JP7297502B2 - Toner and method for producing the toner - Google Patents

Description

The present invention relates to a toner used in electrophotography, electrostatic recording, and toner jet recording, and a method for producing the toner.

2. Description of the Related Art In recent years, energy saving has been considered as a major technical issue in electrophotographic apparatuses, and considerable reduction in the amount of heat applied to a fixing device has been studied. In particular, there is an increasing need for so-called "low-temperature fixability" in which toner can be fixed with lower energy.
Techniques for enabling fixing at low temperatures include lowering the glass transition temperature (Tg) of the binder resin in the toner. However, since lowering the Tg leads to lower heat-resistant storage stability of the toner, it is considered difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner in this method.
Therefore, in order to achieve both low-temperature fixability and heat-resistant storage stability of the toner, a method of using a crystalline vinyl resin as the binder resin has been studied. Amorphous resins generally used as binder resins for toners do not show a clear endothermic peak in differential scanning calorimeter (DSC) measurement. An endothermic peak appears.
A crystalline vinyl resin has a property that it hardly softens up to the melting point due to the regular arrangement of side chains in the molecule. In addition, the crystal melts abruptly at the boundary of the melting point, resulting in a rapid decrease in viscosity. For this reason, it is attracting attention as a material that has excellent sharp-melt properties and achieves both low-temperature fixability and heat-resistant storage stability.
Generally, a crystalline vinyl resin has a side chain of a long-chain alkyl group in its main chain skeleton, and exhibits crystallinity as a resin when the long-chain alkyl groups of the side chains are crystallized.

Patent Document 1 proposes a toner that uses a crystalline vinyl resin into which a crosslinked structure is introduced and has excellent low-temperature fixability.
Patent Document 2 proposes a toner in which a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and a polymerizable monomer forming an amorphous site is used as a binder resin for a toner core. It is By doing so, it is possible to achieve both low-temperature fixability and heat-resistant storage stability.

JP-A-11-44967 JP 2014-130243 A

However, the binder resin used in the toner described in Patent Document 1 is a crystalline vinyl resin obtained by copolymerizing only a polymerizable monomer having a long-chain alkyl group and a cross-linking agent. It was found to be inferior in durability because it was low.
In addition, since the crystalline vinyl resin is easily crosslinked, it has been found that the low-temperature fixability is lowered when the bending strength of the fixed image is improved.
On the other hand, the binder resin used in the toner described in Patent Document 2 has a high proportion of a structure derived from a polymerizable monomer having a long-chain alkyl group, and has low elasticity at around room temperature. found to be inferior. In addition, it was found that the bending strength of the fixed image tends to decrease when printing is performed at a high coverage rate.
The present invention provides a toner excellent in low-temperature fixability, heat-resistant storage stability, durability and bending resistance, and a method for producing the toner.

（式（Ａ）中、Ｘは、単結合を示し、Ｒ ^１ は、－Ｃ≡Ｎ（ニトリル基）、－Ｃ（＝Ｏ）ＮＨ _２ （アミド基）、又は－ＣＯＯＲ ^１１ （該Ｒ ^１１ は、炭素数１～６のヒドロキシアルキル基を示す。）を示し、Ｒ ^３ は、水素原子、又はメチル基を示す。）
ことを特徴とするトナーである。
The present invention
A toner having toner particles containing a binder resin,
The binder resin is
a first polymerizable monomer,
a second polymerizable monomer different from the first polymerizable monomer, and
Containing a polymer A that is a polymer of a composition containing a cross-linking agent,
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 cross-linking agent has two or more polymerizable double bonds,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0, based on the total number of moles of all polymerizable monomers and cross-linking agents in the composition. is mol %,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0, based on the total number of moles of all polymerizable monomers and cross-linking agents in the composition. is mol %,
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 . and when the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 , the following formulas (1) and (2) are satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)
The second polymerizable monomer is at least one selected from the group consisting of polymerizable monomers represented by the following formula (A),

(In formula (A), X represents a single bond, R ¹ is —C≡N (nitrile group), —C(═O)NH ₂ (amide group), or —COOR ¹¹ (where R ¹¹ is , represents a hydroxyalkyl group having 1 to 6 carbon atoms.), and R ³ represents a hydrogen atom or a methyl group.)
This toner is characterized by:

In addition, the present invention
A method for producing a toner having toner particles, comprising:
forming particles of a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium;
obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles;
The polymerizable monomer composition is
a first polymerizable monomer,
a second polymerizable monomer different from the first polymerizable monomer, and
containing a cross-linking agent,
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 cross-linking agent has two or more polymerizable double bonds,
The content of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 5.0 mol % to 60.0 mol %,
The content of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 20.0 mol % to 95.0 mol %,
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 . and the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 .
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)

According to the present invention, it is possible to provide a toner excellent in low-temperature fixability, heat-resistant storage stability, durability, and bending resistance. Also, a method for producing the toner can be provided.

［式（Ｚ）中、Ｒ_Ｚ１は、水素原子、又はアルキル基（好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基）を表し、Ｒ_Ｚ２は、任意の置換基を表す。］
結晶性樹脂とは、示差走査熱量計（ＤＳＣ）測定において明確な吸熱ピークを示す樹脂を指す。 In the present 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 “monomer unit” is defined as one unit of a carbon-carbon bond section in the main chain of the polymer polymerized by the vinyl-based monomer. A vinyl-based monomer can be represented by the following formula (Z).

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

Generally, a crystalline vinyl resin has side chains of long-chain alkyl groups in its main chain skeleton, and the long-chain alkyl groups of the side chains are crystallized to each other to exhibit crystallinity as a resin.
Therefore, when a crystalline vinyl resin having a long-chain alkyl group is used, the higher the content of the long-chain alkyl group, the higher the degree of crystallinity, the higher the melting point, the higher the sharp melting property, and the lower the fixing temperature. Excellent in nature.
However, when the content of the long-chain alkyl group increases, the elasticity of the crystalline vinyl resin decreases around room temperature. As a result, the toner becomes brittle and its durability and bending resistance are lowered.
On the other hand, in order to improve durability and bending resistance, a polymerizable monomer having a long-chain alkyl group is copolymerized with another polymerizable monomer to keep the content of the long-chain alkyl group constant. If it is lowered more than this, the crystallinity is extremely lowered and the melting point is lowered. As a result, the heat-resistant storage stability is lowered, the sharp-melt property is lowered, and the low-temperature fixability is also lowered.

Also, consider the case where a polymerizable monomer having a long-chain alkyl group and a cross-linking agent having two or more polymerizable double bonds are copolymerized to impart elasticity to the resulting crystalline vinyl resin. . If the two are simply combined to improve the durability and bending resistance, the crystallinity of the resin is lowered and the sharp melt property is lowered. As a result, low-temperature fixability is lowered.
In order to solve these problems, the present inventors have investigated the types and amounts of polymerizable monomers having long-chain alkyl groups, the types and amounts of other polymerizable monomers, and The difference in SP value of those polymerizable monomers was examined. Furthermore, the present invention was discovered by examining the relationship between the SP values of a polymerizable monomer having a long-chain alkyl group, other polymerizable monomers, and a cross-linking agent.

