JP2021140145A - toner - Google Patents

Abstract

To provide a toner that is excellent in low-temperature fixability, electrification maintainability, and scratch resistance.SOLUTION: A toner has a toner particle containing a binder resin and wax. The binder resin contains an amorphous polyester resin, a polymer A, and a component B. The content of the amorphous polyester resin in the binder resin is 50.0 mass% or more. The polymer A has a first monomer unit and a second monomer unit represented by the following formula (C). In the formula (C), RZ3 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms. The content ratio of the first monomer unit in the polymer A is 5.0 to 60.0 mol%.SELECTED DRAWING: None

Description

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

In recent years, as electrophotographic full-color copiers have become widespread, not only higher speeds and higher image quality, but also energy saving, shorter recovery time from sleep mode, and support for a wide variety of media have been added. Performance improvement is also required.
Specifically, as a toner corresponding to energy saving, a toner having excellent low-temperature fixability that can be fixed at a lower temperature is required in order to reduce power consumption in the fixing process.
Further, as a toner capable of shortening the recovery time from the sleep state, there is a demand for a toner having excellent charge retention and having a small change in the charge amount throughout the sleep state for a long time.
Furthermore, thick paper coated paper, which is one of a wide variety of media, contains a large amount of inorganic fine particles such as calcium carbonate in order to enhance the whiteness, so that the coefficient of friction due to rubbing between the papers increases, and the fixed image The toner that forms the paper is easily peeled off from the paper. Therefore, as a fixed image in which the toner does not easily peel off even when the papers are rubbed against each other, the surface of the fixed image can be coated with wax to reduce the coefficient of friction, and the abrasion resistance promotes the exudation of wax. Excellent toner is required.

Patent Document 1 proposes a toner using a crystalline polyvinyl resin as a toner having excellent low-temperature fixability, charge retention, and scratch resistance.
Further, Patent Document 2 proposes a toner having alkenyl succinic acid as a carboxylic acid component of polyester as a toner having excellent scratch resistance.

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

Since the toner described in Patent Document 1 uses a crystalline polyvinyl resin having sharp melt properties and high hydrophobicity, excellent low-temperature fixability and charge retention are possible. Furthermore, by promoting the crystallization of the crystalline resin in the fixed image, a certain effect was obtained in the pencil scratching test. It is considered that this is because the crystallinity of the crystalline resin restores the elasticity of the toner itself in the fixed image and makes it difficult for the toner to be destroyed.
On the other hand, the peeling of the toner of the fixed image by rubbing between the papers, which has been required in recent years, is a phenomenon in which the toner is peeled from the paper rather than the toner being destroyed.
Furthermore, since the crystalline polyvinyl resin has a high affinity with wax, the exudation of wax is suppressed, and the wax layer on the surface of the fixed image is less likely to be formed. From the above, even if the toner described in Patent Document 1 is used, the scratch resistance required in recent years may be inferior.

On the other hand, in the toner described in Patent Document 2, since alkenyl succinic acid has a high affinity with wax, the wax is more easily retained in the fixing image than the wax is transferred to the fixing roller at the time of fixing. Therefore, paper such as plain paper In the seed, a certain effect of scratch resistance was obtained.
However, since the binder resin has a high affinity with wax, wax exudation on the surface of the fixed image is easily suppressed, and the thick coated paper, which has been required in recent years, may have poor scratch resistance.
From the above, there is no toner that satisfies all of low temperature fixability, charge retention, and scratch resistance. Therefore, there is an urgent need to develop a toner that exhibits excellent low-temperature fixability and charge retention, and also exhibits excellent scratch resistance even in a fixed image such as thick coated paper.
The present disclosure provides a toner that exhibits excellent low-temperature fixability and charge retention, and also exhibits excellent scratch resistance even in a fixed image such as thick coated paper.

This disclosure is
A toner having toner particles containing a binder resin and a wax.
The binder resin contains an amorphous polyester resin, a polymer A, and a component B.
The content of the amorphous polyester resin is 50.0% by mass or more based on the total mass of the binder resin.
The polymer A has a first monomer unit represented by the following formula (C) and a second monomer unit different from the first monomer unit.
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A.
When the SP value of the second monomer unit is SP _A21 (J / cm ³ ) ^0.5 , the SP _A21 is 21.00 or more.
The content of the polymer A is 0.10% by mass to 10.00% by mass based on the total mass of the binder resin.
The SP value of the amorphous polyester resin was SP _P (J / cm ³ ) ^0.5 ,
The SP value of the polymer A is SP _A (J / cm ³ ) ^0.5 ,
The SP value of the component B is SP _B (J / cm ³ ) ^0.5 , and
When the SP value of the wax is SP _W (J / cm ³ ) ^0.5 ,
The toner is characterized in that the SP _P , the SP _A , the SP _B , and the SP _W satisfy the relationship of the following formulas (1) and (2).
0.5 ≤ [(SP _P- SP _A )-(SP _A- SP _W )] (1)
0.5 ≤ [(SP _A- SP _W )-(SP _B- SP _A )] (2)

（式（Ｃ）中、Ｒ_Ｚ３は、水素原子又はメチル基を表し、Ｒは、炭素数１８〜３６のアルキル基を表す。）

(In the formula (C), R _Z3 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms.)

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

Hereinafter, the description of "XX or more and YY or less" or "XX to YY" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified.
When the numerical ranges are described step by step, the upper and lower limits of each numerical range can be arbitrarily combined.
The (meth) acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester.
"Monomer unit" refers to the reacted form of a monomeric substance in a polymer. For example, one carbon-carbon bond section in the main chain in which the vinyl-based monomer in the polymer is polymerized is defined as one unit. The vinyl-based monomer can be represented by the following formula (Z).

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

The present inventors have proceeded with the study of a toner having excellent low-temperature fixability and charge retention, and also having excellent scratch resistance in a fixed image such as thick coated paper. As a result, the present inventors impart a specific structure to the first monomer unit forming the polymer A in the binder resin, and further, the amorphous polyester resin, the polymer A, in the toner particles. It has been found that a desired toner can be obtained by controlling the affinity of the component B and the wax based on the SP value.

Specifically, it is preferable to suppress the compatibility of the polymer A with the wax and to facilitate the compatibility of the polymer A with the amorphous polyester resin which is the main resin of the binder resin. Therefore, the binder resin contains the component B which is a compatibilizer.
The reason why the polymer A is easily compatible with the wax is that the absolute value of the polar difference between the polymer A and the wax is small, and the amorphous polyester resin and the polymer have a small polar difference between the polymer A and the wax. The difference in polarity of A is large. As a result, the polymer A acts in the direction of compatibility with the wax, which is the stable direction.

As a result of diligent studies, the present inventors have made the polar difference between the polymer A and the wax heavy with the amorphous polyester resin in order to take advantage of the polymer A having high hydrophobicity and excellent charge retention. We have come to the conclusion that it is impossible to make it larger than the polarity difference of coalescence A. This is because increasing the polar difference between the polymer A and the wax tends to make the polymer A hydrophilic, which may impair the charge retention property.
Then, based on these, the present inventors have studied to reduce the compatibility between the polymer A and the wax. As a result, the component B as a compatibilizer is added so that the polymer A and the amorphous polyester resin can be easily compatible with each other, and the polymer A can be easily compatible with the component B. It has been found that the first monomer unit forming the coalescence A has a specific structure.

That is, the binder resin contains the component B that functions as a compatibilizer, and the first monomer unit that forms the polymer A has a specific structure, so that the polymer A has a specific structure.
Is more easily compatible with component B than wax, and further, the compatible product of the polymer A and component B is more easily compatible with the amorphous polyester resin.
As a result, even when the polymer A is contained, the polymer A and the wax are phase-separated, and the exudation of the wax at the time of fixing is ensured. Therefore, the surface of the fixed image is easily covered with wax, and the coefficient of friction is lowered, so that excellent scratch resistance can be obtained.

The toner particles contain a binder resin and a wax.
In addition, the binder resin contains an amorphous polyester resin, a polymer A, and a component B.
The polymer A is preferably a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer. Further, the polymer A is different from the first monomer unit represented by the following formula (C) and the first polymerizable monomer derived from the first polymerizable monomer. It has a second monomer unit derived from the second polymerizable monomer.

（式（Ｃ）中、Ｒ_Ｚ３は、水素原子又はメチル基を表し、Ｒは、炭素数１８〜３６のアルキル基（好ましくは、炭素数１８〜３０のアルキル基）を表す。）

(In the formula (C), R _Z3 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms (preferably an alkyl group having 18 to 30 carbon atoms).

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

On the other hand, when R is an alkyl group having less than 18 carbon atoms, the chain length of the alkyl group is short, so that the polymer having the monomer unit has low hydrophobicity and high hygroscopicity in a high temperature and high humidity environment, so that it is charged. Poor maintainability. When R is an alkyl group having 37 or more carbon atoms, the polymer having such a monomer unit has an alkyl group having a long chain length, so that the melting point is high and the low temperature fixability is poor.

