Toner and toner manufacturing method

Abstract

To provide a toner that exhibits excellent low temperature fixability and is excellent in resistance against scratching of an image printed on a smooth medium such as coat paper, and can achieve glossiness of an image and prevention of density unevenness on a fixation medium with large irregularities.SOLUTION: A toner has toner particles containing a binder resin and wax. The binder resin contains crystalline resin. The content of the crystalline resin is within a specific range. The storage elastic modulus of the toner at a temperature T(°C) is defined as G'(T) in viscoelasticity measurement of the toner, and in a graph with the temperature T as the horizontal axis and with a value d(logG'(T)) / dT obtained by differentiating LogG'(T) by the temperature T as the vertical axis, the minimum value is present in a specific range. When a temperature at which the toner takes the minimum value is defined as a temperature T1(°C), d(logG'(T1)) / dT, d(logG'(T1+3)) / dT≤0, G'(T1), and G'(T1+30) satisfy the specific relationship.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system, and a method for producing the toner. [Background technology]

[0002] In recent years, there has been a stronger demand than ever for added value such as high productivity, high image quality, and high stability in electrophotographic apparatuses such as full-color printers and full-color copiers. To achieve high productivity, it is important to melt the toner more quickly in the fixing process. Specifically, by using a crystalline resin with sharp melting properties as the main component of the binder resin of the toner, it is possible to achieve superior low-temperature fixing properties compared to toners whose main component is an amorphous resin.

[0003] For example, Patent Document 1 proposes a toner that achieves both low-temperature fixability and heat-resistant storage stability by using an acrylate resin with crystallinity in the side chain. However, it has been found that toners using crystalline resins with low-temperature fixability have low strength at room temperature, and fixed images are vulnerable to rubbing and scratching. Therefore, Patent Document 2 proposes a toner that uses a binder resin that combines a crystalline vinyl resin matrix with an amorphous resin domain, thereby enabling low-temperature fixing and producing images that are resistant to external forces such as rubbing and scratching due to the domain structure. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-130243 [Patent Document 2] Japanese Patent Application Laid-Open No. 2014-142632 Summary of the Invention [Problem to be solved by the invention]

[0005] Meanwhile, the performance demands of electrophotographic devices are increasing year by year, and they are required to consistently produce high-quality print products even when outputting large quantities at high speeds over long periods of time in a variety of environments. Furthermore, the robustness of print products is also becoming increasingly important, with demands for resistance to abrasion and scratches and heat resistance. In addition, there is a demand for image gloss and suppression of density unevenness on uneven fixing media such as rough paper. According to the investigations of the present inventors, the toner described in Patent Document 2 is insufficient for the level of image fastness currently required, and there is a strong demand for improvement, particularly in terms of scratch resistance of images printed on smooth media such as coated paper. At least one aspect of the present disclosure provides a toner that exhibits excellent low-temperature fixability, has excellent scratch resistance for images printed on smooth media such as coated paper, and can achieve high image gloss and reduced density unevenness on fixing media with large irregularities. At least one aspect of the present disclosure also provides a method for producing the toner. [Means for solving the problem]

[0006] At least one embodiment of the present disclosure provides a toner having toner particles containing a binder resin and a wax, The binder resin contains a crystalline resin, the content of the crystalline resin is 30.0 to 95.0 mass% based on the mass of the toner particles, In the viscoelasticity measurement of the toner, the storage modulus of the toner at temperature T (°C) is G'(T), In a graph with the temperature T on the horizontal axis and the value d(logG'(T)) / dT obtained by differentiating LogG'(T) with respect to the temperature T on the vertical axis, There is a minimum value in the range of 50.0 to 70.0°C. When the temperature at which the minimum value is reached is T1 (°C), d(logG´(T1)) / dT is -2.00 to -0.20, d(logG'(T1+3)) / dT≦0, d(logG´(T1+3)) / dT-d(logG´(T1)) / dT is 0.15 to 1.90, G´(T1) is 5.0×10 5 ~2.0×10 7 Pa, G´(T1+30) is 1.0×10 2 ~5.0×10 4 Pa, Regarding toner.

[0007] Furthermore, at least one aspect of the present disclosure is a method for producing the toner, the method comprising: a melt-kneading step of melt-kneading a mixture containing the crystalline resin and the wax; an annealing step of maintaining the melt-kneaded product obtained in the melt-kneading step at a temperature equal to or higher than the melting point of the crystalline resin + 5°C; The present invention relates to a method for producing a toner having the formula (I). [Effects of the Invention]

[0008] According to at least one aspect of the present disclosure, it is possible to provide a toner that not only exhibits excellent low-temperature fixability, but also has excellent scratch resistance for images printed on smooth media such as coated paper, and can achieve high image gloss and suppression of density unevenness on fixing media with large irregularities. Also, according to at least one aspect of the present disclosure, it is possible to provide a toner manufacturing method for manufacturing the toner. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit. The (meth)acrylic acid ester means an acrylic acid ester and / or a methacrylic acid ester. When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way. A "monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, one section of carbon-carbon bond in the main chain of a polymer formed by polymerizing a vinyl monomer is considered to be one unit. A vinyl monomer can be represented by the following formula (Z): [ka]

[0010] 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 optional substituent. A crystalline resin refers to a resin that shows a clear endothermic peak in differential scanning calorimetry (DSC) measurement.

[0011] The toner of the present disclosure will be described in detail below. The present disclosure provides a toner having toner particles containing a binder resin and a wax, The binder resin contains a crystalline resin, the content of the crystalline resin is 30.0 to 95.0 mass% based on the mass of the toner particles, In the viscoelasticity measurement of the toner, the storage modulus of the toner at temperature T (°C) is G'(T), In a graph with the temperature T on the horizontal axis and the value d(logG'(T)) / dT obtained by differentiating LogG'(T) with respect to the temperature T on the vertical axis, There is a minimum value in the range of 50.0 to 70.0°C. When the temperature at which the minimum value is reached is T1 (°C), d(logG´(T1)) / dT is -2.00 to -0.20, d(logG'(T1+3)) / dT≦0, d(logG´(T1+3)) / dT-d(logG´(T1)) / dT is 0.15 to 1.90, G´(T1) is 5.0×10 5 ~2.0×10 7 Pa, G´(T1+30) is 1.0×10 2 ~5.0×10 4 Pa, Regarding toner.

[0012] As a result of extensive research, the inventors have discovered that by controlling the viscoelasticity of a toner containing a crystalline resin within a specific range, a toner can be obtained that has excellent low-temperature fixing properties and scratch resistance of images printed on smooth media.

[0013] The inventors speculate that the reason for solving the above problem is as follows. The crystalline resin used in the toner has a weaker internal cohesion than the amorphous resin, and is easily destroyed by external forces such as scratches or rubbing, resulting in poor image robustness. In the above-mentioned Patent Document 2, a sea-island structure is formed by using a crystalline resin and an amorphous resin in combination, and image strength can be increased to a certain extent, but the sea portion, which is a continuous layer, is made of a crystalline resin with a weak internal cohesion, so no significant improvement in image robustness can be achieved.

[0014] On the other hand, the toner of the present disclosure has the following characteristics. In measuring the viscoelasticity of the toner, the storage modulus of the toner at temperature T (°C) is defined as G'(T), and a graph is obtained with temperature T on the horizontal axis and the value d(logG'(T)) / dT obtained by differentiating LogG'(T) with respect to temperature T on the vertical axis. (i) In the graph, a minimum value exists in the range of 50.0 to 70.0° C. The temperature at which the minimum value is obtained is defined as temperature T1 (° C.). (ii) d(logG´(T1)) / dT is -2.00 to -0.20; (iii) d(logG'(T1+3)) / dT≦0; (iv) d(logG´(T1+3)) / dT-d(logG´(T1)) / dT is 0.15 to 1.90. moreover, (v) G´(T1) is 5.0×10 5 Pa ~ 2.0 × 10 7Pa, (vi) G´(T1+30) is 1.0×10 2 Pa ~ 5.0 × 10 4 It is Pa.

[0015] In a graph with temperature T on the horizontal axis and d(logG'(T)) / dT on the vertical axis, a minimum value is found at temperature T1 (°C) in the range of 50 to 70°C, and d(logG'(T1)) / dT of -2.00 to -0.20 indicates that the storage modulus drops sharply in the range of 50 to 70°C. Note that logG'(T1) indicates LogG'(T) at temperature T1. logG'(T1+3) indicates LogG'(T) at temperature T1+3°C.

[0016] Furthermore, the fact that d(logG'(T1+3)) / dT≦0 and d(logG'(T1+3)) / dT-d(logG'(T1)) / dT is 0.15 to 1.90 indicates that the rate of decrease in storage modulus at T1+3°C is significantly smaller than the rapid rate of decrease in storage modulus at T1°C. The large difference in the degree of decrease in viscoelasticity of the toner despite a small temperature difference of 3° C. is a characteristic not exhibited by conventional toners. Furthermore, according to the study by the present inventors, this behavior is not exhibited unless wax is present, and therefore, the toner according to the present disclosure is presumed to have a structure different from that of conventional toners.

[0017] Specifically, the present inventors speculate that the toner of the present disclosure has a structure in which a discontinuous phase of crystalline resin alone is dispersed in a continuous phase of a eutectic of crystalline resin and wax. If this structure is assumed, the storage modulus drops sharply when the melting point of the crystalline resin is exceeded due to the melting of the crystalline resin in the discontinuous phase. However, once the discontinuous phase of the crystalline resin is completely melted, the viscoelasticity of the entire toner is dominated by the viscoelasticity of the eutectic of the crystalline resin and wax, which is the continuous phase, and this explains why the drop in viscoelasticity suddenly decreases.

[0018] Assuming that images formed with toner also have a similar structure, we believe that the strength of the image can be dramatically increased by the filler effect of the crystalline resin phase existing as a discontinuous phase in addition to the continuous phase whose internal cohesion is increased by the eutectic of the crystalline resin and wax.

[0019] The toner of the present disclosure has a minimum value in the range of 50.0 to 70.0°C in a graph with temperature T as the horizontal axis and d(logG'(T)) / dT as the vertical axis. The temperature at which this minimum value is obtained is designated as temperature T1 (°C). If the minimum value is higher than 70.0°C, low-temperature fixability is likely to decrease. From the viewpoint of achieving both low-temperature fixability and storage stability, the temperature T1 is preferably in the range of 55.0 to 65.0° C., and more preferably in the range of 57.0 to 65.0° C. The temperature T1 can be controlled, for example, by changing the melting point of the crystalline resin. The temperature T1 can also be controlled by changing the glass transition point of the amorphous resin.

[0020] In addition, in a graph in which the horizontal axis represents temperature T and the vertical axis represents d(logG'(T)) / dT, the toner has a d(logG'(T1)) / dT of -2.00 to -0.20. d(logG'(T1)) / dT is preferably -2.00 to -0.30, more preferably -2.00 to -0.40, and even more preferably -1.70 to -0.40. If d(logG'(T1)) / dT is greater than -0.20, the degree of decrease in storage modulus is small, resulting in a decrease in the sharp melting properties of the toner and a decrease in low-temperature fixability. Making d(logG'(T1)) / dT smaller than -2.00 would improve the sharp melting properties, but this is currently difficult to achieve in the presence of other raw materials, such as colorants and external additives, contained in the toner.

[0021] In a graph in which the horizontal axis represents temperature T and the vertical axis represents d(logG'(T)) / dT, the toner of the present disclosure satisfies d(logG'(T1+3)) / dT≦0, and d(logG'(T1+3)) / dT-d(logG'(T1)) / dT is 0.15 to 1.90. If d(logG'(T1+3)) / dT>0, the storage modulus increases with increasing temperature, resulting in a decrease in low-temperature fixability. d(logG'(T1+3)) / dT is preferably from -0.50 to -0.03.