The present invention
A toner having toner particles containing a binder resin,
The binder resin is
a first polymerizable monomer,
Containing a second polymerizable monomer different from the first polymerizable monomer, and a polymer A that is a polymer of a composition containing a cross-linking agent,
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 cross-linking agent has two or more polymerizable double bonds,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0, based on the total number of moles of all polymerizable monomers and cross-linking agents in the composition. is mol %,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0, based on the total number of moles of all polymerizable monomers and cross-linking agents in the composition. is mol %,
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 . and the SP value of the crosslinking agent is SP _C2 (J/cm ³ ) ^0.5 , the toner satisfies the following formulas (1) and (2).
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)

In addition, the present invention
A method for producing a toner having toner particles, comprising:
forming particles of a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium;
obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles;
The polymerizable monomer composition is
a first polymerizable monomer,
Containing a second polymerizable monomer different from the first polymerizable monomer and a cross-linking agent,
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 cross-linking agent has two or more polymerizable double bonds,
The content of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 5.0 mol % to 60.0 mol %,
The content of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 20.0 mol % to 95.0 mol %,
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 . and the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 .
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)

Here, the SP value is an abbreviation for solubility parameter, and is a value that serves as an index of solubility. A calculation method will be described later.

The present invention provides a polymer of a composition in which the binder resin contains a first polymerizable monomer, a second polymerizable monomer different from the first polymerizable monomer, and a cross-linking agent. It contains a polymer A which is
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 crosslinker has two or more polymerizable double bonds.
The binder resin exhibits crystallinity by containing the polymer A, which is the polymer of the composition containing the first polymerizable monomer.
Further, the binder resin is a polymer of a composition containing a first polymerizable monomer, a second polymerizable monomer different from the first polymerizable monomer, and a cross-linking agent. By containing the polymer A, it comes to have a crosslinked structure.
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 . , the following formula (1) is satisfied.
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
The value of (SP ₂₂ −SP ₁₂ ) is preferably 2.00 (J/m ³ ) ^0.5 or more, more preferably 3.00 (J/m ³ ) ^{0.5 or} more. Also, the value of (SP ₂₂ −SP ₁₂ ) is preferably 10.00 (J/m ³ ) ^0.5 or less, more preferably 7.00 (J/m ³ ) ^0.5 or less. The numerical ranges can be combined arbitrarily.
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 .

By satisfying the formula (1), the melting point of the polymer A is maintained without lowering the crystallinity. As a result, both low-temperature fixability and heat-resistant storage stability can be achieved.
I think the reason is as follows. By using polymerizable monomers in which (SP ₂₂ −SP ₁₂ ) falls within the range of formula (1), the first polymerizable monomer and the second polymerizable monomer are randomly polymerized during polymerization. It is thought that the polymerization takes a form that is continuous to some extent, rather than being continuous.
It is considered that the continuous polymerization of the first polymerizable monomer to some extent enables the crystallinity of the resulting polymer to be increased, and the melting point to be maintained.
The reason for this is that when (SP ₂₂ −SP ₁₂ ) is within the range of formula (1), there is a difference in the SP value, so the first and the polymer portion mainly containing the second monomer unit derived from the second polymerizable monomer can form a phase-separated state in a micro region. Conceivable.
Therefore, it is considered that a polymer site in which the first polymerizable monomer is continuously polymerized to some extent can be obtained, the crystallinity of the polymer site can be improved, and the melting point can be maintained.
That is, the polymer A has a crystalline portion containing a first monomer unit derived from a first polymerizable monomer and an amorphous region containing a second monomer unit derived from a second polymerizable monomer. It is preferred to have sex parts.

When (SP ₂₂ −SP ₁₂ ) is smaller than 0.60 (J/cm ³ ) ^0.5 , the melting point of the resulting polymer is lowered and the heat resistant storage stability is lowered. On the other hand, when it is larger than 15.00 (J/cm ³ ) ^0.5 , the copolymerization property of the polymer is considered to be inferior, and heat-resistant storage stability, durability, and bending resistance are lowered.

In addition, when the first polymerizable monomer is a (meth)acrylic acid ester having two or more types of alkyl groups having 18 to 36 carbon atoms, SP ₁₂ is the It is the average value calculated by the molar ratio. For example, the polymerizable monomer A having an SP value of SP ₁₂₁ contains A mol% based on the number of moles of the entire polymerizable monomer that satisfies the requirements for the first polymerizable monomer, and the SP value is SP ₁₂₂ . The SP value (SP ₁₂ ) when the polymerizable monomer B contains (100-A) mol% based on the total number of moles of the polymerizable monomers satisfying the requirements for the first polymerizable monomer is
SP ₁₂ = (SP ₁₂₁ ×A+SP ₁₂₂ ×(100−A))/100
is. A similar calculation is made when three or more polymerizable monomers satisfying the requirements for the first polymerizable monomer are included.
On the other hand, when the second polymerizable monomer is two or more polymerizable monomers, SP ₂₂ represents the SP value of each polymerizable monomer, and (SP ₂₂ −SP ₁₂ ) is It is determined for each second polymerizable monomer.

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} and the following formula (2) is satisfied, where the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 .
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)
In formula (2), when the first polymerizable monomer is a (meth)acrylic acid ester having two or more alkyl groups having 18 to 36 carbon atoms, SP ₁₂ is the first polymerized It is the average value calculated from the molar ratio of the monomer.
When the second polymerizable monomer is two or more polymerizable monomers, SP ₂₂ represents the SP value of each polymerizable monomer, and (SP _C2 <SP ₂₂ +3. 00) is determined for each second polymerizable monomer. In this case, satisfying (SP _C2 <SP ₂₂ +3.00) means that all the second polymerizable monomers satisfy the formula (2).
On the other hand, when two or more cross-linking agents are used, SP _C2 is the average value calculated from the molar ratio of each cross-linking agent.

By satisfying the above formula (2), the polymer A can improve elasticity at room temperature (about 30° C.) and high temperature (about 120° C.) without deteriorating the sharp melt property.
As a result, the durability and bending resistance can be improved without lowering the low-temperature fixability.
Here, bending resistance will be described. Factors necessary for improving the bending resistance include the following.
(1) To adhere to a medium such as paper by melting and spreading the toner during fixing.
(2) Release from a member such as a fixing film after the fixing process.
(3) High embrittlement resistance when the temperature of the toner drops to room temperature after fixing.
That is, high sharp-melting properties, high elasticity at high temperatures, and high elasticity at room temperature are required.

By satisfying the formula (2), it is believed that the cross-linking agent is easily inserted into the polymer portion containing the second monomer unit derived from the second polymerizable monomer. On the other hand, it is considered that the cross-linking agent is unlikely to be inserted into the crystalline site containing the first monomer unit derived from the first polymerizable monomer.
That is, the polymer A has a crosslinked structure formed at a polymer site containing a second monomer unit derived from the second polymerizable monomer, and the first monomer derived from the first polymerizable monomer A crosslinked structure is less likely to be formed in the crystalline site containing the unit. Therefore, a crosslinked structure is formed so that the crystallinity is maintained, the sharp melt property is maintained, and the crosslinked structure is formed in other than the crystalline part, so that the elasticity at normal temperature and high temperature is increased. I think you can.
In addition, when SP _C2 is larger than (SP ₂₂ +3.00), it becomes difficult to form a crosslinked structure at the polymer site containing the second monomer unit derived from the second polymerizable monomer. elasticity is reduced.