R is preferably a linear alkyl group having 18 to 36 carbon atoms, and more preferably a linear alkyl group having 18 to 30 carbon atoms.
On the other hand, examples of the (meth) acrylic acid ester having an alkyl group having 18 to 36 carbon atoms include a (meth) acrylic acid ester having a linear alkyl group having 18 to 36 carbon atoms [(meth) stearyl acrylate, (. Nonadesyl acrylate, Eikosyl acrylate, Heneikosanyl acrylate, Behenyl acrylate, Lignoceryl acrylate, Ceryl acrylate, Octacosyl acrylate, Meta ) Myricyl acrylate, dotriacontyl (meth) acrylate, etc.] and (meth) acrylic acid ester having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth) acrylate, etc.] can be mentioned.
Of these, from the viewpoint of low-temperature fixability, at least one selected from the group consisting of (meth) acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms is preferable, and a linear alkyl having 18 to 30 carbon atoms is preferable. More preferably, at least one selected from the group consisting of (meth) acrylic acid esters having a group.
Among them, at least one selected from the group consisting of stearyl (meth) acrylate and behenyl (meth) acrylate is more preferable, and at least one selected from the group consisting of behenyl (meth) acrylate. Is particularly preferable.
The first polymerizable monomer may be used alone or in combination of two or more.

The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A.
Further, the content ratio of the first polymerizable monomer in the polymerizable monomer composition for producing the polymer A is the total of all the polymerizable monomers in the polymerizable monomer composition. Based on the number of moles, it is 5.0 mol% to 60.0 mol%.
The content ratio of the first monomer unit in the polymer A and the content ratio of the first polymerizable monomer in the polymerizable monomer composition for producing the polymer A are within the above ranges. Therefore, sharp meltability due to crystallinity is likely to be exhibited, and the toner is excellent in low-temperature fixability.
The content ratio of the first monomer unit and the content ratio of the first polymerizable monomer are preferably 10.0 mol% to 60.0 mol%, more preferably 20.0 mol%. ~ 40.0 mol%.

On the other hand, when the content ratio of the first monomer unit or the content ratio of the first polymerizable monomer is less than 5.0 mol%, the ratio of the crystalline portion is small, so that the low temperature fixability is inferior. ..
Further, when the content ratio of the first monomer unit or the content ratio of the first polymerizable monomer is more than 60.0 mol%, the polarity of the polymer A becomes too low and the phase separation property with the wax Is difficult to obtain and is inferior in scratch resistance.

When the polymer A has two or more kinds of monomer units represented by the formula (C), the content ratio of the first monomer unit is represented by the total molar ratio of them. Similarly, when the polymerizable monomer composition for producing the polymer A contains two or more kinds of (meth) acrylic acid esters having an alkyl group having 18 to 36 carbon atoms, the first polymerizable property is also obtained. The content ratio of the monomer is expressed by the molar ratio of their total. When specifying the total number of moles, the number of moles is counted by regarding the carbon-carbon bond (-CC-) constituting the main chain as one unit.

When the SP value of the second monomer unit is SP _A21 (J / cm ³ ) ^0.5 , the SP _A21 is 21.00 or more. The SP _A21 is preferably 24.00 or more, and more preferably 26.00 or more. Further, the SP _A21 is preferably 40.00 or less, and more preferably 30.00 or less.
Here, the SP value is an abbreviation for a solubility parameter, and is a value that serves as an index of solubility. The calculation method will be described later.
The unit of the SP value in the present disclosure is (J / cm ³ ) ^0.5 , but 1 (cal / cm ³ ) ^0.5 = 2.045 × 10 ³ (J / cm ³ ) ^0.5. Can be converted to a unit of (cal / cm ³ ) ^0.5.

When the SP _A21 satisfies the above range, the second monomer unit becomes highly polar, and a polarity difference occurs between the first and second monomer units. Due to this polarity difference, the crystallization of the first monomer unit is further promoted, so that the low temperature fixability and the charge retention property are further improved.
Specifically, the first monomer unit is incorporated into the polymer A, and the first monomer units aggregate with each other to exhibit crystallinity. Normally, the crystallization of the first monomer unit is likely to be inhibited when other monomer units are incorporated, so that it becomes difficult to develop crystallization as a polymer. This tendency becomes remarkable when a plurality of types of monomer units are randomly bonded to each other in one molecule of the polymer. However, by using the first polymerizable monomer and the second polymerizable monomer having different polarities, the first polymerizable monomer and the second polymerizable monomer are randomly selected at the time of polymerization. It is considered that they can be bonded continuously to some extent instead of being bound to. As a result, a block in which the first monomer units are assembled is likely to be formed, and the polymer A is likely to be a block copolymer. As a result, it becomes possible to enhance the crystallinity even if another monomer unit is incorporated, and it is easy to obtain excellent low temperature fixability and charge retention. Furthermore, since the crystalline portion of the first monomer unit has an affinity with the crystalline moiety of the component B, which is a compatibilizer described later, the compatibility between the polymer A and the component B is likely to increase, and conversely. Since the phase separation between the polymer A and the wax can be obtained, excellent scratch resistance can be obtained.

On the other hand, when the SP value of the second monomer unit is SP _A21 (J / cm ³ ) ^0.5 , which does not satisfy the above range, the polarity difference between the polymerizable monomers constituting the polymer A tends to be small. The first polymerizable monomer tends to bind randomly. As a result, it is difficult to form a block in which the first monomer units are aggregated, it is easy to increase the crystallinity, and the charge retention property may be inferior.
Furthermore, since the first monomer unit may have a small number of crystalline sites, the affinity with the component B, which is a compatibilizer described later, may decrease, so that the phase between the polymer A and the wax may decrease. Separability may not be obtained and scratch resistance may be inferior.
The second monomer unit derived from the second polymerizable monomer corresponds to all the monomer units having _{SPA21 satisfying the above range.}
That is, when the second polymerizable monomer is two or more kinds of polymerizable monomers, SP _A21 represents the SP value of the monomer unit derived from each polymerizable monomer.

The SP value of the amorphous polyester resin is SP _P (J / cm ³ ) ^0.5 , the SP value of the polymer A is SP _A (J / cm ³ ) ^0.5 , and the SP value of the component B is SP _B. When (J / cm ³ ) ^0.5 and the SP value of the wax is SP _W (J / cm ³ ) ^0.5 , the following equations (1) and (2) are satisfied.
0.5 ≤ [(SP _P- SP _A )-(SP _A- SP _W )] (1)
0.5 ≤ [(SP _A- SP _W )-(SP _B- SP _A )] (2)

By satisfying the above formulas (1) and (2), the SP values of the amorphous polyester resin, the polymer A, the component B, and the wax are appropriately controlled, so that excellent charge retention and scratch resistance are achieved. Is obtained. Specifically, the polar difference between the amorphous polyester resin and the polymer A (SP _P- SP _A ) is the polar difference between the polymer A and the wax (SP _A- SP _W). Satisfy (1). This indicates that the polymer A has a higher affinity for wax than the amorphous polyester resin. This indicates that the polymer A has a performance of being easily compatible with the wax, but has a low polarity of the polymer A, and can exhibit excellent charge retention. Further, the polarity difference between the polymer A and the wax (SP _A- SP _W ) satisfies the above formula (2) with respect to the polarity difference between the component B and the polymer A (SP _B- SP _A). This indicates that the polymer A has a higher affinity for the component B than the wax. As a result, the compatibility between the polymer A and the component B is increased, and the phase separation between the polymer A and the wax is easily obtained, so that excellent scratch resistance can be obtained.

On the other hand, when the above formula (1) is not satisfied, it indicates that the polarity of the polymer A is high, and although the phase separation property of the wax can be obtained, the charge retention property is inferior. If the above equation (2) is not satisfied,
Since the polarity of the component B is too high with respect to the polymer A, it is difficult to fulfill the function as a compatibilizer, and it is difficult to obtain compatibility between the polymer A and the component B. As a result, it becomes difficult to obtain phase separation between the polymer A and the wax, so that the scratch resistance is inferior.

