Toner

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

Technical Field

[0001] The present disclosure relates to toners used in electrophotographic systems, electrostatic recording systems, electrostatic printing systems, and the like.

Background Art

[0002] In recent years, as full-color copiers using the electrophotographic system have become widespread, there have been demands for further improvements in speed, image quality, energy conservation, reduction of recovery time from the sleep state, and compatibility with a variety of media. Specifically, as a toner compatible with energy conservation, in order to reduce the power consumption in the fixing process, a toner having excellent low-temperature fixability that can be fixed at a lower temperature is required. In addition, as a toner capable of shortening the recovery time from the sleep state, a toner having excellent charge retention property with little change in charge amount through a long sleep state is required. Furthermore, thick coated paper, which is one of a variety of media, contains a large amount of inorganic fine particles such as calcium carbonate to enhance whiteness. Therefore, the coefficient of friction due to rubbing between papers increases, and the toner forming the fixed image is likely to be peeled off from the paper. Therefore, as a fixed image in which the toner is hardly peeled off against rubbing between papers, a toner having excellent scratch resistance that promotes bleeding of wax and can lower the coefficient of friction by coating the surface of the fixed image with wax is required.

[0003] In Patent Document 1, a toner using a crystalline polyvinyl resin has been proposed as a toner having excellent low-temperature fixability, charge retention property, and scratch resistance. In addition, in Patent Document 2, a toner having alkenyl succinic acid as a carboxylic acid component of polyester has been proposed as a toner having excellent scratch resistance.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

[0005] The toner described in Patent Document 1 has sharp meltability and uses a highly hydrophobic crystalline polyvinyl resin, so it enables excellent low-temperature fixability and charge retention. Furthermore, by promoting the crystallization of the crystalline resin in the fixed image, a certain effect was obtained in the pencil scratch test. This is presumably because the elasticity of the toner itself in the fixed image is restored as the crystalline resin crystallizes, making the toner less likely to be destroyed. On the other hand, in recent years, the peeling of the toner from the paper in the fixed image due to rubbing between papers is a phenomenon where the toner peels off from the paper, rather than the toner being destroyed. Furthermore, since the crystalline polyvinyl resin has a high affinity for wax, the bleeding of the wax is suppressed, and it is difficult to form a wax layer on the surface of the fixed image. From the above, even when using the toner described in Patent Document 1, there were cases where it was inferior in the scratch resistance required in recent years.

[0006] On the other hand, in the toner described in Patent Document 2, since alkenyl succinic acid has a high affinity for wax, it is more likely to be retained in the fixed image than to migrate to the fixing roller during fixing. Therefore, in paper types such as plain paper, a certain effect of scratch resistance was obtained. However, since the binder resin has a high affinity for wax, bleeding of the wax on the surface of the fixed image is also likely to be suppressed, and in coated paper for thick paper, which is required in recent years, the scratch resistance may be inferior. 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 in fixed images such as coated paper for thick paper. 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 in fixed images such as coated paper for thick paper. The present disclosure provides a toner that exhibits excellent low-temperature fixability and charge retention property, and also exhibits excellent rubbing resistance in fixed images such as cardboard coated paper.

Means for Solving the Problems

[0007] The present disclosure is a toner having toner particles containing a binder resin and a wax, wherein 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 monomer units in the polymer A, when the SP value of the second monomer unit is SP A21 (J / cm 3 ) 0.5 it is 21.00 or more, A21 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 SP value of the amorphous polyester resin is SP P (J / cm 3 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 then the SP P the SP A ​​, the SP B , and the SP W satisfy the relationships of the following formulas (1) and (2), and are toners characterized thereby. 0.5 ≦ 〔(SP P - SP A ) - (SP A - SP W )〕 (1) 0.5 ≦ 〔(SP A - SP W ) - (SP B - SP A )〕 (2)

[0008]

Chemical Formula

Advantages of the Invention

[0009] 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 rubbing resistance in fixed images such as thick paper and coated paper.

Modes for Carrying Out the Invention

[0010] Hereinafter, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are endpoints, unless otherwise specified. When the numerical ranges are described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined. (Meth)acrylic acid ester means acrylic acid ester and / or methacrylic acid ester. "Monomer unit" means the reacted form of the monomer substance in the polymer. For example, in the main chain of the polymer in which vinyl monomers are polymerized, one section of the carbon-carbon bond is taken as one unit. A vinyl monomer can be represented by the following formula (Z).

[0011]

Chem.

[0012] In formula (Z), R Z1 represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R Z2 represents an arbitrary substituent. A crystalline resin refers to a resin that exhibits a distinct endothermic peak in differential scanning calorimetry (DSC) measurement.

[0013] The present inventors have advanced the study of toners that are excellent in low-temperature fixability and charge retention, and are also excellent in abrasion resistance in fixed images such as coated paperboard. As a result, the present inventors have given a specific structure to the first monomer unit that forms polymer A in the binder resin, and further, by controlling the affinity based on the SP values of the amorphous polyester resin, polymer A, component B, and wax in the toner particles, it has been found that a desired toner can be obtained.

[0014] Specifically, it is preferable to suppress the compatibility of polymer A with wax and make it easier for polymer A to be compatible with the amorphous polyester resin, which is the main resin of the binder resin. For this purpose, component B, which is a compatibilizer, is contained in the binder resin. The factor that makes polymer A easily compatible with wax is that the absolute value of the polarity difference between polymer A and wax is small, and the polarity difference between the amorphous polyester resin and polymer A is large with respect to the polarity difference between polymer A and wax. As a result, polymer A acts in the direction of being compatible with wax, which is the stable direction.

[0015] As a result of intensive studies, the present inventors have reached the conclusion that it is impossible to make the polarity difference between polymer A and wax larger than the polarity difference between the amorphous polyester resin and polymer A in order to take advantage of the high hydrophobicity and excellent charge retention of polymer A. This is because increasing the polarity difference between polymer A and wax may make polymer A prone to hydrophilicity and may impair the charge retention. Then, based on these findings, the present inventors conducted studies to reduce the compatibility between Polymer A and the wax. As a result, in order to make Polymer A and the amorphous polyester resin easily compatible, it was found that Component B as a compatibilizer should be added, and in order to make Polymer A easily compatible with Component B, a specific structure should be given to the first monomer unit forming Polymer A.

[0016] That is, by including Component B that functions as a compatibilizer in the binder resin and giving a specific structure to the first monomer unit forming Polymer A, Polymer A having a specific structure becomes more compatible with Component B than with the wax, and furthermore, the compatibilized product of Polymer A and Component B becomes easily compatible with the amorphous polyester resin. As a result, even when Polymer A is contained, Polymer A and the wax are phase-separated, and bleeding of the wax during fixing is ensured. Therefore, the surface of the fixed image is easily coated with the wax, and since the coefficient of friction is lowered, excellent abrasion resistance can be obtained.

[0017] The toner particles contain a binder resin and a wax. Further, the binder resin contains an amorphous polyester resin, Polymer A, and Component B. 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, Polymer A has a first monomer unit represented by the following formula (C) derived from the first polymerizable monomer and a second monomer unit derived from the second polymerizable monomer different from the first polymerizable monomer.

[0018] [Chemical formula] (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 (preferably an alkyl group having 18 to 30 carbon atoms).)

[0019] The first polymerizable monomer is preferably at least one selected from the group consisting of (meth)acrylic acid esters having an alkyl group with 18 to 36 carbon atoms. Further, the first monomer unit is a monomer unit represented by formula (C) derived from the first polymerizable monomer. Since the (meth)acrylic acid ester has a long-chain alkyl group, it can impart crystallinity 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, its hygroscopicity in a high-temperature and high-humidity environment is also low, and excellent charge retention can be obtained.

[0020] On the other hand, when R is an alkyl group having less than 18 carbon atoms, since the chain length of the alkyl group is short, the polymer having such a monomer unit has low hydrophobicity and high hygroscopicity in a high-temperature and high-humidity environment, resulting in poor charge retention. Further, when R is an alkyl group having 37 or more carbon atoms, the polymer having such a monomer unit has a long-chain alkyl group, so its melting point is high and its low-temperature fixability is poor.

[0021] R is preferably a linear alkyl group having 18 to 36 carbon atoms, 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 with 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms [(meth)stearyl acrylate, (meth)nonadecyl acrylate, (meth)eicosyl acrylate, (meth)heneicosanyl acrylate, (meth)behenyl acrylate, (meth) lignoceryl acrylate, (meth)ceryl acrylate, (meth)octacosyl acrylate, (meth)myricyl acrylate, (meth)dotriacontyl acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group with 18 to 36 carbon atoms [(2-decyltetradecyl (meth)acrylate, etc.]. Among 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 with 18 to 36 carbon atoms is preferable, and at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms is more preferable. Among them, at least one selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate is more preferable, and at least one selected from the group consisting of linear behenyl (meth)acrylate is particularly preferable. The first polymerizable monomer may be used alone or in combination of two or more.