The SP value of the polymerizable monomer showing the maximum SP value in the first polymerizable monomer is SP _12max (J/cm ³ ) ^0.5 ,
The SP value of the polymerizable monomer showing the minimum SP value in the second polymerizable monomer is SP _22min (J/cm ³ ) ^0.5 ,
When the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 ,
The SP _12max , the SP _22min and the SP _C2 preferably satisfy the following formula (3).
(SP _22min −SP _C2 )<(SP _C2 −SP _12max ) (3)
When the first polymerizable monomer and the second polymerizable monomer are of one type each, the SP values of those polymerizable monomers are set to SP _12max and SP _22min , respectively.
In the case of two or more cross-linking agents, SP _C2 is the average value calculated from the molar ratio of each cross-linking agent.
When SP _12max , SP _22min and SP _C2 satisfy formula (3), the cross-linking agent becomes more capable of cross-linking the second polymerizable monomer and the first polymerizable monomer is less cross-linked. It is considered to be. Therefore, the durability and bending resistance can be further improved without lowering the low-temperature fixability.

The cross-linking agent is not particularly limited as long as it has two or more polymerizable double bonds and satisfies the above formula (2).
polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, divinylbenzene, divinylnaphthalene, both ends (meth)acryl-modified silicone.
Moreover, as the cross-linking agent, a long-chain cross-linking agent represented by the following formula (4) is preferable.

In formula (4), m and n are each independently an integer of 1-10, and m+n is 2-16.
The molecular weight of the cross-linking agent is preferably 200 or more, more preferably 300 or more, even more preferably 500 or more. Moreover, the molecular weight is preferably 1,000 or less. In addition, these numerical ranges can be combined arbitrarily.
When the molecular weight of the cross-linking agent is 200 or more, the distance between cross-linking points can be increased due to the large molecular weight. Therefore, for example, even when a crosslinked structure is formed in a crystalline site containing a first monomer unit derived from the first polymerizable monomer, crystal formation derived from an alkyl group having 18 to 36 carbon atoms is inhibited. crystallinity increases. Therefore, it is easy to improve the bending resistance without impairing the low-temperature fixability.
The content of the cross-linking agent in the composition is preferably 0.1 mol % to 5.0 mol % based on the total number of moles of all polymerizable monomers and cross-linking agent in the composition. , more preferably 0.2 mol % to 2.8 mol %.
When the content of the cross-linking agent is 0.1 mol % or more, durability and bending resistance are likely to be improved. When it is 8 mol % or less, it is easier to maintain the low-temperature fixability.

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 the polymerizable monomers and the cross-linking agent in the composition %, and the content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0 mol %.
The content of the first polymerizable monomer is preferably 10.0 mol % to 60.0 mol %, more preferably 20.0 mol % to 40.0 mol %.
The content of the second polymerizable monomer is preferably 40.0 mol % to 95.0 mol %, more preferably 40.0 mol % to 70.0 mol %.
When the content of the first polymerizable monomer in the composition is within the above range, the polymer A can improve the sharp melt property while maintaining the normal temperature elasticity and the high temperature elasticity, and the low temperature fixability. , the toner is excellent in durability and folding resistance.
If the content is less than 5.0 mol %, the amount of crystals in the polymer A will decrease, resulting in a decrease in sharp-melting properties. As a result, low-temperature fixability is lowered.
On the other hand, when the content is more than 60.0 mol %, the room temperature elasticity and high temperature elasticity are lowered, and the durability and bending resistance of the toner are lowered.
When the composition contains two or more (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms, the content of the first polymerizable monomer is the molar ratio of their total is.

When the content of the second polymerizable monomer in the composition is within the above range, the polymer A can improve normal temperature elasticity and high temperature elasticity while maintaining sharp melt properties, and low temperature fixability. , the toner is excellent in durability and folding resistance. In addition, since the polymer A hardly inhibits the crystallization of the composition containing the first polymerizable monomer, the melting point can be maintained.
If the content is less than 20.0 mol %, the room temperature elasticity and high temperature elasticity of the polymer A are lowered, and the durability and bending resistance of the toner are lowered.
On the other hand, when the content is more than 95.0 mol %, the sharp melt property of the polymer A is deteriorated and the low temperature fixability is deteriorated.
When there are two or more second polymerizable monomers satisfying formula (1), the content of the second polymerizable monomers is the total molar ratio.

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, dodriaconta (meth)acrylate, etc.] and (meth)acrylate 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 linear alkyl group having 18 to 36 carbon atoms is preferable from the viewpoint of heat-resistant storage stability and low-temperature fixability of the toner. . More preferably, it is at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group of 18 to 30 carbon atoms. More preferably, it is at least one selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate.
A 1st polymerizable monomer may be used individually by 1 type, or may use 2 or more types together.

Examples of the second polymerizable monomer include polymerizable monomers satisfying the formula (1) among the polymerizable monomers listed below.
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. a monomer.

Urethane group-containing monomers: for example, alcohols having 2 to 22 carbon atoms having an ethylenically unsaturated bond (2-hydroxyethyl methacrylate, vinyl alcohol, etc.) and isocyanates having 1 to 30 carbon atoms [monoisocyanate compounds (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), 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), 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), 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 such as diisocyanate and xylylene diisocyanate)] 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 ethylenically unsaturated bond-containing isocyanate having 2 to 30 carbon atoms [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, cycloxylamine, etc.], and a monomer obtained by reacting an ethylenically unsaturated bond-containing isocyanate having 2 to 30 carbon atoms by a known method.
Carboxy group-containing monomers; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate.
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 preferably, the second polymerizable monomer is a monomer having at least one functional group selected from the group consisting of a nitrile group, an amide group, a hydroxy group, a urethane group, and a urea group and an ethylenically unsaturated bond. Quantity.
By using the polymerizable monomer, the melting point of the polymer tends to be high, and the heat-resistant storage stability tends to be improved. In addition, normal temperature elasticity and high temperature elasticity are increased, and durability and bending resistance are likely to be improved.

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 low reactivity with the first polymerizable monomer. As a result, it is believed that the monomer units derived from the first polymerizable monomer are likely to form a polymerized state in the polymer A, and the crystallinity of the polymer A increases, resulting in low-temperature fixability. It becomes easier to achieve both heat resistance and storage stability.
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 Formulas A and B, X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is a nitrile group (-C≡N),
an amide group (—C(=O)NHR ¹⁰ , said R ¹⁰ being 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 urethane group (-NHCOOR ¹² , said R ¹² being an alkyl group having 1 to 4 carbon atoms),
a urea group (—NH—C(=O)—N(R ¹³ ) ₂ , each R ¹³ being 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 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
indicates
R ² represents an alkyl group having 1 to 4 carbon atoms,
Each ^R3 independently represents a hydrogen atom or a methyl group.
Preferably, R ¹ is a nitrile group (-C≡N),
an amide group (—C(=O)NHR ¹⁰ , said R ¹⁰ being 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 being 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 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4))
indicates
R ² represents an alkyl group having 1 to 4 carbon atoms,
Each ^R3 independently represents 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.

