JP2019219646A - Toner and method for manufacturing the toner - Google Patents

Abstract

To provide a toner that is excellent in low-temperature fixability and heat-resistant storage property, and durability and bending resistance, and a method for manufacturing the toner.SOLUTION: A toner includes toner particles containing a binder resin; the binder resin contains a polymer A that is a polymer of a composition containing a first polymerizable monomer, a second polymerizable monomer, and a crosslinking agent; the first polymerizable monomer is at least one selected from the group consisting of a (meth)acrylic ester with an alkyl group having 18 to 36 carbon atoms; the crosslinking agent has two or more polymerizable double bonds; the content ratio of the first monomer unit in the composition is 5.0 to 60.0 mol%; the content ratio of the second polymerizable monomer is 20.0 to 95.0 mol%; when the SP values of the first polymerizable monomer, second polymerizable monomer, and crosslinking agent are SP, SP, and SP, 0.60≤(SP-SP)≤15.00, and SP<SP<(SP+3.00) are satisfied.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, and a toner jet recording method, and a method for manufacturing the toner.

In recent years, energy saving has been considered as a major technical issue in electrophotographic apparatuses, and significant reduction in the amount of heat applied to a fixing device is being studied. In particular, there is an increasing need for so-called “low-temperature fixability” for toner, which enables fixing with lower energy.
As a technique for enabling fixing at a low temperature, there is a method of lowering the glass transition temperature (Tg) of the binder resin in the toner. However, since lowering the Tg leads to lowering the heat-resistant storage stability of the toner, it is said that it is difficult to achieve both low-temperature fixability and heat-resistant storage stability of the toner in this method.
Therefore, a method of using a crystalline vinyl resin as a binder resin has been studied in order to achieve both low-temperature fixability and heat-resistant storage stability of the toner. An amorphous resin generally used as a binder resin for a toner does not show a clear endothermic peak in a differential scanning calorimeter (DSC) measurement, but when a crystalline resin component is contained, the An endothermic peak appears.
The crystalline vinyl resin has such a property that it hardly softens to its melting point because side chains in the molecule are regularly arranged. Further, the crystal is rapidly melted at the boundary of the melting point, and the viscosity is drastically reduced accordingly. For this reason, it has attracted attention as a material having excellent sharp melt properties and having both low-temperature fixability and heat-resistant storage stability.
In general, a crystalline vinyl resin has a side chain of a long-chain alkyl group in a main chain skeleton, and the long-chain alkyl group of the side chain crystallizes to show crystallinity as a resin.

Patent Document 1 proposes a toner that uses a crystalline vinyl resin having a crosslinked structure and is excellent in low-temperature fixability.
Patent Document 2 proposes a toner using, as a binder resin of a toner core, a crystalline vinyl resin obtained by copolymerizing a polymerizable monomer having a long-chain alkyl group and a polymerizable monomer forming an amorphous portion. Have been. Thereby, it is said that both low-temperature fixing property and heat-resistant storage property can be achieved.

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

However, the binder resin used for 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 crosslinking agent, and has an elasticity near room temperature. It turned out that it is inferior in durability because it is low.
In addition, since the crystalline vinyl resin has a structure that is easily crosslinked, it was found that the low-temperature fixability was reduced when the bending strength of the fixed image was to be 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. It turned out to be inferior. In addition, it was found that the bending strength of the fixed image was apt to decrease when printing at a high printing rate.
SUMMARY OF THE INVENTION The present invention provides a toner having excellent low-temperature fixing property and heat-resistant storage property, and excellent durability and bending resistance, and a method for producing the toner.

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 a polymer A that is a polymer of a composition containing a crosslinking agent,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The cross-linking agent has two or more polymerizable double bonds,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. Mole%,
The content ratio of the second polymerizable monomer in the composition is from 20.0 mol% to 95.0 based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. Mole%,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Wherein the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 , which 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)

Also, the present invention
A method for producing a toner having toner particles,
In an aqueous medium, a step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, and
A step of obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles,
The polymerizable monomer composition,
A first polymerizable monomer,
It contains a second polymerizable monomer different from the first polymerizable monomer, and a crosslinking agent,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The cross-linking agent has two or more polymerizable double bonds,
The content ratio of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. 5.0 mol% to 60.0 mol%,
The content ratio of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. From 20.0 mol% to 95.0 mol%,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Wherein the SP value of the cross-linking agent is SP _C2 (J / cm ³ ) ^0.5 , which 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)

  ADVANTAGE OF THE INVENTION According to this invention, the toner which is excellent in low-temperature fixability and heat storage stability, and durability and bending resistance can be provided. Further, 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, description of “XX or more and YY or less” or “XX to YY” representing a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
In the present invention, the (meth) acrylate means an acrylate and / or a methacrylate.
In the present invention, the “monomer unit” is defined as one unit of one section of a carbon-carbon bond in a main chain obtained by polymerizing a vinyl monomer in a polymer. The vinyl 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 shows a distinct endothermic peak in a differential scanning calorimeter (DSC) measurement.

Usually, a crystalline vinyl resin has a side chain of a long-chain alkyl group in the main chain skeleton, and the long-chain alkyl group of the side chain crystallizes to show 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 crystallinity, the higher the melting point, the sharper the meltability, and the lower-temperature fixing. Excellent in nature.
However, when the content ratio of the long-chain alkyl group increases, the elasticity of the crystalline vinyl resin decreases at around room temperature. As a result, the toner becomes brittle, and durability and bending resistance are reduced.
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. When it is lowered as described above, the crystallinity is extremely lowered and the melting point is lowered. As a result, the heat-resistant storage stability decreases, the sharp-melt property decreases, and the low-temperature fixability also decreases.

Also, consider a case where a polymerizable monomer having a long-chain alkyl group is copolymerized with a crosslinking agent having two or more polymerizable double bonds to impart elasticity to the obtained crystalline vinyl resin. . If the two are simply combined to improve durability and bending resistance, the crystallinity of the resin is reduced, and the sharp melt property is reduced. As a result, the low-temperature fixability decreases.
The present inventors, in order to solve these, the type and amount of the polymerizable monomer having a long-chain alkyl group in the polymer used for the binder resin, the type and amount of other polymerizable monomers, and The difference in SP value between these polymerizable monomers was examined. Furthermore, the present inventors have studied the relationship between the polymerizable monomer having a long-chain alkyl group, other polymerizable monomers, and the SP value of the crosslinking agent, and have found the present invention.