[0022] d(logG'(T1+3)) / dT-d(logG'(T1)) / dT indicates the difference in the degree of decrease in storage modulus between the temperatures T1 and T1+3°C at which the minimum value is reached. d(logG'(T1+3)) / dT-d(logG'(T1)) / dT is preferably 0.20 to 1. The range is preferably 0.90, more preferably 0.25 to 1.90, even more preferably 0.30 to 1.90, and even more preferably 0.30 to 1.60. If d(logG'(T1+3)) / dT-d(logG'(T1)) / dT is less than 0.15, the difference in the degree of decrease in storage modulus is small, suggesting that the crystalline resin is also present in the continuous phase, and the scratch resistance of the formed image is reduced.

[0023] Regarding the means for controlling d(logG'(T1)) / dT, d(logG'(T1)) / dT can be increased by increasing the content of the crystalline resin. When a crystalline vinyl resin is used as the crystalline resin, d(logG'(T1)) / dT can also be increased by increasing the content of the first monomer unit. Furthermore, d(logG'(T1)) / dT can be decreased by decreasing the content of the crystalline resin. When a crystalline vinyl resin is used as the crystalline resin, d(logG'(T1)) / dT can also be decreased by decreasing the content of the first monomer unit. Furthermore, when an amorphous resin is used in combination as the binder resin, d(logG'(T1)) / dT can also be controlled by changing the difference |Tc-Tg| between the melting point of the crystalline resin and the glass transition point of the amorphous resin. Furthermore, in toner production using the melt-kneading method, it is also effective to subject the melt-kneaded product obtained after the melt-kneading process to an annealing treatment in which the melt-kneaded product is held at a temperature equal to or higher than the melting point Tc of the crystalline resin + 5°C for 30 minutes or more in order to control (logG'(T1)) / dT within the above range.

[0024] There are no particular limitations on the means for making d(logG'(T1+3)) / dT≦0, since the storage modulus of a normal toner decreases with increasing temperature. An effective method for controlling the value of d(logG'(T1+3)) / dT-d(logG'(T1)) / dT within the above range is to subject the melt-kneaded product obtained after the melt-kneading step to an annealing step in which the product is kept at a temperature equal to or higher than the melting point Tc+5°C of the crystalline resin for 30 minutes or longer in the toner production method using the melt-kneading method described above. This step promotes eutectic formation between the crystalline resin and wax, forming a continuous layer, while allowing the crystalline resin that did not form a eutectic to independently form a discontinuous phase.

[0025] The toner has a G´(T1) of 5.0×10 5 ~2.0×10 7 Pa. G'(T1) is the value of G'(T) when temperature T is T1. G'(T1) is 5.0×10 5 If the G'(T1) is less than 2.0×10 Pa, the scratch resistance of the fixed image will decrease. 7 If the value of G'(T1) exceeds 5.0×10 Pa, the low-temperature fixability decreases. 5 ~2.0×10 7 Pa, more preferably 1.0×10 6 ~1.0×10 7 It is Pa.

[0026] The storage modulus G'(T1) can be controlled, for example, by the following method. For example, G'(T1) can be controlled by the amount of crystalline resin added, the amount of crystalline component in the crystalline resin, and the amorphous monomer unit of the crystalline resin. Furthermore, G'(T1) can be controlled by adding an amorphous resin to the toner particles and changing the type and content of the amorphous resin. It can also be controlled by adding a filler material to the toner particles. Specifically, G'(T1) can be easily increased by reducing the amount of crystalline resin added, reducing the amount of crystalline component in the crystalline resin, or increasing the amount of filler present in the toner particles. G'(T1) can also be easily decreased by increasing the amount of crystalline resin added, increasing the amount of crystalline component in the crystalline resin, or reducing the amount of filler present in the toner particles.

[0027] The toner further has a G´(T1+30) of 1.0×10 2 ~5.0×10 4 The storage modulus is Pa. G'(T1+30) is the storage modulus at a temperature about 30°C higher than the melting temperature of the crystalline resin, and corresponds to the storage modulus of the toner in the fixing nip. In other words, G'(T1+30) is the value of G'(T) when the temperature T is T1+30°C.

[0028] G´(T1+30) is 1.0×10 2 If the viscosity is less than 5.0×10 Pa, the viscosity at the fixing nip is too low, so that when using a fixing medium with large irregularities such as rough paper, the toner on the protruding parts melts and flows into the recessed parts, which tends to cause density unevenness that reflects the irregularities of the fixing medium, known as mottle. 4 If the pressure exceeds Pa, the toner becomes difficult to melt, and the gloss of the image decreases. G'(T1+30) is preferably 5.0 × 10 2 Pa ~ 3.0 × 10 4 Pa, more preferably 1.0×10 3 Pa ~ 3.0 × 10 4 It is Pa.

[0029] The storage modulus at G'(T1+30) can be controlled by the type and amount of wax and binder resin. The melting point of the wax can be changed to change the melting point of the eutectic of the crystalline resin and wax, thereby changing the storage modulus at G'(T1+30). It is also effective to perform an annealing process on the melt-kneaded product obtained after the melt-kneading process. Specifically, G'(T1+30) can be easily increased by increasing the melting point of the wax. G'(T1+30) can be easily decreased by decreasing the melting point of the wax.

[0030] In addition, in the measurement of the heat absorption of the toner using a differential scanning calorimeter, the total heat absorption J / g per 1 g of wax derived from the wax is defined as ΔH(T).In addition, in the measurement of the heat absorption of the wax, the total heat absorption J / g per 1 g of wax is defined as ΔH(W). At this time, It is preferable that 0.70≦ΔH(T) / ΔH(W)≦0.90; It is more preferable that 0.71≦ΔH(T) / ΔH(W)≦0.87.

[0031] ΔH(T) / ΔH(W) indicates the rate of change in the crystallinity of the wax when it is made into toner from raw materials, and is an index of the compatibility of the wax with the binder resin. When ΔH(T) / ΔH(W) is 0.70 or higher, the amount of wax compatible with the binder resin is appropriate, making it easier to form a eutectic with the crystalline resin. On the other hand, when ΔH(T) / ΔH(W) is 0.90 or lower, the wax does not completely phase separate from the binder resin, making it easier for interactions to occur.

[0032] ΔH(T) / ΔH(W) can be increased by, for example, increasing the SP values ​​of the crystalline resin and wax or increasing the melting point of the wax. ΔH(T) / ΔH(W) can be decreased by, for example, decreasing the SP values ​​of the crystalline resin and wax or decreasing the melting point of the wax. Furthermore, when an amorphous resin is further used as the binder resin, it is also possible to control the value of ΔH(T) / ΔH(W) by similarly controlling the SP values ​​of the amorphous resin and wax. Furthermore, ΔH(T) / ΔH(W) can be controlled by the kneading conditions and annealing conditions. In particular, ΔH(T) / ΔH(W) can be increased by performing annealing. SP value of crystalline resin ((J / cm 3 ) 0.5 ) is preferably 18.0 to 21.0, more preferably 19.0 to 21.0, and even more preferably 19.5 to 21.0. The SP value of the wax is preferably 16.0 to 19.0, and more preferably 16.5 to 17.5.

[0033] The inventors speculate that the wax and the crystalline resin form a eutectic. For this reason, in this disclosure, the endothermic heat "attributable to the wax" of the toner is defined as a peak that has a peak within a range of ±5°C of the endothermic peak temperature observed in the endothermic heat measurement of the wax alone.

[0034] Next, the raw materials will be described. <Crystalline resin> The toner particles contain a binder resin, and the binder resin contains a crystalline resin. The crystalline resin may be any known crystalline resin that can be used in toner. Specific examples include crystalline polyester resins and crystalline vinyl resins. From the viewpoint of charge stability in a high-temperature, high-humidity environment, crystalline vinyl resins are preferred. The crystalline resin preferably has a first monomer unit (hereinafter also simply referred to as the first monomer unit) represented by the following formula (1).

[0035] The content of the first monomer unit in the crystalline resin is preferably 30.0% by mass or more based on the mass of all monomer units in the crystalline resin, and within this range, the crystalline resin has sufficient crystallinity and exhibits better low-temperature fixability. [ka]

[0036] In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R 1 represents an alkyl group having 18 to 36 carbon atoms. 1 is preferably an alkyl group having 18 to 30 carbon atoms, and more preferably an alkyl group having 20 to 24 carbon atoms. In addition, the alkyl group preferably has a linear structure.

[0037] The first monomer unit has R in the side chain. 1 The crystalline resin has an alkyl group having 18 to 36 carbon atoms, and the crystallization of this alkyl group makes it easier for the crystalline resin to exhibit crystallinity. When the content of the first monomer unit in the crystalline resin is 30.0% by mass or more, crystallinity is more easily exhibited and low-temperature fixability is improved. The content of the first monomer unit in the crystalline resin is preferably 30.0 to 100.0% by mass, more preferably 40.0 to 100.0% by mass, and even more preferably 50.0 to 100.0% by mass.

[0038] Crystalline vinyl resins have superior charge retention in high-temperature, high-humidity environments compared to crystalline polyesters, a well-known crystalline resin, possibly because they have a crystalline structure in the side chains. Furthermore, the crystalline vinyl resins have a crystalline structure in the side chains, which is thought to enhance their interaction with wax (described below) and facilitate the formation of a eutectic with the wax.

[0039] The first monomer unit is preferably a monomer unit of at least one (first polymerizable monomer) selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.

[0040] Examples of the (meth)acrylic acid ester having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate]. , heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, dotriacontyl (meth)acrylate, etc.] and (meth)acrylic acid esters having a branched alkyl group having 18 to 36 carbon atoms [2-decyltetradecyl (meth)acrylate, etc.].

[0041] Among these, from the viewpoint of low-temperature fixability of the toner, 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 preferred. 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 preferred. At least one selected from the group consisting of linear stearyl (meth)acrylate and behenyl (meth)acrylate is even more preferred. The monomers forming the first monomer unit may be used alone or in combination of two or more.

[0042] The crystalline vinyl resin may contain other monomer units in addition to the first monomer unit. Examples of polymerizable monomers that form other monomer units other than the first monomer unit include the following. The polymerizable monomers that form the other monomer units may be used alone or in combination of two or more.

[0043] The other monomer units other than the first monomer unit are broadly classified into a second monomer unit (hereinafter also simply referred to as a second monomer unit) represented by the following formula (2), a third monomer unit (hereinafter also simply referred to as a third monomer unit) represented by the following formula (3), and monomer units other than the first, second, and third monomer units. [ka]

[0044] In formula (2), R 2 represents a hydrogen atom or a methyl group. In formula (3), X represents -O- or -NH- (preferably -O-), and R 4 represents a hydrogen atom or a methyl group, and R 3 represents alkylene having 2 to 6 carbon atoms (preferably 2 to 4, more preferably 2 or 3). The second monomer unit has a polar group directly bonded to the main chain of the crystalline vinyl resin. Examples of the polymerizable monomer that forms the second monomer unit include acrylonitrile and methacrylonitrile.

[0045] The third monomer unit has a polar hydroxy group at a position away from the main chain. Examples of the polymerizable monomer that forms the third monomer unit include the following polymerizable monomers: Examples include: 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate amide, 2-hydroxypropyl (meth)acrylate amide.

[0046] Examples of the polymerizable monomer that forms the monomer units other than the first, second, and third monomer units include the following polymerizable monomers. Styrene, o-methylstyrene and other styrene and derivatives thereof, (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate. Unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; and unsaturated polyenes such as butadiene and isoprene.

[0047] Aromatic divinyl compounds; diacrylate compounds bonded by alkyl chains; diacrylate compounds bonded by alkyl chains containing ether bonds; diacrylate compounds bonded by chains containing aromatic groups and ether bonds; polyester-type diacrylates; polyfunctional crosslinking agents. Examples of the aromatic divinyl compounds include divinylbenzene and divinylnaphthalene.

[0048] Examples of the diacrylate compounds bonded with alkyl chains include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylate in the above compounds is replaced with methacrylate. As the polymerizable monomer forming the monomer units other than the first, second and third monomer units, styrene is preferred because it is likely to improve the charging stability under high temperature and high humidity conditions.