[0022] The content ratio of the first monomer unit in polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all monomer units in polymer A. In addition, the content ratio of the first polymerizable monomer in the polymerizable monomer composition for producing polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all polymerizable monomers in the polymerizable monomer composition. When the content ratio of the first monomer unit in polymer A and the content ratio of the first polymerizable monomer in the polymerizable monomer composition for producing polymer A are within the above ranges, sharp meltability due to crystallinity is likely to be exhibited, and the toner has excellent 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%, and more preferably 20.0 mol% to 40.0 mol%.

[0023] 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 part is small, so the low-temperature fixability is poor. In addition, 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 polymer A becomes too low, and it is difficult to obtain phase separability with wax, resulting in poor abrasion resistance.

[0024] When the polymer A has two or more monomer units represented by the formula (C), the content ratio of the first monomer unit is represented by the molar ratio of the total thereof. Similarly, when the polymerizable monomer composition for producing the polymer A contains a (meth)acrylate having two or more alkyl groups having 18 to 36 carbon atoms, the content ratio of the first polymerizable monomer is represented by the molar ratio of the total thereof. In addition, when specifying the total number of moles, the carbon-carbon bond (-C-C-) constituting the main chain is regarded as one unit and the number of moles is counted.

[0025] When the SP value of the second monomer unit is SP A21 (J / cm 3 ) 0.5 when, the SP A21 is 21.00 or more. The SP A21 is preferably 24.00 or more, and more preferably 26.00 or more. Also, the SP A21 is preferably 40.00 or less, and more preferably 30.00 or less. Here, the SP value is an abbreviation for the solubility parameter and is a value serving as an index of solubility. The calculation method will be described later. Note that 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 by which (cal / cm 3 ) 0.5 can be converted to the unit of.

[0026] By the SP A21 satisfying the above range, the second monomer unit becomes highly polar, and a polarity difference occurs between the first and second monomer units. Due to such a polarity difference, the crystallization of the first monomer unit is further promoted, so that the low-temperature fixing property and the charge retention property are further improved. unit is more promoted, so that the low-temperature fixing property and the charge retention property are further improved. Specifically, the first monomer unit is incorporated into polymer A, and crystallinity is exhibited by the aggregation of the first monomer units. In a normal case, the crystallization of the first monomer unit is likely to be inhibited when other monomer units are incorporated, making it difficult for the polymer to exhibit crystallinity. This tendency becomes prominent when multiple types of monomer units are randomly bonded within a single molecule of the polymer. However, by using a first polymerizable monomer and a second polymerizable monomer having a polarity difference, it is considered that the first polymerizable monomer and the second polymerizable monomer can be bonded continuously to some extent rather than randomly during polymerization. As a result, a block formed by the aggregation of the first monomer units is likely to be formed, and polymer A is likely to become a block copolymer. Consequently, even when other monomer units are incorporated, it is possible to enhance crystallinity, and excellent low-temperature fixability and charge retention are easily obtained. Furthermore, the crystalline site of the first monomer unit has an affinity with the crystalline site of component B, which is a compatibilizer described later, so the compatibility between polymer A and component B is likely to increase, and conversely, phase separation between polymer A and wax can be obtained, resulting in excellent abrasion resistance.

[0027] On the other hand, when the SP value of the second monomer unit is SP A21 (J / cm 3 ) 0.5 does not satisfy the above range, the polarity difference in the polymerizable monomers constituting polymer A tends to be small, and the first polymerizable monomer is likely to be randomly bonded. As a result, it is difficult to form a block in which the first monomer units aggregate, it is likely to be difficult to enhance crystallinity, and the charge retention may be inferior. Furthermore, since there may be few crystalline sites of the first monomer unit, the affinity with component B, which is a compatibilizer described later, may decrease, resulting in no phase separation between polymer A and wax and inferior abrasion resistance in some cases. Note that all monomer units having an SP A21 satisfying the above range among the second monomer units derived from the second polymerizable monomer are applicable. 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.

[0028] Also, let the SP value of the amorphous polyester resin be SP P (J / cm 3 ), 0.5 the SP value of polymer A be SP A (J / cm 3 ), 0.5 the SP value of component B be SP B (J / cm 3 ), 0.5 and the SP value of the wax be SP W (J / cm 3 ). 0.5 When this is the case, the following formulas (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)

[0029] By satisfying the above formulas (1) and (2), the SP values of the amorphous polyester resin, polymer A, component B, and wax are appropriately controlled, so excellent charge retention and abrasion resistance can be obtained. Specifically, with respect to the polarity difference between polymer A and the wax (SP A - SP W ), the polarity difference between the amorphous polyester resin and polymer A (SP P - SP A ) satisfies the above formula (1). This indicates that polymer A has a higher affinity for the wax than the amorphous polyester resin. This shows that polymer A has a performance of being easily compatible with the wax, while also indicating that the polarity of polymer A is low, and excellent charge retention can be demonstrated. Furthermore, with respect to the polarity difference between component B and polymer A (SP B - SP A ), the polarity difference between polymer A and the wax (SPA -SP W ) satisfies the above formula (2). This indicates that polymer A has a higher affinity for component B than wax. As a result, the compatibility between polymer A and component B increases, and the phase separation between polymer A and wax is easily obtained, thus excellent abrasion resistance is obtained.

[0030] On the other hand, when the above formula (1) is not satisfied, it indicates that the polarity of polymer A is high. Although the phase separation of wax can be obtained, the charge retention property is poor. Also, when the above formula (2) is not satisfied, since the polarity of component B is too high relative to polymer A, it is difficult to function as a compatibilizer, and it is difficult to obtain the compatibility between polymer A and component B. As a result, it is difficult to obtain the phase separation between polymer A and wax, so the abrasion resistance is poor.

[0031] The SP P 、the SP A 、the SP B 、and the SP W preferably 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’) Also, it is preferable that SP P -SP A > 0, SP A -SP W > 0, SP B -SP A > 0.

[0032] The content of 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 polymer A satisfies the above range, since the content of polymer A is properly controlled, excellent low-temperature fixability and abrasion resistance can be obtained. Specifically, it indicates that a certain amount of crystalline resin showing sharp meltability is present in the binder resin, and excellent low-temperature fixability can be obtained. Furthermore, since an excessive amount of polymer A that is easily compatible with the wax does not exist in the binder resin, excellent rubbing resistance can be obtained. On the other hand, when the content of polymer A is less than 0.10% by mass, it indicates that a certain amount of crystalline material showing sharp meltability does not exist in the binder resin, and the low-temperature fixability is poor. Also, when the content of polymer A is more than 10.00% by mass, since an excessive amount of polymer A that is easily compatible with the wax exists in the binder resin, the rubbing resistance is poor. The content of polymer A is preferably 3.00% to 10.00% by mass, and more preferably 5.00% to 10.00% by mass.

[0033] 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’)

[0034] By satisfying formula (3), since the polarities of the amorphous polyester resin and component B are appropriately controlled, more excellent rubbing resistance can be easily obtained. Specifically, when the polarity difference (SP P - SP B ) between the amorphous polyester resin and component B is 3.0 or less, it indicates that the amorphous polyester resin and component B are less likely to phase-separate. As a result, component B easily acts as a compatibilizer and further promotes the phase separation of polymer A and the wax, so excellent rubbing resistance can be obtained. Also, the polarity difference (SP P - SP B) is 1.0 or more, it indicates that the polarity of Component B is not too high. As a result, it indicates that Component B easily acts as a compatibilizer, promotes the phase separation of Polymer A and wax more, and excellent abrasion resistance can be obtained.

[0035] 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’)

[0036] By satisfying the above formula (4), since the polarity of Polymer A is properly controlled, more excellent charge retention and abrasion resistance can be obtained. Specifically, when SP A is 24.0 or less, it indicates that the polarity of Polymer A is not too high. As a result, the charge retention characteristic of Polymer A is easily ensured, and more excellent charge retention can be obtained. Also, when SP A is 18.0 or more, it indicates that the polarity of Polymer A is not too low. As a result, it does not dissolve too much with wax, and more excellent abrasion resistance can be obtained.

