peak is the peak at which the endothermic amount is maximum when there are a plurality of peaks.

<Method for measuring charge decay rate coefficient of polymer A>
The charge decay rate coefficient of polymer A is measured using a static electricity diffusion rate measuring device NS-D100 (manufactured by Nanoseeds Co., Ltd.).
First, a sample pan is filled with about 100 mg of polymer A, and the surface is scraped to make it smooth. The sample pan is irradiated with X-rays for 30 seconds by an X-ray static eliminator to remove static charges from the polymer A. Place the neutralized sample pan on the measurement plate. A metal plate is simultaneously placed as a reference for zero correction of the surface potential meter. The measurement plate on which the sample is placed is left in an environment of 30° C. and 80% RH for 1 hour or more before measurement.
Measurement conditions are set as follows.
Charge time: 0.1 second Measurement time: 1800 seconds Measurement interval: 1 second Discharge polarity: -
Electrode: Yes The initial potential is set to -600 V, and the change in surface potential immediately after charging is measured. By fitting the obtained results to the following equation, the charge decay rate coefficient α is obtained.
V _t =V ₀ exp(−αt ^1/2 )
V _t : surface potential (V) at time t
V ₀ : initial surface potential (V)
t: Time (seconds) after charging is applied
α: charge decay rate coefficient

<Method for measuring acid value of polymer A>
The acid value is the mass (mg) of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of polymer A in the present invention is measured according to JIS K 0070-1992, and specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 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. After leaving it for 3 days in an alkali-resistant container so as not to come into contact with carbon dioxide gas, etc., it is filtered to obtain a potassium hydroxide solution. The resulting potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was obtained by taking 25 mL of 0.1 mol/L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. Determined from the amount of potassium solution. The above 0.1 mol/L hydrochloric acid is prepared according to JIS K 8001-1998.
(2) Operation (A) Main test A 2.0 g sample of pulverized polymer A is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene/ethanol (2:1) is added, and dissolved over 5 hours. . Then, several drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator continues for 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene/ethanol (2:1) is used).
(3) Calculate the acid value by substituting the obtained result into the following formula.
A = [(CB) x f x 5.61]/S
Here, A: acid value (mgKOH / g), B: added amount of potassium hydroxide solution for blank test (mL), C: added amount of potassium hydroxide solution for main test (mL), f: potassium hydroxide Solution factor, S: mass of sample (g).

<Measurement of Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measurement device, a precision particle size distribution measurement device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. The attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) is used for setting the measurement conditions and analyzing the measurement data. The measurement is performed with 25,000 effective measurement channels.
Electrolytic aqueous solution used for measurement can be prepared by dissolving special grade sodium chloride in deionized water to a concentration of 1.0%, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.). .
Before performing measurement and analysis, set the dedicated software as follows.
On the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total number of counts in control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman Coulter, Inc.) is used to set the value obtained. By pressing the "threshold/noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1,600 μA, the gain to 2, the electrolyte to ISOTON II, and put a check in the “Flush aperture tube after measurement” box.
On the "pulse-to-particle size conversion setting" screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

A specific measuring method is as follows.
(1) Put 200.0 mL of an electrolytic aqueous solution into a 250 mL glass round-bottomed beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 revolutions/second. Then, remove the dirt and air bubbles inside the aperture tube using the dedicated software's "Flush Aperture Tube" function.
(2) Put 30.0 mL of the electrolytic aqueous solution into a 100 mL flat-bottom glass beaker. As a dispersant, "Contaminon N" (a 10% aqueous solution of a neutral detergent for cleaning precision measuring instruments at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) was used as a dispersant. ) is diluted with ion-exchanged water to 3 times the mass, and 0.3 mL of the diluted solution is added.
(3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two oscillators with an oscillation frequency of 50 kHz built in with a phase shift of 180 degrees. do. 3.3 L of deionized water is placed in the water tank of the ultrasonic disperser, and 2.0 mL of Contaminon N is added to this water tank.
(4) The beaker of (2) above is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) above is being irradiated with ultrasonic waves, 10 mg of toner particles are added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water in the water tank is appropriately adjusted to 10°C or higher and 40°C or lower.
(6) The electrolytic aqueous solution of (5) above, in which toner particles are dispersed, is dropped into the round-bottomed beaker of (1) above set in the sample stand, and the measured concentration is adjusted to 5%. . The measurement is continued until the number of measured particles reaches 50,000.
(7) Analyze the measurement data with dedicated software attached to the apparatus to calculate the weight average particle size (D4) and the number average particle size (D1). In addition, when graph / volume% is set with dedicated software, the "average diameter" on the "analysis / volume statistical value (arithmetic mean)" screen is the weight average particle diameter (D4), and graph / number% with dedicated software The "average diameter" on the "analysis/number statistical value (arithmetic mean)" screen when setting is the number average particle diameter (D1).

The present invention will be specifically described by way of examples shown below. However, this does not limit the invention in any way. "Parts" and "%" in Examples and Comparative Examples are all based on mass unless otherwise specified.

<Production example of polymerizable monomer>
<Urethane group-containing monomer>
50.0 parts of methanol was charged into the reactor. After that, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] (Showa Denko KK) was added dropwise at 40° C. while stirring. After the dropwise addition was completed, the mixture was stirred for 2 hours while maintaining the temperature at 40°C. Then, a urethane group-containing monomer was prepared by removing unreacted methanol with an evaporator.