[0049] The crystalline resin preferably has a second monomer unit, more preferably has at least two monomer units selected from the second monomer units, or has the second monomer unit and a third monomer unit, and even more preferably has the second monomer unit and a third monomer unit. In these cases, the polymerizable monomer forming the second monomer unit is preferably at least one selected from the group consisting of acrylonitrile and methacrylonitrile, and the polymerizable monomer forming the third monomer unit is preferably at least one selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0050] The combined use of a polymerizable monomer other than the polymerizable monomer that forms this first monomer unit is preferred because it makes it easier to form a eutectic with the wax and more likely to achieve the effect of improving gloss unevenness on rough paper. It is believed that the combined use of a polymerizable monomer other than the polymerizable monomer that forms the first monomer unit allows components that are highly compatible with the wax and components that are poorly compatible with the wax to coexist in the crystalline resin, making it easier for them to form nuclei for eutectic formation with the wax.

[0051] Furthermore, when the toner is melted, electric dipole interactions occur between the polar groups in the crystalline vinyl resin, which increases the viscosity and elastic modulus of the toner compared to resins that do not have polar groups. The second monomer unit has a polar functional group directly bonded to the main chain, which contributes greatly to molecular mobility, and therefore has a higher storage modulus after melting the toner than a crystalline vinyl resin that does not have a polar group directly bonded to the main chain.

[0052] On the other hand, the third monomer unit has a polar hydroxy group at a position away from the main chain. Therefore, after the toner is melted, the storage modulus is less likely to become high compared to a resin having a polar group directly bonded to the main chain of the crystalline vinyl resin. When the second monomer unit and the third monomer unit coexist, it may be easier to form a eutectic with the wax.

[0053] The content of the second monomer unit in the crystalline resin is preferably 3.0 to 25.0 mass %, more preferably 5.0 to 20.0 mass %. The content of the third monomer unit in the crystalline resin is preferably 1.0 to 10.0% by mass, and more preferably 3.0 to 7.0% by mass.

[0054] The content of monomer units other than the first, second, and third monomer units (other monomer units) in the crystalline resin is preferably 10.0 to 60.0 mass%, more preferably 15.0 to 25.0 mass%, and the other monomer units are preferably styrene monomer units.

[0055] When the crystalline vinyl resin is a vinyl-based resin, it can be produced using the exemplified polymerizable monomer and polymerization initiator. From the viewpoint of efficiency, the polymerization initiator is preferably used in an amount of 0.05 to 10.00 parts by mass per 100.00 parts by mass of the polymerizable monomer.

[0056] Examples of the polymerization initiator include the following. 2,2'-Azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetonitrile Ketone peroxides such as ethyl acetone peroxide and cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-Trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxy Diisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate.

[0057] From the viewpoint of charging stability, the crystalline resin used as the binder resin preferably has an acid value of 0 mgKOH / g to 100 mgKOH / g, more preferably 10 mgKOH / g to 60 mgKOH / g, and most preferably 15 mgKOH / g to 50 mgKOH / g. It is more preferable, and particularly preferable that it is 20 mgKOH / g to 30 mgKOH / g. Similarly, the hydroxyl value is preferably 0 mgKOH / g to 100 mgKOH / g, more preferably 0 mgKOH / g to 75 mgKOH / g, further preferably 0 mgKOH / g to 20 mgKOH / g, and particularly preferably 0 mgKOH / g.

[0058] The melting point Tc of the crystalline resin is preferably 50 to 90°C, and more preferably 55 to 70°C.

[0059] The content of the crystalline resin is 30.0 to 95.0% by mass, based on the mass of the toner particles. When the content of the crystalline resin is within the above range, excellent low-temperature fixability can be obtained. If the content of the crystalline resin is less than 30.0% by mass, the low-temperature fixability decreases. The content of the crystalline resin is preferably 40.0 to 90.0% by mass, and more preferably 45.0 to 65.0% by mass, based on the mass of the toner particles.

[0060] <Wax> The toner particles contain wax. The wax to be used may be selected to be optimal in combination with the crystalline resin. Examples of wax include the following: Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; waxes whose main component is fatty acid esters such as carnauba wax; partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0061] Further examples include 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 with 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; methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylene saturated fatty acid bisamides such as m-xylenebisstearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; aromatic bisamides such as m-xylenebisstearamide and N,N'-distearyl isophthalamide; fatty metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxy groups obtained by hydrogenating vegetable oils and fats.

[0062] The wax preferably contains a hydrocarbon wax, more preferably a Fischer-Tropsch wax, and has a melting point of preferably 75°C to 120°C, more preferably 84°C to 120°C, and even more preferably 88°C to 110°C. When the wax contains hydrocarbon, it is likely to crystallize in the toner, and the crystallized wax is likely to interact with the crystalline resin having an alkyl group on the side chain. It is believed that this makes it easier to form a eutectic with the crystalline resin, thereby improving the strength of the image.

[0063] The wax content is preferably 2.0 to 30.0% by mass, and more preferably 4.0 to 20.0% by mass, based on the mass of the toner particles.

[0064] Furthermore, when the melting point of the wax is Tw (°C) and the melting point of the crystalline resin is Tc (°C), it is preferable that Tw and Tc satisfy the relationship 20≦Tw−Tc≦50. Preferably, it is 25≦Tw−Tc≦45, and more preferably, it is 25≦Tw−Tc≦35. When Tw−Tc is within the above range, it becomes easier to form a continuous phase by a eutectic of the crystalline resin and wax.

[0065] Here, the melting point Tc of the crystalline resin and the melting point Tw of the wax can be measured using the crystalline resin and wax separated by a method for separating each material from the toner, which will be described later.

[0066] Furthermore, when the crystalline resin contains the monomer unit represented by the above formula (1), the content ratio of the monomer unit represented by formula (1) based on the mass of the toner particles is defined as W(C), and the content ratio of the wax based on the mass of the toner particles is defined as W(W). In this case, it is preferable that W(C) and W(W) satisfy the relationship 1.8≦W(C) / W(W)≦7.0.

[0067] It is preferable that W(C) / W(W) is within the above range because the interaction between the crystalline monomer component of the crystalline resin and the wax is likely to occur, making it easier to keep the viscoelasticity of the toner within the above range. It is more preferable that W(C) / W(W) is 2.0≦W(C) / W(W)≦5.0, and even more preferable that W(C) / W(W) is 2.5≦W(C) / W(W)≦4.5.

[0068] <Amorphous resin> The toner may contain an amorphous resin as a binder resin in addition to the crystalline resin. When an amorphous resin is further contained as the binder resin, known amorphous resins can be used. For example, the following can be mentioned.

[0069] Polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin, vinyl-based resin. Among these, it is preferable to contain at least one resin selected from the group consisting of a hybrid resin in which a vinyl resin and a polyester resin are bonded, a polyester resin, and a vinyl resin.

[0070] More preferably, the amorphous polyester resin is an amorphous polyester resin. That is, the amorphous resin preferably contains an amorphous polyester resin. By using an amorphous polyester resin, it is possible to reduce the interaction with the wax, and the crystallinity of the wax and the amorphous resin that is eutectic with the wax can be improved. This is preferable because it makes it easier to improve the scratch resistance of the image.

[0071] The amorphous polyester resin may be a polyester resin typically used in toners. Monomers used in the polyester resin include polyhydric alcohols (dihydric, trihydric or higher alcohols), polycarboxylic acids (dihydric, trihydric or higher carboxylic acids), acid anhydrides thereof, or lower alkyl esters thereof.

[0072] Examples of the polyhydric alcohol include the following: Examples of dihydric alcohols include the following bisphenol derivatives: 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, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane, etc.

[0073] Other polyhydric alcohols 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, and 1,3,5-trihydroxymethylbenzene. These polyhydric alcohols can be used alone or in combination.

[0074] Examples of the polycarboxylic acid include the following. Examples of dicarboxylic 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-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, n-dodecenylsuccinic acid, and adipic acid are preferably used.

[0075] Examples of trivalent or higher carboxylic acids, acid anhydrides thereof, or lower alkyl esters thereof include the following. 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, acid anhydrides thereof, or lower alkyl esters thereof.

[0076] Among these, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its derivatives such as acid anhydride are preferably used because they are inexpensive and the reaction can be easily controlled. These polycarboxylic acids can be used alone or in combination.

[0077] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the above-mentioned polyhydric alcohol and polycarboxylic acid are simultaneously charged and polymerized through an esterification reaction or transesterification reaction and a condensation reaction to produce the polyester resin. The polymerization temperature is not particularly limited, but is preferably in the range of 180°C to 290°C. For the polymerization of the polyester resin, for example, a polymerization catalyst such as a titanium-based catalyst, a tin-based catalyst, zinc acetate, antimony trioxide, or germanium dioxide can be used. . The polyester resin used for the amorphous resin is preferably one that has been polycondensed using at least one of a titanium-based catalyst and a tin-based catalyst.

[0078] The amorphous polyester resin is preferably a condensation polymer of a polyhydric alcohol and a polycarboxylic acid. The polyhydric alcohol preferably includes at least one selected from the group consisting of bisphenol derivatives. The polycarboxylic acid preferably includes at least one selected from the group consisting of fumaric acid, succinic acid, terephthalic acid, and adipic acid. The polycarboxylic acid preferably includes trimellitic acid or its anhydride.

[0079] Examples of vinyl resins used as amorphous resins include polymers of polymerizable monomers containing ethylenically unsaturated bonds, which refer to carbon-carbon double bonds capable of radical polymerization, such as vinyl, propenyl, acryloyl, and methacryloyl groups.

[0080] Examples of the polymerizable monomer include the following. Styrenic monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene; acrylic acid and acrylic acid esters such as acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; α-methylene aliphatic monocarboxylic acids and their esters, such as methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; Also, acrylonitrile, methacrylonitrile, acrylamide, etc.

[0081] Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and polymerizable monomers having a hydroxy group such as 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene can be used alone or in combination.

[0082] Among these, it is preferable to use a monomer that is a condensate of acrylic acid or methacrylic acid with an alcohol having 6 to 22 carbon atoms, such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, or stearyl methacrylate.

[0083] These monomers easily interact with the long-chain alkyl units having 18 to 30 carbon atoms of the crystalline vinyl resin, and can appropriately increase the viscoelasticity.

[0084] In addition to the above, vinyl resins may contain various polymerizable monomers capable of vinyl polymerization as needed. They may be used in combination. Examples of the polymerizable monomer include the following. Unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenylsuccinic acid, fumaric acid, and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, and benzoic acid. unsaturated dibasic acid anhydrides such as alkenylsuccinic anhydride; half esters of unsaturated basic acids such as methyl maleate half ester, ethyl maleate half ester, butyl maleate half ester, methyl citraconic acid half ester, ethyl citraconic acid half ester, butyl citraconic acid half ester, methyl itaconic acid half ester, methyl alkenylsuccinic acid half ester, methyl fumaric acid half ester, and methyl mesaconic acid half ester; unsaturated basic acid esters such as dimethylmaleic acid and dimethylfumaric acid; acid anhydrides of α,β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; anhydrides of such α,β-unsaturated acids and lower fatty acids; and polymerizable monomers having a carboxy group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof, and monoesters thereof.

[0085] Furthermore, the vinyl resin may be a polymer crosslinked with a crosslinkable polymerizable monomer as exemplified below, if necessary. Examples of the crosslinkable polymerizable monomer include the following. Aromatic divinyl compounds; diacrylate compounds linked by alkyl chains; diacrylate compounds linked by alkyl chains containing ether bonds; diacrylate compounds linked by chains containing aromatic groups and ether bonds; polyester-type diacrylates; polyfunctional crosslinkers. Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.

[0086] Examples of diacrylate compounds linked by alkyl chains include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylate in the above compounds is replaced with methacrylate.

[0087] Vinyl resins include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, acrylic acid, and methyl acrylate. acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, It is preferably a polymer of a polymerizable monomer containing at least one selected from the group consisting of phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene, and 4-(1-hydroxy-1-methylhexyl)styrene.