[0037] The content ratio of the second monomer unit in Polymer A is preferably 20.0 mol% to 90.0 mol% based on the total number of moles of all monomer units in Polymer A. Also, the content ratio of the second polymerizable monomer in the polymerizable monomer composition for producing Polymer A is preferably 20.0 mol% to 90.0 mol% based on the total number of moles of all polymerizable monomers in the polymerizable monomer composition. Since 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 Polymer A is easily and properly controlled, and more excellent charge retention and abrasion resistance can be 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 indicates that the polarity of polymer A does not become too low. As a result, it becomes less likely to be overly compatible with wax, and thus more excellent abrasion resistance can be obtained. Also, 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 polymer A is not too high. As a result, the charge retention property, which is a characteristic of polymer A, is easily ensured, and more excellent charge retention property can be obtained. Furthermore, the fact that the content ratio of the second monomer unit and the content ratio of the second polymerizable monomer are within the above range indicates that a certain amount of the content ratio of the first monomer unit and the content ratio of the first polymerizable monomer are present. Therefore, it is easy to exhibit crystallinity by the aggregation of the first monomer units, and more excellent low-temperature fixability can be obtained.

[0038] Also, from the viewpoints of charge retention property and abrasion resistance, the content ratio of the second monomer unit in polymer A is more preferably 40.0 mol% to 90.0 mol%, and even more preferably 40.0 mol% to 70.0 mol%, based on the total number of moles of all monomer units in polymer A. For the same reason, the content ratio of the second polymerizable monomer in the polymerizable monomer composition for producing polymer A is preferably 40.0 mol% to 90.0 mol%, and even more preferably 40.0 mol% to 70.0 mol%, based on the total number of moles of all polymerizable monomers in the polymerizable monomer composition. In polymer A, the above SP A21 When there are two or more monomer units derived from the second polymerizable monomer that satisfy the above range, the content ratio of the second monomer unit is represented by the total molar ratio thereof. Similarly, when the composition used for polymer A contains two or more second polymerizable monomers, the content ratio of the second polymerizable monomers is represented by the total molar ratio thereof.

[0039] The second polymerizable monomer preferably has an ethylenically unsaturated bond, and more preferably has one ethylenically unsaturated bond. For example, it is preferable that the second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B).

[0040]

Chemical formula

[0041] Also, for example, it is preferable that the second monomer unit is at least one selected from the group consisting of monomer units represented by the following formulas (D) and (E). -unit.

[0042]

Chemical formula

[0043] In 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), a hydroxy group, -COOR 11 (R 11 is a hydrogen atom, an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms or a hydroxyalkyl group having 1 to 6 (preferably 1 to 4) carbon atoms), -NH-C(=O)-N(R 13 )2 (the two Rs 13 are each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms), -COO(CH2)2NHCOOR 14 (R 14 is an alkyl group having 1 to 4 carbon atoms), or, -COO(CH2)2-NH-C(=O)-N(R 15 )2 (the two Rs 15 are each independently a hydrogen atom or an alkyl group having 1 to 6 (preferably 1 to 4) carbon atoms) represents, R 2 represents a hydrogen atom or a methyl group.

[0044] In 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.

[0045] 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 property, and abrasion resistance can be obtained. 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, a polarity difference occurs between the first and second monomer units, and due to such a polarity difference, the crystallization of the first monomer unit is more promoted, and more excellent low-temperature fixability and charge retention property can be obtained. Specifically, the first monomer unit is incorporated into polymer A, and crystallinity is exhibited by the aggregation of the first monomer units with each other. In a normal case, the crystallization of the first monomer unit is likely to be inhibited when other monomer units are incorporated, so it becomes difficult for the polymer to exhibit crystallinity. This tendency becomes prominent when a plurality of types of monomer units are randomly bonded within one molecule of the polymer. However, by using the first polymerizable monomer and the second polymerizable monomer having a polarity difference, it is considered that the first polymerizable monomer and the second polymerizable monomer can be bonded continuously to some extent rather than randomly during polymerization. Thereby, a block formed by the aggregation of the first monomer units is formed, and polymer A is likely to become a block copolymer, and it becomes possible to enhance the crystallinity even when other monomer units are incorporated, and more excellent low-temperature fixability and charge retention property are likely to be obtained. Furthermore, the crystalline site of the first monomer unit has an affinity with the crystalline site of component B which is a compatibilizer, so the compatibility between polymer A and component B increases. Conversely, the compatibility between polymer A and wax Phase separation properties are more easily obtained. Therefore, better abrasion resistance is more easily obtained. 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, since it is nonionic, it has high hydrophobicity and better charge retention properties can be obtained.

[0046] Also, as the second polymerizable monomer, specifically, for example, the following polymerizable monomers can be used. Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc. Monomers having a hydroxy group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by a known method.

[0047] Monomers having a urethane group: For example, alcohols having 2 to 22 carbon atoms with an ethylenically unsaturated bond (such as 2-hydroxyethyl methacrylate, vinyl alcohol, etc.), and isocyanates having 1 to 30 carbon atoms [monoisocyanate compounds (such as benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, butyl isocyanate, hexyl isocyanate, t-butyl isocyanate, cyclohexyl isocyanate, octyl isocyanate, 2-ethylhexyl isocyanate, dodecyl isocyanate, adamantyl isocyanate, 2,6-dimethylphenyl isocyanate, 3,5-dimethylphenyl isocyanate, and 2,6-dipropylphenyl isocyanate, etc.), aliphatic diisocyanate compounds (such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate, etc.), alicyclic diisocyanate compounds (such as 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate, etc.), and aromatic diisocyanate compounds (such as phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate, etc.)] are reacted by a known method to obtain monomers, and Alcohols with carbon numbers from 1 to 26 (such as methanol, ethanol, propanol, isopropyl alcohol, butanol, t-butyl alcohol, pentanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, nonadecyl alcohol, heneicosanol, behenyl alcohol, erucyl alcohol, etc.) and isocyanates with 2 to 30 carbon atoms having ethylenic unsaturated bonds [such as 2-isocyanatoethyl (meth)acrylate, 2-(0-[1'-methylpropylideneamino]carboxamido)ethyl (meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, and 1,1-(bis(meth)acryloyloxymethyl)ethyl isocyanate, etc.] are reacted by a known method to obtain monomers, etc.

[0048] Monomers having a urea group: For example, amines with 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine, and isopropylamine, etc.), secondary amines (such as dinormal ethylamine, dinormal propylamine, dinormal butylamine, etc.), aniline, cyclohexylamine, etc.] and isocyanates with 2 to 30 carbon atoms having ethylenic unsaturated bonds are reacted by a known method to obtain monomers, etc. Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate.

[0049] Among them, it is preferable to use monomers 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 ethylenic unsaturated bond.

[0050] Also, as the second polymerizable monomer, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl capric acid, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octylate are also preferably used. Among them, vinyl esters are non-conjugated monomers, and their reactivity with the first polymerizable monomer is likely to be appropriately maintained, and the crystallinity of the polymer is likely to be increased. Therefore, they are preferable from the viewpoint of low-temperature fixing property.

[0051] Also, when the SP value (J / cm 3 ) 0.5 of the first monomer unit is defined as SP A11 , SP A11 is preferably less than 20.00, more preferably 19.00 or less, and even more preferably 18.40 or less. The lower limit is not particularly limited, but is preferably 17.00 or more.

[0052] Polymer A may contain a third monomer unit derived from a third polymerizable monomer that is not within the range of the above SP value (J / cm 3 ) 0.5 (that is, different from the first polymerizable monomer and the second polymerizable monomer) as long as the molar ratio of the first monomer unit derived from the above-described first polymerizable monomer and the second monomer unit derived from the second polymerizable monomer is not impaired. As the third polymerizable monomer, among the monomers exemplified as the second polymerizable monomer above, monomers that do not satisfy the range of the above SP A21 (J / cm 3 ) 0.5 can be used. Also, for example, the following monomers having no nitrile group, amide group, urethane group, hydroxy group, urea group, or carboxy group can also be used.

[0053] Styrene and its derivatives such as styrene and o-methylstyrene, and (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. 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 polymer A and component B described below is further enhanced, and more excellent abrasion resistance can be obtained. Specifically, when component B described below is a styrene-acrylic resin, π-π interaction occurs between the styrene moiety of polymer A and the styrene moiety of component B, more than the affinity based only on the polarity of polymer A and component B, resulting in increased affinity. As a result, phase separation between polymer A and wax is more easily obtained, and excellent abrasion resistance is obtained.

[0054] For example, polymer A has a third monomer unit different from the first monomer unit and the second monomer unit represented by formula (C), and the third monomer unit is preferably a monomer unit represented by the following formula (F).

[0055]

Chemical formula

[0056] 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.