<Urea group-containing monomer>
A reaction vessel was charged with 50.0 parts of dibutylamine. After that, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] was added dropwise at room temperature while stirring. After the dropwise addition was completed, the mixture was stirred for 2 hours. Then, the urea group-containing monomer was prepared by removing unreacted dibutylamine with an evaporator.

<Production example of amorphous resin>
<Amorphous resin 1>
The following materials were added into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device and a stirring device.
・Terephthalic acid 32.3 parts (50.0 mol%) ・Bisphenol A-propylene oxide 2 mol adduct 67.7 parts (50.0 mol%) ・Titanium potassium oxalate (catalyst) 0.02 parts The reaction was carried out at 220° C. under nitrogen atmosphere and normal pressure until the desired molecular weight was reached. After the temperature was lowered, the mixture was pulverized to obtain an amorphous resin 1. Table 1 shows the physical properties of the amorphous resin 1.

<Amorphous Resin 2>
The following materials were added into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device and a stirring device.
・Terephthalic acid 29.1 parts (45.0 mol%) ・Isophthalic acid 3.2 parts (5.0 mol%)
・67.7 parts of bisphenol A-propylene oxide 2 mol adduct (50.0 mol%)
• Potassium titanium oxalate (catalyst) 0.02 parts Subsequently, the reaction was carried out at 220°C under normal pressure in a nitrogen atmosphere until the desired molecular weight was reached. After the temperature was lowered, the mixture was pulverized to obtain an amorphous resin 2. Table 1 shows the physical properties of the amorphous resin 2.

<Amorphous resin 3>
In a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, the following materials were charged under a nitrogen atmosphere.
・Solvent toluene 100.0 parts ・Styrene 91.7 parts ・Methyl methacrylate 2.5 parts ・Methacrylic acid 3.3 parts ・Methacrylate-2-hydroxyethyl 2.5 parts ・Polymerization initiator t-butyl peroxypi Valate (manufactured by NOF Corporation: Perbutyl PV) 5.0 parts While stirring the reaction vessel at 200 rpm, the polymerization reaction is performed by heating to 70 ° C. for 12 hours, and the polymer of the monomer composition is dissolved in toluene. A dissolved solution was obtained. Subsequently, after the solution was cooled to 25° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was separated by filtration, washed with methanol, and vacuum-dried at 40° C. for 24 hours to obtain an amorphous resin 3 . Table 1 shows the physical properties of the amorphous resin 3.

<Amorphous resins 4 to 6>
Amorphous resins 4 to 6 were obtained in the same manner as in the production method of amorphous resin 3, except that the charged amount of the polymerizable monomer was changed to that shown in Table 1. Table 1 shows the physical properties of the amorphous resins 4 to 6.

<Crystalline resin 1>
The following materials were added into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device and a stirring device.
・64.2 parts (50.0 mol%) of sebacic acid ・35.8 parts (50.0 mol%) of 1,6-hexanediol ・0.06 parts of potassium titanium oxalate (catalyst) Subsequently, under a nitrogen atmosphere and normal pressure at 220° C. until the desired molecular weight was obtained. After the temperature was lowered, the mixture was pulverized to obtain a crystalline resin 1. Table 1 shows the physical properties of the crystalline resin 1.

（※表１中、ＰＥＳはポリエステル、ＢＰＡ－ＰＯ２モル付加物はビスフェノールＡ－プロピレンオキサイド２モル付加物、２－ＨＥＭＡはメタクリル酸２－ヒドロキシエチルをそれぞれ表す。）

(*In Table 1, PES represents polyester, BPA-PO 2 mol adduct represents bisphenol A-propylene oxide 2 mol adduct, and 2-HEMA represents 2-hydroxyethyl methacrylate.)

<Production Example of Amorphous Resin Fine Particle Dispersion>
<Amorphous Resin Fine Particle Dispersion 1>
The following materials were weighed into a reaction vessel equipped with a thermometer.
・Ion-exchanged water 350.0 parts ・Sodium dodecylbenzenesulfonate 5.0 parts ・Sodium laurate 10.0 parts K. While stirring at 7000 rpm using Robomix (manufactured by Primix), the temperature was raised to 90° C. to obtain an aqueous medium S1. Separately, 100.0 parts of amorphous resin 1 was dissolved in 100.0 parts of toluene at 90°C. The obtained toluene solution of the amorphous resin 1 was added to the aqueous medium S1 under stirring under the above conditions, and stirred under the above conditions. Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.).
After toluene was removed using an evaporator, the concentration was adjusted to 20% by mass with deionized water to obtain an amorphous resin fine particle dispersion liquid 1 in which fine particles of the amorphous resin 1 were dispersed.
The 50% particle diameter (Dv50) based on volume distribution of the amorphous resin fine particles 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso) and found to be 0.12 μm.

<Amorphous Resin Fine Particle Dispersions 2 to 6>
Amorphous resin fine particle dispersions 2 to 6 were obtained in the same manner as in the production example of amorphous resin fine particle dispersion 1, except that the materials used were changed to those shown in Table 2.