It is preferable that the SP _P , the SP _A , the SP _B , and the SP _W satisfy the relationship of the following formula.
0.6 ≤ [(SP _P- SP _A )-(SP _A- SP _W )] ≤ 3.0 (1')
0.6 ≤ [(SP _A- SP _W )-(SP _B- SP _A )] ≤ 2.5 (2')
Further, it is preferable that _{SP P-} SP _A > 0, SP _A- SP _W > 0, and SP _B- SP _{A> 0.}

The content of the polymer A is 0.10% by mass to 10.00% by mass based on the total mass of the binder resin. When the content of the polymer A satisfies the above range, the content of the polymer A is appropriately controlled, so that excellent low-temperature fixability and scratch resistance can be obtained.
Specifically, it shows that a certain amount of crystalline resin exhibiting sharp meltability is present in the binder resin, and excellent low-temperature fixability can be obtained. Furthermore, since the polymer A, which is easily compatible with the wax, is not excessively present in the binder resin, excellent scratch resistance can be obtained.
On the other hand, when the content of the polymer A is less than 0.10% by mass, it indicates that a certain amount of crystalline material exhibiting sharp meltability does not exist in the binder resin, and the low temperature fixability is inferior. Further, when the content of the polymer A is more than 10.00% by mass, the polymer A that is excessively easily compatible with the wax is present in the binder resin, so that the scratch resistance is inferior.
The content of the polymer A is preferably 3.00% by mass to 10.00% by mass, and more preferably 5.00% by mass to 10.00% by mass.

SP _P (J / cm ³ ) ^0.5 and SP _B (J / cm ³ ) ^0.5 preferably satisfy the following formula (3), and more preferably satisfy the following formula (3').
1.0 ≤ (SP _P- SP _B ) ≤ 3.0 (3)
2.0 ≤ (SP _P- SP _B ) ≤ 3.0 (3')

By satisfying the formula (3), the polarities of the amorphous polyester resin and the component B are appropriately controlled, so that more excellent scratch resistance can be easily obtained.
Specifically, when the polar difference between the amorphous polyester resin and the component B (SP _P- SP _B ) is 3.0 or less, it is shown that the amorphous polyester resin and the component B are difficult to phase-separate. .. As a result, the component B easily acts as a compatibilizer and further promotes the phase separation between the polymer A and the wax, so that excellent scratch resistance can be obtained. Further, when the polarity difference between the amorphous polyester resin and the component B (SP _P- SP _B ) is 1.0 or more, it indicates that the polarity of the component B is not too high. As a result, it is shown that the component B easily acts as a compatibilizer and further promotes the phase separation between the polymer A and the wax, so that excellent scratch resistance can be obtained.

SP _A (J / cm ³ ) ^0.5 preferably satisfies the following formula (4), and more preferably satisfies the following formula (4').
18.0 ≤ SP _A ≤ 24.0 (4)
20.0 ≤ SP _A ≤ 24.0 (4')

By satisfying the above formula (4), the polarity of the polymer A is appropriately controlled, so that more excellent charge retention and scratch resistance can be obtained. Specifically, if SP _A is 24.0 or less, indicating that the polarity of the polymer A is not too high. As a result, the charge-retaining property, which is a characteristic of the polymer A, is easily ensured, and more excellent charge-retaining property can be obtained. Also, if SP _A is 18.0 or more, indicating that the polarity of the polymer A is not too low. As a result, it does not dissolve excessively with the wax, so that better scratch resistance can be obtained.

The content ratio of the second monomer unit in the polymer A is preferably 20.0 mol% to 90.0 mol% based on the total number of moles of all the monomer units in the polymer A.
Further, the content ratio of the second polymerizable monomer in the polymerizable monomer composition for producing the polymer A is the total of all the polymerizable monomers in the polymerizable monomer composition. It is preferably 20.0 mol% to 90.0 mol% based on the number of moles.
When the content ratio of the second monomer unit and the content ratio of the second polymerizable monomer are within the above ranges, the polarity of the polymer A can be easily controlled appropriately, so that the charge retention and resistance are more excellent. Scratchability is obtained.
Specifically, when the content ratio of the second monomer unit and the content ratio of the second polymerizable monomer are 20.0 mol% or more, it is shown that the polarity of the polymer A does not become too low. .. As a result, it becomes excessively difficult to be compatible with the wax, so that more excellent scratch resistance can be obtained.
Further, when the content ratio of the second monomer unit and the content ratio of the second polymerizable monomer are 90.0 mol% or less, it indicates that the polarity of the polymer A is not too high. As a result, the charge-retaining property, which is a characteristic of the polymer A, is easily ensured, and more excellent charge-retaining property can be obtained.
Furthermore, the content ratio of the second monomer unit and the content ratio of the second polymerizable monomer are within the above ranges, that is, the content ratio of the first monomer unit and the first polymerizable monomer. It shows that a certain amount of content is present. Therefore, by assembling the first monomer units together, crystallinity is easily exhibited, and more excellent low-temperature fixability can be obtained.

From the viewpoint of charge retention and scratch resistance, the content ratio of the second monomer unit in the polymer A is 40.0 mol% to 40.0 mol% based on the total number of moles of all the monomer units in the polymer A. It is more preferably 90.0 mol%, further preferably 40.0 mol% to 70.0 mol%. For the same reason, the content ratio of the second polymerizable monomer in the polymerizable monomer composition for producing the polymer A is the total polymerizable monomer in the polymerizable monomer composition. Based on the total number of moles of the body, it is preferably 40.0 mol% to 90.0 mol%, more preferably 40.0 mol% to 70.0 mol%.
When there are two or more types of monomer units derived from the second polymerizable monomer satisfying the range of _SPA21 in the polymer A, the content ratio of the second monomer unit is the total molar ratio of them. It is represented by. Similarly, when the composition used for the polymer A contains two or more kinds of second polymerizable monomers, the content ratio of the second polymerizable monomer is expressed by the total molar ratio of them. ..

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

Further, for example, the second monomer unit is preferably at least one selected from the group consisting of the monomer units represented by the following formulas (D) and (E).

In the formula (A) or (D), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is -C ≡ N,
-C (= O) NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms),
Hydroxy group,
-COOR ¹¹ (R ¹¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4) or a hydroxyalkyl group having 1 to 6 carbon atoms (preferably 1 to 4)),
-NH-C (= O) -N (R ¹³ ) ₂ (The two R ^13s are independent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms (preferably 1 to 4)),
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms),
Or
-COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ (The two R ^15s are independent hydrogen atoms or alkyl having 1 to 6 carbon atoms (preferably 1 to 4). Group)
Represents
R ² represents a hydrogen atom or a methyl group.

In the formula (B) or (E), R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.

By using at least one selected from the group consisting of the above formulas (A) and (B) as the second polymerizable monomer, more excellent low temperature fixability, charge retention, and scratch resistance can be obtained. Be done. This is because when the second polymerizable monomer is at least one selected from the group consisting of the above formulas (A) and (B), the second monomer unit becomes highly polar and the first and second monomers become highly polar. This is because a polarity difference is generated between the units, and the polarity difference further promotes the crystallization of the first monomer unit, and more excellent low temperature fixability and charge retention can be obtained.
Specifically, the first monomer unit is incorporated into the polymer A, and the first monomer units aggregate with each other to exhibit crystallinity. Normally, the crystallization of the first monomer unit is likely to be inhibited when other monomer units are incorporated, so that it becomes difficult to develop crystallization as a polymer. This tendency becomes remarkable when a plurality of types of monomer units are randomly bonded to each other in one molecule of the polymer. However, by using the first polymerizable monomer and the second polymerizable monomer having different polarities, the first polymerizable monomer and the second polymerizable monomer are randomly selected at the time of polymerization. It is considered that they can be bonded continuously to some extent instead of being bound to. As a result, a block in which the first monomer units are assembled is formed, and the polymer A tends to be a block copolymer, and even if other monomer units are incorporated, the crystallinity can be enhanced, which is more excellent. It becomes easy to obtain low-temperature fixability and charge retention.
Further, the crystalline portion of the first monomer unit has an affinity with the crystalline moiety of the component B which is a compatibilizer, so that the compatibility between the polymer A and the component B is increased, and conversely, the polymer A It becomes easy to obtain the phase separation between the polymer and the wax. Therefore, it becomes easy to obtain better scratch resistance. Further, when the second polymerizable monomer is a monomer containing at least one selected from the group consisting of a nitrile group, a hydroxy group, a hydroxyalkyl group, a urea group, a urethane group and an amide group, it is nonionic. Therefore, the hydrophobicity is high, and more excellent charge retention can be obtained.

Further, as the second polymerizable monomer, specifically, for example, the following polymerizable monomers can be used.
Monomer having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.
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 an ethylenically unsaturated bond having 2 to 30 carbon atoms (acrylic acid, methacrylic acid, etc.) are reacted by a known method. Monomer.