A composition containing a first polymerizable monomer, a second polymerizable monomer different from the first polymerizable monomer, and a cross-linking agent is the first polymerizable monomer in the composition. not included in the range of the above formula (1) as long as it does not impair the content ratio of the first polymerizable monomer and the content ratio of the second polymerizable monomer (i.e., the first polymerizable monomer, and A third polymerizable monomer (different from the second polymerizable monomer) may be included.

As the third polymerizable monomer, among the monomers exemplified as the second polymerizable monomer, a monomer that does not satisfy the above formula (1) can be used.
Moreover, the following monomers can also be used.
Styrene, styrene and its derivatives such as o-methylstyrene, (meth)acrylic acids such as n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate esters. In addition, when the monomer satisfies the above formula (1), it can be used as the second polymerizable monomer.
The third polymerizable monomer is preferably at least one selected from the group consisting of styrene, methyl methacrylate and methyl acrylate in order to improve the storage stability of the toner.

From the viewpoint of maintaining crystallinity, the acid value of the polymer A is preferably 30.0 mgKOH/g or less, more preferably 20.0 mgKOH/g or less. When the acid value is more than 30.0 mgKOH/g, the crystallization of polymer A is likely to be inhibited, and the melting point may be lowered. In addition, the acid value of the polymer A is preferably 0 mgKOH/g or more.

The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble portion of the polymer A measured by gel permeation chromatography (GPC) is preferably from 10,000 to 200,000, preferably from 20,000 to More preferably 150,000.
When the weight-average molecular weight (Mw) is within the above range, it becomes easier to maintain elasticity around room temperature.
The melting point of the polymer A is preferably 50° C. to 80° C., more preferably 53° C. to 70° C., from the viewpoint of compatibility between low temperature fixability and heat resistant storage stability. When the melting point is within the above range, heat-resistant storage stability and low-temperature fixability are further improved.
The melting point can be adjusted by the type and amount of the first polymerizable monomer and the type and amount of the second polymerizable monomer used.

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 further improved. It is more preferably 80.0% by mass to 100.0% by mass, and it is even more preferable that the binder resin is the polymer A.
Resins that can be used as the binder resin other than the polymer A include conventionally known vinyl resins, polyester resins, polyurethane resins, epoxy resins, and the like. Among them, vinyl resins, polyester resins, and polyurethane resins are preferable from the viewpoint of electrophotographic properties.
The polymerizable monomers that can be used for the vinyl resin are the polymerizable monomers that can be used for the first polymerizable monomer, the second polymerizable monomer, and the third polymerizable monomer. body, etc. You may use it in combination of 2 or more types as needed.

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, their anhydrides or their lower alkyl esters; maleic acid, fumaric acid, itaconic acid and Aliphatic unsaturated dicarboxylic acids such as citraconic acid; 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 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. The alkyl portion of alkylene glycols and alkylene ether glycols may be linear or branched. In addition, glycerin, trimethylolethane, trimethylolpropane and 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, monovalent acids such as acetic acid and benzoic acid and monovalent 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.

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.

The toner particles may contain a colorant. Examples of the coloring agent include known organic pigments, organic dyes, inorganic pigments, carbon black as a black coloring agent, and magnetic substances. In addition, colorants that are conventionally used in toners may be used.
Examples of yellow colorants include the following.
condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds;
Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.
Colorants for magenta include the following.
condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds.
Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.

Examples of cyan colorants include the following.
Copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.
Colorants are selected in terms of hue angle, chroma, brightness, lightfastness, OHP transparency, and dispersibility in toner particles.
The content of the colorant is preferably 1.0 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. When a magnetic material is used as the colorant, the content thereof is preferably 40.0 parts by mass or more and 150.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

The toner particles may contain wax (release agent). The type of wax is not particularly limited, and conventionally known waxes can be used.
Specifically, the following can be mentioned.
Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax and Fischer-Tropsch wax; oxidation of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; or block copolymers thereof; vegetable waxes such as candelilla wax, carnauba wax, Japan wax and jojoba wax; animal waxes such as beeswax, lanolin and spermaceti; waxes mainly composed of aliphatic esters, such as montan acid ester wax and castor wax; and partially or wholly deoxidized aliphatic esters, such as deoxidized carnauba wax.
The wax content in the toner particles is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 2.0% by mass or more and 25.0% by mass or less.

The toner particles may optionally contain a charge control agent. It may also be added externally to the toner particles. By blending the charge control agent, it becomes possible to stabilize the charge characteristics and control the optimum amount of triboelectrification according to the development system.
As the charge control agent, a known one can be used, and a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is particularly preferable.
As the charge control agent, an organic metal compound and a chelate compound are effective for controlling the toner particles to be negatively charged. Carboxylic acid- and dicarboxylic acid-based metal compounds can be mentioned. On the other hand, nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganostin borates, guanidine compounds, and imidazole compounds can be used to control toner particles to be positively charged.
The content of the charge control agent is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. It is more preferable to have

The toner particles may be used as the toner as they are, or may be used as the toner by adding an external additive such as inorganic fine particles to the toner particles.
Inorganic fine particles are preferably added to the toner particles. The inorganic fine particles added to the toner particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, and composite oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable for improving fluidity and uniformizing charging.
Silica particulates include dry silica or fumed silica produced by vapor phase oxidation of silicon halides, and wet silica made from water glass. Among them, dry silica having less silanol groups on the surface and inside the silica fine particles and less Na ₂ O and SO ₃ ^2- is preferable. Dry silica may also be composite fine particles of silica and other metal oxides produced by using a metal halide compound such as aluminum chloride or titanium chloride together with a silicon halide compound in the production process.

In addition, by hydrophobilizing silica fine particles, it is possible to adjust the charge amount of toner particles, improve environmental stability, and improve characteristics under high humidity environments. is more preferred. Hydrophobization treatment prevents silica fine particles from absorbing moisture, maintains the charge amount of toner particles, and improves developability and transferability.
Treatment agents for hydrophobic treatment of silica fine particles include silicone oil, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. These treating agents may be used alone or in combination.

As the silicone oil, any known silicone oil can be used without any particular limitation, but straight silicone is particularly preferred.
Specific examples include dimethylsilicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, fluorine-modified silicone oil, and methylhydrogensilicone oil.
The viscosity of the silicone oil is preferably 30 mm ² /s or more and 1200 mm ² /s or less, more preferably 70 mm ² /s or more and 800 mm ² /s or less.
The silicone oil treatment may be performed by directly mixing the silica fine particles and the silicone oil using a mixer such as a Henschel mixer, or by stirring the silica fine particles while spraying the silicone oil. Alternatively, a method of dissolving or dispersing silicone oil in an appropriate solvent (preferably adjusted to pH 4 with an organic acid or the like) and then mixing with fine silica particles and removing the solvent may be used. Furthermore, silica fine particles are placed in a reaction tank, alcohol water is added while stirring in a nitrogen atmosphere, a silicone oil-based treatment liquid is introduced into the reaction tank to perform surface treatment, and the solvent is removed by heating and stirring. can be a method.