[0057] From the viewpoint of improving the charge retention property in a high-temperature and high-humidity environment, the acid value (Av) of polymer A is preferably 30.0 mgKOH / g or less, and more preferably 20.0 mgKOH / g or less. When the acid value is within the above range, the hygroscopicity under high temperature and high humidity environment is reduced, so that better charge retention can be exhibited. The lower limit of the acid value is not particularly limited, but is preferably 0 mgKOH / g or more.

[0058] Polymer A preferably has a weight average molecular weight (Mw) of 10,000 to 200,000, more preferably 20,000 to 150,000, as measured by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble content. When Mw is within the above range, the elasticity near room temperature is easily maintained. Further, the melting point (Tp) of Polymer A is preferably 50°C to 80°C, more preferably 53°C to 70°C. When the melting point of Polymer A is within the above range, better low temperature fixability is exhibited. The melting point of Polymer A can be adjusted by the type and amount of the first polymerizable monomer used, the type and amount of the second polymerizable monomer, and the like. Polymer A is preferably a vinyl polymer. Examples of the vinyl polymer include polymers of monomers containing ethylenically unsaturated bonds. 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.

[0059] Component B is not particularly limited as long as it can satisfy the above formulas (2) and (3). It may be a low molecular weight component such as a crystalline ester compound, but is preferably a resin component (high molecular weight compound) having high affinity with Polymer A and easily obtaining phase separation with wax. In particular, in order to increase the affinity with Polymer A, it is preferably a resin component having 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 by the above second polymerizable monomer may be contained as its constituent components. 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 onto a styrene-acrylic polymer, and a polymer obtained by graft polymerizing a styrene-acrylic polymer onto a hydrocarbon compound. When component B is, for example, a polymer obtained by graft-polymerizing a hydrocarbon compound onto a styrene-acrylic polymer, the compatibility between polymer A and component B is further increased, and therefore better abrasion resistance can be obtained. When component B described later contains, for example, a styrene-acrylic polymer, polymer A and component In addition to the affinity due to the polarity of component B, if polymer A has a styrene moiety, π-π interactions will occur at the styrene moiety of component B, further increasing the affinity. Furthermore, the affinity is increased because of the affinity between the alkyl group having 18 to 36 carbon atoms derived from the first polymerizable monomer in polymer A and the alkyl group derived from the hydrocarbon compound in component B. As a result, the phase separation between polymer A and the wax is improved, and thus better abrasion resistance is obtained.

[0060] Regarding the graft polymer of a hydrocarbon compound and a styrene-acrylic polymer, the hydrocarbon compound is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon having one double bond, and various polyolefins can be used. In particular, polyethylene-based and polypropylene-based polyolefins are preferably used. In other words, the graft polymer is preferably a graft polymer of a polyolefin and a styrene-acrylic polymer. Examples of the polymerizable monomer for producing a styrene-acrylic polymer include the following polymerizable monomers. Styrenic polymerizable monomers such as styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, p-methoxystyrene, p-hydroxystyrene, p-acetoxystyrene, vinyltoluene, ethylstyrene, phenylstyrene, and benzylstyrene; Alkyl esters of unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate (the alkyl group has 1 to 17 carbon atoms); Vinyl ester-based polymerizable monomers such as vinyl acetate; vinyl ether-based polymerizable monomers such as vinyl methyl ether; halogen element-containing vinyl-based polymerizable monomers such as vinyl chloride; diene-based polymerizable monomers such as butadiene and isobutylene, and combinations thereof are included. The graft copolymer of a hydrocarbon compound and a styrene acrylic polymer can be obtained by a known method.

[0061] Component B may also contain a crystalline polyester resin. When component B contains a crystalline polyester resin, the compatibility between polymer A and component B is further increased, so that more excellent abrasion resistance can be obtained. Specifically, the alkyl group having 18 to 36 carbon atoms derived from the first polymerizable monomer of polymer A and the alkyl group derived from the aliphatic diol and aliphatic dicarboxylic acid of component B also exhibit affinity, so that the affinity is further increased. As a result, the phase separation property between polymer A and the wax is further improved, so that more excellent abrasion resistance can be obtained. The crystalline polyester resin is preferably a polycondensate of 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.

[0062] 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 a straight chain) 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, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol can be mentioned. Among these, linear aliphatic, α,ω-diol such as 1,6-hexanediol is preferably exemplified. Among the above alcohol components, preferably 50% by mass or more, more preferably 70% by mass or more is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms.

[0063] 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, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, and those obtained by hydrolyzing acid anhydrides or lower alkyl esters thereof are also included. Among the above carboxylic acid components, preferably 50% by mass or more, more preferably 70% by mass or more is a carboxylic acid selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms. The crystalline polyester resin can be produced according to a usual polyester synthesis method. For example, after subjecting the above-mentioned carboxylic acid monomer and alcohol monomer to an esterification reaction or a transesterification reaction, a crystalline polyester resin can be obtained by carrying out a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. Thereafter, by further adding the above aliphatic compound and carrying out an esterification reaction, a desired crystalline polyester resin can be obtained. The above esterification or transesterification reaction can be carried out using a conventional esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, magnesium acetate, etc., if necessary. In addition, the above polycondensation reaction can be carried out using a known catalyst such as a conventional polymerization catalyst, for example, titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide, etc. The polymerization temperature and the amount of the catalyst are not particularly limited and may be determined appropriately.

[0064] The content of 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 component B is more preferably 3.00% by mass to 10.00% by mass based on the total mass of the binder resin, and even more preferably 5.00% by mass to 10.00% by mass. When the content of component B satisfies the above range, since component B is controlled to an appropriate amount, excellent abrasion resistance can be obtained. Specifically, when the content of component B is within the above range, it indicates that the necessary amount for compatibility with polymer A is ensured, the compatibility between polymer A and component B is further increased, and the phase separation property between polymer A and wax is further improved, so that more excellent abrasion resistance can be obtained.

[0065] 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. Also, the content is preferably 95.0% by mass or less. Examples of the polymerizable monomer for producing the amorphous polyester resin include polyhydric alcohols (di- or trihydric or higher alcohols), polyhydric carboxylic acids (di- or trihydric or higher carboxylic acids), their acid anhydrides or their lower alkyl esters. As the polyhydric alcohol, the following polyhydric alcohols can be used. As the dihydric alcohol, a bisphenol derivative is preferred. Examples of bisphenol derivatives include polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, 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-hydroxyphenyl)propane, polyoxypro pylene(6)-2,2-bis(4-hydroxyphenyl)propane, and the like. Examples of other alcohol components include ethylene glycol, diethylene glycol, triethylene 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, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene. These polyhydric alcohols can be used alone or in combination of two or more.

[0066] As the polyvalent carboxylic acid, the following polyvalent carboxylic acids can be used. Examples of the divalent carboxylic acids 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, 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 lower alkyl esters of these acids. Examples of the trivalent or higher carboxylic acids, their acid anhydrides, or their lower alkyl esters include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimer acid, anhydrides of these acids, or lower alkyl esters of these acids. Among these, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or its derivatives, are preferably used because they are inexpensive and the reaction control is easy. These divalent carboxylic acids and trivalent or higher carboxylic acids can be used alone or in combination of two or more.

[0067] The method for producing the amorphous polyester resin is not particularly limited, and known methods can be used. For example, the aforementioned polyhydric alcohol and polyvalent carboxylic acid are charged simultaneously, and polymerized through an esterification reaction or transesterification reaction, and a condensation reaction to produce a polyester resin. The polymerization temperature is not particularly limited, but a range of 180°C or higher and 290°C or lower is preferable. When polymerizing the polyester, for example, polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used.

[0068] 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. Further, the hydroxyl value of the amorphous polyester resin is preferably 20 mgKOH / g to 70 mgKOH / g from the viewpoints of low-temperature fixability and storage stability.

[0069] The 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, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; and their block copolymers; Waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or completely deoxidizing fatty acid esters such as deacidified carnauba wax. Saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; Saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; Esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid and alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; Fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; Saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; Unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, and N,N'-dioleyl sebacic acid amide; Aromatic bisamides such as m-xylene bisstearic acid amide and N,N'-distearyl isophthalic acid amide; Aliphatic metal salts (commonly referred to as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; Partial esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; Methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats. Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, or fatty acid ester waxes such as carnauba wax are preferable from the viewpoint of abrasion resistance. From the viewpoint of abrasion resistance, the wax content is preferably 3% by mass to 8% by mass based on the total mass of the binder resin.

[0070] The toner particles may contain a colorant if necessary. Examples of the colorant include the following. Examples of the black colorant include carbon black; Those obtained by toning to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, or a dye and a pigment may be used in combination. From the viewpoint of the image quality of full-color images, it is preferable to use a dye and a pigment in combination.