Monomer having a urethane group: For example, an alcohol having 2 to 22 carbon atoms (-2-hydroxyethyl methacrylate, vinyl alcohol, etc.) having an ethylenically unsaturated bond and an isocyanate having 1 to 30 carbon atoms [monoisocyanate compound]. (Benzenesulfonyl isocyanate, tosyl isocyanate, phenylisocyanate, p-chlorophenylisocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl Isocyanate, 3,5-dimethylphenylisocyanate and 2,6-dipropylphenylisocyanate, etc.), aliphatic diisocyanate compounds (trymethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1, , 3-Butylene diisocyanate, dodecamethylene diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate, etc.), alicyclic diisocyanate compounds (1,3-cyclopentenediisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, etc. Isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated tetramethylxylylene diisocyanate, etc.), and aromatic diisocyanate compounds (phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6 -Torylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalene Diisocyanate, xylylene diisocyanate, etc.)] and a monomer reacted by a known method, and alcohols having 1 to 26 carbon atoms (methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, etc.) Heptanol, octanol, 2-ethylhexanol, nonanol, decanol Le, undecyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, setanol, heptadecanol, stearyl alcohol, isostearyl alcohol, ellaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecil Alcohol, heneicosanol, behenyl alcohol, elcil alcohol, etc.) and isocyanate with 2 to 30 carbon atoms having an ethylenically unsaturated bond [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) acryloyloxymethyl) ethyl isocyanate Etc.] and the like by reacting with a known method.

Monomers having urea groups: For example, amines having 3 to 22 carbon atoms [primary amines (normal butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (dinormal ethylamine, dinormal propylamine, di). Normal butylamine, etc.), aniline, cycloxylamine, etc.] and isocyanate having an ethylenically unsaturated bond having 2 to 30 carbon atoms are reacted by a known method, etc.
Monomer 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, a hydroxy group, a hydroxyalkyl group, a urea group, a urethane group and an amide group. More preferably, it is a monomer having at least one functional group selected from the group consisting of a nitrile group, a hydroxy group, a hydroxyalkyl group, a urea group, a urethane group and an amide group and an ethylenically unsaturated bond.

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

Further, when the SP value (J / cm ³ ) ^0.5 of the first monomer unit is set to SP _A11 , SP _A11 is preferably less than 20.00, and more preferably 19.00 or less. It is preferably 18.40 or less, and more preferably 18.40 or less. The lower limit is not particularly limited, but is preferably 17.00 or more.

The polymer A is described above as long as the molar ratio of the first monomer unit derived from the first polymerizable monomer and the second monomer unit derived from the second polymerizable monomer is not impaired. SP value (J / cm ³ ) A ^{third polymerizable monomer that is not within the range of 0.5} (that is, different from the first polymerizable monomer and the second polymerizable monomer) It may contain a third monomer unit derived from.
As the third polymerizable monomer, among the monomers exemplified as the second polymerizable monomer, a monomer that does not satisfy the range of _{SP A21} (J / cm ³ ) ^{0.5 is used.} Can be used.
Further, for example, the following monomers having no nitrile group, amide group, urethane group, hydroxy group, urea group, carboxy group or the like can also be used.

Styrene, styrene such as o-methylstyrene and its derivatives, methyl (meth) acrylate, -n-butyl (meth) acrylate, -t-butyl (meth) acrylate, -2-ethylhexyl (meth) acrylate Such (meth) acrylic acid esters.
Among them, the third polymerizable monomer preferably contains at least one selected from the group consisting of styrene, methyl methacrylate and methyl acrylate. For example, when the third polymerizable monomer contains styrene, the compatibility between the polymer A and the component B described later is further increased, and more excellent scratch resistance can be obtained. Specifically, when the component B described later is a styrene acrylic resin, π is present in the styrene moiety of the polymer A and the styrene moiety of the component B, which is greater than the affinity of only the polarities of the polymer A and the component B. Since the −π interaction works, the affinity increases. As a result, the phase separation between the polymer A and the wax can be more easily obtained, and excellent scratch resistance can be obtained.

For example, the polymer A has a first monomer unit represented by the formula (C) and a third monomer unit different from the second monomer unit, and the third monomer unit is the following formula (F). It is preferably a monomer unit represented by.

In formula (F), R ⁵ represents a hydrogen atom or a methyl group, and Ph represents a phenyl group.
The phenyl group may have a substituent.

The acid value (Av) of the polymer A is preferably 30.0 mgKOH / g or less, and more preferably 20.0 mgKOH / g or less, from the viewpoint of improving charge retention in a high temperature and high humidity environment.
When the acid value is in the above range, the hygroscopicity in a high temperature and high humidity environment is low, so that more excellent charge retention can be exhibited. The lower limit of the acid value is not particularly limited, but is preferably 0 mgKOH / g or more.

The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble component measured by gel permeation chromatography (GPC) of the polymer A is preferably 10,000 to 200,000, preferably 20,000 to 200,000. More preferably, it is 150,000. When Mw is within the above range, elasticity near room temperature can be easily maintained.
The melting point (Tp) of the polymer A is preferably 50 ° C to 80 ° C, more preferably 53 ° C to 70 ° C. When the melting point of the polymer A is within the above range, it exhibits better low-temperature fixability.
The melting point of the polymer A can be adjusted depending on the type and amount of the first polymerizable monomer used, the type and amount of the second polymerizable monomer, and the like.
The polymer A is preferably a vinyl polymer. Examples of the vinyl polymer include a polymer of a monomer containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, and examples thereof include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

The component B is not particularly limited as long as it is a component that can satisfy the above formulas (2) and (3). A low molecular weight component such as a crystalline ester compound may be used, but a resin component (high molecular weight compound) having a high affinity with the polymer A and easily obtaining a phase separation property with the wax is preferable. In particular, in order to increase the affinity with the polymer A, it is preferable that the resin component has a hydrocarbon group (preferably an alkyl group) having 2 to 22 carbon atoms (preferably 6 to 12 carbon atoms). Further, in order to adjust the polarity, those exemplified in the above-mentioned second polymerizable monomer may be contained as a constituent component thereof.
Component B may be a resin component containing a graft polymer of a hydrocarbon compound and a styrene-acrylic polymer. Examples of the graft polymer include a polymer obtained by graft-polymerizing a hydrocarbon compound to a styrene-acrylic polymer, and a polymer obtained by graft-polymerizing a styrene-acrylic polymer to a hydrocarbon compound.
When the component B is, for example, a polymer obtained by graft-polymerizing a hydrocarbon compound onto a styrene-acrylic polymer, the compatibility between the polymer A and the component B is further increased, so that more excellent scratch resistance can be obtained.
When the component B described later contains, for example, a styrene-acrylic polymer, in addition to the affinity due to the polarities of the polymer A and the component B, if the polymer A has a styrene moiety, in the styrene moiety of the component B, for example. , Π-π interaction works, so the affinity increases.
Further, since the affinity also works between the alkyl group having 18 to 36 carbon atoms derived from the first polymerizable monomer of the polymer A and the alkyl group derived from the hydrocarbon compound of the component B, more Affinity increases. As a result, the phase separation between the polymer A and the wax is further improved, so that more excellent scratch resistance can be obtained.

Regarding the graft polymer of the hydrocarbon compound and the styrene acrylic polymer, the hydrocarbon compound is not particularly limited as long as it is an unsaturated hydrocarbon polymer or copolymer having one double bond, and various polyolefins are used. be able to. In particular, polyethylene-based and polypropylene-based are preferably used. That is, the graft polymer is preferably a graft polymer of polyolefin and styrene-acrylic polymer.
In addition, the following polymerizable monomers can be exemplified as the polymerizable monomers that produce the styrene-acrylic polymer.
Styrene-based polymerizable simples such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, benzylstyrene, etc. Styrene;
Alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and 2-ethylhexyl methacrylate (the alkyl has 1 to 17 carbon atoms);
Vinyl ester-based polymerizable monomer such as vinyl acetate; Vinyl ether-based polymerizable monomer such as vinyl methyl ether; Halogen element-containing vinyl-based polymerizable monomer such as vinyl chloride; Diene-based such as butadiene and isobutylene Polymerizable monomers and combinations thereof can be mentioned.
A graft polymer of a hydrocarbon compound and a styrene-acrylic polymer can be obtained by a known method.

Further, the component B may contain a crystalline polyester resin.
When the component B contains a crystalline polyester resin, the compatibility between the polymer A and the component B is further increased, so that more excellent scratch resistance can be obtained.
Specifically, also in the alkyl group having 18 to 36 carbon atoms derived from the first polymerizable monomer of the polymer A and the alkyl group derived from the aliphatic diol and the aliphatic dicarboxylic acid of the component B. , Affinity works, so the affinity increases.
As a result, the phase separation between the polymer A and the wax is further improved, so that more excellent scratch resistance can be obtained.
The crystalline polyester resin is a composition containing an alcohol component containing 50% by mass or more of an aliphatic diol having 2 to 22 carbon atoms and an acid component containing 50% by mass or more of an aliphatic dicarboxylic acid having 2 to 22 carbon atoms. It is preferably a polycondensate.

The aliphatic diol having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic diol.
For example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 4-butanediol, 1,4-butadiene glycol, tetramethylene glycol, pentamethylene glycol, hexa. Examples thereof include methylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol and neopentyl glycol.
Among these, linear aliphatic compounds such as 1,6-hexanediol and α, ω-diol are preferably exemplified.
Of the above alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from an aliphatic diol having 2 to 22 carbon atoms.