The number average particle diameter of the primary particles of the silica fine particles is preferably 5 nm or more and 20 nm or less. Within the above range, it becomes easier to improve the fluidity of the toner particles.
The content of the inorganic fine particles is preferably 0.1 parts by mass or more and 4.0 parts by mass or less, and is 0.2 parts by mass or more and 3.5 parts by mass or less with respect to 100.0 parts by mass of the toner particles. is more preferable.

The toner particles may be produced by any conventionally known method such as a suspension polymerization method, an emulsion aggregation method, a dissolution suspension method, and a pulverization method, as long as the toner particles are within the scope of the present configuration.
Above all, the first polymerizable monomer, the second polymerizable monomer different from the first polymerizable monomer, and the cross-linking agent can be uniformly dispersed, and the toner particles are controlled to be spherical. Suspension polymerization is preferable because the crystallinity and durability can be easily improved by

That is, the present invention
A method for producing a toner having toner particles, comprising:
forming particles of a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium;
obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles;
The polymerizable monomer composition is
a first polymerizable monomer,
Containing a second polymerizable monomer different from the first polymerizable monomer and a cross-linking agent,
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 cross-linking agent has two or more polymerizable double bonds,
The content of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 5.0 mol % to 60.0 mol %,
The content of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 20.0 mol % to 95.0 mol %,
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 . and the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 .
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)

For example, polymerizable monomers that form a binder resin containing polymer A, and, if necessary, polymerizable monomers containing other materials such as colorants, waxes, charge control agents, and polymerization initiators. A polymerizable monomer composition is prepared by uniformly dissolving or dispersing the body composition.
Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare particles of the polymerizable monomer composition. After that, the toner particles are obtained by polymerizing the polymerizable monomer contained in the particles.
After polymerization, the toner particles are filtered, washed and dried by a known method, and if necessary, an external additive is added to obtain a toner.

A known polymerization initiator can be used as the polymerization initiator.
For example, 2,2′-azobis-(2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis(cyclohexane-1-carbonitrile), 2,2′ - azo or diazo polymerization initiators such as azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, t -butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide and lauroyl peroxide are included.
Also, known chain transfer agents and polymerization inhibitors may be used.

The aqueous medium may contain an inorganic or organic dispersion stabilizer.
A known dispersion stabilizer can be used as the dispersion stabilizer.
Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate; bentonite; silica;
On the other hand, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch.
When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the above inorganic compound may be used after being generated in an aqueous medium.
For example, in the case of calcium phosphates such as hydroxyapatite and tribasic calcium phosphate, it is preferable to mix the phosphate aqueous solution and the calcium salt aqueous solution under high agitation.
The aqueous medium may contain a surfactant. A known surfactant can be used as the surfactant. Examples thereof include anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

Next, the method for measuring each physical property according to the present invention will be described.
<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
・Number of accumulated times: 64 times ・Measurement temperature: 30℃
・Sample: 50 mg of a sample to be measured is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40° C. to prepare.
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 obtained as follows using the integral values S ₁ , S ₂ and S ₃ . Note that n ₁ , n _{2 , and} n ₃ are the numbers of hydrogen atoms in the constituent elements to which the focused peaks for the respective sites are assigned.
Content ratio (mol%) of monomer units derived from the first polymerizable monomer =
{(S ₁ /n ₁ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
Similarly, the content ratio of monomer units derived from the second polymerizable monomer and the third polymerizable monomer is obtained as follows.
Content ratio (mol%) of monomer units derived from the second polymerizable monomer =
{(S ₂ /n ₂ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×100
Content ratio (mol%) of monomer units derived from the third polymerizable monomer =
{(S ₃ /n ₃ )/((S ₁ /n ₁ )+(S ₂ /n ₂ )+(S ₃ /n ₃ ))}×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.
Further, when toner particles are produced by a suspension polymerization method, the peaks of waxes 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 wax or other resins, and the polymer A' can be regarded as the polymer A for analysis.

<Method for calculating SP value>
SP ₁₂ , SP ₂₂ , and SP _C2 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 .

<Measuring method of melting point>
The melting point of polymer A is 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 temperature rising process be the melting point.
Note that the maximum endothermic peak is the peak with the maximum endothermic amount when there are a plurality of peaks.

<Method for measuring acid value>
The acid value is mg of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of the polymer 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. The solution is placed in an alkali-resistant container so as not to come in contact with carbon dioxide gas, etc., and left for 3 days, then 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 0.1 mol/L hydrochloric acid used is prepared according to JIS K 8001-1998.
(2) Operation (A) Main test Sample (for example, pulverized polymer A) 2.0 g was precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of toluene / ethanol (2: 1) mixed solution was added, and it took 5 hours. to dissolve.
A few drops of the phenolphthalein solution are then added as an indicator, and the potassium hydroxide solution is used for titration. 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).

<Method for measuring weight average molecular weight (Mw) of polymer A>
The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble portion of the 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: 1.0 mL/min
・Oven temperature: 40.0°C
・Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, a standard polystyrene resin (trade name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500" manufactured by Tosoh Corporation) is used.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these. In the following formulations, "parts" are based on mass unless otherwise specified.

<Preparation of monomer having urethane group>
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 monomer having a urethane group was prepared by removing unreacted methanol with an evaporator.

<Preparation of monomer having urea group>
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, a monomer having a urea group was prepared by removing unreacted dibutylamine with an evaporator.

<Preparation 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.
Toluene 100.00 parts Monomer composition 100.00 parts (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, styrene, and polypropylene glycol diacrylate in the following proportions do)
- Behenyl acrylate (first polymerizable monomer) 65.66 parts (28.7 mol%)
- Methacrylonitrile (second polymerizable monomer) 21.56 parts (53.5 mol%)
- Styrene (third polymerizable monomer) 10.78 parts (17.2 mol%)
・Polypropylene glycol diacrylate 2.00 parts (0.6 mol%)
(manufactured by Shin-Nakamura Chemical Co., Ltd., APG-400, molecular weight 536)
・ 0.50 parts of t-butyl peroxypivalate (polymerization initiator, manufactured by NOF Corporation: Perbutyl PV)
While stirring the inside of the reaction vessel at 200 rpm, it was heated to 70° C. and a polymerization reaction was carried out for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the temperature of the solution was lowered to 25° C., the solution was poured into 1000.00 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 an acid value of 0.0 mgKOH/g and a melting point of 62°C.

<Preparation of amorphous resin>
The following raw materials were introduced into a heat-dried two-necked flask while introducing nitrogen.
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane
30.00 parts Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane
33.00 parts・Terephthalic acid 21.00 parts・Dodecenylsuccinic acid 15.00 parts・Dibutyltin oxide 0.10 parts After the inside of the system was replaced with nitrogen by pressure reduction, the mixture was stirred at 215° C. for 5 hours. After that, the temperature was gradually raised to 230° C. under reduced pressure while stirring was continued, and the temperature was maintained for an additional 2 hours. When the mixture became viscous, it was air-cooled to terminate the reaction, thereby synthesizing an amorphous resin, which is an amorphous polyester. The amorphous resin had a number average molecular weight (Mn) of 5,200, a weight average molecular weight (Mw) of 23,000, and a glass transition temperature (Tg) of 55°C.