<Production example of polymer A0>
In a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, the following materials were charged under a nitrogen atmosphere.
Solvent toluene 100.0 parts Monomer composition 100.0 parts (monomer composition is the following behenyl acrylate (monomer unit SP value: 18.25, monomer SP value: 17.69) Methacrylonitrile (monomer unit SP value: 25.96, monomer SP value: 21.97) and styrene (monomer unit SP value: 20.11, monomer SP value: 17.94) in the following ratios shall be mixed with
- Behenyl acrylate (22 carbon atoms) 67.0 parts (28.9 mol%)
- 22.0 parts of methacrylonitrile (53.8 mol%)
・ Styrene 11.0 parts (17.3 mol%)
・Polymerization initiator t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 0.5 parts While stirring the inside of the reaction vessel at 200 rpm, the polymerization reaction is performed by heating to 70 ° C. for 12 hours. A solution was obtained in which the polymer of the solid composition was dissolved in toluene. Subsequently, after the solution was cooled to 25° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was separated by filtration, washed with methanol, and vacuum-dried at 40° C. for 24 hours to obtain polymer A0. Polymer A0 had a weight average molecular weight of 68400, an acid value of 0.0 mgKOH/g, and a melting point of 62°C.
When the polymer A0 was analyzed by NMR, the monomer unit derived from behenyl acrylate was 28.9 mol%, the monomer unit derived from methacrylonitrile was 53.8 mol%, and the monomer unit derived from styrene was 17.3 mol%. was included.

<Production Example of Toner Core Dispersion>
<Toner Core Dispersion 1 (Emulsion Aggregation Method)>
[Production Example of Polymer Fine Particle Dispersion E1]
The following materials were weighed into a reaction vessel equipped with a thermometer.
・Ion-exchanged water 350.0 parts ・Sodium dodecylbenzenesulfonate 5.0 parts ・Sodium laurate 10.0 parts K. While stirring at 7000 rpm using Robomix (manufactured by Primix), the temperature was raised to 90° C. to obtain an aqueous medium E1. Separately, 100.0 parts of polymer A0 was dissolved in 100.0 parts of toluene at 90°C. The obtained toluene solution of the polymer A0 was added to the aqueous medium E1 under stirring under the above conditions, and stirred under the above conditions. Furthermore, emulsification was performed at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.).
After toluene was removed using an evaporator, the concentration was adjusted to 20% by mass with deionized water to obtain polymer fine particle dispersion E1 in which polymer fine particles E1 were dispersed.
The 50% particle diameter (Dv50) based on volume distribution of the polymer fine particles E1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

[Production Example of Wax Fine Particle Dispersion Liquid E1]
The following materials were weighed into a reaction vessel equipped with a thermometer.
・Wax Paraffin wax 100.0 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51 melting point Tm: 74 ° C.)
・ Anionic surfactant 5.0 parts (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK)
・Ion-exchanged water 395.0 parts K. Dispersion treatment was performed for 60 minutes by heating to 90° C. while stirring at 7000 rpm using Robomix (manufactured by Primix).
After the dispersion treatment, the mixture was cooled to 40° C. to obtain a wax fine particle dispersion E1 having a concentration of 20% by mass.
The 50% particle diameter (Dv50) based on volume distribution of the fine wax particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.

[Production Example of Colorant Fine Particle Dispersion E1]
- Colorant 50.0 parts (cyan pigment made by Dainichiseika: Pigment Blue 15:3)
・Anionic surfactant Neogen RK (Daiichi Kogyo Seiyaku Co., Ltd.) 7.5 parts ・Ion-exchanged water 442.5 parts and dispersed for about 1 hour to obtain an aqueous dispersion (colorant fine particle dispersion E1) having a concentration of 10 mass % of colorant fine particles in which the colorant is dispersed.
The 50% particle size (Dv50) based on volume distribution of the fine colorant particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

[Production example of toner core]
The following materials were weighed into a reaction vessel equipped with a thermometer.
・Polymer fine particle dispersion E1 (20% by mass) 500.0 parts ・Wax fine particle dispersion E1 (20% by mass) 100.0 parts ・Colorant fine particle dispersion E1 (10% by mass) 65.0 parts ・Ion exchange Water 160.0 parts The above materials were dispersed in a reactor at 5000 r/min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). After adjusting the pH to 3.0 by adding a 1.0% nitric acid aqueous solution, the mixture was heated to 58°C in a water bath for heating while adjusting the number of revolutions so that the mixture was stirred using a stirring blade. heated to When aggregated particles having a weight average particle diameter (D4) of 6.5 μm were formed, the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution. After that, the mixture was heated to 75° C. while stirring was continued. Then, the aggregated particles were fused by holding at 75° C. for 1 hour.
After that, it was cooled to 25° C., filtered, solid-liquid separated, and then washed with ion-exchanged water. After washing, the toner core 1 having a weight average particle size (D4) of 6.5 μm was obtained by drying using a vacuum dryer.

[Production of Toner Core Dispersion]
・Ion-exchanged water 395.0 parts ・Toner core 1 100.0 parts ・Anionic surfactant 5.0 parts (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK)
The above materials were placed in a beaker and stirred at 3000 rpm for 3 minutes using Disper (manufactured by Tokushu Kika Co., Ltd.) to obtain Toner Core Dispersion Liquid 1.