On the other hand, the aliphatic dicarboxylic acid having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but is preferably a chain (more preferably linear) aliphatic dicarboxylic acid. ..
Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, sveric acid, glutaconic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, and dodecandicarboxylic acid. Examples thereof include acids, maleic acids, fumaric acids, mesaconic acids, citraconic acids and itaconic acids, and those obtained by hydrolyzing these acid anhydrides or lower alkyl esters are also included.
Of the above carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more is a carboxylic acid selected from an aliphatic dicarboxylic acid having 2 to 22 carbon atoms.
The crystalline polyester resin can be produced according to a usual polyester synthesis method. For example, after the above-mentioned carboxylic acid monomer and alcohol monomer are subjected to an esterification reaction or a transesterification reaction, the crystalline polyester is subjected to a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Resin can be obtained. Then, by further adding the above aliphatic compound and carrying out an esterification reaction, a desired crystalline polyester resin can be obtained.
The esterification or transesterification reaction can be carried out using a usual esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate and magnesium acetate, if necessary.
Further, the above-mentioned polymerization reaction can be carried out using a usual polymerization catalyst, for example, a known catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. .. The polymerization temperature and the amount of catalyst are not particularly limited and may be appropriately determined.

The content of the component B is preferably 0.10% by mass to 10.00% by mass based on the total mass of the binder resin. The content of the component B is more preferably 3.00% by mass to 10.00% by mass, and more preferably 5.00% by mass to 10.00% by mass, based on the total mass of the binder resin. Is even more preferable.
When the content of the component B satisfies the above range, the component B is controlled to an appropriate amount, so that excellent scratch resistance can be obtained. Specifically, when the content of the component B is within the above range, it is shown that the necessary amount of compatibility with the polymer A is guaranteed, the compatibility between the polymer A and the component B is further increased, and the polymer A is further increased. Since the phase separation between the polymer and the wax is further improved, better scratch resistance can be obtained.

The binder resin contains an amorphous polyester resin. The content of the amorphous polyester resin is 50.0% by mass or more based on the total mass of the binder resin. The content of the amorphous polyester resin in the binder resin is preferably 80.0% by mass or more, and more preferably 85.0% by mass or more. The content is preferably 95.0% by mass or less.
The polymerizable monomer that produces the amorphous polyester resin includes a polyhydric alcohol (divalent or trivalent or higher alcohol), a polyvalent carboxylic acid (divalent or trivalent or higher carboxylic acid), and an acid anhydride thereof. A thing or a lower alkyl ester thereof.
As the polyhydric alcohol, the following polyhydric alcohols can be used.
As the divalent alcohol, a bisphenol derivative is preferable.
Examples of the bisphenol derivative include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane. , Polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxy) Phenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane and the like can be mentioned.
Other alcohol components include ethylene glycol, diethylene glycol, triolethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1, 5-Pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbit, 1,2,3,6-hexanetetrol, 1 , 4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2, Examples thereof include 4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethylbenzene. These polyhydric alcohols can be used alone or in combination of two or more.

As the polyvalent carboxylic acid, the following polyvalent carboxylic acids can be used.
Examples of the divalent carboxylic acid include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid and n. -Dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids and these Lower alkyl esters of.
Examples of the trivalent or higher valent carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalentricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. , 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empoltrimeric acid, acid anhydrides thereof or lower alkyl esters thereof.
Of these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or a derivative thereof, is preferably used because it is inexpensive and reaction control is easy. These divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination of two or more.

The method for producing the amorphous polyester resin is not particularly limited, and a known method can be used. For example, the above-mentioned polyhydric alcohol and polyvalent carboxylic acid are charged at the same time and polymerized through an esterification reaction, a transesterification reaction, and a condensation reaction to produce a polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C. or higher and 290 ° C. or lower. In the polymerization of polyester, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used.

The acid value of the amorphous polyester resin is preferably 5 mgKOH / g to 20 mgKOH / g from the viewpoint of charge retention in a high temperature and high humidity environment. The hydroxyl value of the amorphous polyester resin is preferably 20 mgKOH / g to 70 mgKOH / g from the viewpoint of low temperature fixability and storage stability.

Toner particles contain wax. Examples of the wax include the following.
Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, Fishertropch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof. Stuff;
Waxes containing fatty acid esters such as carnauba wax as the main component; deoxidized fatty acid esters such as carnauba wax partially or wholly deoxidized.
Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brushzic acid, eleostearic acid, and parinalic acid;
Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol, melicyl alcohol; polyhydric alcohols such as sorbitol;
Esters of fatty acids such as palmitic acid, stearic acid, bechenic acid and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvir alcohol, ceryl alcohol and melicyl alcohol;
Fatty acid amides such as linoleic acid amides, oleic acid amides, lauric acid amides; saturated fatty acid bisamides such as methylene bisstearic acid amides, ethylene biscapric acid amides, ethylene bislauric acid amides, hexamethylene bisstearic acid amides; Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N'diorail adipic acid amide, N, N'diorail sebacic acid amide; m-xylene bisstearic acid amide, N , Aromatic bisamides such as N'dystearyl isophthalic acid amides;
Aliper metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate (commonly referred to as metal soap);
Partial esterification of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; methyl ester compounds with hydroxyl groups obtained by hydrogenation of vegetable fats and oils.
Among these waxes, hydrocarbon waxes such as paraffin wax and Fishertropsh wax, and fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of scratch resistance.
The wax content is preferably 3% by mass to 8% by mass based on the total mass of the binder resin from the viewpoint of scratch resistance.

The toner particles may contain a colorant, if necessary. Examples of the colorant include the following.
Examples of the black colorant include those that have been toned to black using carbon black; a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, the pigment may be used alone, or the dye and the pigment may be used in combination. From the viewpoint of the image quality of a full-color image, it is preferable to use a dye and a pigment together.

Examples of the magenta toner pigment include the following.
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57: 1, 58, 60, 63, 64, 68, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C.I. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.
Examples of the magenta toner dye include the following.
C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Disperse thread 9; C.I. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. An oil-soluble dye such as Disperse Violet 1.
C. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22,
23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C.I. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of the cyan toner pigment include the following.
C. I. Pigment Blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; C.I. I. Bat Blue 6; C.I. I. Acid blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalocyanine groups are substituted in the phthalocyanine skeleton.
Examples of dyes for cyan toner include C.I. I. Solvent blue 70 can be mentioned.
Examples of the pigment for yellow toner include the following.
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C.I. I. Bat Yellow 1, 3, 20.
Examples of the dye for yellow toner include C.I. I. Solvent Yellow 162 can be mentioned.

These colorants can be used alone or in admixture, and even in the form of a solid solution.
The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner.
The content of the colorant is preferably 0.1 part by mass to 30.0 parts by mass with respect to 100 parts by mass of the total amount of the resin components.

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

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

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

The method for producing the toner particles and the toner is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, and a dispersion polymerization method can be used.
Hereinafter, the procedure for producing toner particles and toner using the pulverization method will be described.
In the raw material mixing step, as materials constituting the toner particles, for example, an amorphous polyester resin, a binder resin containing the polymer A and the component B, and a wax, and if necessary, a colorant and charge control. A predetermined amount of other components such as an agent is weighed, blended, and mixed.
Examples of the mixing device include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, a mechano hybrid (manufactured by Nippon Coke Industries, Ltd.) and the like.

Next, the mixed materials are melt-kneaded to disperse wax and the like in the resin component. In the melt-kneading step, a batch-type kneader such as a pressure kneader or a Bambary mixer or a continuous kneader can be used. Single-screw or twin-screw extruders have become the mainstream because of their superiority in continuous production. For example, KTK type twin-screw extruder (manufactured by Kobe Steel), TEM type twin-screw extruder (manufactured by Toshiba Machinery Co., Ltd.), PCM kneader (manufactured by Ikegai Iron Works), twin-screw extruder (manufactured by KCC). ), Co-kneader (manufactured by Bus), Kneedex (manufactured by Nippon Coke Industries Co., Ltd.), etc. Further, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

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

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

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

<Method for measuring the content ratio of monomer units derived from amorphous polyester resin, polymer A, component B, and various (polymerizable) monomers in wax>
The content ratio of the monomer unit derived from the amorphous polyester resin, the polymer A, the component B, and various (polymerizable) monomers in the wax is measured by ¹ H-NMR under the following conditions.
Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0 μs
Frequency range: 10500Hz
Number of integrations: 64 times Measurement temperature: 30 ° C
Sample: 50 mg of the measurement sample is placed in a sample tube having an inner diameter of 5 mm, deuterated chloroform (CDCl ₃ ) is added as a solvent, and this is dissolved in a constant temperature bath at 40 ° C. to prepare the sample.
From the obtained ¹ H-NMR chart, for example, in the polymer A, among the peaks attributed to the components of the monomer unit derived from the first polymerizable monomer, the monomer unit derived from the other select separate peak and peak attributable to the components, to calculate the integral values S ₁ for the peak.
Similarly, from the peaks attributed to the components of the monomer unit derived from the second polymerizable monomer, a peak independent of the peaks attributed to the components of the monomer unit derived from other sources is selected. , an integrated value S ₂ is calculated for this peak.
Further, when the third polymerizable monomer is used, the peaks attributed to the components of the monomer unit derived from the third polymerizable monomer are used, and the components of the monomer unit derived from other components are derived from the peaks. 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 integrated values S 1} , S ₂ and S _3. In addition, n ₁ , n _{2, and} n ₃ are the number of hydrogens in the component to which the peak focused on each site is assigned.