[0088] The vinyl resin may also be a copolymer of at least one polymerizable monomer selected from the above group and at least one crosslinkable polymerizable monomer selected from the group consisting of divinylbenzene, divinylnaphthalene, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and neopentyl glycol dimethacrylate. The content of the crosslinkable polymer in the monomers is preferably about 0.5% to 5.0% by mass.

[0089] The vinyl resin may be a resin produced using a polymerization initiator. From the viewpoint of efficiency, the polymerization initiator is preferably used in an amount of 0.05 parts by mass or more and 10.00 parts by mass or less per 100.00 parts by mass of the polymerizable monomer. Examples of the polymerization initiator include the following.

[0090] 2,2'-Azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetonitrile Ketone peroxides such as ethyl acetone peroxide and cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-Trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxy Diisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate.

[0091] Used to form hybrid resins that combine vinyl and polyester resins As the vinyl resin and polyester resin, the same vinyl resin and polyester resin as those used as the amorphous resin described above can be used.

[0092] A method for producing a hybrid resin in which a vinyl resin and a polyester resin are bonded together includes, for example, a polymerization method using a compound that can react with both of the monomers that produce both resins (hereinafter referred to as a "bireactive compound").

[0093] The bireactive compounds include compounds such as fumaric acid, acrylic acid, methacrylic acid, citraconic acid, maleic acid, and dimethyl fumarate, among which fumaric acid, acrylic acid, and methacrylic acid are preferably used.

[0094] When a hybrid resin in which a vinyl resin and a polyester resin are bonded is used, the content of the vinyl resin in the hybrid resin is preferably 10% by mass or more, 20% by mass or more, 40% by mass or more, 60% by mass or more, or 80% by mass or more, and is preferably 100% by mass or less, or 90% by mass or less.

[0095] From the viewpoint of charging stability, the amorphous resin used as the binder resin preferably has an acid value of 0 mgKOH / g to 100 mgKOH / g, more preferably 10 mgKOH / g to 60 mgKOH / g, further preferably 15 mgKOH / g to 50 mgKOH / g, and particularly preferably 20 mgKOH / g to 30 mgKOH / g. Similarly, the hydroxyl value is preferably 0 mgKOH / g to 100 mgKOH / g, more preferably 10 mgKOH / g to 75 mgKOH / g, further preferably 15 mgKOH / g to 70 mgKOH / g, and particularly preferably 18 mgKOH / g to 60 mgKOH / g.

[0096] From the viewpoint of low-temperature fixability and heat-resistant storage stability, the amorphous resin used as the binder resin preferably has a glass transition temperature (Tg) measured by differential scanning calorimetry (DSC) of 40 to 70°C, more preferably 45 to 65°C, and even more preferably 50 to 60°C.

[0097] When an amorphous resin is used as the binder resin, from the viewpoint of controlling the values ​​of d(logG'(T1)) / dT and d(logG'(T1+3)) / dT-d(logG'(T1)) / dT, the melting point Tc (°C) of the crystalline resin and the glass transition temperature Tg (°C) of the amorphous resin preferably satisfy the relationship |Tc-Tg|≦20, more preferably |Tc-Tg|≦15, and even more preferably |Tc-Tg|≦10.

[0098] The content of the amorphous resin based on the mass of the toner particles is not particularly limited, but is preferably 0.0 to 50.0 mass%, more preferably 10.0 to 45.0 mass%, and even more preferably 15.0 to 40.0 mass%.

[0099] When an amorphous resin is further contained as a binder resin, it is preferable that a domain matrix structure composed of a matrix containing a crystalline resin and a domain containing an amorphous resin be observed in a cross section of the toner using a transmission electron microscope. By appropriately changing the composition of the crystalline resin and the amorphous resin, the toner particles can have a domain matrix structure. The presence of the amorphous domain is preferred because it tends to improve the crystallinity of the crystalline resin and the eutectic of the crystalline resin and wax, and tends to increase the image strength. Furthermore, when a cross section of the toner is observed using a transmission electron microscope, the number average diameter of the domains is preferably 0.05 to 3.00 μm, and more preferably 0.10 to 1.00 μm.

[0100] <Other resins> The binder resin may contain a resin other than the above-mentioned crystalline resin and amorphous resin to the extent that the effects of the present disclosure are not impaired, for the purpose of improving pigment dispersibility, etc. The content ratio of the above-mentioned crystalline resin and amorphous resin in the binder resin is preferably 80 to 100 mass %, more preferably 90 to 100 mass %. Examples of such resins include the following: Polyvinyl chloride, phenolic resin, natural resin modified phenolic resin, natural resin modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum-based resin.

[0101] <Inorganic filler particles> The toner particles may contain inorganic filler particles as required for adjusting viscoelasticity. Preferred inorganic filler particles include silica, titanium oxide, aluminum oxide, metal titanates such as strontium titanate and calcium titanate, calcium carbonate, kaolin, etc. In particular, calcium carbonate and kaolin are preferred from the viewpoint of interaction with the crystalline resin.

[0102] The inorganic filler particles are preferably treated with a fatty acid, because the surface treatment of the filler particles with a fatty acid allows the filler particles to interact with the alkyl groups of the crystalline resin via the fatty acid, thereby more effectively exerting the filler effect.

[0103] The number average particle diameter of the primary particles of the inorganic filler particles added internally to the toner particles is preferably 0.15 to 0.45 μm, and more preferably 0.20 to 0.40 μm. The number average particle diameter of the primary particles of the inorganic filler particles can be measured using a known means such as a scanning electron microscope.

[0104] The content of the inorganic filler particles based on the mass of the toner particles is preferably 0 to 20 mass %, and more preferably 0 to 7 mass %.

[0105] <Coloring agent> The toner particles may contain a colorant, if necessary. Examples of the colorant include the following. Examples of black colorants include carbon black and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. Although a pigment may be used alone as the colorant, it is preferable to use a dye and a pigment in combination to improve the clarity of the colorant in terms of the image quality of a full-color image.

[0106] Examples of pigments for magenta toner include the following: CI 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; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0107] Examples of dyes for magenta toner include the following: Solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0108] Examples of pigments for cyan toner include the following: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Vat Blue 6; CI Acid Blue 45, copper phthalocyanine pigments with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton. An example of a dye for cyan toner is CI Solvent Blue 70.

[0109] Examples of pigments for yellow toner include the following: CI 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; CI Bat Yellow 1, 3, 20. An example of a yellow toner dye is CI Solvent Yellow 162.

[0110] These colorants can be used alone or in combination, or in the form of a solid solution. The colorant is selected in consideration of hue angle, chroma, brightness, lightfastness, transparency on an overhead projector, and dispersibility in toner. The content of the colorant is preferably 0.1 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0111] <Charge control agent> The toner particles may contain a charge control agent as needed. Known charge control agents can be used, but particularly preferred are metal compounds of aromatic carboxylic acids, which are colorless, have a high charging speed, and can stably maintain a constant charge amount.

[0112] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0113] 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 to 10.0 parts by mass, more preferably 0.5 to 10.0 parts by mass, per 100 parts by mass of the binder resin.

[0114] <External additives> The toner may contain an external additive. For example, the toner may be prepared by externally adding an external additive to toner particles. As the external additive, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and metal titanate are preferred. The inorganic fine particles used as the external additive are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0115] As an external additive to improve fluidity, a BET specific surface area of ​​50m 2 / g~400m 2 / g of inorganic fine particles are preferred, and for stabilizing durability, a BET specific surface area of ​​10 m 2 / g~50m 2 / g of inorganic fine particles. In order to simultaneously improve fluidity and stabilize durability, inorganic fine particles having a BET specific surface area in the above range may be used in combination. The toner particles and the external additive may be mixed using a known mixer such as a Henschel mixer. The content of the external additive is preferably 0.1 to 10.0 parts by mass, and more preferably 2.0 to 7.0 parts by mass, relative to 100 parts by mass of the toner particles.

[0116] <Developer> The toner can be used as a one-component developer, but it is preferable to mix it with a magnetic carrier and use it as a two-component developer, since this allows stable images to be obtained over a long period of time. That is, it is more preferable that the toner is a two-component developer containing a toner and a magnetic carrier, and the toner is the toner described above. Examples of magnetic carriers include generally known ones such as iron powder or surface-oxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, or oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing the magnetic material and a binder resin that holds the magnetic material in a dispersed state.

[0117] When the toner is mixed with a magnetic carrier and used as a two-component developer, the toner content in the two-component developer is preferably 2.0% by mass or more and 15.0% by mass or less, and more preferably 4.0% by mass or more and 13.0% by mass or less.

[0118] <Toner manufacturing method> The method for producing the toner is not particularly limited, and any of the conventionally known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension methods can be used. A preferred method for producing a toner is a method for producing a toner, which includes a melt-kneading step of melt-kneading a toner composition containing a binder resin containing a crystalline resin and an amorphous resin and a wax to obtain a melt-kneaded product, and a pulverizing step of cooling and solidifying the melt-kneaded product and pulverizing the cooled and solidified product to obtain a pulverized product. That is, the toner particles are preferably melt-kneaded and pulverized toner particles. By using the above-mentioned production method, a mixture in which the ratio of crystalline resin to amorphous resin is controlled is melt-kneaded, making it easy to obtain a matrix domain structure composed of a matrix containing a crystalline resin and domains containing an amorphous resin.

[0119] The toner manufacturing method is A melt-kneading step of melt-kneading a mixture containing a crystalline resin and a wax; and It is preferable to have an annealing step in which the melt-kneaded product obtained in the melt-kneading step is maintained at a temperature equal to or higher than the melting point of the crystalline resin +5°C.

[0120] The procedure for producing toner using the melt-kneading pulverization method will be described below. <Raw material mixing process> In the raw material mixing process, materials constituting the toner particles, such as a binder resin containing a crystalline resin and an amorphous resin, wax, and optionally other components such as a colorant and a charge control agent, are weighed out in predetermined amounts, blended, and mixed. Examples of mixing devices include a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0121] <Melting and kneading process> Next, the mixed materials are melt-kneaded to form a binder resin containing a crystalline resin and an amorphous resin. Wax or the like is dispersed in the mixture. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used, but single-screw or twin-screw extruders are the mainstream due to their advantage of allowing continuous production. Examples include a KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), a TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), a PCM kneader (manufactured by Ikegai Iron Works), a twin-screw extruder (manufactured by KCK Corporation), a Co-Kneader (manufactured by Buss Co., Ltd.), and Kneedex (manufactured by Nippon Coke and Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled using a twin roll or the like and cooled with water or the like in a cooling process.

[0122] In the melt-kneading step, it is preferable to use a twin-screw extruder for melt-kneading. The dispersion state of the crystalline resin and the amorphous resin, the number-average diameter of the domains, etc. can be controlled by the kneading temperature, the screw rotation speed, etc. in the melt-kneading step. The kneading temperature is preferably 110 to 140° C., more preferably 115 to 130° C. The screw rotation speed during kneading is not particularly limited and may be changed appropriately depending on the device, but is preferably 200 to 300 rpm, for example.

[0123] <Cooling process> The cooling step is not particularly limited by the means. Examples include a method in which the kneaded resin composition is rolled with two rollers or a drum and then cooled with a steel belt cooler (manufactured by Nippon Steel Conveyor Co., Ltd.), or a method in which the kneaded resin composition is rolled while being cooled with a press roller and a drum equipped with an internal cooling mechanism, such as a belt drum flaker (manufactured by Nippon Coke Co., Ltd.). In the cooling step, it is preferable to roll the kneaded resin composition while being cooled with a belt drum flaker.

[0124] <Crushing process> The cooled resin composition is then pulverized to a desired particle size in a pulverization process, which involves coarse pulverization using a pulverizer such as a crusher, hammer mill, or feather mill, followed by further pulverization using a pulverizer such as a Kryptron System (Kawasaki Heavy Industries), a Super Rotor (Nisshin Engineering), a Turbo Mill (Turbo Kogyo), or an air jet pulverizer.