<Toner core dispersion liquid 2 (pulverization method)>
[Production of Toner Core]
・Binder resin Polymer A0 100.0 parts ・Colorant Pigment Blue 15:3 6.5 parts ・Wax Paraffin wax 20.0 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51, melting point Tm: 74° C.)
The above materials were pre-mixed with a Henschel mixer (manufactured by Nippon Coke Co., Ltd.), and then melt-kneaded with a twin-screw kneading extruder (manufactured by Ikegai Iron Works Co., Ltd.: PCM-30 type).
The resulting kneaded product is cooled, coarsely pulverized with a hammer mill, and then pulverized with a mechanical pulverizer (manufactured by Turbo Kogyo Co., Ltd.: T-250), and the resulting finely pulverized powder is multi-divided using the Coanda effect. Classification was performed using a classifier to obtain a toner core 2 having a weight average particle diameter (D4) of 6.6 μm.

[Production of Toner Core Dispersion]
・Ion-exchanged water 395.0 parts ・Toner core 2 100.0 parts ・Anionic surfactant 5.0 parts (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK)
The above materials were placed in a beaker and stirred at 3000 rpm for 3 minutes using Disper (manufactured by Tokushu Kika Co., Ltd.) to obtain Toner Core Dispersion Liquid 2.

<Toner Core Dispersion 3 (Dissolution Suspension Method)>
[Preparation of Fine Particle Dispersion Y1]
The following materials were put into a reaction vessel equipped with a stirring bar and a thermometer.
Water 683.0 parts Sodium salt of methacrylic acid EO adduct sulfate ester 11.0 parts (manufactured by Sanyo Chemical Industries, Ltd.: Eleminol RS-30)
・Styrene 130.0 parts ・Methacrylic acid 138.0 parts ・N-Butyl acrylate 184.0 parts ・Ammonium persulfate 1.0 parts When the inside of the reaction vessel was stirred at 400 rpm for 15 minutes, a white suspension was formed. Got. The system temperature was raised to 75° C. by heating, and the reaction was carried out for 5 hours. Further, 30.0 parts of a 1% aqueous ammonium persulfate solution was added, and the mixture was aged at 75° C. for 5 hours to obtain a vinyl polymer fine particle dispersion liquid Y1. The volume average particle diameter of fine particle dispersion Y1 was 0.15 μm.

[Preparation of Colorant Dispersion Y1]
・C. I. Pigment Blue 15:3 100.0 parts Ethyl acetate 150.0 parts Glass beads (1 mm) 200.0 parts The above materials were placed in a heat-resistant glass container, dispersed for 5 hours with a paint shaker, and then mixed with a nylon mesh. , the glass beads were removed to obtain a colorant dispersion liquid Y1.

[Preparation of Wax Dispersion Y1]
・Wax Paraffin wax 20.0 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51 melting point Tm: 74 ° C.)
Ethyl acetate 80.0 parts The above ingredients were placed in a sealable reaction vessel and heated at 80°C with stirring. Then, the inside of the system was slowly stirred at 50 rpm and cooled down to 25° C. over 3 hours to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 30.0 parts of glass beads with a diameter of 1 mm, dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki), and the glass beads were removed with a nylon mesh to obtain a wax dispersion liquid Y1. rice field.

[Preparation of oil phase Y1]
- Polymer A0 100.0 parts - Ethyl acetate 85.0 parts The above materials were placed in a beaker and stirred at 3000 rpm for 1 minute using Disper (manufactured by Tokushu Kika Co., Ltd.).
・Wax dispersion liquid Y1 (solid content: 20% by mass) 50.0 parts ・Colorant dispersion liquid Y1 (solid content: 40% by mass) 12.5 parts ・Ethyl acetate 5.0 parts (manufactured by Tokushu Kika Co., Ltd.) and stirred at 6000 rpm for 3 minutes to prepare oil phase Y1.

[Preparation of aqueous phase Y1]
・ Fine particle dispersion liquid Y1 15.0 parts ・ Sodium dodecyl diphenyl ether disulfonate aqueous solution 30.0 parts (manufactured by Sanyo Chemical Industries, Ltd.: Eleminol MON7)
- Ion-exchanged water 955.0 parts The above materials were placed in a beaker and stirred at 3000 rpm for 3 minutes using Disper (manufactured by Tokushu Kika) to prepare an aqueous phase Y1.

[Production of Toner Core]
The oil phase Y1 was added to the water phase Y1 and dispersed for 10 minutes at 10000 rpm with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.). After that, the solvent was removed for 30 minutes at 30° C. under reduced pressure of 50 mmHg. Next, filtration was performed, and the operations of filtration and re-dispersion in ion-exchanged water were repeated until the conductivity of the slurry reached 100 μS, thereby removing the surfactant and obtaining a filter cake.
After vacuum-drying the filter cake, air classification was performed to obtain toner cores 3 having a weight average particle diameter (D4) of 6.6 μm.

[Production of Toner Core Dispersion]
・Ion-exchanged water 395.0 parts ・Toner core 3 100.0 parts ・Anionic surfactant 5.0 parts (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK)
The above materials were placed in a beaker and stirred at 3000 rpm for 3 minutes using Disper (manufactured by Tokushu Kika Co., Ltd.) to obtain Toner Core Dispersion 3.