Content ratio (mol%) of monomer unit 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 unit derived from the second polymerizable monomer and the third polymerizable monomer is determined as follows.
Content ratio (mol%) of monomer unit 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 the 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 is used in the constituent elements other than the vinyl group in the polymer A, the measurement nucleus is set to ^{13 C by using 13} C-NMR, and the single pulse mode is used. Measure in ¹ H-NMR and calculate in the same way.
Further, when the toner is produced by the suspension polymerization method, the peaks of wax and other resins may overlap and independent peaks may not be observed. As a result, the content ratio of the monomer units derived from various polymerizable monomers in the polymer A may not be calculated. In that case, the polymer A'can be produced by performing the same suspension polymerization without using wax or other resin, and the polymer A'can be regarded as the polymer A and analyzed.

<Calculation method of SP value>
The SP value of the polymerizable monomer, the SP value of the monomer unit derived from the polymerizable monomer, the polymer A, the component B, the amorphous polyester resin, and the wax are determined according to the calculation method proposed by Fedors. , Obtain as follows.
Regarding the above substances, for atoms or atomic groups in the molecular structure, evaporation energy (Δei) (cal / mol) (cal / mol) from the table described in “volume. Eng. Sci., 14 (2), 147-154 (1974)”. ) And the molar volume (Δvi) (cm ³ / mol), and let (4.184 × ΣΔei / ΣΔvi) ^0.5 be the SP value (J / cm ³ ) ^0.5 .
The monomer unit such as SP _A21 is calculated by the same calculation method as above for an atom or an atomic group having a molecular structure in which the double bond of the polymerizable monomer is cleaved by polymerization.
SP _A21 is determined by dividing the evaporation energy of the monomer unit by the molar volume, and SP _A , SP _B , SP _P , or SP _W is the evaporation energy (Δei) of the monomer unit derived from the constituent polymerizable monomer. And the molar volume (Δvi) was obtained for each monomer unit, and the product of each monomer unit with the molar ratio (j) at _{SP A} , SP _B , SP _P , or SP _{W was calculated, and the evaporation energy of each monomer unit was calculated.} It is calculated by dividing the sum of the above by the sum of the molar volumes, and is calculated by the following formula.
SP = {4.184 × (Σj × ΣΔei) / (Σj × ΣΔvi)} ^0.5

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

<Measurement method of weight average molecular weight (Mw) of crystalline resin such as polymer A using gel permeation chromatography (GPC)>
The weight average molecular weight (Mw) of the toluene-soluble component of a crystalline resin such as polymer A at 100 ° C. is measured by gel permeation chromatography (GPC) as follows.
First, the object to be measured is dissolved in toluene at 100 ° C. for 1 hour. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Maeshori 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 toluene is about 0.1% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
Column: TSKgel GMHHR-HHT (7.8 cm ID x 30 cm) 2 stations (manufactured by Tosoh Corporation)
Detector: RI for high temperature
Temperature: 135 ° C
Solvent: Toluene Flow rate: 1.0 mL / min
Sample: Inject 0.4 mL of 0.1% by mass sample The molecular weight calibration curve prepared from the monodisperse polystyrene standard sample is used to calculate the molecular weight of the sample. Further, it is calculated by converting to polyethylene by a conversion formula derived from the Mark-Houwink viscosity formula.

<Measurement method of acid value>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value is measured according to JIS-K0070-1992, but specifically, the following procedure is followed.
(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion-exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was that 25 mL of 0.1 mol / L hydrochloric acid was placed in a triangular flask, several drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / L hydrochloric acid, those prepared according to JIS-K8001-1998 are used.
(2) Operation (A) Main test 2.0 g of the crushed sample is precisely weighed in a 200 mL Erlenmeyer flask, 100 mL of a mixed solution of toluene / ethanol (2: 1) is added, and the mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Solution factor, S: mass (g) of the sample.

<Measurement method of hydroxyl value>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when acetylating 1 g of a sample. The hydroxyl value is measured according to JIS-K0070-1992, but specifically, the following procedure is followed.
(1) Preparation of Reagents 25 g of special grade acetic anhydride is placed in a 100 mL volumetric flask, pyridine is added to make the total volume 100 mL, and the mixture is sufficiently shaken to obtain an acetylation reagent. The obtained acetylation reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide, etc.
Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution.
Dissolve 35 g of special grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was that 25 mL of 0.5 mol / L hydrochloric acid was placed in a triangular flask, several drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.5 mol / L hydrochloric acid, those prepared according to JIS-K8001-1998 are used.
(2) Operation (A) Main test 1.0 g of the crushed sample is precisely weighed into a 200 mL round bottom flask, and 5.0 mL of the acetylation reagent is accurately added to this using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylation reagent, a small amount of special grade toluene is added to dissolve the sample.
A small funnel is placed on the mouth of the flask, and about 1 cm of the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with thick paper having a round hole.
After 1 hour, remove the flask from the glycerin bath and allow to cool. After allowing to cool, add 1 mL of water from the funnel and shake to hydrolyze acetic anhydride. The flask is heated again in a glycerin bath for 10 minutes for further complete hydrolysis. After allowing to cool, wash the funnel and flask walls with 5 mL of ethyl alcohol.
Add a few drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used.
(3) Substitute the obtained result into the following formula to calculate the hydroxyl value.
A = [{(BC) x 28.05 x f} / S] + D
Here, A: hydroxyl value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: potassium hydroxide Factor of solution, S: mass of sample (g), D: acid value of the sample (mgKOH / g).

<Measuring method of melting point>
The melting points of the polymer A and the wax are measured using DSC Q1000 (manufactured by TA Instruments) under the following conditions.
Temperature rise rate: 10 ° C / min
Measurement start temperature: 20 ° C
Measurement end temperature: 180 ° C
The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value.
Specifically, about 5 mg of a sample is precisely weighed and placed in an aluminum pan to measure 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 (unit: ° C.).
The maximum endothermic peak is a peak having the maximum endothermic amount when there are a plurality of peaks.

<Measurement method of softening point of resin>
The softening point of the resin is measured using a constant load extrusion type thin tube rheometer "Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve showing the relationship between and temperature can be obtained.
Further, the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D" is set as the softening point. The melting temperature in the 1/2 method is calculated as follows.
First, the difference between the piston descent amount at the end of the outflow (outflow end point, Smax) and the piston descent amount at the start of the outflow (minimum point, Smin) is calculated to be 1/2. (Let this be X. X = (Smax-Smin) / 2). The temperature of the flow curve when the amount of descent of the piston is the sum of X and Smin is the melting temperature in the 1/2 method.
As a measurement sample, about 1.0 g of resin was compression-molded in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) at about 10 MPa for about 60 seconds. Use a columnar one with a diameter of about 8 mm.
Specific operations in the measurement are performed according to the manual attached to the device.
The measurement conditions of CFT-500D are as follows.
Test mode: Hot compress Start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Heating rate: 4.0 ° C / min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0 mm

Hereinafter, the present disclosure will be specifically described with reference to Examples. However, these do not limit this disclosure in any way. Unless otherwise specified, all "parts" in the following formulas are based on mass.

<Production example of polymer A1>
-Solvent: 100.0 parts of toluene-100.0 parts of monomer composition (The monomer composition shall be a mixture of behenyl acrylate, acrylonitrile, and styrene in the following proportions).
Behenyl acrylate (first polymerizable monomer) 67.0 parts (25.3 mol%)
-Acrylonitrile (second polymerizable monomer) 22.0 parts (59.5 mol%)
11.0 parts (15.2 mol%) of styrene (third polymerizable monomer)
-Polymerization initiator: 0.5 part [t-butyl peroxypivalate (manufactured by NOF Corporation: perbutyl PV)]

The above materials were put into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube under a nitrogen atmosphere. The inside of the reaction vessel was stirred at 200 rpm and heated to 70 ° C. for 12 hours to carry out a polymerization reaction to obtain a solution in which the polymer of the monomer composition was dissolved in toluene.
Subsequently, after the temperature of the solution was lowered to 25 ° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the insoluble methanol.
The obtained insoluble methanol was filtered off, washed with methanol, and vacuum dried at 40 ° C. for 24 hours to obtain polymer A1.
The weight average molecular weight (Mw) of the polymer A1 was 30,000, the melting point (Tp) was 62 ° C., and the acid value was 0.0 mgKOH / g.
When the above polymer A1 was analyzed by NMR, 25.3 mol% of the monomer unit derived from behenyl acrylate, 59.5 mol% of the monomer unit derived from acrylonitrile, and 15.2 mol% of the monomer unit derived from styrene were contained. Was there. Moreover, the monomer unit derived from the polymerizable monomer and the SP value (unit: (J / cm ³ ) ^0.5 ) of the polymer A were calculated by the above method.

