Toner and toner manufacturing method

Abstract

To provide a toner that exhibits excellent low temperature fixability, can prevent fusion of toner to a drum even when a large amount of prints are output at a high speed in a high-temperature and high-humidity environment over a long period, and can provide a high-quality print product.SOLUTION: A toner has toner particles containing a binder resin having crystalline resin and amorphous resin, and wax. In observation of a cross section of the toner, a matrix-domain structure is present which is formed of a matrix including the crystalline resin and domains including the amorphous resin. The crystalline resin has a specific monomer unit. In a differential curve obtained by differentiating, by temperature, a temperature-storage elastic modulus curve with temperature as the horizontal axis and the common logarithm LogG' of the storage elastic modulus G' as the vertical axis, which is obtained in viscoelasticity measurement of the toner, the toner has the minimum values P1 and P2, which are specific values, within specific temperature ranges, and the storage elastic modulus G' at a temperature at each of the minimum values P1 and P2 is within a specific range.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] On the other hand, the performance required of electrophotographic devices is increasing year by year, and they are required to stably obtain high-quality print products even when outputting a large amount of prints at high speed over a long period of time in various environments. One of the factors that degrade the quality of print products is the phenomenon of toner fusing to the surface of the photosensitive drum, which causes uneven image density, white spots, and image deletion. When a toner having low-temperature fixability as disclosed in Patent Document 2 is output in large quantities at high speed over a long period of time in a high-temperature and high-humidity environment, the viscosity tends to decrease due to temperature rise caused by frictional heat in the cleaning portion of the photosensitive drum. As a result, the toner tends to fuse to the surface of the photosensitive drum, leaving room for further improvement. At least one aspect of the present disclosure provides a toner that exhibits excellent low-temperature fixability and can suppress drum fusion even when outputting a large amount of data at high speed over a long period of time under a high-temperature and high-humidity environment, thereby producing high-quality print products. 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 having a crystalline resin and an amorphous resin, and a wax, 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 crystalline resin has a first monomer unit represented by the following formula (1): The common logarithm LogG of the storage modulus G' obtained by measuring the viscoelasticity of the toner is expressed as In the differential curve obtained by differentiating the temperature-storage modulus curve with ´ as the vertical axis, It has a minimum value P1 in the range of 50 to 70°C, and the minimum value P1 is -0.50 to -0.20, The minimum value P2 is in the range of 80 to 120°C, and the minimum value P2 is -0.20 to -0.03; The storage modulus G' of the toner at the temperature at which the minimum value P1 is reached is 5.0×10 5 ~2.0×10 7 Pa, The storage modulus G' of the toner at the temperature at which the minimum value P2 is reached is 1.0×10 2 ~1.0×10 4 Pa, which is aimed at toner. TIFF0007757375000001.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)

[0007] At least one aspect of the present disclosure is a method for producing the toner, comprising: The manufacturing method comprises: a melt-kneading step of melt-kneading a mixture containing a binder resin having a crystalline resin and an amorphous resin, and a wax; and The present invention relates to a toner manufacturing method, which further comprises an annealing step of holding the melt-kneaded product obtained after the melt-kneading step at 40 to 60° C. for 30 minutes or more. [Effects of the Invention]

[0008] According to at least one aspect of the present disclosure, it is possible to provide a toner that exhibits excellent low-temperature fixability and is capable of suppressing drum fusion even when outputting a large amount of data at high speed over a long period of time under a high-temperature and high-humidity environment, thereby producing high-quality print products. 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): TIFF0007757375000002.tif21153

[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 according to the present disclosure will be described in detail below. The present disclosure provides a toner having toner particles containing a binder resin having a crystalline resin and an amorphous resin, and a wax, 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 crystalline resin has a first monomer unit represented by the following formula (1): In a differential curve obtained by differentiating a temperature-storage modulus curve, which is obtained by measuring the viscoelasticity of the toner and has temperature as the horizontal axis and the common logarithm LogG' of the storage modulus G' as the vertical axis, with respect to temperature, It has a minimum value P1 in the range of 50 to 70°C, and the minimum value P1 is -0.50 to -0.20, The minimum value P2 is in the range of 80 to 120°C, and the minimum value P2 is -0.20 to -0.03; The storage modulus G' of the toner at the temperature at which the minimum value P1 is reached is 5.0×10 5 ~2.0×10 7 Pa, The storage modulus G' of the toner at the temperature at which the minimum value P2 is reached is 1.0×10 2 ~1.0×10 4 Pa, relating to toner. TIFF0007757375000003.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)

[0012] As a result of extensive research, the present inventors have found that the toner has a matrix domain structure consisting of a matrix containing a crystalline resin and a domain containing an amorphous resin, and that the above-mentioned problems can be solved by controlling the viscoelasticity of the toner within a specific range.