[0125] <Classification process> Thereafter, if necessary, the mixture may be classified using a classifier or sieve such as an inertial classification type Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), a centrifugal classification type Turboplex (manufactured by Hosokawa Micron Corporation), a TSP Separator (manufactured by Hosokawa Micron Corporation), or a Faculty (manufactured by Hosokawa Micron Corporation) to obtain toner particles.

[0126] <External addition process> The obtained toner particles may be used as they are as toner. Alternatively, toner may be obtained by externally adding an external additive to the surface of the toner particles. Examples of a method for externally adding an external additive include a method in which the classified toner and various known external additives are blended in predetermined amounts, and stirred and mixed using a mixer such as a double con mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation) as an external additive machine.

[0127] <Annealing process> In the production of toner, it is preferable to anneal the melt-kneaded product obtained after the melt-kneading step by holding it at a temperature of at least 5°C above the melting point of the crystalline resin for at least 10 minutes. Annealing may be performed after the melt-kneading and cooling steps, but is preferably performed before the cooling step. Annealing at a temperature of at least 5°C above the melting point of the crystalline resin promotes eutectic formation between the crystalline resin and the wax to form a continuous phase, while the crystalline resin that has not formed a eutectic crystallizes as a discontinuous phase, making it easier to achieve the effect of increasing image strength.

[0128] Specifically, the melt-kneaded product obtained after the melt-kneading step is preferably maintained at a temperature equal to or higher than the melting point of the crystalline resin +5°C. Furthermore, maintaining the product at a temperature equal to or lower than the melting point of the wax -5°C is preferred from the viewpoints of improving image strength and material dispersibility. The maintenance time is, for example, 10 minutes or more, preferably 20 to 120 minutes, and more preferably 30 to 60 minutes. Furthermore, annealing after melt-kneading and before the pulverization step is more preferred from the viewpoint of production stability, as this makes it less likely for toner particles to coalesce.

[0129] Furthermore, when the melting point of the wax is Tw (°C) and the annealing temperature is Ta (°C), it is preferable that the relationship between Tw and Ta satisfies 2≦Tw−Ta≦20, since this makes it easier to adjust the viscoelasticity of the toner. It is even more preferable that the relationship satisfies 5≦Tw−Ta≦20. The average circularity of the toner is preferably 0.920 to 0.995, and more preferably 0.960 to 0.990.

[0130] The methods for measuring various physical properties of the toner and raw materials are described below. <Measurement of storage modulus G' of toner> The measuring device was a rotating plate type rheometer "ARES" (TA INSTRUMENT The measurement sample is prepared by press-molding (at 20 MPa for 30 seconds) the toner into a disk shape with a diameter of 8 mm and a thickness of 2.0±0.3 mm using a tablet press at 25°C. The sample is mounted on a parallel plate and heated from room temperature (25°C) to 60°C over 15 minutes to adjust the sample shape. After that, the sample is cooled to the viscoelasticity measurement starting temperature, and the measurement is started to measure the complex viscosity. At this time, the measurement sample is set so that the initial normal force is 0. Furthermore, as described below, the influence of the normal force can be canceled in subsequent measurements by turning on the auto tension adjustment (Auto Tension Adjustment).

[0131] The measurement is carried out under the following conditions: (1) Use parallel plates with a diameter of 8 mm. (2) The frequency is set to 6.28 rad / sec (1.0 Hz). (3) The initial applied strain is set to 1.0%. (4) Measurement is carried out between 40°C and 150°C at a temperature ramp rate of 2.0°C / min. (5) The measurement interval (Steptime) is 15 seconds. The measurement is performed under the following automatic adjustment mode setting conditions: Measurement is performed in automatic strain adjustment mode (Auto Strain). (6) Set the maximum applied strain to 40.0%. (7) Set the maximum torque (Max Allowed Torque) to 150.0 g·cm and the minimum torque (Min Allowed Torque) to 0.2 g·cm. (8) Set the strain adjustment to 20.0% of the current strain. The measurement is performed in the auto tension adjustment mode. (9) Set Auto Tension Direction to Compression. (10) Set the initial static force to 10.0 g and the auto tension sensitivity to 40.0 g. (11) The operating condition of the auto tension is a sample modulus of 1.0 × 10 3 Pa or more.

[0132] The measurement results of the storage modulus G' obtained in the above measurement are plotted against temperature, with the horizontal axis representing temperature and the vertical axis representing the common logarithm of the storage modulus G' (LogG'). After plotting, the points are smoothly connected to obtain a temperature-storage modulus curve. Next, the slope of the obtained temperature-storage modulus curve is found, and a differential curve obtained by differentiating the common logarithm LogG' with respect to temperature is graphed. This makes it possible to obtain a graph with the horizontal axis representing temperature T and the vertical axis representing the value d(logG'(T)) / dT obtained by differentiating LogG'(T) with respect to temperature T, where G'(T) is the storage modulus of the toner at temperature T (°C). Based on the differential curve of this graph, the minimum value within the range of 50.0 to 70.0°C is confirmed, and the temperature at which this minimum value is reached is designated as temperature T1 (°C).The values ​​of d(logG'(T1)) / dT, d(logG'(T1+3)) / dT, and d(logG'(T1+3)) / dT-d(logG'(T1)) / dT are then obtained. Also, obtain the values ​​of G'(T1) and G'(T1+30). If there are multiple minimum values ​​within the range of 50°C to 70°C, the smallest and lowest value is taken as the minimum value, and this temperature is selected as T1.

[0133] If it is difficult to smoothly connect the temperature vs. storage modulus plots, the measured values ​​may be smoothed to make it easier to connect them. The smoothing method is the simple moving average method using plots of three points before and after.

[0134] <Cross-section observation of toner and measurement of domain matrix structure> First, a thin section is prepared as a reference sample for the abundance. After thoroughly dispersing the crystalline resin in a visible light-curable resin (Aronix LCR Series D800), it is cured by irradiating it with short-wavelength light. The resulting cured product is cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin flake samples. Thin flake samples of the amorphous resin are also prepared in the same manner.

[0135] Crystalline resin and amorphous resin were also mixed at 30 / 70 and 70 / 30 mass ratios, and melt-kneaded to prepare kneaded materials. These were also similarly dispersed in visible light-curable resin, cured, and then cut out to prepare thin flake samples. Next, the cross sections of the cut samples are observed using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX), and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen. The mapping conditions are as follows: Accelerating voltage: 200 kV Electron beam irradiation size: 1.5 nm Live time limit: 600 seconds Dead time: 20~30 Mapping resolution: 256 x 256

[0136] Based on the spectral intensity of each element (average over a 10 nm square area), calculate (oxygen element intensity / carbon element intensity) and (nitrogen element intensity / carbon element intensity), and create a calibration curve for the mass ratio of crystalline resin to amorphous resin. If the crystalline resin monomer unit contains nitrogen atoms, use the calibration curve of (nitrogen element intensity / carbon element intensity) for future quantification.

[0137] The toner samples are then analyzed. After thoroughly dispersing the toner in a visible light curable resin (Aronix LCR Series D800), the resin is cured by irradiating it with short wavelength light. The cured product is then cut into 250 nm thin slice samples using an ultramicrotome equipped with a diamond knife. Next, the cut sample is observed using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX). Element mapping is performed using X. The elements to be mapped are carbon, oxygen, and nitrogen.

[0138] The toner cross section to be observed is selected as follows: First, the cross-sectional area of ​​the toner is calculated from the toner cross-sectional image, and then the diameter of a circle having the same area as that cross-sectional area (equivalent circle diameter) is calculated. Only toner cross-sectional images where the absolute value of the difference between this equivalent circle diameter and the toner weight-average particle diameter (D4) is within 1.0 μm are observed.

[0139] For the observed image, the cross section of the toner particle is divided into 10 nm square areas. For each area, the (oxygen element intensity / carbon element intensity) and / or (nitrogen element intensity / carbon element intensity) ratio is calculated based on the spectral intensity of each element (average of 10 nm squares), and the crystalline resin and amorphous resin are distinguished by comparing with the calibration curve. If the crystalline resin or amorphous resin is contained in an amount of 80 mass% or more, the 10 nm square area is considered to be occupied by that crystalline resin or amorphous resin.

[0140] Here, when an area group occupied by an amorphous resin exists isolated and surrounded by an area group of a crystalline resin, the area occupied by the amorphous resin is identified as a domain containing the amorphous resin. Furthermore, when an area group of a crystalline resin exists as a continuous phase, the continuous phase is identified as a matrix containing the crystalline resin. By confirming whether or not such a matrix and domains are present, the toner particles are identified as having a domain matrix structure composed of a matrix containing a crystalline resin and a domain containing an amorphous resin.

[0141] The areas of the matrix and domain identified as described above are calculated, and the proportion of the domain in the combined area of ​​the matrix and domain can be calculated.

[0142] After that, binarization processing is performed and the domain particle diameters present in the toner cross-sectional image are measured. The particle diameter is the major axis of the domain. For 10 toner cross-sections, the domain particle diameters are measured at 10 points per toner cross-section, and the arithmetic mean value of the total 100 domain particle diameters is taken as the number-average diameter (μm) of the domains. The crystalline resin and amorphous resin samples may be those separated from the toner by the method described below.

[0143] <Method for separating each material from toner> The materials contained in the toner can be separated from the toner by utilizing the difference in solubility in the solvent of each material. First separation: The toner is dissolved in methyl ethyl ketone (MEK) at 23°C, and the soluble matter (amorphous resin) is separated from the insoluble matter (crystalline resin, wax, colorant, inorganic filler particles, etc.). Second separation: The insoluble matter obtained in the first separation (crystalline resin, wax, colorant, inorganic filler particles, etc.) is dissolved in MEK at 100°C, and the soluble matter (crystalline resin, wax) is separated from the insoluble matter (colorant, inorganic filler particles, etc.). Third separation: The soluble matter (crystalline resin, wax) obtained in the second separation is dissolved in chloroform at 23°C, and the soluble matter (crystalline resin) is separated from the insoluble matter (wax).

[0144] (Measurement of the content of crystalline resin and amorphous resin in the binder resin, and inorganic filler particles in the toner) In each separation step, the masses of the soluble and insoluble components are measured to calculate the contents of the crystalline resin and amorphous resin in the binder resin in the toner. The amount of inorganic filler particles in the toner is calculated by fluorescent X-ray measurement. The fluorescent X-ray measurement of each element conforms to JIS K0119-1969. Specifically, is.

[0145] The measurement equipment used was a wavelength dispersive X-ray fluorescence analyzer (product name: Axios, manufactured by PANalytical) and the accompanying dedicated software (product name: SuperQ ver. 4.0F, manufactured by PANalytical) for setting measurement conditions and analyzing measurement data. Rh was used as the anode of the X-ray tube, the measurement atmosphere was vacuum, the measurement diameter (collimator mask diameter) was 27 mm, and the measurement time was 10 seconds. When measuring light elements with this equipment, detection was performed using a proportional counter (PC), and when measuring heavy elements, detection was performed using a scintillation counter (SC). The measurement sample was prepared by placing 4 g of toner in a special aluminum ring press and flattening it. Then, using a tablet press (product name: BRE-32, manufactured by Mayekawa Testing Machinery Manufacturing Co., Ltd.), the toner was pressed at 20 MPa for 60 seconds to form a pellet with a thickness of 2 mm and a diameter of 39 mm. Measurements were performed under the above conditions, and elements were identified based on the peak positions of the obtained X-rays. The concentration of the element was calculated from the count rate (unit: cps), which is the number of X-ray photons per unit time.