<Preparation of monomer having urethane group>
50.0 parts of methanol was charged into the reaction vessel. Then, under stirring, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] (Showa Denko KK) was added dropwise at 40 ° C. After completion of the dropping, stirring was performed for 2 hours while maintaining 40 ° C. Then, the unreacted methanol was removed by an evaporator to prepare a monomer having a urethane group.

<Production example of polymers A2 to A21>
In the production example of the polymer A1, the reaction was carried out in the same manner except that the respective polymerizable monomers and the number of copies were changed as shown in Table 1, to obtain the polymers A2 to A21. The physical characteristics of the polymers A1 to A21 are shown in Tables 2 and 3.

The abbreviations in Tables 1 to 3 are as follows.
BEA: Behenyl Acrylate STA: Stearyl Acrylate MYA: Millicyl Acrylate HA: Hexadecyl Acrylate AN: Acrylonitrile HEMA: 2-Hydroxyethyl Methacrylate UT: Monomer with Urethane Group VA: Vinyl Acetate St: Styrene MM: Methyl Methacrylate

表中のＳＰ値の単位は、（Ｊ／ｃｍ^３）^０．５である。

The unit of the SP value in the table is (J / cm ³ ) ^0.5 .

<Production example of component B1>
-Solvent: 100.0 parts of toluene-100.0 parts of monomer composition (monomer composition is a mixture of the following polyethylene, acrylonitrile, butyl acrylate, and styrene in the proportions shown below).
・ 10.0 parts of polyethylene (1.2 mol%)
-Acrylonitrile 40.0 parts (60.8 mol%)
-Butyl acrylate 5.0 parts (3.1 mol%)
45.0 parts of styrene (34.9 mol%)
-Polymerization initiator: 0.5 part [t-butyl peroxypivalate (manufactured by NOF Corporation: perbutyl PV)]

The above materials were put into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen introduction tube under a nitrogen atmosphere. The inside of the reaction vessel was stirred at 200 rpm and heated to 70 ° C. for 12 hours to carry out a polymerization reaction to obtain a solution in which the polymer of the monomer composition was dissolved in toluene.
Subsequently, after the temperature of the solution was lowered to 25 ° C., the solution was poured into 1000.0 parts of methanol with stirring to precipitate the insoluble methanol.
The obtained methanol-insoluble matter was filtered off, washed with methanol, and vacuum dried at 40 ° C. for 24 hours to obtain component B1. The weight average molecular weight of component B1 was 20000.
When the above component B1 was analyzed by NMR, the monomer unit derived from polyethylene was 1.2 mol%, the monomer unit derived from acrylonitrile was 60.8 mol%, the monomer unit derived from butyl acrylate was 3.1 mol%, and the monomer unit was derived from styrene. The monomer unit of was contained in an amount of 34.9 mol%. The monomer unit derived from the polymerizable monomer and the SP value of component B (unit: (J / cm ³ ) ^0.5 ) were calculated by the above method.

<Production example of component B2 to component B10>
In the production example of component B1, the reaction was carried out in the same manner except that the polymerizable monomers and the number of copies of each were changed as shown in Table 4, to obtain component B2 to component B10. Table 5 shows the physical characteristics of the components B1 to B10.

The abbreviations in Tables 4 to 5 are as follows.
PE: Polyethylene AN: Acrylonitrile BA: Butyl acrylate St: Styrene HD: Hexanediol SA: Sebacic acid

表中のＳＰ値の単位は、（Ｊ／ｃｍ^３）^０．５である。

The unit of the SP value in the table is (J / cm ³ ) ^0.5 .

<Production example of amorphous polyester resin P1>
-Bisphenol A / propylene oxide adduct (average number of moles added 2.0):
37.0 parts (13.6 mol%)
-Ethylene glycol: 13.0 parts (35.5 mol%)
-Terephthalic acid: 50.0 parts (50.9 mol%)
-Titanium tetrabutoxide (esterification catalyst): 0.5 parts

The above materials were weighed in a cooling tube, a stirrer, a nitrogen introduction tube, and a reaction vessel equipped with a thermocouple.
Next, the inside of the reaction vessel was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 2 hours while stirring at a temperature of 200 ° C.
Further, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was carried out for 5 hours while maintaining the temperature at 200 ° C., and after confirming that the softening point reached the temperature of 100 ° C., the temperature was lowered to stop the reaction. , Amorphous polyester resin P1 was obtained.
The weight average molecular weight (Mw) of the obtained amorphous polyester resin P1 was 12000.
When the above amorphous polyester resin P1 was analyzed by NMR, the monomer unit derived from polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane was 13.6 mol%, and it was derived from ethylene glycol. It contained 35.5 mol% of monomer units and 50.9 mol% of terephthalic acid-derived monomer units. ^{The SP value (unit: (J / cm 3} ) ^0.5 ) of the monomer unit derived from the polymerizable monomer and the amorphous polyester resin was calculated by the above method.

<Production example of amorphous polyester resin P2 to amorphous polyester resin P10>
In the production example of the amorphous polyester resin P1, the reaction was carried out in the same manner except that the polymerizable monomers and the number of copies of each were changed as shown in Table 6, and the amorphous polyester resin P2 to the amorphous polyester resin was carried out in the same manner. Obtained P10. The physical characteristics of the amorphous polyester resin P2 to the amorphous polyester resin P10 are shown in Tables 7 and 8.

The abbreviations in Tables 6 to 7 are as follows.
PO2: Bisphenol A / propylene oxide adduct (average number of moles added 2.0)
PO3: Bisphenol A / propylene oxide adduct (average number of moles added 3.0)
ED: Ethylene glycol THM: Pentaerythritol TPA: Terephthalic acid TMA: Trimellitic anhydride AA: Adipic acid

表中、ＳＰ値の単位は、（Ｊ／ｃｍ^３）^０．５であり、酸価及び水酸基価の単位は、ｍｇＫＯＨ／ｇである。

In the table, the unit of SP value is (J / cm ³ ) ^0.5 , and the unit of acid value and hydroxyl value is mgKOH / g.

<Manufacturing example of toner 1>
-Amorphous polyester resin P1: 90.00 parts-Polymer A1: 5.00 parts-Component B1: 5.00 parts-Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90 ° C):
5.00 parts ・ Colorant (carbon black): 10.00 parts

The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mine Co., Ltd.) at a rotation speed of 1500 rpm and a rotation time of 5 min, and then a twin-screw kneader (PCM-30 type, set to a temperature of 130 ° C., Kneaded at Ikekai Co., Ltd.).
The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product.
The obtained coarse crushed product was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, using Faculti (F-300, manufactured by Hosokawa Micron Co., Ltd.), classification was performed to obtain toner particles 1. The operating conditions were a classification rotor rotation speed of 11000 rpm and a distributed rotor rotation speed of 7200 rpm.

-Toner particles: 100.0 parts-Silica fine particles: 4.0 parts [Fumed silica surface-treated with hexamethyldisilazane (median diameter (D50) on a number basis is 120 nm)]
-Small particle size inorganic fine particles: 1.0 part [Titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (median diameter (D50) is 10 nm based on the number)]

The above materials were mixed with a Henschel mixer (FM-75 type, manufactured by Mitsui Miike Machinery Co., Ltd.) at a rotation speed of 1900 rpm and a rotation time of 10 min to obtain toner 1.
Toner 1 [(SP _P- SP _A )-(SP _A- SP _W )] is 0.9, (SP _P- SP _B ) is 2.0, and [(SP _A- SP _W )-(SP _B-). SP _A )] was 1.1.

<Manufacturing example of toners 2-37>
In the toner 1 production example, the same operation as in the toner 1 production example was performed except that the type and addition amount of the polymer A and the type and addition amount of the component B were changed as shown in Table 8. ~ 37 was obtained. Table 8 shows the physical characteristics of the obtained toner.