[0013] The inventors speculate that the reason for solving the above problem is as follows. When the binder resin of the toner is a crystalline resin having many alkyl groups, such as the monomer unit represented by formula (1), the wax becomes more compatible with the crystalline resin binder. As a result, the viscoelasticity decreases suddenly at the melting point of the binder resin, which makes it difficult to use the toner in a high-temperature, high-humidity environment. During use, the temperature rises due to frictional heat at the cleaning portion of the photosensitive drum, and the toner tends to fuse to the surface of the photosensitive drum.

[0014] On the other hand, the toner according to the present disclosure has the following characteristics: A temperature-storage modulus curve, obtained by measuring the viscoelasticity of the toner, is differentiated with respect to temperature to obtain a differential curve. The differential curve has a minimum value P1 in the range of 50 to 70°C, and this minimum value P1 is -0.50 to -0.20. Furthermore, a minimum value P2 is present in the range of 80 to 120°C, and this minimum value P2 is -0.20 to -0.03. In addition, the storage modulus G' at the temperature where the toner has a minimum value P1 is 5.0 × 10 5 ~2.0×10 7 Pa, and the storage modulus G' at the temperature at which the toner has a minimum value P2 is 1.0 × 102 ~1.0×10 4 It is Pa.

[0015] The temperature range of 50 to 70°C corresponds to the temperature range during temperature rise due to frictional heat in the cleaning portion of the photosensitive drum. Therefore, the fact that the minimum value P1 described above is in the range of 50 to 70°C and that this minimum value is between -0.50 and -0.20 indicates that the viscoelasticity of the toner can decrease to a certain extent during temperature rise due to frictional heat in the cleaning portion of the photosensitive drum. Furthermore, the temperature of 80 to 120°C corresponds to the temperature in the vicinity of the fixing nip. Therefore, the fact that the minimum value P2 described above is in the range of 80 to 120°C and that this minimum value is -0.20 or more and -0.03 or less indicates that the viscoelasticity of the toner may decrease in the vicinity of the fixing nip.

[0016] Therefore, the presence of both the minimum value P1 and the minimum value P2 indicates that the viscoelasticity of the toner decreases stepwise within a specific range in each temperature region on the temperature-storage modulus curve: when the temperature rises due to frictional heat in the cleaning section of the photosensitive drum, and when passing through the fixing nip. On the other hand, conventional toners whose binder resin is a crystalline resin do not have the minimum value P2 because their viscoelasticity decreases suddenly at the melting point of the crystalline resin.

[0017] In the differential curve, the minimum value P1 is preferably −0.40 to −0.20, and more preferably −0.35 to −0.25, and the minimum value P2 is preferably −0.15 to −0.05, and more preferably −0.13 to −0.07.

[0018] If the minimum value P1 exceeds −0.20, the toner cannot exhibit sharp melting properties, and the low-temperature fixability decreases.

[0019] If the minimum value P2 exceeds -0.03, the toner does not melt sufficiently in the fixing nip, resulting in poor low-temperature fixability. On the other hand, if the minimum value P2 is less than -0.20, the viscosity in the fixing nip decreases too much, causing hot offset and poor fixing.

[0020] In addition, the storage modulus G' of the toner at the temperature P1 is 5.0 × 10 5 ~2.0×10 7 Pa, 1.0 x 10 6 ~8.0×10 6 It is preferable that the storage modulus G' at the temperature P2 is 1.0×10 Pa. 2 ~1.0×10 4 is 1.0 × 10 3 ~9.0×10 3 It is preferable that:

[0021] The storage modulus G' at the temperature of P1 is 5.0×10 5 If the storage modulus G' at the temperature P1 is less than 2.0×10 Pa, the viscosity is too low at the cleaning portion of the photosensitive drum, and toner fusion tends to occur. 7 If the pressure exceeds Pa, the low temperature fixability decreases.