[0071] Examples of the pigment for magenta toner 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; C.I. Pigment Violet 19; C.I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35. Examples of dyes for magenta toners 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. Disperse Red 9; oil-soluble dyes such as C.I. Solvent Violet 8, 13, 14, 21, 27; C.I. 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; basic dyes such as C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0072] Examples of pigments for cyan toners include the following. C.I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. Vat Blue 6; copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton, C.I. Acid Blue 45. An example of a dye for cyan toners is C.I. Solvent Blue 70. Examples of pigments for yellow toners 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. Vat Yellow 1, 3, 20. Examples of the yellow toner dye include C.I. Solvent Yellow 162.

[0073] These colorants can be used alone, in combination, or even in the form of a solid solution. The colorant is selected in terms of hue angle, chroma, lightness, lightfastness, OHP transparency, and dispersibility in the 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 component.

[0074] The toner particles may contain a charge control agent as needed. By blending a charge control agent, the charge characteristics can be stabilized and the optimal triboelectric charge amount can be controlled according to the development system. As the charge control agent, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a fast charging speed of the toner, and can stably maintain a certain charge amount is preferred. Examples of the negative charge control agent include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymer-type compounds having sulfonic acid or carboxylic acid in the side chain, polymer-type compounds having sulfonate or sulfonic acid esterified products in the side chain, polymer-type compounds having carboxylate or carboxylic acid esterified products in the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes. 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 part by mass to 10.0 parts by mass with respect to 100 parts by mass of the binder resin, and more preferably 0.5 part by mass to 10.0 parts by mass.

[0075] The toner may contain inorganic fine particles as needed. The inorganic fine particles may be incorporated into the toner particles or 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, or complex oxide fine particles thereof. Among the inorganic fine particles, silica fine particles and titanium oxide fine particles are preferable for improving fluidity and charge uniformity. 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 fluidity, the inorganic fine particles as an external additive preferably have a specific surface area of 50 m 2 / g to 400 m 2 / g. Also, from the viewpoint of improving durable stability, the inorganic fine particles as an external additive preferably have a specific surface area of 10 m 2 / g to 50 m 2 / g. In order to achieve both improved fluidity and durable stability, inorganic fine particles having a specific surface area within the above range may be used in combination. 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. Mixing of the toner particles and the external additive can be performed using a known mixer such as a Henschel mixer.

[0076] The toner can be used as a one-component developer, but in order to further improve dot reproducibility and supply a stable image over a long period, it may be mixed with a magnetic carrier and used as a two-component developer. Examples of the magnetic carrier include iron oxide; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earths, alloy particles thereof, oxide particles thereof; magnetic materials such as ferrite; magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin for holding the magnetic material in a dispersed state; and the like, and generally known ones can be used. When toner is mixed with a magnetic carrier and used as a two-component developer, the mixing ratio of the magnetic carrier at that time is preferably 2% to 15% by mass, more preferably 4% to 13% by mass, as the toner concentration in the two-component developer.

[0077] The toner particles and the method for producing the toner are 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 manufacturing procedure of the toner particles and the 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 polymer A, and a binder resin containing component B, as well as wax, and other components such as a colorant and a charge control agent as required are weighed in predetermined amounts, blended, and mixed. Examples of the mixing device include a double cone 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 & Engineering Co., Ltd.), and the like.

[0078] Next, the mixed materials are melt-kneaded to disperse wax and the like in the resin component. In the melt-kneading step, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single-screw or twin-screw extruders are the mainstream. For example, a KTK-type twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM-type twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by K.C.K. Co., Ltd.), a co-kneader (manufactured by Busse Co., Ltd.), a Neidex (manufactured by Nippon Coke & Engineering Co., Ltd.), and the like can be mentioned. Further, the resin composition obtained by melt-kneading may be rolled with a two-roll or the like and cooled with water or the like in the cooling step.

[0079] Subsequently, the cooled resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarsely pulverizing with a pulverizer such as a crusher, a hammer mill, or a feather mill, further fine pulverization is performed using, for example, a cryotron system (manufactured by Kawasaki Heavy Industries, Ltd.), a super rotor (manufactured by Nisshin Engineering Co., Ltd.), a turbo mill (manufactured by Turbo Industry), or a fine pulverizer using an air jet method.

[0080] Thereafter, if necessary, classification is performed using a classifier or a sieve such as an elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) using an inertial classification method, a turbo plex (manufactured by Hosokawa Micron Corporation) using a centrifugal classification method, a TSP separator (manufactured by Hosokawa Micron Corporation), or a faculty (manufactured by Hosokawa Micron Corporation). Furthermore, if necessary, an external additive is externally 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 blended, and a double cone 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 & Engineering Co., Ltd.), a Nobilta (manufactured by Hosokawa Micron Corporation), etc. are used as an external addition machine and stirred and mixed. is mentioned.

[0081] The measurement methods for various physical properties of the toner and raw materials will be described below. (Method for Separating Each Material from the Toner) Each material can be separated from the toner by utilizing the difference in solubility of each material contained in the toner in a solvent. First separation: Dissolve the toner in methyl ethyl ketone (MEK) at 23°C to separate the soluble component (amorphous polyester resin, component B) and the insoluble component (polymer A, wax, colorant, inorganic fine particles, etc.). Second separation: Dissolve the insoluble component (polymer A, wax, colorant, inorganic fine particles, etc.) obtained in the first separation in MEK at 100°C to separate the soluble component (polymer A, wax) and the insoluble component (colorant, inorganic fine particles, etc.). Third Separation: Dissolve the soluble components (polymer A, wax) obtained in the second separation in chloroform at 23°C to separate the soluble components (polymer A) from the insoluble components (wax). Fourth Separation: Dissolve the soluble components (amorphous polyester resin, component B) obtained in the first separation in a mixed solution of methyl ethyl ketone (MEK) and toluene at 23°C to separate the soluble components (component B) from the insoluble components (amorphous polyester resin).

[0082] <Method for Measuring the Content Ratio of Monomer Units Derived from Various (Polymerizable) Monomers in Amorphous Polyester Resin, Polymer A, Component B, and Wax> The measurement of the content ratio of monomer units derived from various (polymerizable) monomers in amorphous polyester resin, polymer A, component B, and wax is 1 performed under the following conditions by H-NMR. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400 MHz Pulse condition: 5.0 μs Frequency range: 10500 Hz Number of integrations: 64 times Measuring temperature: 30°C Sample: Put 50 mg of the measurement sample into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve it in a constant temperature bath at 40°C for preparation. Obtained 1 From the obtained H-NMR chart, for example, in polymer A, select a peak that is independent of the peaks attributed to the components of monomer units derived from other monomer units from among the peaks attributed to the components of monomer units derived from the first polymerizable monomer, and calculate the integral value S1 of this peak. Similarly, select a peak that is independent of the peaks attributed to the components of monomer units derived from other monomer units from among the peaks attributed to the components of monomer units derived from the second polymerizable monomer, and calculate the integral value S2 of this peak. Furthermore, when a third polymerizable monomer is used, select a peak independent of the peaks attributed to the components of the monomer units derived from other monomers from the peaks attributed to the components of the monomer units derived from the third polymerizable monomer, and calculate the integral value S3 of this peak. The content ratio of the monomer units derived from the first polymerizable monomer is determined as follows using the above integral values S1, S2, and S3. Note that n1, n 2、 n3 are the numbers of hydrogens in the components to which the peaks focused on for each site are attributed.

[0083] Content ratio (mol%) of the monomer units derived from the first polymerizable monomer = {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 Similarly, the content ratios of the monomer units derived from the second polymerizable monomer and the third polymerizable monomer are determined as follows. Content ratio (mol%) of the monomer units derived from the second polymerizable monomer = {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 Content ratio (mol%) of the monomer units derived from the third polymerizable monomer = {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3))}×100 In the case where a polymerizable monomer that does not contain a hydrogen atom in the components other than the vinyl group is used in polymer A, 13 using C-NMR, the measured nucleus is 13 C, and measurement is performed in single pulse mode, 1 and it is calculated in the same manner by H-NMR. Also, when the toner is manufactured by the suspension polymerization method, the peaks of wax and other resins may overlap, and independent peaks may not be observed. As a result, there may be cases where the content ratio of monomer units derived from various polymerizable monomers in polymer A cannot be calculated. In such cases, by performing the same suspension polymerization without using wax or other resins, polymer A' can be manufactured and analyzed by regarding polymer A' as polymer A.