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 a polymer A that is a polymer of a composition containing a crosslinking agent,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The cross-linking agent has two or more polymerizable double bonds,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. Mole%,
The content ratio of the second polymerizable monomer in the composition is from 20.0 mol% to 95.0 based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. Mole%,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Wherein the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 , which 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)

Also, the present invention
A method for producing a toner having toner particles,
In an aqueous medium, a step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, and
A step of obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles,
The polymerizable monomer composition,
A first polymerizable monomer,
It contains a second polymerizable monomer different from the first polymerizable monomer, and a crosslinking agent,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The cross-linking agent has two or more polymerizable double bonds,
The content ratio of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. 5.0 mol% to 60.0 mol%,
The content ratio of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. From 20.0 mol% to 95.0 mol%,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Wherein the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 , which 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)

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

The present invention relates to 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 crosslinking agent. The polymer A which is is contained.
The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylates having an alkyl group having 18 to 36 carbon atoms,
The crosslinking agent has two or more polymerizable double bonds.
When the binder resin contains the polymer A which is a polymer of the composition containing the first polymerizable monomer, the binder resin becomes crystalline.
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 crosslinking agent. By containing the polymer A, it has a crosslinked structure.
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Satisfies the following expression (1).
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. Further, 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 arbitrarily combined.
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 ) It can be converted to a unit of ^0.5 .

By satisfying the formula (1), the melting point of the polymer A is maintained without lowering the crystallinity. Thereby, both low-temperature fixability and heat-resistant storage stability are achieved.
I think the reason is as follows. (SP 22 _{-SP 12)} is to use a polymerizable monomer in the range of formula (1), Polymerization first polymerizable monomer and a second polymerizable monomer randomly during polymerization Instead, it is considered to take a somewhat continuous polymerization form.
It is thought that by polymerizing the first polymerizable monomer continuously to some extent, it is possible to increase the crystallinity of the obtained polymer and maintain the melting point.
The reason is that, when (SP ₂₂ -SP ₁₂ ) is within the range of the formula (1), there is a difference in SP value, so that the first polymerizable monomer derived from the first polymerizable monomer in the polymer A has A polymer site mainly containing a monomer unit of, and a polymer site mainly containing a second monomer unit derived from the second polymerizable monomer, can form a phase separation state in a micro region Conceivable.
Therefore, it is considered that a polymer site in which the first polymerizable monomer is polymerized to some extent continuously can be obtained, the crystallinity of the polymer site can be increased, and the melting point is maintained.
That is, the polymer A has a crystalline portion containing the first monomer unit derived from the first polymerizable monomer, and an amorphous portion containing the second monomer unit derived from the second polymerizable monomer. It is preferable to have a sex site.

If _(SP 22 _{-SP 12)} is less than ^{0.60 (J / cm 3) 0.5} , melting point of the resulting polymer is reduced, heat-resistant storage stability is lowered. On the other hand, when it is larger than 15.00 (J / cm ³ ) ^0.5 , it is considered that the copolymerizability of the polymer is inferior, and the heat-resistant storage stability, durability, and bending resistance are reduced.

Incidentally, of the first polymerizable monomer, the case of having two or more alkyl groups having a carbon number of 18 to 36 (meth) acrylic acid ester, SP ₁₂ are each of the first polymerizable monomer The average value is calculated as a molar ratio. For example, SP value comprises A mole percent based on the moles of total polymerizable monomer a polymerizable monomer A meets the requirements of the first polymerizable monomer SP _121, SP value of 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 monomer satisfying the requirement of the first polymerizable monomer is:
SP ₁₂ = (SP ₁₂₁ × A + SP ₁₂₂ × (100−A)) / 100
It is. The same calculation is performed when three or more polymerizable monomers satisfying the requirements of the first polymerizable monomer are included.
On the other hand, said second polymerizable monomer, when two or more kinds of polymerizable monomers, _{SP 22} denotes a SP value of each of the polymerizable _monomer, (SP 22 _{-SP 12)} is Determined for each second polymerizable monomer.

The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^{0. .5,} when the SP value of the crosslinking agent was ^{_{SP C2 (J / cm 3)}} 0.5, satisfying the following formula (2).
SP ₁₂ <SP _C2 <(SP ₂₂ +3.00) (2)
In the 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 polymerizable monomer. Average value calculated from the molar ratio of the reactive monomer.
When the second polymerizable monomer is two or more types of polymerizable monomers, SP ₂₂ represents the SP value of each polymerizable monomer, and (SP _C2 <SP ₂₂ +3. Whether or not the condition (00) is satisfied is determined for each second polymerizable monomer. In this case, satisfying (SP _C2 <SP ₂₂ +3.00) means a case where the formula (2) is satisfied in all the second polymerizable monomers.
On the other hand, when the cross-linking agent is two or more cross-linking agents, _SPC2 is an average value calculated by the molar ratio of each cross-linking agent.

By satisfying the above formula (2), the polymer A can improve the elasticity at normal temperature (about 30 ° C.) and high temperature (about 120 ° C.) without lowering the sharp melt property.
Thereby, the durability and the bending resistance can be improved without lowering the low-temperature fixability.
Here, the bending resistance will be described. Factors necessary for improving the bending resistance include the following.
(1) Adhesion to a medium such as paper by melting the toner at the time of fixing and spreading it appropriately.
(2) Release from a member such as a fixing film after the fixing step.
(3) High brittleness resistance when the temperature of the toner is lowered to normal temperature after fixing.
That is, it is required that the sharp melt property is high, the elasticity at high temperature is high, and the elasticity at normal temperature is high.

By satisfying the formula (2), it is considered that the crosslinking 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 hardly inserted into a crystalline site including the first monomer unit derived from the first polymerizable monomer.
That is, the polymer A has a crosslinked structure formed at the polymer site containing the second monomer unit derived from the second polymerizable monomer, and the first monomer derived from the first polymerizable monomer. It becomes difficult to form a crosslinked structure in a crystalline site containing a unit. Therefore, a crosslinked structure is formed so that the crystallinity is maintained, sharp meltability is maintained, and the crosslinked structure is formed in a portion other than the crystalline portion, thereby increasing the elasticity at room temperature and high temperature. I think it can be done.
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, and at room temperature and high temperature. Is reduced in elasticity.

The SP value of the polymerizable monomer exhibiting the maximum SP value in the first polymerizable monomer is set to SP _12max (J / cm ³ ) ^0.5 ,
The SP value of the polymerizable monomer exhibiting the minimum SP value in the second polymerizable monomer is set to SP _{22 min} (J / cm ³ ) ^0.5 ,
When the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 ,
It is preferable that the SP _12max , the SP _22min, and the SP _C2 satisfy the following expression (3).
_{(SP 22min -SP C2) <(} SP C2 -SP 12max) (3)
When the first polymerizable monomer and the second polymerizable monomer are each one kind, the SP values of those polymerizable monomers are set to _SP12max and _SP22min , respectively.
In the case of two or more types of crosslinking agents, SP _C2 is an average value calculated by the molar ratio of each crosslinking agent.
_SP 12max, SP 22min and _{SP C2} is, if satisfying the expression (3), the cross-linking agent is able to further crosslink the second polymerizable monomer, hardly first polymerizable monomer is more cross-linked It is considered to be. Therefore, the durability and the bending resistance can be further improved without lowering the low-temperature fixability.

The crosslinking agent has two or more polymerizable double bonds and is not particularly limited as long as it satisfies the above formula (2), and examples thereof include the following.
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, divinyl benzene, divinyl naphthalene, and both-terminal (meth) acryl-modified silicone.
Further, as the crosslinking agent, a long-chain crosslinking agent represented by the following formula (4) is preferable.