<Toner production example>
<Toner 1>
・Monomer composition 100.0 parts (monomer composition is the following behenyl acrylate (monomer unit SP value: 18.25, monomer SP value: 17.69) ・Methacrylonitrile (monomer unit SP value: 25.96, monomer SP value: 21.97) and styrene (monomer unit SP value: 20.11, monomer SP value: 17.94) are mixed in the following proportions)
- Behenyl acrylate 67.0 parts (28.9 mol%)
- 22.0 parts of methacrylonitrile (53.8 mol%)
・ Styrene 11.0 parts (17.3 mol%)
・Colorant Pigment Blue 15:3 6.5 parts ・Amorphous resin 1 4.0 parts ・Wax Paraffin wax 20.0 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51 melting point Tm: 74 ° C.)
- A mixture of 100.0 parts of toluene was prepared. The above mixture was put into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads with a diameter of 5 mm to obtain a raw material dispersion.
On the other hand, 735.0 parts of ion-exchanged water and 16.0 parts of trisodium phosphate (12-hydrate) were added to a container equipped with a high-speed stirring device Homomixer (manufactured by Primix) and a thermometer, and stirred at 12000 rpm. The temperature was raised to 60° C. while A calcium chloride aqueous solution prepared by dissolving 9.0 parts of calcium chloride (dihydrate) in 65.0 parts of ion-exchanged water was added thereto, and the mixture was stirred at 12000 rpm for 30 minutes while maintaining the temperature at 60°C. 10% Hydrochloric acid was added thereto to adjust the pH to 6.0 to obtain an aqueous medium in which an inorganic dispersion stabilizer containing hydroxyapatite was dispersed in water.
Subsequently, the raw material dispersion was transferred to a container equipped with a stirrer and a thermometer, and the temperature was raised to 60° C. while stirring at 100 rpm. There, 8.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) as a polymerization initiator was added and stirred at 100 rpm for 5 minutes while maintaining 60 ° C., and then added to the high-speed stirring device. into an aqueous medium stirred at 12000 rpm. Stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device while maintaining the temperature at 60° C. to obtain a granulation liquid.
The granulation liquid was transferred to a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer and a nitrogen inlet tube, and heated to 70° C. under a nitrogen atmosphere while being stirred at 150 rpm. A polymerization reaction was carried out at 150 rpm for 10 hours while maintaining the temperature at 70°C. Thereafter, the reflux condenser was removed from the reaction vessel, and the temperature of the reaction solution was raised to 95° C., followed by stirring at 150 rpm for 5 hours while maintaining the temperature at 95° C. to remove toluene, thereby obtaining a toner particle dispersion.
The obtained toner particle dispersion was cooled to 20° C. while being stirred at 150 rpm, and diluted hydrochloric acid was added until the pH reached 1.5 while stirring to dissolve the dispersion stabilizer. The solid content was separated by filtration, thoroughly washed with deionized water, and vacuum-dried at 40° C. for 24 hours to obtain toner particles 1 containing the polymer A1 of the monomer composition.
To the obtained toner particles 1: 100.0 parts, silica fine particles (hydrophobization treatment with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m ² / 2.0 parts of g) were added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 1. Physical properties of Toner 1 are shown in Tables 5-1, 5-2 and 6.
In addition, a polymer a1 was obtained in the same manner as in the production example of the toner 1 except that the coloring agent, the amorphous resin and the wax were omitted. Polymer a1 had a weight average molecular weight of 56,000, an acid value of 0.0 mgKOH/g, and a melting point of 62°C. When polymer a1 was analyzed by NMR, it contained 28.9 mol% of behenyl acrylate-derived monomer units, 53.8 mol% of methacrylonitrile-derived monomer units, and 17.3 mol% of styrene-derived monomer units. It was The physical property values of the polymer a1 were used as the physical property values of the polymer A1.

<Toners 9, 10, 13 to 36, 38, 41 to 48>
Toners 9, 10, 13-36, 38, 41-48 were obtained in the same manner as in Toner 1 except that the materials used were changed as shown in Table 3. In the manufacturing examples of toners 27 and 28, t-butylperoxy 2-ethylhexanoate (PERBUTYL O manufactured by NOF Corporation) was added to the reaction liquid by 1.5°C before heating the reaction liquid to 95°C. Added 5 parts. Physical properties of the obtained toner are shown in Tables 5-1, 5-2 and 6. Table 7 shows the SP values of the monomers used.

<Toner 2>
The following materials were weighed into a reaction vessel equipped with a thermometer.
・Toner core dispersion liquid 1 (20% by mass) 500.0 parts ・Amorphous resin fine particle dispersion liquid 1 (20% by mass) 30.0 parts The above materials are placed in a reaction vessel and homogenizer Ultra Turrax T50 (manufactured by IKA). at 5000 rpm for 10 minutes. After adjusting the pH to 3.0 by adding a 1.0% nitric acid aqueous solution, the mixture was heated to 58°C in a water bath for heating while adjusting the number of revolutions so that the mixture was stirred using a stirring blade. to adhere the amorphous resin fine particles to the toner core. When particles having a weight average particle diameter (D4) of 6.7 μm were formed, the pH was adjusted to 9.0 using a 5% aqueous sodium hydroxide solution. After that, the mixture was heated to 75° C. while stirring was continued. Then, the aggregated particles were fused by holding at 75° C. for 1 hour.
After that, it was cooled to 25° C., filtered, solid-liquid separated, and then washed with ion-exchanged water. After washing, the toner particles 2 having a weight average particle size (D4) of 6.7 μm were obtained by drying using a vacuum dryer.
To the obtained toner particles 2: 100.0 parts, silica fine particles (hydrophobization treatment with hexamethyldisilazane, primary particle number average particle diameter: 10 nm, BET specific surface area: 170 m ² / Toner 2 was obtained by adding 2.0 parts of g) and mixing them for 15 minutes at 3000 rpm using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.). Physical properties of Toner 2 are shown in Tables 5-1, 5-2 and 6.