[0146] For example, when the inorganic filler particles are calcium carbonate fine particles, the calcium carbonate fine particles are mixed with the toner particles in amounts of 0.1 parts by mass, 1.0 parts by mass, and 2.5 parts by mass per 100 parts by mass of toner particles, respectively, and these are used as samples for the calibration curve. For each sample, pellets for the calibration curve sample are prepared using the above-mentioned tablet molding compression machine as described above, and the count rate (unit: cps) of Si-Kα rays observed at a diffraction angle (2θ) = 109.08° when PET is used as the analyzing crystal is measured. The acceleration voltage and current of the X-ray generator are set to 24 kV and 100 mA, respectively. A linear calibration curve is obtained by plotting the count rate of the obtained X-rays on the vertical axis and the amount of calcium carbonate fine particles in the calibration curve sample on the horizontal axis. Next, the toner to be analyzed is pelletized as described above using the tablet compression machine, and the count rate of the Ca-Kα rays is measured. The content of calcium carbonate fine particles in the toner particles is then calculated from the calibration curve.

[0147] <Method for identifying monomer units constituting crystalline resin and amorphous resin and measuring the content ratio of the monomer units> The monomer units constituting the crystalline resin and the amorphous resin are identified and the content ratio of the monomer units is measured by the following method: 1 H-NMR was performed under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Accumulation count: 64 times Measurement temperature: 30℃ Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, deuterated chloroform (CDCl3) is added as a solvent, and the sample is dissolved in a thermostatic bath at 40°C.

[0148] obtained 1 From the H-NMR chart, a peak that is independent of the peaks attributable to the components of the first monomer unit is selected from the peaks attributable to the components of the other monomer units, and the integral value S1 of this peak is calculated. Similarly, a peak that is independent of the peaks attributable to the components of the second monomer unit is selected from the peaks attributable to the components of the other monomer units, and the integral value S2 of this peak is calculated.

[0149] If the resin further has a third monomer unit, a peak that is independent of the peaks that are assigned to the components of the other monomer units is selected from the peaks that are assigned to the components of the third monomer unit, and the integral value S3 of this peak is calculated. Similarly, when the resin further contains another monomer unit, such as a monomer unit X, the integral value S x Calculate. The content of the first monomer unit is determined by the integrals S1, S2, S3 and S x It is calculated as follows using n1, n2, n3, n x is the number of hydrogen atoms in the constituent element to which the peak of interest for each site is assigned. Content of first monomer unit (mol%)= {(S1 / n1) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(S x / n x ))}×100 Similarly, the content ratios of the second monomer unit and the third monomer unit are determined as follows. Content of second monomer unit (mol%)= {(S2 / n2) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(Sx / n x ))}×100 Content of third monomer unit (mol%)= {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(S x / n x ))}×100

[0150] In addition, in the crystalline resin and the amorphous resin, for example, when a polymerizable monomer that does not contain a hydrogen atom in the constituent elements other than the vinyl group is used, 13 Measured nuclei using C-NMR 13 C, and measurements were taken in single pulse mode. 1 Calculation is performed in the same manner as for H-NMR. Based on the molecular weight of the monomer unit, it can be converted from mol% to mass%.

[0151] <Measuring methods for melting points of toners, resins, etc., as well as endothermic peaks and endothermic amounts> The melting points of the toner and resin, as well as the endothermic peak and endothermic amount, are measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃

[0152] The melting points of indium and zinc are used to correct the temperature of the device's detector, and the heat of fusion of indium is used to correct the heat quantity. Specifically, 5 mg of sample is precisely weighed and placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference. The peak temperature of the maximum endothermic peak during the first heating process is taken as the melting point. Note that the maximum endothermic peak is the peak with the largest endothermic amount when there are multiple peaks. The endothermic amount of this maximum endothermic peak is then calculated. The assignment of each peak can be determined by performing DSC measurements on each material separated from the toner as described above. Based on measurements using toner as a sample and measurements using wax separated from the toner as a sample, ΔH(T) and ΔH(W) can be calculated. Additionally, the melting point Tc of the crystalline resin and the melting point Tw of the wax can be obtained.

[0153] <Method for measuring the glass transition temperature of toner, resin, etc.> The melting points of the toner and resin, as well as the endothermic peak and endothermic amount, were measured by DSC. Measurements are taken using a Q1000 (manufactured by TA Instruments) under the following conditions: Measurements are taken in the range of 20 to 180°C, with a heating rate of 10°C / min. During the measurement, the resin is first heated to 200°C and held there for 10 minutes, then cooled to 20°C, and then heated again. During this second heating process, the specific heat change is obtained in the temperature range of 20 to 100°C. The point at which the line midpoint between the baselines before and after the specific heat change appears and the differential thermal curve intersects is taken as the glass transition temperature (Tg) of the toner, resin, etc.

[0154] <Method for measuring the softening point (Tm) of a resin> The softening point of a resin is measured using a constant-load extrusion capillary rheometer, the "Flow Tester CFT-500D Flow Property Evaluation Device" (Shimadzu Corporation), according to the manual that comes with the device. With this device, a constant load is applied from above the sample by a piston, while the sample filled in a cylinder is heated and melted, and the molten sample is extruded from a die at the bottom of the cylinder, allowing a flow curve to be obtained that shows the relationship between the piston's descent amount and temperature. The softening point is the "melting temperature in the 1 / 2 method" described in the manual attached to the "Flow Tester CFT-500D, a flow property evaluation device." The melting temperature in the 1 / 2 method is calculated as follows.

[0155] First, calculate half the difference between the amount of piston descent when the outflow ends (end of outflow, Smax) and the amount of piston descent when the outflow starts (lowest point, Smin) (this is called X; X = (Smax - Smin) / 2). Then, the temperature on the flow curve when the amount of piston descent is the sum of X and Smin is the melting temperature in the 1 / 2 method. The measurement sample is prepared by compressing 1.0 g of resin at approximately 10 MPa for approximately 60 seconds using a tablet compression machine (e.g., NT-100H, manufactured by NPA Systems Co., Ltd.) at 25°C to form a cylindrical shape with a diameter of approximately 8 mm. The specific procedures for measurement are carried out according to the manual that comes with the device. The measurement conditions for the CFT-500D are as follows: Test mode: Temperature rising method Starting temperature: 50℃ Achieved temperature: 200℃ Measurement interval: 1.0℃ Heating rate: 4.0℃ / min Piston cross-sectional area: 1.000cm 2 Test load (piston load): 10.0 kgf (0.9807 MPa) Preheat time: 300 seconds Die hole diameter: 1.0mm Die length: 1.0mm

[0156] <Method for measuring weight average particle size (D4) of toner (particles)> The weight average particle size (D4) of the toner (particles) is measured with an effective number of 25,000 measurement channels using a precision particle size distribution measuring device, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), which is equipped with a 100 μm aperture tube and uses the narrow hole electrical resistance method, and the accompanying dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.), for setting measurement conditions and analyzing measurement data. The weight average particle size (D4) of the toner (particles) is measured with an effective number of measurement channels of 25,000, and the measurement data is analyzed and calculated. The electrolyte solution used for the measurement is prepared by dissolving special-grade sodium chloride in ion-exchange water to a concentration of approximately 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter). Before performing the measurement and analysis, the dedicated software must be set up as follows:

[0157] In the dedicated software's "Change Standard Measurement Method (SOM) screen," set the total count number in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, gain to 2, electrolyte to ISOTON II, and check the box to flush the aperture tube after measurement. In the dedicated software's "Pulse to particle size conversion setting screen," set the bin interval to logarithmic particle size, particle size bin to 256 particle size bins, and particle size range. The specific measurement method is as follows.

[0158] (1) Pour approximately 200 mL of electrolyte solution into a 250 mL round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture Tube Flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 mL of the electrolyte solution is placed in a 100 mL flat-bottom glass beaker, and approximately 0.3 mL of a diluted solution prepared by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A specified amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 mL of Contaminon N is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While ultrasonic waves are irradiating the electrolyte solution in the beaker from (4), approximately 10 mg of toner (particles) is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion process, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, add the electrolytic solution (5) containing dispersed toner particles to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to approximately 5%. Then, measure the number of particles measured until it reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) is calculated. Note that when the dedicated software is set to Graph / Volume %, the "Average diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen is the weight-average particle size (D4).

[0159] <Method for measuring the acid value of resin> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid values ​​of crystalline resins and amorphous resins are measured in accordance with JIS K 0070-1992, specifically by the following procedure. (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume) and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution. Dissolve 7 g of special-grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place the solution in an alkali-resistant container to avoid contact with carbon dioxide and leave for 3 days, then filter to obtain a potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution to determine the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0160] (2) Operation (A) Main test A 2.0 g sample of crushed crystalline or amorphous resin is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a 2:1 toluene / ethanol mixture is added and allowed to dissolve for 5 hours. Next, a few drops of the phenolphthalein solution are added as an indicator, and the solution is titrated with the potassium hydroxide solution. The titration endpoint is when the indicator retains a light red color for approximately 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no sample is used (i.e., only the toluene / ethanol (2:1) mixed solution is used).

[0161] (3) The obtained results are substituted into the following formula to calculate the acid value. A=[(CB)×f×5.61] / S where A is the acid value (mgKOH / g), B is the amount of potassium hydroxide solution added for the blank test (mL), C is the amount of potassium hydroxide solution added for the main test (mL), f is the factor of the potassium hydroxide solution, and S is the mass of the sample (g).

[0162] <Method for measuring the hydroxyl value of resin> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl groups when acetylating 1 g of a sample. The hydroxyl value is measured in accordance with JIS K 0070-1992, specifically, by the following procedure. (1) Preparation of reagents Place 25 g of special-grade acetic anhydride in a 100 mL volumetric flask, add pyridine to make the total volume 100 mL, and shake thoroughly to obtain the acetylation reagent. Store the obtained acetylation reagent in an amber bottle to avoid contact with moisture, carbon dioxide, etc. Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), and add ion-exchanged water to make 100 mL to obtain a phenolphthalein solution. Dissolve 35 g of special-grade potassium hydroxide in 20 mL of water and add ethyl alcohol (95% by volume) to make 1 L. Place in an alkali-resistant container to avoid contact with carbon dioxide and leave for 3 days, then filter to obtain potassium hydroxide solution. Store the resulting potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by placing 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, adding several drops of the phenolphthalein solution, and titrating with the potassium hydroxide solution to determine the amount of potassium hydroxide solution required for neutralization. The 0.5 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0163] (2) Operation (A) Main test Accurately weigh 1.0 g of crushed crystalline or amorphous resin sample into a 200 mL round-bottom flask, and accurately add 5.0 mL of the acetylation reagent using a volumetric pipette. If 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 neck of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at about 97°C. To prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is recommended to cover the base of the neck of the flask with a piece of cardboard with a round hole. After 1 hour, remove the flask from the glycerin bath and allow it to cool. After allowing it to cool, add 1 mL of water through the funnel and shake to hydrolyze the acetic anhydride. To further complete the hydrolysis, heat the flask again in the glycerin bath for 10 minutes. After allowing it to cool, wash the funnel and the walls of the flask with 5 mL of ethyl alcohol. Add a few drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The endpoint of the titration is when the light red color of the indicator lasts for about 30 seconds. (B) Blank test The titration is carried out in the same manner as above, except that no crystalline or amorphous resin sample is used.

[0164] (3) The obtained results are substituted into the following formula to calculate the hydroxyl value. A = [{(BC) × 28.05 × f} / S] + D where A is the hydroxyl value (mgKOH / g), B is the amount (mL) of potassium hydroxide solution added for the blank test, C is the amount (mL) of potassium hydroxide solution added for the main test, f is the factor of the potassium hydroxide solution, S is the mass (g) of the sample, and D is the acid value (mgKOH / g) of the sample.

[0165] <Measurement of average circularity> The average circularity of the toner is measured using a flow particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions used during the calibration process. The specific measurement method is as follows. First, about 20 mL of ion-exchanged water, from which impurities such as solids have been removed, is placed in a glass container. About 0.2 mL of a solution prepared by diluting Contaminon N (a 10% aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) approximately three times by mass with ion-exchanged water is added as a dispersant.

[0166] Approximately 0.02 g of the sample to be measured was then added and dispersed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. The dispersion was then cooled appropriately so that its temperature was between 10°C and 40°C. A tabletop ultrasonic cleaner disperser (VS-150, manufactured by Vervoclear) with an oscillation frequency of 50 kHz and an electrical output of 150 W was used as the ultrasonic disperser. A predetermined amount of ion-exchanged water was placed in the water tank, and approximately 2 mL of Contaminon N was added to the water tank.