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

The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. %, And the content ratio of the second polymerizable monomer in the composition is 20.0 mol% to 20.0 mol% based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. 95.0 mol%.
The content ratio of the first polymerizable monomer is preferably from 10.0 mol% to 60.0 mol%, more preferably from 20.0 mol% to 40.0 mol%.
The content ratio of the second polymerizable monomer is preferably from 40.0 mol% to 95.0 mol%, and more preferably from 40.0 mol% to 70.0 mol%.
When the content ratio of the first polymerizable monomer in the composition is within the above range, the polymer A can improve sharp meltability while maintaining room-temperature elasticity and high-temperature elasticity, and has a low-temperature fixing property. The toner has excellent durability, bending resistance, and durability.
When the content ratio is less than 5.0 mol%, the amount of crystals in the polymer A decreases, and the sharp melt property decreases. As a result, the low-temperature fixability decreases.
On the other hand, when the content ratio is more than 60.0 mol%, the room-temperature elasticity and the high-temperature elasticity decrease, and the durability and the fold resistance of the toner decrease.
When the composition contains two or more (meth) acrylic esters having an alkyl group having 18 to 36 carbon atoms, the content ratio of the first polymerizable monomer is determined by the total molar ratio thereof. It is.

When the content ratio of the second polymerizable monomer in the composition is within the above range, the polymer A can improve the room temperature elasticity and the high temperature elasticity while maintaining the sharp melt property, and the low temperature fixability can be improved. The toner is excellent in durability, durability and bending resistance. In addition, since the crystallization of the composition containing the first polymerizable monomer in the polymer A is not easily inhibited, the melting point can be maintained.
If the content is less than 20.0 mol%, the room-temperature elasticity and the high-temperature elasticity of the polymer A decrease, and the durability and folding resistance of the toner decrease.
On the other hand, when the content ratio is more than 95.0 mol%, the sharp melt property of the polymer A decreases, and the low-temperature fixability decreases.
When two or more second polymerizable monomers satisfying the formula (1) are present, the content ratio of the second polymerizable monomer is the total molar ratio of the second polymerizable monomers.

The first polymerizable monomer is at least one selected from the group consisting of (meth) acrylates having an alkyl group having 18 to 36 carbon atoms.
As the (meth) acrylate having an alkyl group having 18 to 36 carbon atoms, for example, a (meth) acrylate 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, lignoseryl (meth) acrylate, seryl (meth) acrylate, octacosa (meth) acrylate, (meth) And a (meth) acrylic ester having a branched alkyl group having 18 to 36 carbon atoms [such as 2-decyltetradecyl (meth) acrylate].
Among them, from the viewpoints of heat resistance storage stability and low-temperature fixability of the toner, it is preferably at least one selected from the group consisting of (meth) acrylates having a linear alkyl group having 18 to 36 carbon atoms. . More preferably, it is at least one selected from the group consisting of (meth) acrylates having a linear alkyl group having 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.
As the first polymerizable monomer, one type may be used alone, or two or more types may be used in combination.

Examples of the second polymerizable monomer include polymerizable monomers satisfying the formula (1) among the following polymerizable monomers.
As the second polymerizable monomer, one type may be used alone, or two or more types may be used in combination.
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 (such as acrylic acid and methacrylic acid) are reacted by a known method. Monomer.

Monomer having a urethane group: for example, an alcohol having an ethylenically unsaturated bond and having 2 to 22 carbon atoms (such as 2-hydroxyethyl methacrylate and vinyl alcohol) and an isocyanate having 1 to 30 carbon atoms [monoisocyanate compound (Benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl Isocyanate, 3,5-dimethylphenyl isocyanate, 2,6-dipropylphenyl isocyanate, etc.) Aliphatic diisocyanate compounds (trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, etc. ), Alicyclic diisocyanate compounds (1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated Added tetramethyl xylylene 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'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate, xylylene diisocyanate, etc.) and a C1-C26 alcohol. (Methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, Decyl 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, hen Eicosanol, behenyl alcohol, erucyl alcohol, etc.) and an isocyanate having an ethylenically unsaturated bond and having 2 to 30 carbon atoms [2-isocyanatoethyl (meth) acrylate, (meth) acrylic acid 2- (0- [1 '-Methylpropylideneamino] carboxyamino) ethyl, 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl (meth) acrylate and 1,1- (bis (meth) acryloyl Oxymethyl) ethyl isocyanate] with a known method.

Monomers having a urea group: for example, amines having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine and isopropylamine), and secondary amines (dinalethylamine, dinormalpropylamine, diamine A normal butylamine, etc.), aniline and cycloxylamine, etc.] and an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond by a known method.
Monomers having a carboxy group; 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 single 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. Is a monomer.
By using the polymerizable monomer, the melting point of the polymer is easily increased, and the heat-resistant storage stability is easily improved. Further, the room temperature elasticity and the high temperature elasticity are increased, and the durability and the bending resistance are easily 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 considered that a state in which monomer units derived from the first polymerizable monomer are aggregated and polymerized in the polymer A is likely to be formed, and the crystallinity of the polymer A is increased, and the low-temperature fixing property is improved. And heat-resistant storage stability are more easily achieved.
The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond.
Further, it is preferable that the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

In the 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 , wherein R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
Hydroxy group,
—COOR ¹¹ (where R ¹¹ is an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms);
A urethane group (—NHCOOR ¹² , wherein R ¹² is an alkyl group having 1 to 4 carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ , wherein R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms)
Indicates that
R ² represents an alkyl group having 1 to 4 carbon atoms,
R ³ each 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 , wherein R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
Hydroxy group,
—COOR ¹¹ (where R ¹¹ is an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms);
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ , wherein R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms),
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms)
Indicates that
R ² represents an alkyl group having 1 to 4 carbon atoms,
R ³ each independently represents a hydrogen atom or a methyl group.

  The polymer A is preferably a vinyl polymer. The vinyl polymer includes, for example, a polymer of a monomer containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of undergoing radical polymerization, and examples thereof include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

  A composition comprising a first polymerizable monomer, a second polymerizable monomer different from the first polymerizable monomer, and a cross-linking agent, wherein the first polymerizable monomer in the composition is As long as the content ratio of the polymerizable monomer and the content ratio of the second polymerizable monomer are not impaired, they are not included in the range of the above formula (1) (that is, the first polymerizable monomer, 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.
The following monomers can also be used.
Styrene and its derivatives such as styrene and o-methylstyrene, (meth) acrylic acid such as n-butyl (meth) acrylate, t-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate Esters. When the monomer satisfies the above formula (1), it can be used as a 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.

  The acid value of the polymer A is preferably 30.0 mgKOH / g or less, more preferably 20.0 mgKOH / g or less, from the viewpoint of maintaining crystallinity. When the acid value is larger than 30.0 mgKOH / g, crystallization of the polymer A is liable to be inhibited and the melting point may be lowered. 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, and preferably from 20,000 to More preferably, it is 150,000.
When the weight average molecular weight (Mw) is within the above range, elasticity near room temperature can be easily maintained.
The melting point of the polymer A is preferably from 50 ° C. to 80 ° C., more preferably from 53 ° C. to 70 ° C., from the viewpoint of compatibility between low-temperature fixability and heat-resistant storage stability. When the melting point is in 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.