<Toners 3 to 5, 7, 8, 11, 12, 39, 40>
Toners 5, 7, 8, 11, 12, 39, and 40 were produced in the same manner as in Toner 2 except that the materials and conditions used were changed as shown in Table 4. Physical properties are shown in Tables 5-1, 5-2 and 6.

<Toner 6>
The following materials were weighed into a reaction vessel equipped with a stirrer and thermometer.
Toner core dispersion liquid 2 500.0 parts The inside of the reaction vessel was adjusted to pH 4 with a 1 mol/L aqueous solution of p-toluenesulfonic acid. 4 parts of an aqueous solution of prepolymerized hexamethylolmelamine (Milben resin SM-607 (solid concentration: 80 mass %) manufactured by Showa Denko KK) was added to this solution. 300.0 parts of ion-exchanged water was added while stirring, the temperature was raised at a rate of 1° C./min while stirring, and the temperature was maintained at 70° C. for 2 hours. It was then cooled to room temperature and adjusted to pH7. Toner particles 6 having a weight average particle diameter (D4) of 6.6 μm were obtained by performing filtration, washing, drying and classification.
To the obtained toner particles 6: 100.0 parts, silica fine particles (hydrophobization treatment with hexamethyldisilazane, primary particle number average particle size: 10 nm, BET specific surface area: 170 m ² / 3.0 parts of g) were added and mixed at 3000 rpm for 15 minutes using a Henschel mixer (manufactured by Nippon Coke Co., Ltd.) to obtain Toner 6. Physical properties of Toner 6 are shown in Tables 5-1, 5-2 and 6.

<Toner 37>
Toner core 1: 100.0 parts of silica fine particles (hydrophobic treatment with hexamethyldisilazane, number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ² /g) as an external additive2. Add 0 parts and use a Henschel mixer (manufactured by Nippon Coke Co., Ltd.),
Toner 37 was obtained by mixing for 15 minutes at 3000 rpm. The physical properties of Toner 37 are shown in Tables 5-1, 5-2 and 6.

（表３中、ＤＰ－１８はジペンタエリスリトールヘキサステアレートを表す。２－ＨＰＭＡは２－ヒドロキシプロピルメタクリレートを表す。）

(In Table 3, DP-18 represents dipentaerythritol hexastearate. 2-HPMA represents 2-hydroxypropyl methacrylate.)

（表５－１中、２－ＨＰＭＡは２－ヒドロキシプロピルメタクリレートを表す。）

(In Table 5-1, 2-HPMA represents 2-hydroxypropyl methacrylate.)

[Examples 1 to 36, Comparative Examples 1 to 11]
Using the above toners 1 to 47, the combinations shown in Table 8 were evaluated. Table 8 shows the evaluation results.

The evaluation method and evaluation criteria of the present invention are described below.
<1. Evaluation of transferability>
As an image forming apparatus, a commercial laser printer LBP-712Ci (manufactured by Canon Inc.) having an intermediate transfer belt as an intermediate transfer member was used. The secondary transfer bias was made variable, and the process speed was modified to 240 mm/sec. A toner cartridge 040H (cyan) (manufactured by Canon Inc.), which is a commercially available process cartridge, was used. After removing the product toner from the inside of the cartridge and cleaning it by an air blow, 165 g of the toner to be evaluated was filled.
The product toner was removed from each station of yellow, magenta, and black, and evaluation was performed by inserting yellow, magenta, and black cartridges in which the remaining toner amount detection mechanism was disabled.

<1-1. Evaluation of Initial Transferability in Normal Temperature and Normal Humidity Environment (N/N Initial Transferability)>
The process cartridge, the remodeled laser printer, and the evaluation paper (GF-C081 (manufactured by Canon) A4: 81.4 g/m ² ) were placed in a normal temperature and normal humidity environment (25 ° C./50% RH, hereinafter N/N environment). for 48 hours.
The secondary transfer bias of the modified laser printer is set to a potential that makes the potential difference 300 V smaller than the normal potential. The apparatus was stopped, and the amount of toner applied on the intermediate transfer member M1 (mg/cm ² ) before the transfer step and the amount of toner applied on the intermediate transfer member M2 (mg/cm ² ) after the transfer step were measured. From the obtained toner lay-on amount, (M1−M2)×100/M1 was defined as the transfer efficiency (%).
The above evaluation was performed while changing the potential difference by 50 V, and the transfer efficiency at each secondary transfer bias was measured.
Transferability was evaluated according to the following evaluation criteria. The better the transferability, the better the transfer efficiency even if the secondary transfer bias is low. As a result, the toner image on the drum can be faithfully transferred onto the paper, and a high-quality image can be obtained.
(Transferability evaluation criteria)
A: Shows a transfer efficiency of 98% or more even at a potential lower than normal by 200V.
B: Shows a transfer efficiency of 98% or more even at a potential lower than normal by 100V.
C: Shows a transfer efficiency of 98% or more at a normal potential.
D: Shows less than 98% transfer efficiency at normal potential.