[0084] <Calculation method of SP value> The SP values of the polymerizable monomer, the monomer unit derived from the polymerizable monomer, polymer A, component B, the amorphous polyester resin, and the wax are determined as follows according to the calculation method proposed by Fedors. For the above substances, for the atoms or atomic groups in the molecular structure, the evaporation energy (Δei) (cal / mol) and the molar volume (Δvi) (cm 3 / mol) are obtained from the table described in "polym.Eng.Sci.,14(2),147-154(1974)", and (4.184×ΣΔei / ΣΔvi) 0.5 is taken as the SP value (J / cm 3 ) 0.5 and set as such. Note that monomer units such as SP A21 are calculated by the same calculation method as above for the atoms or atomic groups in the molecular structure in the state where the double bond of the polymerizable monomer is cleaved by polymerization. SP A21 is obtained by dividing the evaporation energy of the monomer unit by the molar volume, and SP A , SP B , SP P , or SP W is obtained by determining the evaporation energy (Δei) and the molar volume (Δvi) of the monomer units derived from the constituent polymerizable monomers for each monomer unit, and the SP A , SP B , SP P , or SP WCalculate the product with the molar ratio (j) in each case, and obtain it by dividing the sum of the evaporation energies of each monomer unit by the sum of the molar volumes, and calculate according to the following formula. SP = {4.184×(Σj×ΣΔei) / (Σj×ΣΔvi)} 0.5

[0085] <Method for Measuring Weight-Average Molecular Weight (Mw) of Amorphous Resin etc. Using Gel Permeation Chromatography (GPC)> The weight-average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble component of the amorphous polyester resin, Component B, is measured by gel permeation chromatography (GPC) as follows. First, dissolve the measurement target in tetrahydrofuran (THF) over 24 hours at room temperature. Then, filter the obtained solution through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in THF is about 0.8 mass%. Using this sample solution, measure under the following conditions. Apparatus: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: 7-connected Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Oven temperature: 40.0 °C Sample injection volume: 0.10 mL When calculating the molecular weight of the sample, use the molecular weight calibration curve prepared using a standard polystyrene resin (trade name "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation).

[0086] <Method for Measuring Weight-Average Molecular Weight (Mw) of Crystalline Resins Such as Polymer A Using Gel Permeation Chromatography (GPC)> The weight-average molecular weight (Mw) of the toluene-soluble fraction of crystalline resins such as Polymer A at 100 °C is measured by gel permeation chromatography (GPC) as follows. First, the measurement target is dissolved in toluene over 1 hour at 100 °C. Then, the resulting solution is filtered through a solvent-resistant membrane filter "MAESORIDISC" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the components soluble in toluene is about 0.1 mass%. Using this sample solution, the measurement is carried out under the following conditions. Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation) Column: TSKgel GMHHR-H HT (7.8 cm I.D × 30 cm), two columns connected in series (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 a 0.1 mass% sample When calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample is used. Furthermore, it is calculated by performing polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity equation.

[0087] <Method for Measuring Acid Value> The acid value is the number of milligrams 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, and specifically, the following procedure is followed. (1) Preparation of Reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add ion-exchanged water to make 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, add ethyl alcohol (95% by volume) to make up to 1 L. Put it in an alkali-resistant container to avoid contact with carbon dioxide gas, etc., leave it for 3 days, and then filter 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 is determined from the amount of the potassium hydroxide solution required for neutralization by taking 25 mL of 0.1 mol / L hydrochloric acid into an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. The 0.1 mol / L hydrochloric acid used is prepared according to JIS-K8001-1998. (2) Procedure (A) This test Precisely weigh 2.0 g of the pulverized sample into a 200 mL Erlenmeyer flask, add 100 mL of a mixed solution of toluene / ethanol (2:1), and dissolve it over 5 hours. Then, add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of the titration is when the pale red color of the indicator persists for about 30 seconds. (B) Blank test Conduct the same titration as the above operation except without using a sample (i.e., using only the mixed solution of toluene / ethanol (2:1)). (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(C - B) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: the added amount of the potassium hydroxide solution in the blank test (mL), C: the added amount of the potassium hydroxide solution in this test (mL), f: the factor of the potassium hydroxide solution, S: the mass of the sample (g).

[0088] <Method for measuring hydroxyl value> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize acetic acid combined with hydroxyl groups when acetylating 1 g of the sample. The hydroxyl value is measured according to JIS-K0070-1992, and specifically, the following procedure is followed. (1) Preparation of reagents Put 25 g of special grade acetic anhydride into a 100 mL volumetric flask, add pyridine to make the total volume 100 mL, shake well to obtain an acetylation reagent. The obtained acetylation reagent shall be stored in a brown bottle so as not to contact moisture, carbon dioxide, etc. Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), 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, add ethyl alcohol (95% by volume) to make 1 L. Put it in an alkali-resistant container and let it stand for 3 days so as not to contact carbon dioxide, etc., then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution shall be stored in an alkali-resistant container. The factor of the potassium hydroxide solution is determined from the amount of the potassium hydroxide solution required for neutralization by taking 25 mL of 0.5 mol / L hydrochloric acid into an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution. The 0.5 mol / L hydrochloric acid used shall be prepared according to JIS-K8001-1998. (2) Procedure (A) This test Precisely weigh 1.0 g of the pulverized sample into a 200 mL round-bottom flask, and accurately add 5.0 mL of the acetylation reagent thereto using a whole pipette. At this time, when the sample is difficult to dissolve in the acetylation reagent, add a small amount of special grade toluene to dissolve it. Place a small funnel on the mouth of the flask, immerse about 1 cm of the bottom of the flask in a glycerin bath at about 97 °C and heat. 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 root of the neck of the flask with thick paper with round holes. After 1 hour, take out the flask from the glycerin bath and let it cool. After cooling, add 1 mL of water from the funnel and shake to hydrolyze the acetic anhydride. For more complete hydrolysis, heat the flask in the glycerin bath for 10 minutes again. After cooling, wash the funnel and the walls of the flask with 5 mL of ethyl alcohol. Add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. Note that the end point of the titration is when the light red color of the indicator continues for about 30 seconds. (B) Blank test Perform titration in the same manner as the above operation, except without using a sample. (3) Substitute the obtained result into the following formula to calculate the hydroxyl value. A = [{(B - C) × 28.05 × f} / S] + D Here, A: hydroxyl value (mgKOH / g), B: amount of potassium hydroxide solution added in the blank test (mL), C: amount of potassium hydroxide solution added in this test (mL), f: factor of potassium hydroxide solution, S: mass of sample (g), D: acid value of the sample (mgKOH / g).

[0089] <Method for measuring melting point> The melting points of polymer A and wax are measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10 °C / min Measurement start temperature: 20 °C Measurement end temperature: 180 °C For temperature correction of the device detection part, use the melting points of indium and zinc, and for heat quantity correction, use the heat of fusion of indium. Specifically, accurately weigh about 5 mg of the sample, place it in an aluminum pan, and perform differential scanning calorimetry. Use a silver empty pan as a reference. Take the peak temperature of the maximum endothermic peak in the first heating process as the melting point (unit: °C). Note that the maximum endothermic peak refers to the peak with the maximum endothermic quantity when there are multiple peaks.

[0090] <Method for measuring softening point of resin> The softening point of the resin is measured using a capillary tube type rheometer "Flow Characteristic Evaluation Device Flow Tester CFT - 500D" (manufactured by Shimadzu Corporation) with a constant load extrusion method, and is performed 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 measurement sample filled in the cylinder is heated to melt, and the melted measurement sample is extruded from the die at the bottom of the cylinder, and a flow curve showing the relationship between the piston descent amount and temperature at this time can be obtained. Also, the softening point is defined as the "melting temperature in the 1 / 2 method" described in the manual attached to the "Flow Property Evaluation Device, Flow Tester CFT-500D". The melting temperature in the 1 / 2 method is calculated as follows. First, find 1 / 2 of the difference between the piston drop amount at the end of the outflow (referred to as the outflow end point, Smax) and the piston drop amount at the start of the outflow (referred to as the lowest point, Smin) (let this be X. X = (Smax - Smin) / 2). Then, the temperature of the flow curve when the piston drop amount becomes the sum of X and Smin is the melting temperature in the 1 / 2 method. As the measurement sample, use a resin of about 1.0 g, which is compression molded at about 10 MPa for about 60 seconds using a tablet molding compressor (for example, NT-100H, manufactured by NPE Systems Co., Ltd.) in an environment of 25°C to form a cylindrical shape with a diameter of about 8 mm. The specific operations in the measurement are carried out according to the manual attached to the device. The measurement conditions of CFT-500D are as follows. Test mode: Heating rate method Start temperature: 50°C Reach 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 Diameter of die hole: 1.0 mm Length of die: 1.0 mm

Example

[0091] Hereinafter, the present disclosure will be specifically described by way of examples. However, these do not limit the present disclosure in any way. In the following formulations, "parts" are all based on mass unless otherwise specified.