The content of the polymer A in the binder resin is preferably 50.0% by mass or more.
When the content is 50.0% by mass or more, the sharp melt property of the toner is easily maintained, and the low-temperature fixability is further improved. The content is more preferably 80.0% by mass to 100.0% by mass, and the binder resin is more preferably the polymer A.
Examples of resins that can be used other than the polymer A as the binder resin include conventionally known vinyl resins, polyester resins, polyurethane resins, and epoxy resins. Among them, vinyl resins, polyester resins and polyurethane resins are preferred from the viewpoint of electrophotographic properties.
The polymerizable monomer that can be used for the vinyl resin is a polymerizable monomer that can be used for the first polymerizable monomer, the second polymerizable monomer, and the third polymerizable monomer described above. Body and the like. If necessary, two or more kinds may be used in combination.

The polyester resin can be obtained by reacting a divalent or higher polyvalent carboxylic acid with a polyhydric alcohol.
Examples of the polyvalent carboxylic acid include the following compounds.
Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, dodecenylsuccinic acid, anhydrides or lower alkyl esters thereof; 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, anhydrides thereof or lower alkyl esters thereof. These may be used alone or in combination of two or more.

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

Next, the polyurethane resin will be described. The 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.
The following are mentioned as a diisocyanate component. Aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbon in the NCO group, the same applies hereinafter), aliphatic diisocyanate having 2 to 18 carbon atoms, alicyclic diisocyanate having 4 to 15 carbon atoms, and these diisocyanates (Modified products containing a urethane group, carbodiimide group, allophanate group, urea group, buret group, uretdione group, uretoimine group, isocyanurate group or oxazolidone group; hereinafter also referred to as "modified diisocyanate"); A mixture of two or more of the above.

Examples of the aromatic diisocyanate include the following. m- and / or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate.
The following are examples of the aliphatic diisocyanate. Ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI) and dodecamethylene diisocyanate.
The following are examples of the 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 are XDI , IPDI and HDI.
Further, in addition to the diisocyanate component, a tri- or higher functional isocyanate compound can be used.
As the diol component that can be used for the polyurethane resin, the same diol component as the divalent alcohol that can be used for the polyester resin described above can be used.

The toner particles may contain a colorant. Examples of the colorant include known organic pigments, organic dyes, inorganic pigments, carbon black as a black colorant, and magnetic substances. In addition, colorants conventionally used in toners may be used.
Examples of the colorant for yellow 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.
Examples of the magenta colorant 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.

The following are examples of the cyan colorant.
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.
The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner particles.
The content of the colorant is preferably from 1.0 part by mass to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin. When a magnetic material is used as the colorant, the content is preferably from 40.0 parts by mass to 150.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

The toner particles may contain a wax (release agent). The type of the wax is not particularly limited, and a conventionally known wax can be used.
Specifically, the following can be mentioned.
Low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, aliphatic hydrocarbon wax such as Fischer-Tropsch wax; oxidation of aliphatic hydrocarbon wax such as oxidized polyethylene wax Or a block copolymer thereof; plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax; animal wax such as beeswax, lanolin, whale wax; ozokerite, ceresin, petrolactam Mineral waxes such as these; waxes mainly containing aliphatic esters such as montanic acid ester wax and caster wax; and those obtained by partially or entirely deoxidizing aliphatic esters such as deoxidized carnauba wax.
The content of the wax in the toner particles is preferably 1.0% by mass to 30.0% by mass, and more preferably 2.0% by mass to 25.0% by mass.

The toner particles may optionally contain a charge control agent. Further, it may be externally added to the toner particles. By blending a charge control agent, the charge characteristics can be stabilized, and the optimal amount of triboelectric charge can be controlled according to the development system.
As the charge control agent, a known charge control agent can be used. In particular, a charge control agent having a high charging speed and capable of stably maintaining a constant charge amount is preferable.
As a charge control agent, an organic metal compound and a chelate compound are effective for controlling the toner particles to be negatively charged, and a monoazo metal compound, an acetylacetone metal compound, an aromatic oxycarboxylic acid, an aromatic dicarboxylic acid, Examples thereof include carboxylic acid and dicarboxylic acid-based metal compounds. On the other hand, those that control the toner particles to be positively charged include nigrosine, quaternary ammonium salts, metal salts of higher fatty acids, diorganotin borates, guanidine compounds, and imidazole compounds.
The content of the charge control agent is preferably 0.01 to 20.0 parts by mass, and more preferably 0.5 to 10.0 parts by mass, based on 100.0 parts by mass of the toner particles. More preferably, there is.

The toner particles may be used as they are, or an external additive such as inorganic fine particles may be added to the toner particles to form a toner.
It is preferable to add inorganic fine particles to the toner particles. Examples of the inorganic fine particles to be added to the toner particles include fine particles such as silica fine particles, titanium oxide fine particles, alumina fine particles, and double oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable for improving the fluidity and making the charge uniform.
Examples of the silica fine particles include dry silica or fumed silica produced by vapor phase oxidation of a silicon halide, and wet silica produced from water glass. Above all, dry silica having less silanol groups on the surface and inside the silica fine particles and having less Na ₂ O and SO ₃ ²⁻ is preferred. Further, the fumed silica may be composite fine particles of silica and another metal oxide produced by using a metal halide such as aluminum chloride and titanium chloride together with a silicon halide in the production process.

In addition, by subjecting the silica fine particles to the hydrophobic treatment, the charge amount of the toner particles can be adjusted, the environmental stability can be improved, and the characteristics can be improved in a high humidity environment. It is more preferable to use The hydrophobic treatment prevents moisture absorption of the silica fine particles, maintains the charge amount of the toner particles, and improves developability and transferability.
Examples of the treating agent for hydrophobizing silica fine particles include silicone oil, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treating agents may be used alone or in combination.

As the silicone oil, a known silicone oil can be used without any particular limitation, and straight silicone is particularly preferable.
Specific examples include dimethyl silicone oil, alkyl-modified silicone oil, α-methylstyrene-modified silicone oil, fluorine-modified silicone oil, and methyl hydrogen silicone oil.
It is preferable that the viscosity of the silicone oil is less than 30 mm ² / s or more 1200 mm ² / s, more preferably at most 70 mm ² / s or more 800 mm ² / s.
As a method of the silicone oil treatment, the silica fine particles and the silicone oil may be directly mixed using a mixer such as a Henschel mixer, or may be a method of stirring while spraying the silicone oil onto the silica fine particles. Alternatively, the silicone oil may be dissolved or dispersed in a suitable solvent (preferably adjusted to pH 4 with an organic acid or the like) and then mixed with silica fine particles to remove the solvent. Further, silica fine particles are put into a reaction tank, alcohol water is added with stirring under a nitrogen atmosphere, a silicone oil-based treatment liquid is introduced into the reaction tank, surface treatment is performed, and heating and stirring are performed to remove the solvent. It may be a method.