<Preparation of silica fine particles 1>
Fumed silica (trade name; AEROSIL 380S, specific surface area 380 m ² /g by BET method, number average particle diameter of primary particles 7 nm, manufactured by Nippon Aerosil Co., Ltd.) Per 100 parts, 10.0 parts of polydimethylsiloxane (viscosity = 100 mm ² /s) and continued stirring for 30 minutes. After that, the temperature was raised to 300° C. while stirring, and the mixture was further stirred for 2 hours to prepare silica fine particles 1 .

<Example 1>
[Production of Toner by Suspension Polymerization]
(Production of toner particles 1)
- Monomer composition 100.00 parts (monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, styrene, and polypropylene glycol diacrylate in the following proportions)
- Behenyl acrylate (first polymerizable monomer) 65.66 parts (28.7 mol%)
- Methacrylonitrile (second polymerizable monomer) 21.56 parts (53.5 mol%)
- Styrene (third polymerizable monomer) 10.78 parts (17.2 mol%)
・Polypropylene glycol diacrylate 2.00 parts (0.6 mol%)
(manufactured by Shin-Nakamura Chemical Co., Ltd., APG-400, molecular weight 536)
Pigment Blue 15:3 6.50 parts Di-t-butyl salicylic acid aluminum 1.00 parts Fischer-Tropsch wax 20.00 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51, melting point: 74 ° C.)
- A mixture of 100.00 parts of toluene was prepared. The mixture was placed in 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, 735.00 parts of ion-exchanged water and 16.00 parts of trisodium phosphate (dodecahydrate) 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 9.00 parts of calcium chloride (dihydrate) in 65.00 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 containing a dispersion stabilizer.
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, 8.00 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.
Polymer A1′ was obtained in the same manner as in the method for producing toner particles 1 except that Pigment Blue 15:3, aluminum di-t-butylsalicylate, and Fischer-Tropsch wax were not used. Polymer A1′ had an acid value of 0.0 mgKOH/g and a melting point of 62°C.
Since the above polymer A1 and polymer A1' were prepared in the same manner, it was determined that they had equivalent physical properties.

(Preparation of Toner 1)
The toner particles 1 were externally added. 100.0 parts of toner particles 1 and 1.8 parts of silica fine particles 1 were dry mixed for 5 minutes using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain toner 1 . Table 2 shows the physical properties of Toner 1 obtained, and Table 4 shows the evaluation results.

表中の略号は以下の通り。
ＢＥＡ ：アクリル酸ベヘニル
ＢＥＭＡ：メタクリル酸ベヘニル
ＳＡ ：アクリル酸ステアリル
ＭＹＡ ：アクリル酸ミリシル
ＯＡ ：アクリル酸オクタコサ
ＨＡ ：アクリル酸ヘキサデシル
ＭＮ ：メタクリロニトリル
ＡＮ ：アクリロニトリル
ＨＰＭＡ：メタクリル酸２ヒドロキシプロピル
ＡＭ ：アクリルアミド
ＵＴ ：ウレタン基を有する単量体
ＵＲ ：ウレア基を有する単量体
ＡＡ ：アクリル酸
ＶＡ ：酢酸ビニル
ＭＡ ：アクリル酸メチル
Ｓｔ ：スチレン
ＭＭ ：メタクリル酸メチル
表中の架橋剤において、
１：ポリプロピレングリコールジアクリレート
２：トリプロピレングリコールジアクリレート
３：１，１０－デカンジオールジアクリレート
４：１，６－ヘキサンジオールジアクリレート
５：ジビニルベンゼン
また、表中の製造方法におけるＡは、懸濁重合法を表し、Ｂは乳化凝集法を表し、Ｃは粉砕法を表す。
また、表中の架橋剤における、トリプロピレングリコールジアクリレートは、新中村化学工業株式会社製、ＡＰＧ－２００、分子量３００である。

Abbreviations in the table are as follows.
BEA: Behenyl acrylate BEMA: Behenyl methacrylate SA: Stearyl acrylate MYA: Myricyl acrylate OA: Octacosa acrylate HA: Hexadecyl acrylate MN: Methacrylonitrile AN: Acrylonitrile HPMA: 2-hydroxypropyl methacrylate AM: Acrylamide UT: Urethane group-containing monomer UR: Urea group-containing monomer AA: Acrylic acid VA: Vinyl acetate MA: Methyl acrylate St: Styrene MM: Methyl methacrylate In the cross-linking agents in the table,
1: polypropylene glycol diacrylate 2: tripropylene glycol diacrylate 3: 1,10-decanediol diacrylate 4: 1,6-hexanediol diacrylate 5: divinylbenzene In addition, A in the production method in the table is suspension It represents the polymerization method, B represents the emulsion aggregation method, and C represents the pulverization method.
The tripropylene glycol diacrylate in the cross-linking agent in the table is APG-200, molecular weight 300, manufactured by Shin-Nakamura Chemical Co., Ltd.

表中のＸは、結着樹脂中の重合体Ａの含有量（質量％）を表し、
Ｔｍは、重合体Ａの融点（℃）を表す。

X in the table represents the content (% by mass) of the polymer A in the binder resin,
Tm represents the melting point of polymer A (°C).

<Examples 2 to 25, 31, 32>
Toner particles 2 to 25, 31 and 32 were obtained in the same manner as in Example 1 except that the type and amount of the polymerizable monomer composition used were changed as shown in Table 1.
Furthermore, the same external addition step of silica fine particles as in Example 1 was carried out to obtain toners 2 to 25, 31 and 32. Table 2 shows the physical properties of toners 2 to 25, 31 and 32, and Table 4 shows the evaluation results.

<Example 26>
[Production of Toner by Emulsion Aggregation Method]
(Preparation of polymer dispersion)
- Monomer composition 100.00 parts (monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, and styrene in the proportions shown below)
- Behenyl acrylate (first polymerizable monomer) 65.66 parts (28.7 mol%)
- Methacrylonitrile (second polymerizable monomer) 21.56 parts (53.5 mol%)
- Styrene (third polymerizable monomer) 10.78 parts (17.2 mol%)
A monomer solution is prepared by mixing each of the above components, and an aqueous surfactant solution in which 10 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK) is dissolved in 1130 parts of ion-exchanged water, and the monomer solution was put into a two-necked flask, and emulsified by stirring at a rotation speed of 10000 r/min using a homogenizer (manufactured by IKA: Ultra Turrax T50).
Thereafter, the inside of the flask was replaced with nitrogen, and the contents were heated in a water bath with slow stirring until the temperature reached 70° C., followed by polypropylene glycol diacrylate (APG-400, molecular weight 536, manufactured by Shin-Nakamura Chemical Co., Ltd.)2. 00 parts of ion-exchanged water was added to initiate polymerization.
After continuing the reaction for 8 hours, the reaction solution was cooled to room temperature, and the concentration was adjusted with deionized water to obtain an aqueous dispersion (polymer fine particle 1 dispersion) having a polymer fine particle 1 concentration of 20% by mass.
The 50% particle diameter (D50) based on volume distribution of the polymer fine particles 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso) and found to be 0.40 μm.