[0092] <Production Example of Polymer A1> · Solvent: Toluene 100.0 parts · Monomer composition 100.0 parts (The monomer composition is a mixture of behenyl acrylate, acrylonitrile, and styrene in the following proportions shown below.) · Behenyl acrylate (first polymerizable monomer): 67.0 parts (25.3 mol%) · Acrylonitrile (second polymerizable monomer): 22.0 parts (59.5 mol%) · Styrene (third polymerizable monomer): 11.0 parts (15.2 mol%) · Polymerization initiator: 0.5 part [t-Butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV)]

[0093] The above materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. While stirring the inside of the reaction vessel at 200 rpm, it was heated to 70 °C and subjected to a polymerization reaction for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after cooling the above solution to 25 °C, the above solution was charged into 1000.0 parts of methanol while stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered off, further washed with methanol, and then vacuum-dried at 40 °C for 24 hours to obtain Polymer A1. The weight-average molecular weight (Mw) of Polymer A1 was 30000, 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, it contained 25.3 mol% of monomer units derived from behenyl acrylate, 59.5 mol% of monomer units derived from acrylonitrile, and 15.2 mol% of monomer units derived from styrene. Also, the monomer units derived from the polymerizable monomers and the SP value of Polymer A (unit: (J / cm 3 ) 0.5 ) were calculated by the above method.

[0094] <Preparation of Monomer Having Urethane Group> 50.0 parts of methanol was charged into a reaction vessel. Then, 5.0 parts of Karenz MOI [2-isocyanatoethyl methacrylate] (Showa Denko K.K.) was added dropwise at 40°C with stirring. After the addition was completed, stirring was carried out for 2 hours while maintaining the temperature at 40°C. Then, unreacted methanol was removed using an evaporator to prepare a monomer having a urethane group.

[0095] <Production Examples of Polymer A2 to A21> In the production example of Polymer A1, the reaction was carried out in the same manner except that the respective polymerizable monomers and the number of parts were changed as shown in Table 1, and Polymers A2 to A21 were obtained. The physical properties of Polymers A1 to A21 are shown in Tables 2 and 3.

[0096]

Table 1

[0097] The abbreviations in Tables 1 to 3 are as follows. BEA: Behenyl acrylate STA: Stearyl acrylate MYA: Myristyl acrylate HA: Hexadecyl acrylate AN: Acrylonitrile HEMA: 2-Hydroxyethyl methacrylate UT: Monomer having a urethane group VA: Vinyl acetate St: Styrene MM: Methyl methacrylate

[0098]

Table 2

[0099]

Table 3

[0100] <Production Example of Component B1> · Solvent: 100.0 parts of toluene · 100.0 parts of monomer composition (The monomer composition is a mixture of the following polyethylene, acrylonitrile, butyl acrylate, and styrene in the following proportions) · 10.0 parts (1.2 mol%) of polyethylene · 40.0 parts (60.8 mol%) of acrylonitrile · 5.0 parts (3.1 mol%) of butyl acrylate · 45.0 parts (34.9 mol%) of styrene · Polymerization initiator: 0.5 part [t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV)]

[0101] The above materials were charged into a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. While stirring the inside of the reaction vessel at 200 rpm, it was heated to 70 °C and subjected to a polymerization reaction for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after cooling the above solution to 25 °C, the solution was charged into 1000.0 parts of methanol while stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered off, washed further with methanol, and then dried under vacuum at 40 °C for 24 hours to obtain Component B1. The weight average molecular weight of Component B1 was 20,000. When the above Component B1 was analyzed by NMR, the monomer units derived from polyethylene were 1.2 mol%, the monomer units derived from acrylonitrile were 60.8 mol%, the monomer units derived from butyl acrylate were 3.1 mol%, and the monomer units derived from styrene were 34.9 mol%. The monomer units derived from the polymerizable monomer and the SP value of Component B (unit: (J / cm 3 ) 0.5 ) were calculated by the above method.

[0102] <Production Examples of Components B2 to B10> In the production example of Component B1, the reaction was carried out in the same manner except that each polymerizable monomer and the number of parts were changed as shown in Table 4, and Components B2 to B10 were obtained. The physical properties of Components B1 to B10 are shown in Table 5.

[0103]

Table 4

[0104] The abbreviations in Tables 4 to 5 are as follows. PE: Polyethylene AN: Acrylonitrile BA: Butyl acrylate St: Styrene HD: Hexanediol SA: Sebacic acid

[0105]

Table 5

[0106] <Production Example of Amorphous Polyester Resin P1> · Bisphenol A - propylene oxide adduct (average number of added moles 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 part

[0107] The above materials were weighed into a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. Next, after replacing the inside of the reaction vessel 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. Furthermore, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 5 hours while maintaining the temperature at 200 °C. After confirming that the temperature reached 100 °C of the softening point, the temperature was lowered to stop the reaction, and an amorphous polyester resin P1 was obtained. The weight average molecular weight (Mw) of the obtained amorphous polyester resin P1 was 12,000. 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%, the monomer unit derived from ethylene glycol was 35.5 mol%, and the monomer unit derived from terephthalic acid was 50.9 mol%. The monomer unit derived from the polymerizable monomer and the SP value (unit: (J / cm 3 ) 0.5 ) were calculated by the above method.

[0108] <Production Examples of Amorphous Polyester Resins P2 to P10> In the production example of the amorphous polyester resin P1, the reaction was carried out in the same manner except that each polymerizable monomer and the number of parts were changed as shown in Table 6, and amorphous polyester resins P2 to P10 were obtained. The physical properties of the amorphous polyester resins P2 to P10 are shown in Tables 7 and 8.

[0109]

Table 6

[0110] The abbreviations in Tables 6 to 7 are as follows. PO2: Bisphenol A·propylene oxide adduct (average number of added moles 2.0) PO3: Bisphenol A·propylene oxide adduct (average number of added moles 3.0) ED: Ethylene glycol THM: Pentaerythritol TPA: Terephthalic acid TMA: Trimellitic anhydride AA: Adipic acid

[0111]

Table 7

[0112] <Production 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 the maximum endothermic peak 90 °C): 5.00 parts · Colorant (carbon black): 10.00 parts

[0113] The above materials were mixed using a Henschel mixer (FM-75 type, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 1500 rpm for a rotation time of 5 minutes, and then kneaded using a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corporation) set at a temperature of 130 °C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized using a mechanical pulverizer (T-250, manufactured by Turbo Industry Co., Ltd.). Further, classification was performed using a Faculity (F-300, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions were a classifier rotor rotation speed of 11000 rpm and a dispersion rotor rotation speed of 7200 rpm.

[0114] · Toner particles: 100.0 parts · Silica fine particles: 4.0 parts [Fumed silica surface-treated with hexamethyldisilazane (median diameter (D50) based on the number of particles is 120 nm)] · Small particle size inorganic fine particles: 1.0 part [Titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (median diameter (D50) based on the number of particles is 10 nm)]

[0115] The above materials were mixed in a Henschel mixer (Model FM-75, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotational speed of 1900 rpm for 10 minutes to obtain Toner 1. For Toner 1, [(SP P -SP A )-(SP A -SP W )] was 0.9, (SP P -SP B ) was 2.0, and [(SP A -SP W )-(SP B -SP A )] was 1.1.

[0116] <Production Examples of Toners 2 to 37> In the production example of Toner 1, the same operations as in the production example of Toner 1 were carried out except that the type and addition amount of Polymer A and the type and addition amount of Component B were changed as shown in Table 8 to obtain Toners 2 to 37. The physical properties of the obtained toners are shown in Table 8.

[0117]

Table 8

[0118] <Production Example of Magnetic Carrier 1> · Magnetite 1 with a number average particle diameter of 0.30 μm and a magnetization strength of 65 A·m 2 / kg under a magnetic field of 1000 / 4π (kA / m) · Magnetite 2 with a number average particle diameter of 0.50 μm and a magnetization strength of 65 A·m 2 / kg under a magnetic field of 1000 / 4π (kA / m) To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and high-speed mixing and stirring were carried out at 100 °C or higher in a container to treat each fine particle. · 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 2: 26% by mass

[0119] 100 parts of the above material, 5 parts of 28% aqueous ammonia solution, and 20 parts of water were placed in a flask, heated to 85 °C in 30 minutes while stirring and mixing, held for 3 hours to cause a polymerization reaction, and the resulting phenol resin was cured. Thereafter, 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 spherical magnetic carrier 1 with dispersed magnetic bodies. The volume-based 50% particle size (D50) of the magnetic carrier 1 was 34.2 μm.