<1-2. Evaluation of transferability after endurance use in normal temperature and humidity environment (transferability after N/N endurance)>
After the initial transferability evaluation under normal temperature and normal humidity environment, 25,000 sheets of images with a printing ratio of 0.5% were continuously printed on evaluation paper under N/N environment. After standing in the same environment for 24 hours, the same evaluation as the initial transferability evaluation in the normal temperature and normal humidity environment was performed.
Evaluation was made in accordance with the evaluation criteria for transferability described above, and evaluation of transferability after durability under a normal temperature and normal humidity environment was made.

<1-3. Evaluation of Initial Transferability in High Temperature and High Humidity Environment (H/H Initial Transferability)>
The process cartridge, the remodeled laser printer, and the evaluation paper (GF-C081 (manufactured by Canon) A4: 81.4 g/m ² ) were placed in a high-temperature and high-humidity environment (30° C./80% RH, hereinafter H/H environment). for 48 hours. Subsequently, the same evaluation as the initial transferability evaluation in the normal temperature and normal humidity environment was performed.
Evaluation was made according to the evaluation criteria for transferability, and the initial transferability was evaluated in a high-temperature, high-humidity environment.

<1-4. Initial transcription property evaluation after storage (initial transcription property after storage)>
The above process cartridge was subjected to a cyclical high temperature and high humidity environment (heating from 25° C. to 50° C. over 11 hours, holding at 55° C. for 1 hour, dropping to 25° C. over 11 hours, holding at 25° C. for 1 hour, and repeating this cycle. Humidity was 95. % RH.) for 30 days.
The process cartridge after standing, the modified laser printer, and the evaluation paper (GF-C081 (manufactured by Canon) A4: 81.4 g / m ² ) were placed in a normal temperature and normal humidity environment (25 ° C./50% RH, hereinafter N /N environment) for 48 hours. Subsequently, the same evaluation as the initial transferability evaluation in the normal temperature and normal humidity environment was performed.
Evaluation was made according to the evaluation criteria for transferability described above, and evaluation of initial transferability after storage was performed.

<2. Low-temperature fixability>
As an image forming apparatus, a commercially available laser printer LBP-712Ci (manufactured by Canon) was remodeled to operate even if the fixing device is removed, and a toner cartridge 040H (cyan) (Canon), which is a commercially available process cartridge. ) was used. After removing the product toner from the inside of the cartridge and cleaning it by an air blow, 165 g of the toner to be evaluated was filled. Product toner was removed from each station of yellow, magenta, and black, and evaluation was performed by inserting yellow, magenta, and black cartridges in which the remaining toner amount detection mechanism was disabled.
The process cartridge, the modified laser printer, and the transfer paper (Fox River Bond (90 g/m ² )) were allowed to stand in a normal temperature and normal humidity environment (25° C./50% RH, hereinafter N/N environment) for 48 hours. . The process cartridge was set in the laser printer, and an unfixed image of an image pattern in which 9 points of square images of 10 mm×10 mm were evenly arranged on the transfer paper was output. The toner laying amount on the transfer paper was 0.80 mg/cm ² and the fixation start temperature was evaluated.
As a fixing device, the fixing device of the LBP-712Ci was removed to the outside, and an external fixing device was used so that it could operate outside the laser beam printer. Note that the external fixing device sets the fixing temperature to temperature 1
The temperature was raised from 00° C. in increments of 10° C., and fixing was performed under the conditions of a process speed of 240 mm/sec.
The fixed image was rubbed with Silbon paper [Lenz Cleaning Paper "dasper (R)" (Ozu Paper Co. Ltd.)] with a load of 50 g/ ^cm2 . Then, the temperature at which the rate of density decrease before and after rubbing became 20% or less was defined as the fixation start temperature, and the low-temperature fixability was evaluated according to the following criteria. Table 8 shows the evaluation results.
(Evaluation Criteria for Fixing Temperature)
A: Fixing start temperature is 100°C or less B: Fixing start temperature is 110°C
C: Fixing start temperature is 120°C
D: Fixing start temperature is 130° C. or higher

Claims (16)