The number average particle diameter of the primary silica fine particles is preferably 5 nm or more and 20 nm or less. When the content is in the above range, the fluidity of the toner particles can be easily improved.
The content of the inorganic fine particles is preferably from 0.1 to 4.0 parts by mass, more preferably from 0.2 to 3.5 parts by mass, based on 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 within the range of the present configuration.
Among them, the first polymerizable monomer, the second polymerizable monomer different from the first polymerizable monomer, and the crosslinking agent can be uniformly dispersed, and the toner particles are controlled to be spherical. By doing so, the suspension polymerization method is preferable because the crystallinity and durability are easily improved.

That is, the present invention
A method for producing a toner having toner particles,
In an aqueous medium, a step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, and
A step of obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles,
The polymerizable monomer composition,
A first polymerizable monomer,
It contains a second polymerizable monomer different from the first polymerizable monomer, and a crosslinking agent,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The cross-linking agent has two or more polymerizable double bonds,
The content ratio of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. 5.0 mol% to 60.0 mol%,
The content ratio of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. From 20.0 mol% to 95.0 mol%,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Wherein the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 , wherein 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)

For example, a polymerizable monomer containing a polymerizable monomer that forms a binder resin containing the polymer A, and, if necessary, a colorant, a wax, a charge control agent, and other materials such as a polymerization initiator. The 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. Thereafter, toner particles are obtained by polymerizing the polymerizable monomer contained in the particles.
After the polymerization, the toner particles may be filtered, washed and dried by a known method, and an external additive may be added as necessary to obtain a toner.

As the polymerization initiator, a known polymerization initiator can be used.
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 and azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, t -Butylperoxypivalate, t-butylperoxyisobutyrate, t-butylperoxyneodecanoate, methylethylketone peroxide, diisopropylperoxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl Peroxide-based polymerization initiators such as peroxide and lauroyl peroxide; You.
Further, known chain transfer agents and polymerization inhibitors may be used.

The aqueous medium may contain an inorganic or organic dispersion stabilizer.
As the dispersion stabilizer, a known dispersion stabilizer can be used.
Examples of the inorganic dispersion stabilizer include phosphates such as hydroxyapatite, tribasic calcium phosphate, dibasic calcium 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 the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salts of carboxymethyl cellulose, polyacrylic acid and salts thereof, 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 inorganic compound may be formed and used in an aqueous medium.
For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is preferable to mix the aqueous phosphate solution and the aqueous calcium salt solution under high stirring.
The aqueous medium may contain a surfactant. As the surfactant, a known surfactant can be used. Examples thereof include anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

Next, methods for measuring physical properties 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 measurement of the content ratio of the monomer units derived from various polymerizable monomers in the polymer A is performed 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
・ Total number of times: 64 ・ Measurement temperature: 30 ℃
Sample: 50 mg of a sample to be measured is placed in a sample tube having an inner diameter of 5 mm, and chloroform (CDCl ₃ ) is added as a solvent and dissolved in a 40 ° C. constant temperature bath.
From the obtained ¹ H-NMR chart, among peaks attributed to the constituent elements of the monomer unit derived from the first polymerizable monomer, peaks attributed to the constituent elements of the monomer unit derived from the other are selects the independent peaks, calculates an integrated values S ₁ for the peak.
Similarly, from among the peaks attributed to the components of the monomer unit derived from the second polymerizable monomer, a peak independent of the peak attributed to the components of the monomer unit derived from the other is selected. , an integrated value S ₂ is calculated for this peak.
Furthermore, when using the third polymerizable monomer, 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 the other the peak attributable to select the independent peaks, calculates an integrated value S ₃ of the peak.
The content ratio of the monomer unit derived from the first polymerizable monomer is determined as follows using the above integral values S ₁ , S ₂ and S ₃ . Note that n ₁ , n _{2, and} n ₃ are the numbers of hydrogen in the constituent elements to which the peaks of interest are assigned for each site.
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 the monomer units derived from the second polymerizable monomer and the third polymerizable monomer is determined 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 unit derived from third polymerizable monomer =
{(S ₃ / n ₃ ) / ((S ₁ / n ₁ ) + (S ₂ / n ₂ ) + (S ₃ / n ₃ ))} × 100
When a polymerizable monomer containing no hydrogen atom in the constituents other than the vinyl group is used in the polymer A, the measured nuclei are set to ¹³ C by ¹³ C-NMR, and the single pulse mode is used. , And similarly calculated by ¹ H-NMR.
Further, when the toner particles are produced by a suspension polymerization method, peaks of wax and other resins may overlap, and an independent peak may not be observed. As a result, the content of monomer units derived from various polymerizable monomers in the polymer A may not be calculated. In this case, by performing the same suspension polymerization without using a wax or other resin, the polymer A ′ can be produced, and the polymer A ′ can be analyzed as the polymer A.

<Method of calculating SP value>
SP ₁₂ , SP ₂₂ , and SP _C2 are obtained as follows in accordance with the calculation method proposed by Fedors.
For each polymerizable monomer, the evaporation energy (Δei) from the table described in “polym. Eng. Sci., 14 (2), 147-154 (1974)” with respect to the atom or atomic group in the molecular structure. ) (Cal / mol) and molar volume (Δvi) (cm ³ / mol) are determined, and (4.184 × ΣΔei / ΣΔvi) ^0.5 is defined as SP value (J / cm ³ ) ^0.5 .

<Measurement method of melting point>
The melting point of the 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 temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of the calorific value uses the heat of fusion of indium.
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.
The peak temperature of the maximum endothermic peak in the first heating process is defined as the melting point.
Note that the maximum endothermic peak is a peak at which the amount of endotherm becomes maximum when there are a plurality of peaks.

<Method of measuring acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the polymer in the present invention is measured according to JIS K 0070-1992. Specifically, the acid value is measured according to the following procedure.
(1) Preparation of reagent Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. After leaving the container in an alkali-resistant container for 3 days so as not to be exposed to carbon dioxide gas, the solution is filtered to obtain a potassium hydroxide solution.
The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 mL of 0.1 mol / L hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution was added, and titration was performed with the potassium hydroxide solution. Determined from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) This test 2.0 g of a sample (for example, pulverized polymer A) was precisely weighed in a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene / ethanol (2: 1) was added thereto, and it took 5 hours. To dissolve.
Next, several drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is defined as the time when the light red color of the indicator continues for 30 seconds.
(B) Blank test The titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The obtained result is substituted into the following equation to calculate an acid value.
A = [(CB) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in main test, f: potassium hydroxide Solution factor, S: mass (g) of sample.

<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, a sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Maisho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. The measurement is performed under the following conditions using this sample solution.
-Equipment: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: 7 stations of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
・ 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).

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. 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 to the reaction vessel. Thereafter, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] (Showa Denko KK) was added dropwise at 40 ° C. with stirring. After completion of the dropwise addition, stirring was performed for 2 hours while maintaining the temperature at 40 ° C. Thereafter, a monomer having a urethane group was prepared by removing unreacted methanol with an evaporator.