[0167] For the measurement, the flow type particle image analyzer equipped with a standard objective lens (10x) was used, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the above procedure was introduced into the flow type particle image analyzer, and 3,000 toner particles were counted in HPF measurement mode and total count mode. The binarization threshold for particle analysis is set to 85%, the particle diameters to be analyzed are limited to equivalent circle diameters of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner is calculated.

[0168] Before starting the measurement, automatic focus adjustment is performed using standard latex particles (Duke Scientific's "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" diluted with ion-exchanged water). After that, it is preferable to perform focus adjustment every two hours from the start of the measurement.

[0169] In the examples, a flow particle image analyzer was used that had been calibrated by Sysmex Corporation and had a calibration certificate issued by Sysmex Corporation. Measurements were carried out under the same measurement and analysis conditions as when the calibration certificate was received, except that the particle diameters to be analyzed were limited to equivalent circle diameters of 1.985 μm or more and less than 39.69 μm.

[0170] <Method for separating toner particles from toner> The external additives can be separated to obtain toner particles by the following method: Using the obtained toner particles, each material can be separated by the above-mentioned method, and the content can be measured. Add 160 g of sucrose (manufactured by Kinoshita Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve it while stirring with hot water to prepare a thick sucrose solution. Put 31 g of the above thick sucrose solution and 6 mL of Contaminon N (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7, composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1.0 g of toner to this dispersion and loosen the toner lumps with a spatula or the like. Shake the centrifuge tube with a shaker (sold by AS ONE Corporation) at 350 spm (strokes per min) for 20 min. After shaking, transfer the solution to a glass tube (50 mL) for a swinging rotor and centrifuge it (H-9R manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 min. By this operation, the toner particles and the externally added agents that have come off are separated. Visually confirm that the toner particles and the aqueous solution are sufficiently separated, and collect the separated toner particles in the uppermost layer with a spatula or the like. After filtering the collected toner with a vacuum filter, dry it with a dryer for 1 hour or more to obtain toner particles. Repeat this operation a plurality of times to ensure the required amount.

[0171] <Calculation method of SP value> The SP values of the crystalline resin and the wax are determined as follows according to the calculation method proposed by Fedors. For each resin or wax, 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 used.

Example

[0172] The basic configuration and features of the present disclosure have been described above. The present disclosure will now be described in detail based on examples. However, the present disclosure is not limited to these examples. Unless otherwise specified, parts and percentages are by mass.

[0173] <Production Example of Crystalline Resin 1> Solvent: toluene 100.0 parts Monomer composition 100.0 parts (The monomer composition is a mixture of behenyl acrylate, styrene, acrylonitrile, and 2-hydroxyethyl acrylate in the ratios shown below.) (Behenyl acrylate 60.0 parts) (styrene 20.0 parts) (Acrylonitrile 15.0 parts) (2-hydroxyethyl acrylate 5.0 parts) Polymerization initiator 0.5 parts [t-Butyl peroxypivalate (NOF Corporation: Perbutyl PV)] The above materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70°C while stirring at 200 rpm, and a polymerization reaction was carried out for 12 hours, yielding a solution in which a polymer of the monomer composition was dissolved in toluene. Subsequently, the temperature of the solution was lowered to 25°C, and the solution was then poured into 1000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The resulting methanol-insoluble matter was filtered, washed with methanol, and vacuum-dried at 40°C for 24 hours to obtain crystalline resin 1. The melting point (Tc) of the obtained crystalline resin 1 was 61°C.

[0174] <Production Examples of Crystalline Resins 2 to 5> Crystalline resins 2 to 5 were obtained by carrying out the reaction in the same manner as in the production example of crystalline resin 1, except that the monomers and the parts by mass thereof were changed as shown in Table 1.

[0175] <Production Example of Crystalline Resin 6> The above materials were weighed and placed in a reaction vessel equipped with 1,6-hexanediol (50 mol%; 11.82 parts by mass), adipic acid (50 mol%; 14.61 parts by mass), a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised with stirring. The mixture was allowed to react at 140°C for 3 hours with stirring. Tin 2-ethylhexanoate was added in an amount of 0.5% by mass relative to the total mass of the monomers, and then the above materials were added. The pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200°C. After that, the pressure in the reaction vessel was gradually released and returned to normal pressure, and crystalline resin 6 was obtained.

[0176] <Production Example of Crystalline Resin 7> In the production example of crystalline resin 6, hexanediol was changed to 1,12-dodecanediol, adipic acid was changed to sebacic acid, and the mass parts were changed so that the mol% of each was 50 mol%, but the reaction was carried out in the same manner to obtain crystalline resin 7.

[0177] [Table 1] The unit of SP value is (J / cm 3 ) 0.5 is.

[0178] The abbreviations in Table 1 are as follows: Note that with regard to parts by mass in Table 1, 1,6-hexanediol, 1,12-dodecanediol, adipic acid, and sebacic acid are in mol%. BEA: Behenyl acrylate St: styrene ACN: Acrylonitrile HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate MA: methacrylic acid

[0179] <Production example of amorphous resin 1> The following materials were placed in a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 72.9 parts (50.0 mol parts) Terephthalic acid: 15.0 parts (25.0 mol parts) Adipic acid: 7.9 parts (15.0 mol parts) Fumaric acid: 4.2 parts (10.0 mol parts) Titanium tetrabutoxide: 2.0 parts Next, the atmosphere in the flask was replaced with nitrogen gas, and the temperature was gradually raised with stirring, and the mixture was stirred at 200°C and reacted for 2 hours while distilling off the generated water. The pressure in the reaction vessel was then reduced to 8.3 kPa and maintained at this temperature for 1 hour, after which the vessel was cooled to 180°C and returned to atmospheric pressure (first reaction step). Trimellitic anhydride: 8.2 parts (2.5 mol parts) tert-butylcatechol (polymerization inhibitor): 0.1 parts Then, the above materials were added, the pressure in the reactor was reduced to 8.3 kPa, and the temperature was maintained at 150°C. The mixture was allowed to react for 4 hours while kept at this temperature, and the reaction was stopped by lowering the temperature (second reaction step), to obtain amorphous resin 1. The glass transition temperature Tg of the amorphous resin was 56°C.

[0180] [Table 2] The abbreviations in Table 2 are as follows: BPA-EO: Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane TPA: Terephthalic acid FA: Fumaric acid AA: Adipic acid

[0181] <Wax> The following waxes were used: [Table 3]

[0182] <Production Example of Toner Particle 1> ·Crystalline resin 1: 50 parts Amorphous resin 1: 30 parts Wax 1: 10 parts Colorant 1: 5 parts (Cyan pigment manufactured by Dainichi Seika Chemicals: Pigment Blue 15:3) Inorganic filler: 5 parts (Calcium carbonate, number average particle size 0.3 μm, fatty acid (stearic acid) treated) The above materials were mixed using a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 25 s for 5 min, and then kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 120°C at a screw rotation speed of 250 rpm and a discharge temperature of 130°C. The resulting molten and kneaded material was placed in a stainless steel tray and annealed by holding it at 75°C for 45 minutes. The resulting resin composition was cooled to room temperature and coarsely crushed to 1 mm or less using a hammer mill to obtain a coarsely crushed material. The coarsely crushed material was then finely crushed using a mechanical crusher (T-250, manufactured by Freund Turbo Corporation).

[0183] Further, classification was carried out using Faculty F-300 (manufactured by Hosokawa Micron Corporation), and toner particles 1 having a weight average particle size (D4) of 6.0 μm, an average circularity of 0.965, and a domain number average diameter of 0.20 μm were obtained. The operating conditions were a classification rotor rotation speed of 130 s -1 , distributed rotor Rotation speed: 120s -1 It was decided.

[0184] <Production Examples of Toner Particles 2 to 20> Toner particles 2 to 20 were obtained by the same production procedure as in the production example of toner particle 1, except that the type and amount of crystalline resin added, the type and amount of amorphous resin added, kneading conditions, and annealing conditions were changed as shown in Tables 4 and 5.

[0185] [Table 4] The unit of SP value is (J / cm3 ) 0.5 is.

[0186] [Table 5]

[0187] <Toner 1 manufacturing example> 100 parts of toner particles Silica particles 1 (fumed silica treated with silicone oil and having a number average diameter of 30 nm), 2.0 parts The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 30 s -1 The mixture was mixed for a rotation time of 10 minutes to obtain Toner 1. The viscoelasticity and the rate of change in wax crystallinity of the obtained toner were measured by the above-mentioned methods and are shown in Table 6. The cross section of the obtained toner was measured by the above-mentioned method, and it was confirmed that the matrix contained a crystalline resin and the domain contained an amorphous resin.

[0188] <Production example of toners 2 to 20> Toners 2 to 20 were obtained by carrying out the same production procedure as in the production example of Toner 1, except that the toner particles were changed to Toner Particles 2 to 20, respectively. The content of the crystalline resin, the content of the first monomer unit in the crystalline resin, and the content of the inorganic filler particles in the obtained toners 1 to 20 were measured using the methods described above, and it was confirmed that they matched the amounts added during toner production.

[0189] <Magnetic Carrier 1 Manufacturing Example> Number average particle size: 0.30 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite 1 Number average particle size: 0.50 μm, magnetization strength: 65 Am under a magnetic field of 1000 / 4π (kA / m) 2 / kg) of magnetite2 To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles.

[0190] Phenol: 10% by weight 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 mass% Magnetite treated with the above silane compound 2: 26 mass% 100 parts of the above material, 5 parts of a 28% by weight aqueous ammonia solution, and 20 parts of water were placed in a flask, and the mixture was heated to 85°C over 30 minutes while stirring and mixing, and then maintained at that temperature for 3 hours to polymerize and harden the resulting phenolic resin. The hardened phenolic resin was then cooled to 30°C, and water was added. The supernatant was removed, and the precipitate was washed with water and air-dried. This was then dried under reduced pressure (5 mmHg or less) at 60°C to obtain spherical magnetic carrier 1 with dispersed magnetic material. The volume-based 50% particle size (D50) of magnetic carrier 1 was 34.2 μm.

[0191] <Production example of two-component developer 1> To 92.0 parts of magnetic carrier 1, 8.0 parts of toner 1 were added and mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[0192] <Production examples of two-component developers 2 to 20> In the production example of two-component developer 1, toners 2 to 20 were used to obtain two-component developers 2 to 20, respectively.

[0193] [Table 6] In the table, X indicates the value of d(logG'(T1)) / dT, Y indicates the value of d(logG'(T1+3)) / dT, and Z indicates the value of d(logG'(T1+3)) / dT-d(logG'(T1)) / dT. For example, 4.8E+06 is 4.8 x 10 6 This indicates that The rate of change in wax crystallinity is expressed as the value of ΔH(T) / ΔH(W). In the MD structure column, if a matrix domain structure is present in cross-sectional observation of the toner with a transmission electron microscope, it is recorded as "present." The domain composition indicates the type of resin that forms the domain in the matrix domain structure.

[0194] Example 1 [Low temperature fixability] The above two-component developer 1 was used for evaluation. The image forming apparatus used was a modified Canon imageRUNNER ADVANCE C5560 digital commercial printing printer, with two-component developer 1 loaded into the cyan developer unit. The apparatus was modified so that the fixing temperature, process speed, developer carrier DC voltage VDC, electrostatic latent image carrier charging voltage VD, and laser power could be freely set. Image output evaluation involved outputting an FFh image (solid image) with the desired image ratio, and adjusting VDC, VD, and laser power so that the toner coverage on the FFh image on the paper was as desired, to evaluate low-temperature fixability. FFh is a value that represents 256 gradations in hexadecimal, with 00h being the first gradation of the 256 gradations (white background) and FFh being the 256th gradation of the 256 gradations (solid area).