A toner having toner particles in which a toner core containing a binder resin is coated with a shell layer,
The binder resin comprises a first monomer unit derived from a first polymerizable monomer and a second monomer unit derived from a second polymerizable monomer different from the first polymerizable monomer. Containing a polymer A having a monomer unit,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all monomer units in the polymer A,
The content ratio of the second monomer unit in the polymer A is 20.0 mol% to 95.0 mol% based on the total number of moles of all monomer units in the polymer A,
When the SP value of the first monomer unit is SP ₁₁ (J/cm ³ ) ^0.5 and the SP value of the second monomer unit is SP ₂₁ (J/cm ³ ) ^0.5 , the following formula satisfy (1),
3.00≦(SP ₂₁ −SP ₁₁ )≦25.00 (1)
In an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM), a shell layer is observed over 90% or more of the outer periphery of the cross section of the toner,
the shell layer is composed of at least one amorphous resin selected from the group consisting of homopolymers, alternating copolymers, and random copolymers;
When the shell layer is composed of two or more amorphous resins,
Resin S1 is a resin having the highest SP value among the resins constituting the shell layer,
Resin S2 is a resin having the lowest SP value among the resins constituting the shell layer,
When the SP value of the resin S1 is SP _S1 (J/cm ³ ) ^0.5 and the SP value of the resin S2 is SP _S2 (J/cm ³ ) ^0.5 , the following formula (2) is satisfied. A toner characterized by:
SP _S1 -SP _S2 ≤ 3.0 (2) A toner having toner particles in which a toner core containing a binder resin is coated with a shell layer,
a polymer A in which the binder resin is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer; contains,
The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the composition can be,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition can be,
The SP value of the first polymerizable monomer is SP ₁₂ (J/cm ³ ) ^0.5 , and the SP value of the second polymerizable monomer is SP ₂₂ (J/cm ³ ) ^0.5 . When the following formula (3) is satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (3)
In an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM), a shell layer is observed over 90% or more of the outer periphery of the cross section of the toner,
the shell layer is composed of at least one amorphous resin selected from the group consisting of homopolymers, alternating copolymers, and random copolymers;
When the shell layer is composed of two or more kinds of amorphous resins,
Resin S1 is a resin having the highest SP value among the resins constituting the shell layer,
Resin S2 is a resin having the lowest SP value among the resins constituting the shell layer,
When the SP value of the resin S1 is SP _S1 (J/cm ³ ) ^0.5 and the SP value of the resin S2 is SP _S2 (J/cm ³ ) ^0.5 , the following formula (2) is satisfied. A toner characterized by:
SP _S1 -SP _S2 ≤ 3.0 (2) 1. The content ratio of the second monomer unit in the polymer A is 40.0 mol % to 95.0 mol % based on the total number of moles of all the monomer units in the polymer A. Toner described in . The content of the second polymerizable monomer in the composition is 40.0 mol% to 95.0 mol% based on the total number of moles of all polymerizable monomers in the composition. 3. The toner of claim 2. 5. Any one of claims 1 to 4, wherein the first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms. 1. The toner according to item 1. The toner according to any one of claims 1 to 5, wherein the polymer A has an acid value of 30 mgKOH/g or less. The toner according to any one of claims 1 to 6, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ¹ is −C≡N ,
- C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms ),
hydroxy group,
—COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms) ,
- NHCOOR ¹² (R ¹² is an alkyl group having 1 to 4 carbon atoms) ,
- NH-C(=O)-N(R ¹³ ) ₂ (each R ¹³ is independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms ),
—COO(CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(=O)—N(R ¹⁵ ) ₂ (R ¹⁵ is each independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
and R ³ is a hydrogen atom or a methyl group. )
(In formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) 8. The toner according to claim 7, wherein the second polymerizable monomer is at least one selected from the group consisting of formulas (A) and (B) below.

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ¹ is −C≡N ,
- C(=O)NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms ),
hydroxy group,
—COOR ¹¹ (R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
—COO(CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO(CH ₂ ) ₂ —NH—C(=O)—N(R ¹⁵ ) ₂ (R ¹⁵ is each independently, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
and R ³ is a hydrogen atom or a methyl group. )
(In formula (B), R ² is an alkyl group having 1 to 4 carbon atoms, and R ³ is a hydrogen atom or a methyl group.) The polymer A has a first monomer unit derived from the first polymerizable monomer and a second monomer unit derived from the second polymerizable monomer, and Having a third monomer unit derived from a third polymerizable monomer different from the one polymerizable monomer and the second polymerizable monomer,
According to any one of claims 1 to 8, wherein the third monomer unit is a monomer unit derived from at least one polymerizable monomer selected from the group consisting of styrene, methyl methacrylate, and methyl acrylate. Toner as described. the toner contains wax;
The polymer A has a first monomer unit derived from the first polymerizable monomer and a second monomer unit derived from the second polymerizable monomer,
When the content of the polymer A in the toner is 100 parts by mass, the content of the wax is W parts by mass, and the content of the first monomer unit is A parts by mass, the following formula The toner according to any one of claims 1 to 9, which satisfies (4).
0.2×A≦W≦A (4) 11. The toner of any one of claims 1 to 10, wherein the endothermic amount of the endothermic peak derived from the melting of the polymer A is 20 (J/g) to 100 (J/g) when the toner is measured with a differential scanning calorimeter. A toner according to any one of the preceding clauses. The toner according to any one of claims 1 to 11, wherein the charge decay constant of the polymer A is 100 or less. The amorphous resin constituting the shell layer is at least one selected from the group consisting of polyester resins, polyurethane resins, melamine resins, vinyl resins, and urea resins, according to any one of claims 1 to 12. Toner as described. 14. The toner according to any one of claims 1 to 13, wherein the shell layer is composed of one type of amorphous resin. 15. The toner according to any one of claims 1 to 14, wherein the shell layer has a thickness of 2 nm to 100 nm in an image obtained by observing a cross section of the toner with a transmission electron microscope (TEM). The toner according to any one of claims 1 to 15, wherein the polymer A is a vinyl polymer.