<Preparation of monomer having urea group>
50.0 parts of dibutylamine was charged to the reaction vessel. Thereafter, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] was added dropwise at room temperature under stirring. After completion of the dropwise addition, stirring was performed for 2 hours. Then, a monomer having a urea group was prepared by removing unreacted dibutylamine with an evaporator.

<Preparation of polymer A0>
The following materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere.
Toluene 100.00 partsMonomer composition 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%)
-2.00 parts (0.6 mol%) of polypropylene glycol diacrylate
(Shin-Nakamura Chemical Co., Ltd., APG-400, molecular weight 536)
T-butyl peroxypivalate 0.50 parts (polymerization initiator, NOF Corporation: Perbutyl PV)
The polymerization reaction was performed for 12 hours by heating to 70 ° C. while stirring the inside of the reaction vessel at 200 rpm 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 methanol-insoluble components. The obtained methanol-insoluble matter was separated by filtration, further washed with methanol, and vacuum-dried at 40 ° C. for 24 hours to obtain a polymer A0. The acid value of the polymer A0 was 0.0 mgKOH / g, and the melting point was 62 ° C.

<Preparation of amorphous resin>
The following raw materials were charged into a heated and 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, 21.00 parts of terephthalic acid, 15.00 parts of dodecenylsuccinic acid, 0.10 part of dibutyltin oxide After the inside of the system was replaced with nitrogen by a reduced pressure operation, the mixture was stirred at 215 ° C. for 5 hours. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure while continuing stirring, and further maintained for 2 hours. When the mixture became viscous, the mixture was air-cooled to stop the reaction, thereby synthesizing an amorphous resin as 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>
For 100 parts of fumed silica (trade name: AEROSIL 380S, specific surface area by BET method: 380 m ² / g, number average particle diameter of primary particles: 7 nm, manufactured by Nippon Aerosil Co., Ltd.), 10.0 parts of polydimethylsiloxane (viscosity) = 100 mm ² / s) and stirring was continued for 30 minutes. Thereafter, the temperature was raised to 300 ° C. with stirring, and the mixture was further stirred for 2 hours to prepare silica fine particles 1.

<Example 1>
[Production of toner by suspension polymerization method]
(Production of toner particles 1)
-Monomer composition 100.00 parts (The monomer composition is a mixture of the following behenyl acrylate, methacrylonitrile, styrene, and polypropylene glycol diacrylate in the ratio 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%)
-2.00 parts (0.6 mol%) of polypropylene glycol diacrylate
(Shin-Nakamura Chemical Co., Ltd., APG-400, molecular weight 536)
・ Pigment Blue 15: 3 6.50 parts ・ Di-t-butylsalicylate aluminum 1.00 part ・ Fisher tropushwax 20.00 parts (Nippon Seiro Co., Ltd .: HNP-51, melting point: 74 ° C.)
A mixture consisting of 100.00 parts of toluene was prepared. The mixture was charged into an attritor (manufactured by Nippon Coke Co., Ltd.) and dispersed at 200 rpm for 2 hours using zirconia beads having a diameter of 5 mm to obtain a raw material dispersion.
On the other hand, to a vessel equipped with a high-speed stirrer homomixer (manufactured by Primix) and a thermometer, 735.00 parts of ion-exchanged water and 16.00 parts of trisodium phosphate (decahydrate) were added, and the mixture was stirred at 12000 rpm. While heating, the temperature was raised to 60 ° C. An aqueous calcium chloride solution obtained 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 12,000 rpm for 30 minutes while maintaining the temperature at 60 ° C. There, 10% hydrochloric acid was added 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. After adding 8.00 parts of t-butyl peroxypivalate (manufactured by NOF CORPORATION: Perbutyl PV) as a polymerization initiator and stirring the mixture at 100 rpm for 5 minutes while maintaining the temperature at 60 ° C, the mixture was added to the high-speed stirring apparatus. Into an aqueous medium stirred at 12000 rpm. While maintaining the temperature at 60 ° C., stirring was continued at 12,000 rpm for 20 minutes with the high-speed stirring device to obtain a granulated liquid.
The granulated 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. while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was performed at 150 rpm for 10 hours while maintaining 70 ° C. Thereafter, the reflux condenser was removed from the reaction vessel, the temperature of the reaction solution was raised to 95 ° C., and the mixture was stirred at 150 rpm for 5 hours while maintaining the temperature at 95 ° C. to remove toluene, thereby obtaining a toner particle dispersion.
After cooling the obtained toner particle dispersion to 20 ° C. while stirring at 150 rpm, dilute hydrochloric acid was added to dissolve the dispersion stabilizer until the pH reached 1.5 while maintaining the stirring. The solid content was separated by filtration, sufficiently washed with ion-exchanged water, and vacuum-dried at 40 ° C. for 24 hours to obtain toner particles 1 containing polymer A1 of the monomer composition.
Further, a polymer A1 ′ was obtained in the same manner as in the method for producing the toner particles 1, except that Pigment Blue 15: 3, aluminum di-t-butylsalicylate, and Fischer-Tropsch wax were not used. The acid value of the polymer A1 ′ was 0.0 mgKOH / g, and the melting point was 62 ° C.
Since the polymer A1 and the polymer A1 ′ were produced in the same manner, it was determined that they had the same physical properties.

(Preparation of Toner 1)
The toner particles 1 were externally added. 100.0 parts of the toner particles 1 and 1.8 parts of the 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 thus 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: myristyl 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
1: polypropylene glycol diacrylate 2: tripropylene glycol diacrylate 3: 1,10-decanediol diacrylate 4: 1,6-hexanediol diacrylate 5: divinylbenzene A in the production method in the table is a suspension B represents a polymerization method, B represents an emulsion aggregation method, and C represents a pulverization method.
Tripropylene glycol diacrylate in the cross-linking agents 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 (° C.) of the polymer A.

<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 kind and amount of the polymerizable monomer composition used were changed as shown in Table 1.
Further, an external addition process of silica fine particles was carried out in the same manner as in Example 1 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 (The 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 was prepared by mixing the above components, and a surfactant aqueous solution in which 10 parts of an anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK) was dissolved in 1130 parts of ion-exchanged water; Was put into a two-necked flask, and the mixture was stirred at a rotation speed of 10,000 r / min using a homogenizer (Ultra Turrax T50, manufactured by IKA) to emulsify.
Then, the inside of the flask was replaced with nitrogen, and the contents were heated to 70 ° C. in a water bath with slow stirring, and then polypropylene glycol diacrylate (APG-400, molecular weight 536, manufactured by Shin-Nakamura Chemical Co., Ltd.) 7 parts of ion-exchanged water in which 00 parts were dissolved were added, and polymerization was started.
After the reaction was continued for 8 hours, the reaction solution was cooled to room temperature, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (polymer particle 1 dispersion) having a concentration of polymer particles 1 of 20% by mass.
The 50% particle size (D50) based on the volume distribution of the polymer fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.40 μm.