[0120] <Production Example of Binary Developer 1> To 92.0 parts of the magnetic carrier 1, 8.0 parts of toner 1 was added and mixed by a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a binary developer 1.

[0121] <Production Examples of Binary Developers 2 to 37> In the production example of the binary developer 1, the same operations were performed except for changing as shown in Table 9 to obtain binary developers 2 to 37.

[0122]

Table 9

[0123] <Example 1> Evaluation was performed using the above binary developer 1. As an image forming apparatus, a modified machine of the Canon digital commercial printer imageRUNNER ADVANCE C5560 was used, and the two-component developer 1 was put into the cyan developer. The modification points of the apparatus included changing the fixing temperature, process speed, DC voltage V of the developer carrier, charging voltage V of the electrostatic latent image carrier, and laser power so that they could be freely set. For the image output evaluation, an FFh image (solid image) with a desired image ratio was output, and V, V, and the laser power were adjusted so that the toner loading amount on the FFh image on the paper became as desired, and the evaluation described below was performed. DC and the charging voltage V of the electrostatic latent image carrier D and the laser power were changed so that they could be freely set. For the image output evaluation, an FFh image (solid image) with a desired image ratio was output, and V, V, and the laser power were adjusted so that the toner loading amount on the FFh image on the paper became as desired, and the evaluation described below was performed. DC V D and the laser power were adjusted to perform the evaluation described below. FFh is a value representing 256 gradations in hexadecimal notation, where 00h is the first gradation (blank part) of 256 gradations, and FFh is the 256th gradation (solid part) of 256 gradations. The evaluation was performed based on the following evaluation method, and the results are shown in Table 10.

[0124] <Scratch resistance> · Paper: Image Coat Gloss 158 (158.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) · Toner loading amount on paper: 0.05 mg / cm 2 (2Fh image) (Adjusted by the DC voltage V of the developer carrier, the charging voltage V of the electrostatic latent image carrier, and the laser power) DC and the charging voltage V of the electrostatic latent image carrier D and the laser power) · Evaluation image: A 3 cm × 15 cm image was placed at the center of the above A4 paper. · Fixing test environment: Normal temperature and humidity environment (temperature 23°C / humidity 50% RH (hereinafter N / N)) · Fixing temperature: 180°C · Process speed: 377 mm / sec The above evaluation image was output, and the scratch resistance was evaluated. The difference value of the reflectance was used as the evaluation index for the scratch resistance. First, apply a load of 0.5 kgf to the image area of the evaluation image using a Gakushin-type friction fastness tester (AB-301: manufactured by Tester Sangyo Co., Ltd.) and rub it (10 round trips) with a new evaluation paper. Then, using a reflectometer (REFLECTOMETER MODEL TC-6DS: manufactured by Tokyo Denshoku Co., Ltd.), measure the reflectance of the rubbed part and the non-rubbed part of the new evaluation paper. Then, the difference in reflectance before and after rubbing was calculated using the following formula. The obtained difference in reflectance was evaluated according to the following evaluation criteria. Difference in reflectance = Reflectance before rubbing - Reflectance after rubbing (Evaluation criteria) 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

[0125] <Low-temperature fixing property> · Paper: GFC-081 (81.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) · Toner loading amount on paper: 0.50 mg / cm 2 (DC voltage V of the developer carrier DC , charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) · Evaluation image: Place a 2 cm × 5 cm image at the center of the above A4 paper · Test environment: Low-temperature and low-humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L / L") · Fixing temperature: 150°C · Process speed: 377 mm / sec The above evaluation image was output and the low-temperature fixing property was evaluated. The value of the image density reduction rate was used as an evaluation index for the low-temperature fixing property. For the image density reduction rate, using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), first measure the image density at the center. Next, apply a pressure of 4.9 kPa (50 g / cm 2) Apply the load of and rub the fixed image (5 round trips) with sylvon paper, and measure the image density again. Then, using the following formula, the reduction rate of the image density before and after rubbing was calculated. The obtained reduction rate of the image density was evaluated according to the following evaluation criteria. Reduction rate of image density = (Image density before rubbing - Image density after rubbing) / Image density before rubbing × 100 (Evaluation criteria) A: Reduction rate of image density less than 3% B: Reduction rate of image density 3% or more and less than 5% C: Reduction rate of image density 5% or more and less than 8% D: Reduction rate of image density 8% or more

[0126] <Charge retention rate in high temperature and high humidity environment> · Paper: GFC-081 (81.0 g / m 2 ) (Canon Marketing Japan Inc.) · Toner loading amount on paper: 0.35 mg / cm 2 (DC voltage V of the developer carrier DC , charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) · Evaluation image: Place a 2 cm × 5 cm image in the center of the above A4 paper · Fixing test environment: High temperature and high humidity environment: Temperature 30°C / Humidity 80% RH (hereinafter referred to as "H / H") · Process speed: 377 mm / sec The triboelectric charge amount of the toner on the electrostatic latent image carrier was calculated by sucking and collecting the toner on the electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter. Specifically, the triboelectric charge amount of the toner on the electrostatic latent image carrier was measured by a Faraday-Cage. A Faraday cage is a coaxial double cylinder, where the inner cylinder and the outer cylinder are insulated. Suppose a charged body with a charge amount Q is placed inside this inner cylinder. Due to electrostatic induction, it becomes as if there is a metal cylinder with a charge amount Q. The induced charge amount was measured with an electrometer (Keithley 6517A, manufactured by Keithley Instruments), and (Q / M), where Q (mC) is divided by the toner mass M (kg) in the inner cylinder, was defined as the triboelectric charge amount of the toner. Triboelectric charge amount of toner (mC / kg) = Q / M First, the above evaluation image was formed on the electrostatic latent image carrier. Before being transferred to the intermediate transfer body, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was suction-collected by a metal cylinder tube and a cylindrical filter, and [initial Q / M] was measured. Subsequently, after leaving the developing device in the evaluation machine in the "H / H" environment for two weeks, the same operations as before the leaving were performed, and the charge amount Q / M (mC / kg) per unit mass on the electrostatic latent image carrier after leaving was measured. The Q / M per unit mass on the electrostatic latent image carrier before the above leaving was defined as [initial Q / M], and the Q / M per unit mass on the electrostatic latent image carrier after leaving was defined as [Q / M after leaving]. ([Q / M after leaving] / [initial Q / M] × 100) was calculated as the retention rate and judged according to the following criteria. (Evaluation criteria) A: Retention rate is 95% or more B: Retention rate is 90% or more and less than 95% C: Retention rate is 85% or more and less than 90% D: Retention rate is less than 85%

[0127] <Examples 2 to 29, and Comparative Examples 1 to 8> Evaluations were performed in the same manner as in Example 1, except that two-component developers 2 to 37 were used. The evaluation results are shown in Table 10.

[0128]

Table 10

Claims

【Claim 1】 A method for manufacturing a toner having toner particles containing a binder resin and a hydrocarbon wax, comprising: 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 is a polymer of a composition containing a first polymerizable monomer and a second polymerizable monomer different from the first polymerizable monomer, The first polymerizable monomer is a (meth)acrylate having a linear alkyl group having 18 to 36 carbon atoms, The second polymerizable monomer is at least one selected from the group consisting of the following formulas (A) and (B), (In formula (A), X represents a single bond or an alkylene group having 1 to 6 carbon atoms, R １ is -C≡N, -C(=O)NHR １０ (R １０ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), a 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 (two Rs １３ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -COO(CH ２ ) ２ NHCOOR １４ (R １４ is an alkyl group having 1 to 4 carbon atoms), or, -COO(CH ２ ) ２ -NH-C(=O)-N(R １５ ) ２ (Two Rs １５ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) represents, R ２ represents a hydrogen atom or a methyl group. In formula (B), R ３ represents an alkyl group having 1 to 4 carbon atoms, and R ４ represents a hydrogen atom or a methyl group.) 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 a linear alkyl group having 18 to 36 carbon atoms, The content ratio of the first monomer unit in the polymer A is 5.0 mol% to 60.0 mol% based on the total number of moles of all monomer units in the polymer A, 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 component B is a graft polymer of a hydrocarbon compound and a styrene acrylic polymer, or a crystalline polyester resin, Let the SP value of the amorphous polyester resin be SP Ｐ (J / cm ３ ) ０．５ , Let the SP value of the polymer A be 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 then The SP Ｐ 、 the SP Ａ 、 the SP Ｂ 、 and the SP Ｗ satisfy the relationships 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) A melt-kneading step of melt-kneading the amorphous polyester resin, the polymer A, the component B, and the hydrocarbon wax, and A pulverizing step of pulverizing the resin composition obtained by melt-kneading after the melt-kneading step, A method for manufacturing a toner, characterized by obtaining toner particles through these steps.

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