(Preparation of Wax Dispersion 1)
Fischer-Tropsch wax 100.00 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51, melting point: 74 ° C.)
・5.00 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ・395.00 parts of ion-exchanged water Dispersion treatment was performed for 60 minutes by circulating to Mix W Motion (manufactured by M Technic). The conditions for distributed processing were as follows.
・Rotor outer diameter 3cm
・Clearance 0.3mm
・Rotor speed 19000r/min
・Screen rotation speed 19000r/min
After the dispersion treatment, the wax dispersion liquid having a concentration of 20% by mass of the wax fine particles 1 is cooled to 40° C. under the cooling treatment conditions of a rotor rotation speed of 1000 r/min, a screen rotation speed of 0 r/min, and a cooling rate of 10° C./min. got 1.
The 50% particle diameter (D50) based on volume distribution of the wax fine particles 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso) and found to be 0.15 μm.

(Preparation of colorant dispersion liquid 1)
- Colorant 50.00 parts (cyan pigment made by Dainichiseika: Pigment Blue 15:3)
・ Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.50 parts ・ Ion-exchanged water 442.50 parts Weigh and mix the above materials, and use a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain 1 A colorant dispersion liquid 1 having a concentration of 10 mass % of the colorant fine particles 1 in which the colorant is dispersed was obtained by dispersing the colorant over time.
The 50% particle diameter (D50) based on volume distribution of the fine colorant particles 1 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.

(Manufacture of toner 26)
・Polymer dispersion 500.00 parts ・Wax dispersion 1 50.00 parts ・Colorant dispersion 1 80.00 parts bottom. Subsequently, the mixture was dispersed 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
The volume average particle size of the formed aggregated particles is appropriately confirmed using Coulter Multisizer III, and when aggregated particles having a volume average particle size of about 6.0 μm are formed, a 5% aqueous sodium hydroxide solution is used. to pH 9.0.
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.
Thereafter, the temperature was lowered to 50° C. and held for 3 hours to promote crystallization of the polymer.
After that, it was cooled to 25° C., filtered, solid-liquid separated, and then washed with ion-exchanged water.
After washing, the toner particles 26 having a weight average particle size (D4) of 6.07 μm were obtained by drying using a vacuum dryer.
Toner particles 26 were externally added in the same manner as in Example 1 to obtain toner 26 . Table 2 shows the physical properties of the toner 26, and Table 4 shows the evaluation results.

<Example 27>
[Production of Toner by Pulverization Method]
- Polymer A0 100.00 parts - C.I. I. Pigment Blue 15:3 6.50 parts Fischer-Tropsch wax 2.00 parts (manufactured by Nippon Seiro Co., Ltd.: HNP-51, melting point: 74 ° C.)
・ Charge control agent (T-77: manufactured by Hodogaya Chemical Industry Co., Ltd.) 2.00 parts After pre-mixing the above materials with an FM mixer (manufactured by Nippon Coke Industry Co., Ltd.), It was melt-kneaded by PCM-30 type manufactured by Co., Ltd.).
The resulting kneaded product is cooled, coarsely pulverized with a hammer mill, and then pulverized with a mechanical pulverizer (T-250 manufactured by Turbo Kogyo Co., Ltd.). Classification was performed using a division classifier to obtain toner particles 27 having a weight average particle size (D4) of 7.0 μm.
Toner particles 27 were externally added in the same manner as in Example 1 to obtain toner 27 . Table 2 shows the physical properties of the toner 27, and Table 4 shows the evaluation results.

<Examples 28-30>
(Preparation of amorphous resin dispersion)
- Toluene 300.00 parts - Amorphous resin 100.00 parts The above materials were weighed, mixed, and dissolved at 90°C.
Separately, 5.0 parts of sodium dodecylbenzenesulfonate was added to 700.0 parts of ion-exchanged water.
10.0 parts of sodium laurate was added and dissolved by heating at 90°C.
Next, the above toluene solution and aqueous solution are mixed together and stirred in an ultra-high speed stirrer T.P. K. The mixture was stirred at 7000 rpm using Robomix (manufactured by Primix).
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 that, the toluene was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an amorphous resin dispersion having a concentration of amorphous resin fine particles of 20% by mass.
The 50% particle diameter (D50) based on volume distribution of the fine amorphous resin particles was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.38 μm.

(Production of Toners 28-30)
Toner Particles 28 to 30 were obtained in the same manner as in (Production of Toner 26) except that the amount of dispersion used was changed as shown in Table 3.
Toner particles 28 to 30 were externally added in the same manner as in (production of toner 26) to obtain toners 28 to 30. Table 2 shows the physical properties of Toners 28 to 30, and Table 4 shows the evaluation results.

<Comparative Examples 1 to 8>
Comparative toner particles 1 to 8 and comparative toners 1 to 8 were obtained in the same manner as in Example 1, except that the type and amount of the polymerizable monomer composition used were changed as shown in Table 1. .
Table 2 shows the physical properties of Comparative Toners 1 to 8, and Table 4 shows the evaluation results.

<Toner evaluation method>
<1> Low Temperature Fixability A process cartridge filled with toner was left in a normal temperature and normal humidity (N/N) environment (23° C., 60% RH) for 48 hours. A Canon printer, LBP-712Ci, modified to operate even if the fixing device is removed, was used to output an unfixed image of an image pattern in which 9 points of square images of 10 mm x 10 mm were evenly arranged on the transfer paper. .
The toner laying amount on the transfer paper was 0.80 mg/cm ² and the fixing start temperature was evaluated. As the transfer paper, Canon Oce Red Label (80 g/m ² ) was used.
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. The fixing temperature of the external fixing device was increased from 100° C. by 10° C., and the process speed was 280 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 4 shows the evaluation results.
[Evaluation criteria]
A: Fixing start temperature is 110°C
B: Fixing start temperature is 120°C
C: Fixing start temperature is 130°C
D: Fixing start temperature is 140° C. or higher

<2> Bending Resistance A process cartridge filled with toner was left in a normal temperature and normal humidity (N/N) environment (23° C., 60% RH) for 48 hours. Using a Canon printer LBP-712Ci modified to operate even if the fixing device is removed, an unfixed image of an image pattern in which 9-point square images of 30 mm×30 mm are evenly arranged on the transfer paper was output.
The toner laying amount on the transfer paper was 1.20 mg/cm ² . As the transfer paper, Canon Oce Red Label (80 g/m ² ) was used.
As a fixing device, the fixing device of LBP-712Ci was removed to the outside, and an external fixing device was used so that it could operate outside the laser beam printer. In the <1> low-temperature fixability, a fixed image was obtained under the conditions of a process speed of 280 mm/sec and a fixing temperature 10° C. higher than the fixing start temperature of each toner.
Next, the fixed image was folded crosswise and rubbed back and forth five times with soft thin paper (trade name: "Dasper", manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 kPa. In this case, a sample is obtained in which the toner is peeled off at the folded cross portion and the texture of the paper is visible.
The folded cross section was then photographed with a CCD camera at a resolution of 800 pixels/inch over an area of 512 pixels square.
The threshold was set to 60% and the images were binarized. The part where the toner is peeled off is the white part, and the smaller the area ratio of the white part, the better the folding resistance. Table 4 shows the evaluation results. (Evaluation criteria)
A: Area ratio of white portion is less than 1.0% B: Area ratio of white portion is 1.0% or more and less than 2.0% C: Area ratio of white portion is 2.0% or more and less than 3.0% D : Area ratio of white part is 3.0% or more