(Preparation of wax dispersion 1)
・ Fischer Tropsch wax 100.00 parts (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.) 39.00 parts of ion-exchanged water The above materials were weighed and placed in a mixing vessel equipped with a stirrer. The mixture was circulated through Mix W Motion (manufactured by M Technique) to perform a dispersion treatment for 60 minutes. The conditions of the distributed processing were as follows.
・ Rotor outer diameter 3cm
・ Clearance 0.3mm
・ Rotor rotation speed 19000r / min
・ Screen rotation speed 19000r / min
After the dispersion treatment, the wax dispersion 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, so that a wax dispersion having a concentration of the wax fine particles 1 of 20% by mass is obtained. 1 was obtained.
The 50% particle size (D50) based on the volume distribution of the wax fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.15 μm.

(Preparation of Colorant Dispersion 1)
・ Coloring agent 50.00 parts (cyan pigment manufactured by Dainichi Seika: Pigment Blue 15: 3)
7.50 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 442.50 parts of ion-exchanged water The above materials are weighed and mixed, and are mixed with a high pressure impact dispersing machine Nanomizer (manufactured by Yoshida Kikai Kogyo). After time dispersion, a colorant dispersion liquid 1 having a concentration of 10% by mass of the colorant fine particles 1 obtained by dispersing the colorant was obtained.
The 50% particle size (D50) based on the volume distribution of the colorant fine particles 1 was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.20 μm.

(Production of Toner 26)
-500.00 parts of polymer dispersion-50.00 parts of wax dispersion 1-80.00 parts of colorant dispersion-160.00 parts of ion-exchanged water The above-mentioned materials are put into a round stainless steel flask and mixed. did. Subsequently, the mixture was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra Turrax T50 (manufactured by IKA). A 1.0% aqueous nitric acid solution was added to adjust the pH to 3.0, and then the mixture was stirred at 58 ° C. in a heating water bath using a stirring blade while appropriately adjusting the number of revolutions so that the mixture was stirred. Until heated.
The volume average particle size of the formed aggregated particles is appropriately checked using a Coulter Multisizer III, and when the aggregated particles having a volume average particle size of about 6.0 μm are formed, a 5% aqueous sodium hydroxide solution is used. To bring the pH to 9.0.
Then, it heated to 75 degreeC, continuing stirring. Then, the particles were kept at 75 ° C. for 1 hour to fuse the aggregated particles.
Thereafter, the temperature was cooled to 50 ° C. and maintained for 3 hours to promote crystallization of the polymer.
Thereafter, the mixture was cooled to 25 ° C., filtered and solid-liquid separated, and then washed with ion-exchanged water.
After the completion of the washing, the toner particles were dried using a vacuum dryer to obtain toner particles 26 having a weight average particle diameter (D4) of 6.07 μm.
The toner particles 26 were externally added in the same manner as in Example 1 to obtain a toner 26. Table 2 shows the physical properties of Toner 26 and Table 4 shows the evaluation results.

<Example 27>
[Production of toner by pulverization method]
-100.00 parts of polymer A0-C.I. I. Pigment Blue 15: 3 6.50 parts, Fischer-Tropsch wax 2.00 parts (Nippon Seiro Co., Ltd .: HNP-51, melting point: 74 ° C.)
Charge control agent (T-77: Hodogaya Chemical Industry Co., Ltd.) 2.00 parts After the above materials are premixed with an FM mixer (Nippon Coke Industry Co., Ltd.), a twin-screw kneading extruder (Ikegai Iron Works) (PCM-30 type manufactured by K.K.)).
The obtained kneaded material was cooled, coarsely crushed by a hammer mill, and then crushed by a mechanical crusher (T-250 manufactured by Turbo Kogyo Co., Ltd.). Classification was performed using a split classifier to obtain toner particles 27 having a weight average particle size (D4) of 7.0 μm.
External addition was performed on the toner particles 27 in the same manner as in Example 1 to obtain a toner 27. Table 2 shows the physical properties of Toner 27, and Table 4 shows the evaluation results.

<Examples 28 to 30>
(Preparation of amorphous resin dispersion)
-Toluene 300.00 parts-Amorphous resin 100.00 parts The above materials were weighed and 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.
Then, the toluene solution and the aqueous solution were mixed, and the mixture was mixed with an ultrahigh-speed stirring device T.I. 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 type dispersing machine Nanomizer (manufactured by Yoshida Kikai Kogyo). Thereafter, 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 size (D50) based on the volume distribution of the amorphous resin fine particles was measured using a dynamic light scattering type particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and found to be 0.38 μm.

(Production of Toners 28 to 30)
Toner particles 28 to 30 were obtained in the same manner as in (Production of toner 26) except that the amount of the dispersion used was changed as shown in Table 3.
The toner particles 28 to 30 were subjected to the same external addition 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 kind 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 The process cartridge filled with the toner was allowed to stand in a normal temperature and normal humidity (N / N) environment (23 ° C., 60% RH) for 48 hours. Using a Canon printer LBP-712Ci modified so that it operates even when the fixing unit is removed, an unfixed image of an image pattern in which a square image of 10 mm × 10 mm is arranged evenly at 9 points on the entire transfer paper was output. .
The toner loading amount on the transfer paper was 0.80 mg / cm ² , and the fixing start temperature was evaluated. The transfer paper used was Canon Oced Red Label (80 g / m ² ).
As the fixing device, an external fixing device was used in which the fixing device of LBP-712Ci was detached and operated outside the laser beam printer. In the external fixing device, the fixing temperature was raised from 100 ° C. in steps of 10 ° C., and the fixing was performed under the conditions of a process speed of 280 mm / sec.
The fixed image was rubbed with silbon paper [Lenz Cleaning Paper “dasper (R)” (Ozu Paper Co. Ltd.)] under a load of 50 g / cm ² . The temperature at which the density reduction rate before and after rubbing became 20% or less was defined as the fixing 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 The process cartridge filled with the 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 so as to operate even when the fixing device was removed, an unfixed image of an image pattern in which a square image of 30 mm × 30 mm was evenly arranged at 9 points on the entire transfer paper was output.
The amount of toner on the transfer paper was 1.20 mg / cm ² . The transfer paper used was Canon Oced Red Label (80 g / m ² ).
As the fixing device, an external fixing device was used in which the fixing device of LBP-712Ci was detached and operated outside the laser beam printer. In the fixing temperature of <1> low-temperature fixability, a fixed image was obtained at a temperature control higher by 10 ° C. than the fixing start temperature of each toner at a process speed of 280 mm / sec.
Then, the fixed image was folded in a cross shape and rubbed 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 peels off at the bent cross portion and the background of the paper is visible.
Next, the folded cross portion was photographed with a CCD camera at a resolution of 800 pixels / inch over an area of 512 pixels square.
The threshold was set at 60% and the image was binarized. The portion where the toner has peeled off is a white portion, and the smaller the area ratio of the white portion, the better the bending resistance. Table 4 shows the evaluation results. (Evaluation criteria)
A: The area ratio of the white portion is less than 1.0% B: The area ratio of the white portion is 1.0% or more and less than 2.0% C: The area ratio of the 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 Canon printer LBP-712Ci.
LBP-712Ci employs one-component contact development, and regulates the amount of toner on a development carrier by a toner regulating member.
The evaluation cartridge used was one in which the toner contained in a commercially available cartridge was extracted, the inside was cleaned with an air blow, and then 200 g of the toner was filled.
The evaluation was performed by mounting the cartridge on the cyan station and mounting a dummy cartridge on the other.
Using a Canon Oced Red Label (80 g / m ² ) in a normal temperature and normal humidity (N / N) environment (23 ° C., 60% RH), an image with a printing rate of 1% was continuously output.
Images were output on 20,000 sheets, solid images and halftone images were output, and the presence or absence of so-called development streaks in the circumferential direction due to fusion of the toner to the regulating member was visually checked. Table 4 shows the evaluation results.
[Evaluation criteria]
A: Not generated B: Development streaks occurred at 1 or more and 2 or less C: Development streaks occurred at 3 or more and 4 or less D: Development streaks occurred at 5 or more