[0195] The evaluation was carried out based on the following evaluation methods, and the results are shown in Table 7. ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.70mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: Place a 2cm x 5cm image in the center of the A4 paper. Test environment: Low temperature and low humidity: 15°C / 10%RH (hereinafter referred to as "L / L") Fixing temperature: 140℃ Process speed: 400mm / sec

[0196] The above evaluation image was output, and the low-temperature fixability was evaluated. The value of the image density decrease rate was used as an evaluation index for the low-temperature fixability. The image density reduction rate was measured using an X-Rite color reflection densitometer (500 series, manufactured by X-Rite Corporation). First, the image density at the center was measured. Next, the area where the image density was measured was subjected to pressure of 4.9 kPa (50 g / cm). 2 The fixed image was rubbed (five times back and forth) with Silbon paper under a load of 1000 kJ / cm2, and the image density was measured again. The rate of decrease in image density before and after rubbing was calculated using the following formula. The resulting rate of decrease in image density was evaluated according to the following evaluation criteria. Image density reduction rate = (Image density before rubbing - Image density after rubbing) / (Image density before rubbing) x 100 (Evaluation criteria) AA: Image density reduction rate less than 1.0% A: Image density reduction rate: 1.0% or more and less than 3.0% B: Image density reduction rate: 3.0% or more and less than 5.0% C: Image density reduction rate: 5.0% or more and less than 8.0% D: Image density reduction rate 8.0% or more

[0197] [Scratch resistance] ·Paper: Color Copy Coated Silk(250g / m 2 ) (Sold by Mondi) Toner amount on paper: 0.70mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: Place a 2cm x 15cm image in the center of the A4 paper. Test environment: Normal temperature and humidity (temperature 23°C, relative humidity 50% (hereinafter referred to as N / N)) Fixing temperature: 160℃ Process speed: 400mm / s The evaluation image was printed and the scratch resistance was evaluated. The paper used for the evaluation was a coated paper with a relatively high smoothness. The scratch resistance was evaluated by placing a 200g weight on the image and scratching it with a 0.75mm diameter needle at a speed of 60mm / min and a length of 30mm, using a HEIDON TYPE 14FW surface tester manufactured by Shinto Scientific Co., Ltd. The ratio of the area where toner peeled off was calculated by binarizing the area where toner peeling occurred relative to the scratched area using image processing. The results are shown in Table 7. (Evaluation criteria) A: The area ratio of toner peeled off due to image scratches is 0% or more but less than 1.0% B: The area ratio of toner peeled off due to image scratches is 1.0% or more but less than 4.0% C: The area ratio of toner peeled off due to image scratches is 4.0% or more but less than 7.0% D: The area ratio of toner peeled off due to image scratches is 7.0% or more

[0198] [Glossiness] ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner coverage on paper: 0.35mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: Place a 2cm x 15cm image in the center of the A4 paper. Test environment: Normal temperature and humidity (temperature 23°C, relative humidity 50% (hereinafter referred to as N / N)) Fixing temperature: 160℃ Process speed: 400mm / sec The evaluation images were printed and the image gloss was evaluated. The image gloss was evaluated by measuring the average value of three arbitrary points on each image using a PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.) at a light incident angle of 60°, and the result was taken as the gloss value. The results are shown in Table 7. (Evaluation criteria) A: Gross value is 30 or more. B: Gross value is 20 or more and less than 30. C: Gloss value is 10 or more but less than 20. D: Gloss value is less than 10.

[0199] [Mottle on rough paper] ·Paper:Canon Red Label Presentation (Basic weight: 80g / m 2 ) Toner amount on paper: 0.40mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) Evaluation image: FFh image with 100% print ratio Test environment: Normal temperature and humidity (temperature 23°C, relative humidity 50% (hereinafter referred to as N / N)) Fixing temperature: 180℃ Process speed: 400mm / sec The evaluation images were printed and evaluated for density unevenness (mottle) on rough paper. Paper with large irregularities was used, and the fixing temperature was set higher than in the evaluations of low-temperature fixability, scratch resistance, and glossiness, to perform the evaluation under conditions that make density unevenness (mottle) more likely to occur. The mottle of the resulting images was visually inspected and judged using the following criteria. Mottling is a type of poorly fixed image, where the toner melt viscosity is too low and the unevenness of the media is reflected in the image, resulting in a rough image. The results are shown in Table 7. (Evaluation criteria) A: No mottle occurred on any of the 100 sheets. B: Out of 100 sheets, 1 to 3 sheets have mottle spots. C: Out of 100 sheets, mottle occurred in 4 to 9 sheets. D: Out of 100 sheets, there are areas where mottle occurs on more than 10 sheets.

[0200] <Examples 2 to 15 and Comparative Examples 1 to 5> Evaluations of low-temperature fixability, scratch resistance, glossiness, and density unevenness on rough paper were carried out in the same manner as in Example 1, except that two-component developers 2 to 20 were used instead of two-component developer 1. The evaluation results are shown in Table 7.

[0201] [Table 7]

[0202] The present disclosure relates to the following configurations and methods. (Configuration 1) A toner having toner particles containing a binder resin and a wax, The binder resin contains a crystalline resin, the content of the crystalline resin is 30.0 to 95.0 mass% based on the mass of the toner particles, In the viscoelasticity measurement of the toner, the storage modulus of the toner at temperature T (°C) is G'(T), In a graph with the temperature T on the horizontal axis and the value d(logG'(T)) / dT obtained by differentiating LogG'(T) with respect to the temperature T on the vertical axis, There is a minimum value in the range of 50.0 to 70.0°C. When the temperature at which the minimum value is reached is T1 (°C), d(logG´(T1)) / dT is -2.00 to -0.20, d(logG'(T1+3)) / dT≦0, d(logG´(T1+3)) / dT-d(logG´(T1)) / dT is 0.15 to 1.90 G´(T1) is 5.0×10 5 ~2.0×10 7 Pa, G´(T1+30) is 1.0×10 2 ~5.0×10 4 Pa, A toner characterized by: (Configuration 2) 2. The toner according to claim 1, wherein Tw and Tc satisfy the following relationship: Tw (° C.) is the melting point of the wax, and Tc (° C.) is the melting point of the crystalline resin. 20≦Tw-Tc≦50 (Configuration 3) When the total amount of heat absorbed per 1 g of the wax in the measurement of the amount of heat absorbed of the toner (J / g) is defined as ΔH(T), and the total amount of heat absorbed per 1 g of the wax in the measurement of the amount of heat absorbed of the wax in J / g is defined as ΔH(W), The ΔH(T) and the ΔH(W) are 0.70≦ΔH(T) / ΔH(W)≦0.90 3. The toner according to claim 1, wherein the above condition is satisfied. (Configuration 4) The toner according to any one of configurations 1 to 3, wherein the crystalline resin contains a monomer unit represented by the following formula (1): TIFF0007802749000011.tif56153 In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R 1 represents an alkyl group having 18 to 36 carbon atoms. (Configuration 5) When the content ratio of the monomer unit represented by the formula (1) based on the mass of the toner particles is W(C), and the content ratio of the wax based on the mass of the toner particles is W(W), 5. The toner according to claim 4, wherein W(C) and W(W) satisfy the following relationship: 1.8≦W(C) / W(W)≦7.0 (Configuration 6) The toner according to any one of Configurations 1 to 5, wherein the wax comprises a hydrocarbon wax. (Configuration 7) 7. The toner according to any one of configurations 1 to 6, wherein the binder resin contains an amorphous resin. (Configuration 8) 8. The toner according to claim 7, wherein, in cross-sectional observation of the toner with a transmission electron microscope, a matrix domain structure composed of a matrix containing the crystalline resin and a domain containing the amorphous resin is present. (Method 9) A method for producing a toner according to any one of configurations 1 to 8, a melt-kneading step of melt-kneading a mixture containing the crystalline resin and the wax; and an annealing step of maintaining the melt-kneaded product obtained in the melt-kneading step at a temperature equal to or higher than the melting point of the crystalline resin + 5°C; A toner manufacturing method comprising:

Claims

1. A toner having toner particles containing a binder resin and a wax, The binder resin contains a crystalline resin, the binder resin contains an amorphous resin, a cross-section of the toner is observed using a transmission electron microscope, and a matrix domain structure is found to be present, the matrix domain structure being composed of a matrix containing the crystalline resin and a domain containing the amorphous resin; the content of the crystalline resin is 30.0 to 95.0% by mass based on the mass of the toner particles, In the viscoelasticity measurement of the toner, the storage modulus of the toner at temperature T (°C) is defined as G'(T), In a graph in which the temperature T is on the horizontal axis and the value d(log G'(T)) / dT obtained by differentiating Log G'(T) with respect to the temperature T is on the vertical axis, There is a minimum value in the range of 50.0 to 70.0 ° C. When the temperature at which the minimum value is reached is defined as temperature T1 (°C), d(log G'(T1)) / dT is -2.00 to -0.20; d(log G′(T+3)) / dT≦0; d(log G'(T1+3)) / dT-d(log G'(T1)) / dT is 0.15 to 1.90, G'(T1) is 5.0 × 10 ５ ~2.0 x 10 ７ Pa, G'(T1+30) is 1.0 × 10 ２ ~5.0 x 10 ４ Pa, A toner characterized by:

2. 2. The toner according to claim 1, wherein when the melting point of said wax is Tw (°C) and the melting point of said crystalline resin is Tc (°C), Tw and Tc satisfy the following relationship: 20≦Tw−Tc≦50

3. When the total amount of heat absorbed per 1 g of the wax in the measurement of the amount of heat absorbed of the toner (J / g) is defined as ΔH(T), and the total amount of heat absorbed per 1 g of the wax in the measurement of the amount of heat absorbed of the wax (J / g) is defined as ΔH(W), The ΔH(T) and the ΔH(W) are 0.70≦ΔH(T) / ΔH(W)≦0.90 The toner according to claim 1 or 2, which satisfies the above formula (1).

4. The toner according to claim 1 or 2, wherein the crystalline resin contains a monomer unit represented by the following formula (1): In formula (1), R Ｚ１ represents a hydrogen atom or a methyl group, R １ represents an alkyl group having 18 to 36 carbon atoms.

5. When the content ratio of the monomer unit represented by the formula (1) based on the mass of the toner particles is W(C), and the content ratio of the wax based on the mass of the toner particles is W(W), 5. The toner according to claim 4, wherein W(C) and W(W) satisfy the following relationship: 1.8≦W(C) / W(W)≦7.0

6. The toner according to claim 1 or 2, wherein the wax comprises a hydrocarbon wax.

7. A method for producing a toner, comprising: The toner has toner particles containing a binder resin and a wax, The binder resin contains a crystalline resin, the content of the crystalline resin is 30.0 to 95.0% by mass based on the mass of the toner particles, In the viscoelasticity measurement of the toner, the storage modulus of the toner at temperature T (°C) is defined as G'(T), In a graph in which the temperature T is on the horizontal axis and the value d(log G'(T)) / dT obtained by differentiating Log G'(T) with respect to the temperature T is on the vertical axis, There is a minimum value in the range of 50.0 to 70.0 ° C. When the temperature at which the minimum value is reached is defined as temperature T1 (°C), d(log G'(T1)) / dT is -2.00 to -0.20; d(log G′(T+3)) / dT≦0; d(log G'(T1+3)) / dT-d(log G'(T1)) / dT is 0.15 to 1.90, G'(T1) is 5.0×10 5 to 2.0×10 7 Pa; G'(T1+30) is 1.0×10 2 to 5.0×10 4 Pa; a melt-kneading step of melt-kneading a mixture containing the crystalline resin and the wax; and an annealing step of maintaining the melt-kneaded product obtained in the melt-kneading step at a temperature equal to or higher than the melting point of the crystalline resin + 5°C; A toner manufacturing method comprising:

8. The binder resin includes an amorphous resin, The method for producing a toner according to claim 7 , wherein a cross-section of the toner is observed with a transmission electron microscope and a matrix domain structure is present, the matrix domain structure being composed of a matrix containing the crystalline resin and a domain containing the amorphous resin.

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