<Manufacturing example of magnetic carrier 1>
-Magnetite 1 with an average number particle size of 0.30 μm and (magnetization strength of 65 Am ^{2 / kg under a magnetic field of 1000 / 4π (kA / m))
-Magnetite 2 with a} number average particle size of 0.50 μm and (magnetization strength of 65 Am 2 / kg under a magnetic field of 1000 / 4π (kA / m))
4.0 parts of a silane compound (3- (2-aminoethylaminopropyl) trimethoxysilane) was added to 100 parts of each of the above materials, and the mixture was mixed and stirred at 100 ° C. or higher in a container at high speed, and each fine particle was mixed. Was processed.
・ Phenol: 10% by mass
・ Formaldehyde solution: 6% by mass
(40% by mass of formaldehyde, 10% by mass of methanol, 50% by mass of water)
-Magnetite treated with the above silane compound 1: 58% by mass
-Magnetite treated with the above silane compound: 26% by mass

100 parts of the above material, 5 parts of a 28 mass% aqueous ammonia solution, and 20 parts of water are placed in a flask, and the temperature is raised to 85 ° C. in 30 minutes while stirring and mixing, and the mixture is held for 3 hours to carry out a polymerization reaction. The phenolic resin was cured.
Then, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried.
Next, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60 ° C. to obtain a magnetic material-dispersed spherical magnetic carrier 1. The volume-based 50% particle size (D50) of the magnetic carrier 1 was 34.2 μm.

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

<Production example of two-component developer 2-two-component developer 37>
In the production example of the two-component developer 1, the same operation was performed except for the changes as shown in Table 9, to obtain the two-component developer 2 to the two-component developer 37.

<Example 1>
Evaluation was performed using the above-mentioned two-component developer 1.
As an image forming apparatus, a Canon digital commercial printing printer imageRUNNER ADVANCE C5560 remodeling machine was used, and a two-component developer 1 was put into a cyan developer. The modification points of the device were changed so that the fixing temperature, process speed, DC voltage V _{DC of the developer carrier, charging voltage V D} of the electrostatic latent image carrier, and laser power could be set freely. Image output evaluation outputs FFh image (solid image) of a desired image ratio, V _DC as the toner amount on the FFh image in paper is _desired, by adjusting the _V D and laser _power, The evaluation described later was performed.
FFh is a value obtained by displaying 256 gradations in hexadecimal, 00h is the first gradation of 256 gradations (white background portion), and FFh is the 256th gradation of 256 gradations (solid portion). ..
Evaluation is performed based on the following evaluation methods, and the results are shown in Table 10.

<Scratch resistance>
-Paper: Image coat gloss 158 (158.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
-Toner loading on paper: 0.05 mg / cm ² (2Fh image)
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
-Evaluation image: An image of 3 cm x 15 cm is placed in the center of the above A4 paper.-Fixing test environment: Room temperature and humidity environment (temperature 23 ° C / humidity 50% RH (hereinafter N / N))
・ Fixing temperature: 180 ℃
-Process speed: 377 mm / sec
The above evaluation image was output and the scratch resistance was evaluated. The value of the difference in reflectance was used as an evaluation index for scratch resistance.
First, a Gakushin type friction fastness tester (AB-301: manufactured by Tester Sangyo Co., Ltd.) was used to apply a load of 0.5 kgf to the image part of the evaluation image, and friction (10 reciprocations) with a new evaluation paper. )do. Then, using a reflector meter (REFLECTOMTER MODEL TC-6DS: manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the rubbed portion and the reflectance of the non-friction portion of the new evaluation paper are measured.
Then, the difference in reflectance before and after friction was calculated using the following formula. The difference in the obtained reflectance was evaluated according to the following evaluation criteria.
Reflectance difference = Reflectance before friction-Reflectance after friction (evaluation standard)
A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 4.0% D: 4.0% or more

<Low temperature fixability>
-Paper: GFC-081 (81.0 g / m ² )
(Sold by Canon Marketing Japan Inc.)
-Toner load on paper: 0.50 mg / cm ²
(Adjusted by the DC voltage V _DC of the developer carrier, the charging voltage V _D of the electrostatic latent image carrier, and the laser power)
-Evaluation image: An image of 2 cm x 5 cm is placed in the center of the above A4 paper.-Test environment: Low temperature and low humidity environment: Temperature 15 ° C / Humidity 10% RH (hereinafter "L / L")
・ Fixing temperature: 150 ℃
-Process speed: 377 mm / sec
The above evaluation image was output and the low temperature fixability was evaluated. The value of the image density reduction rate was used as an evaluation index for low-temperature fixability.
The image density reduction rate is determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). ^{Next, a load of 4.9 kPa (50 g / cm 2} ) is applied to the portion where the image density is measured, and the fixed image is rubbed (5 reciprocations) with Sylbon paper, and the image density is measured again.
Then, the rate of decrease in image density before and after friction was calculated using the following formula. The rate of decrease in the obtained image density was evaluated according to the following evaluation criteria.
Image density reduction rate = (image density before friction-image density after friction) / image density before friction x 100
(Evaluation criteria)
A: Image density reduction rate less than 3% B: Image density reduction rate 3% or more and less than 5% C: Image density reduction rate 5% or more and less than 8% D: Image density reduction rate 8% or more

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

<Examples 2 to 29 and Comparative Examples 1 to 8>
Evaluation was carried out in the same manner as in Example 1 except that the two-component developer 2 to the two-component developer 37 were used. The evaluation results are shown in Table 10.

Claims (9)

A toner having toner particles containing a binder resin and a wax.
The binder resin contains an amorphous polyester resin, a polymer A, and a component B.
The content of the amorphous polyester resin is 50.0% by mass or more based on the total mass of the binder resin.
The polymer A has a first monomer unit represented by the following formula (C) and a second monomer unit different from the first monomer unit.

In formula (C), R _Z3 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms.
The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all the monomer units in the polymer A.
When the SP value of the second monomer unit is SP _A21 (J / cm ³ ) ^0.5 , the SP _A21 is 21.00 or more.
The content of the polymer A is 0.10% by mass to 10.00% by mass based on the total mass of the binder resin.
The SP value of the amorphous polyester resin was SP _P (J / cm ³ ) ^0.5 ,
The SP value of the polymer A is SP _A (J / cm ³ ) ^0.5 ,
The SP value of the component B is SP _B (J / cm ³ ) ^0.5 , and
When the SP value of the wax is SP _W (J / cm ³ ) ^0.5 ,
_A toner characterized in that the SP _P , the SP A, the SP _B , and the SP _W satisfy the relationship of the following formulas (1) and (2).
0.5 ≤ [(SP _P- SP _A )-(SP _A- SP _W )] (1)
0.5 ≤ [(SP _A- SP _W )-(SP _B- SP _A )] (2) The toner according to claim 1, wherein the SP _P (J / cm ³ ) ^0.5 and the SP _B (J / cm ³ ) ^0.5 satisfy the relationship of the following formula (3).
1.0 ≤ (SP _P- SP _B ) ≤ 3.0 (3) The ^{_{SP A (J / cm 3)}} 0.5 is, satisfies the following formula (4) The toner according to claim 1 or 2.
18.0 ≤ SP _A ≤ 24.0 (J / cm ³ ) ^0.5 (4) Any of claims 1 to 3, wherein the content ratio of the second monomer unit is 20.0 mol% to 90.0 mol% based on the total number of moles of all the monomer units in the polymer A. The toner according to item 1. The second monomer unit is at least one selected from the group consisting of the monomer units represented by the following formulas (D) and (E).

In formula (D), X represents a single bond or an alkylene group having 1 to 6 carbon atoms.
R ¹ is
−C≡N,
-C (= O) NHR ¹⁰ (R ¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
Hydroxy group,
-COOR ¹¹ (R ¹¹ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms),
-NH-C (= O) -N (R ¹³ ) ₂ (The two R ^13s are independent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms),
-COO (CH ₂ ) ₂ NHCOOR ¹⁴ (R ¹⁴ is an alkyl group having 1 to 4 carbon atoms) or
-COO (CH ₂ ) _2- NH-C (= O) -N (R ¹⁵ ) ₂ (The two R ^15s are independent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms)
Represents
R ² represents a hydrogen atom or a methyl group.
In formula (E), R ³ represents an alkyl group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or a methyl group.
The toner according to any one of claims 1 to 4. The toner according to any one of claims 1 to 5, wherein the content of the component B is 0.10% by mass to 10.00% by mass based on the total mass of the binder resin. The polymer A has a first monomer unit represented by the formula (C) and a third monomer unit different from the second monomer unit.
The third monomer unit is a monomer unit represented by the following formula (F).

In formula (F), R ⁵ represents a hydrogen atom or a methyl group, and Ph represents a phenyl group.
The toner according to any one of claims 1 to 6. The toner according to any one of claims 1 to 7, wherein the component B contains a graft polymer of a hydrocarbon compound and a styrene-acrylic polymer. The toner according to any one of claims 1 to 7, wherein the component B contains a crystalline polyester resin.