<4> Heat-resistant storage stability In order to evaluate the stability during storage, heat-resistant storage stability was evaluated.
6 g of the toner was placed in a 100 mL polypropylene cup, left for 10 days in an environment of a temperature of 50 ° C. and a humidity of 20%. .
As a measuring device, a device in which a digital display type vibrometer "Digi Vibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) was connected to the side of the shaking table of "Powder Tester" (manufactured by Hosokawa Micron Corporation) was used.
Then, a sieve having a mesh size of 38 μm (400 mesh), a sieve having a mesh size of 75 μm (200 mesh), and a sieve having a mesh size of 150 μm (100 mesh) were set in this order on a vibration table of the powder tester from below. The measurement was performed as follows in a 23 ° C., 60% RH environment.
(1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display type vibrometer was 0.60 mm (peak-to-peak).
(2) The toner left for 10 days as described above was left in advance in an environment of 23 ° C. and 60% RH for 24 hours, and 5 g of the toner was precisely weighed and gently placed on a 150 μm sieve at the uppermost stage. Was.
(3) After the sieve was vibrated for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of aggregation was calculated based on the following equation. Table 4 shows the evaluation results.
Cohesion degree (%) = {(mass of sample on sieve with mesh size of 150 μm (g)) / 5 (g)} × 100
+ {(Sample mass (g) on sieve with mesh size of 75 μm) / 5 (g)} × 100 × 0.6
+ {(Mass of sample (g) on sieve with mesh size of 38 μm) / 5 (g)} × 100 × 0.2
The evaluation criteria are as follows.
A: Aggregation degree is less than 20% B: Aggregation degree is 20% or more and less than 25% C: Aggregation degree is 25% or more and less than 30% D: Aggregation degree 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 a polymer A that is a polymer of a composition containing a crosslinking agent,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The cross-linking agent has two or more polymerizable double bonds,
The content ratio of the first polymerizable monomer in the composition is from 5.0 mol% to 60.0 mol% based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. Mole%,
The content ratio of the second polymerizable monomer in the composition is from 20.0 mol% to 95.0 based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. Mole%,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Wherein the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 , wherein 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 toner according to claim 1, wherein the content of the polymer A in the binder resin is 50.0% by mass or more.   3. The first polymerizable monomer according to claim 1, wherein the first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having a linear alkyl group having 18 to 36 carbon atoms. 4. Toner. 4. The toner according to claim 1, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B). 5.

(In the formula (A), 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 , wherein R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
Hydroxy group,
—COOR ¹¹ (where R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
A urethane group (—NHCOOR ¹² , wherein R ¹² is an alkyl group having 1 to 4 carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ , wherein R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms),
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
And R ³ represents a hydrogen atom or a methyl group. )
(In the formula (B), R ² represents an alkyl group having 1 to 4 carbon atoms;
R ³ represents a hydrogen atom or a methyl group. ) The toner according to any one of claims 1 to 4, wherein the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

(In the formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms,
R ¹ is a nitrile group (—C≡N),
An amide group (—C (＝ O) NHR ¹⁰ (where R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms));
Hydroxy group,
—COOR ¹¹ (where R ¹¹ is an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
A urea group (—NH—C (＝ O) —N (R ¹³ ) ₂ (where R ¹³ is each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)),
—COO (CH ₂ ) ₂ NHCOOR ¹⁴ (where R ¹⁴ is an alkyl group having 1 to 4 carbon atoms), or —COO (CH ₂ ) ₂ —NH—C (＝ O) —N (R ¹⁵ ) ₂ (where R ¹⁵ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)
And R ³ represents a hydrogen atom or a methyl group. )
(In the formula (B), R ² represents an alkyl group having 1 to 4 carbon atoms;
R ³ represents a hydrogen atom or a methyl group. ) The composition comprises:
The first polymerizable monomer, the second polymerizable monomer, different from the crosslinking agent, further contains a third polymerizable monomer,
The toner according to any one of claims 1 to 5, wherein the third polymerizable monomer is at least one polymerizable monomer selected from the group consisting of styrene, methyl methacrylate, and methyl acrylate. . The content ratio of the second polymerizable monomer in the composition is 40.0 mol% to 95.0 based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the composition. 2. The composition of claim 1, wherein
The toner according to any one of claims 1 to 6, wherein The SP value of the polymerizable monomer exhibiting the maximum SP value in the first polymerizable monomer is set to 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 set to SP _{22 min} (J / cm ³ ) ^0.5 ,
When the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 ,
The toner according to any one of claims 1 to 7, wherein the SP _12max , the SP _22min, and the SP _C2 satisfy the following expression (3).
_{(SP 22min -SP C2) <(} SP C2 -SP 12max) (3)   The toner according to any one of claims 1 to 8, wherein the crosslinking agent has a molecular weight of 300 or more.   The toner according to any one of claims 1 to 9, wherein the polymer A is a vinyl polymer. A method for producing a toner having toner particles,
In an aqueous medium, a step of forming particles of a polymerizable monomer composition containing a polymerizable monomer, and
A step of obtaining the toner particles containing the polymer A obtained by polymerizing the polymerizable monomer contained in the particles,
The polymerizable monomer composition,
A first polymerizable monomer,
It contains a second polymerizable monomer different from the first polymerizable monomer, and a crosslinking agent,
The first polymerizable monomer is at least one selected from the group consisting of a (meth) acrylate having an alkyl group having 18 to 36 carbon atoms,
The cross-linking agent has two or more polymerizable double bonds,
The content ratio of the first polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. 5.0 mol% to 60.0 mol%,
The content ratio of the second polymerizable monomer in the polymerizable monomer composition is based on the total number of moles of all the polymerizable monomers and the crosslinking agent in the polymerizable monomer composition. From 20.0 mol% to 95.0 mol%,
The SP value of the first polymerizable monomer is set to SP ₁₂ (J / cm ³ ) ^0.5, and the SP value of the second polymerizable monomer is set to SP ₂₂ (J / cm ³ ) ^0.5 Wherein the SP value of the crosslinking agent is SP _C2 (J / cm ³ ) ^0.5 , wherein 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)