<3> Durability Durability was evaluated using a commercially available printer LBP-712Ci manufactured by Canon.
The LBP-712Ci employs one-component contact development, and regulates the amount of toner on the developing carrier by means of a toner regulation member.
As the evaluation cartridge, the toner contained in the commercially available cartridge was removed, the inside was cleaned by an air blow, and then 200 g of the above toner was filled.
Evaluation was carried out by installing the above cartridge in the cyan station and installing dummy cartridges in the others.
Canon Oce Red Label (80 g/m ² ) was used in a normal temperature and normal humidity (N/N) environment (23° C., 60% RH), and images with a print rate of 1% were continuously output.
Images were output on 20,000 sheets, a solid image and a halftone image were output, and the presence or absence of development streaks, ie, streaks in the circumferential direction due to toner fusion to the regulating member, was visually checked. Table 4 shows the evaluation results.
[Evaluation criteria]
A: Not generated B: Development streaks are generated at 1 or more and 2 or less C: Development streaks are generated at 3 or more and 4 or less D: Development streaks are generated at 5 or more

<4> Heat-resistant storage stability In order to evaluate the stability during storage, the heat-resistant storage stability was evaluated.
6 g of toner was placed in a 100 mL polypropylene cup and allowed to stand for 10 days in an environment of 50° C. and 20% humidity. .
As a measuring device, a digital display type vibration meter "Digivibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) was connected to the side of the shaking table of "Powder Tester" (manufactured by Hosokawa Micron Co., Ltd.).
A sieve with an opening of 38 μm (400 mesh), a sieve with an opening of 75 μm (200 mesh), and a sieve with an opening of 150 μm (100 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed in the following manner under the environment of 23° C. and 60% RH.
(1) The amplitude of vibration of the shaking table was previously adjusted so that the displacement value of the digital display type vibration meter was 0.60 mm (peak-to-peak).
(2) The toner left for 10 days as described above is left for 24 hours in an environment of 23° C. and 60% RH. rice field.
(3) After vibrating the sieve for 15 seconds, the mass of the toner remaining on each sieve was measured, and the aggregation degree was calculated based on the following formula. Table 4 shows the evaluation results.
Aggregation degree (%) = {(sample mass (g) on sieve with mesh size of 150 µm) / 5 (g)} x 100
+ {(Sample mass (g) on a sieve with an opening of 75 μm) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve with an opening of 38 μm) / 5 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: The degree of aggregation is less than 20% B: The degree of aggregation is 20% or more and less than 25% C: The degree of aggregation is 25% or more and less than 30% D: The degree of aggregation is 30% or more

Claims (11)

A toner having toner particles containing a binder resin,
The binder resin is
a first polymerizable monomer,
a second polymerizable monomer different from the first polymerizable monomer, and
Containing a polymer A that is a polymer of a composition containing a cross-linking agent,
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 cross-linking agent has two or more polymerizable double bonds,
The content of the first polymerizable monomer in the composition is 5.0 mol% to 60.0, based on the total number of moles of all polymerizable monomers and cross-linking agents in the composition. is mol %,
The content of the second polymerizable monomer in the composition is 20.0 mol% to 95.0, based on the total number of moles of all polymerizable monomers and cross-linking agents in the composition. is mol %,
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 . and when the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 , the following formulas (1) and (2) are satisfied,
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)
The second polymerizable monomer is at least one selected from the group consisting of polymerizable monomers represented by the following formula (A),

(In formula (A), X represents a single bond, R ¹ is —C≡N (nitrile group), —C(═O)NH ₂ (amide group), or —COOR ¹¹ (where R ¹¹ is , represents a hydroxyalkyl group having 1 to 6 carbon atoms.), and R ³ represents a hydrogen atom or a methyl group.)
A toner characterized by: 2. The toner according to claim 1, wherein the content of said polymer A in said binder resin is 50.0% by mass or more. The first polymerizable monomer is at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms, according to claim 1 or 2. toner. the composition further contains a third polymerizable monomer different from the first polymerizable monomer, the second polymerizable monomer, and the cross-linking agent;
wherein the third polymerizable monomer is styrene ;
The toner according to any one of claims 1-3 . The content of the second polymerizable monomer in the composition is 40.0 mol% to 95.0, based on the total number of moles of all polymerizable monomers and cross-linking agents in the composition. % by mole . The SP value of the polymerizable monomer showing the maximum SP value in the first polymerizable monomer is SP _12max (J/cm ³ ) ^0.5 ,
The SP value of the polymerizable monomer showing the minimum SP value in the second polymerizable monomer is SP _22min (J/cm ³ ) ^0.5 ,
When the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 ,
The SP _12max , the SP _22min , and the SP _C2 satisfy the following formula (3) ,
(SP _22min −SP _C2 )<(SP _C2 −SP _12max ) (3)
The toner according to any one of claims 1-5. The toner according to any one of claims 1 to 6 , wherein the cross-linking agent has a molecular weight of 300 or more. The toner according to any one of claims 1 to 7 , wherein said polymer A is a vinyl polymer. A method for producing a toner having toner particles, comprising:
forming particles of a polymerizable monomer composition containing a polymerizable monomer in an aqueous medium;
obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles;
The polymerizable monomer composition is
a first polymerizable monomer,
a second polymerizable monomer different from the first polymerizable monomer, and
containing a cross-linking agent,
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 cross-linking agent has two or more polymerizable double bonds,
The content of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 5.0 mol % to 60.0 mol %,
The content of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all polymerizable monomers and cross-linking agents in the polymerizable monomer composition , 20.0 mol % to 95.0 mol %,
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 . and the SP value of the cross-linking agent is SP _C2 (J/cm ³ ) ^0.5 .
0.60≦(SP ₂₂ −SP ₁₂ )≦15.00 (1)
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2) 10. The method for producing a toner according to claim 9, wherein the second polymerizable monomer is at least one selected from the group consisting of polymerizable monomers represented by formula (A) below.

(In formula (A), X represents a single bond, R ¹ is —C≡N (nitrile group), —C(═O)NH ₂ (amide group), or —COOR ¹¹ (where R ¹¹ is , represents a hydroxyalkyl group having 1 to 6 carbon atoms.), and R ³ represents a hydrogen atom or a methyl group.) 11. The method for producing a toner according to claim 9, wherein the cross-linking agent has a molecular weight of 300 or more.