[0022] The storage modulus G' at the temperature of P2 is 1.0×10 2 If the viscosity is less than Pa, the viscosity at the fixing nip is too low, causing hot offset and poor fixing. The storage modulus G' at the temperature is 1.0×10 4 If the pressure exceeds Pa, the low temperature fixability decreases.

[0023] The temperature at the minimum value P1 (minimum value temperature) is preferably 55.0 to 65.0°C, and more preferably 58.0 to 62.0°C. The temperature at the minimum value P2 (minimum value temperature) is preferably 85.0 to 100.0°C, and more preferably 90.0 to 95.0°C.

[0024] Examples of toners that can achieve the above-mentioned viscoelasticity will be described below. To obtain the above-described toner, it is preferable to control the crystalline state of the wax, for example. By increasing the degree of crystallinity of the wax in the toner, the wax maintains a moderate crystalline state in the toner, and the filler effect works. Furthermore, the present inventors have found that when the toner has amorphous resin domains, the amorphous resin domains interact with the crystalline resin matrix, and the filler effect of the wax works strongly. As a result, the toner can maintain a moderate viscoelasticity even at temperatures exceeding the melting point of the binder resin, for example, due to frictional heat in the cleaning section of the photosensitive drum. Therefore, even when the toner is heated by frictional heat in the cleaning section of the photosensitive drum during long-term use in a high-temperature, high-humidity environment, it is less likely to fuse to the photosensitive drum surface. Furthermore, because the temperature near the fixing nip, which is high, exceeds the melting point of the wax, the filler effect disappears, and the viscoelasticity of the toner suddenly decreases, resulting in excellent low-temperature fixability.

[0025] Therefore, in order to generate the minimum values ​​P1 and P2 in the toner, it is preferable that the toner has, for example, an amorphous resin domain, a crystalline resin matrix, and wax, and further that the crystallinity of the wax contained in the toner is controlled. The minimum value P1 is manifested by a decrease in viscosity due to melting of the crystalline resin. Therefore, the value of P1 can be reduced by sharpening the melting behavior. For example, increasing the amount of crystalline resin added or increasing the amount of crystalline components in the crystalline resin is effective. The minimum value P1 can be increased by reducing the effect of melting of the crystalline resin on the toner viscosity. For example, this can be achieved by reducing the amount of crystalline resin added.

[0026] The minimum value P2 can be reduced by, for example, increasing the temperature dependence of the melting properties of the wax and crystalline resin. That is, annealing is performed before the temperature at P2 to prevent the wax from dissolving in the crystalline resin, and the value of P2 can be reduced by bringing the SP values ​​of each closer together to increase the melting properties after the temperature at P2. Adding domain-forming amorphous resin or other fillers to enhance the filler effect of the wax is also effective in reducing the value of P2. The minimum value P2 can be increased by, for example, making the wax and the crystalline resin compatible with each other or by broadening the melting behavior of the wax with respect to temperature.

[0027] The storage modulus G' at the temperature at which the minimum value P1 is reached can be controlled, for example, by the amount of crystalline resin added, the amount of crystalline components in the crystalline resin, the type of monomer unit of the crystalline resin, and the type of amorphous resin. It can also be controlled by the domain size of the amorphous resin and the addition of a filler. Effective ways to increase the storage modulus G' at the temperature at which the minimum value P1 is reached include reducing the amount of crystalline resin added, increasing the amount of amorphous resin added, reducing the domain size, or adding a filler. It is also effective to control the compatibility between the wax and the crystalline resin at the temperature at which the minimum value P1 is reached. Furthermore, the storage modulus G' at the temperature at which the minimum value P2 occurs can be controlled by the types and amounts of wax, crystalline resin, and amorphous resin, provided that the minimum value P2 is generated by the above-mentioned means. In particular, the storage modulus G' at the temperature at which the minimum value P2 occurs can be reduced by increasing the compatibility between the wax and the crystalline resin at the temperature at which the minimum value P2 occurs.

[0028] In measuring the heat absorption of 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 measuring the heat absorption of wax, the total heat absorption J / g per 1 g of wax derived from the 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 0.75≦ΔH(T) / ΔH(W)≦0.85.

[0029] ΔH(T) / ΔH(W) indicates the rate of change in the degree of crystallinity of the wax after it is made into a toner compared to when it is in its pure state, and serves as 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, and a more sufficient filler effect is likely to be exhibited. 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, and interaction is more likely to be exhibited.

[0030] ΔH(T) / ΔH(W) can be increased by, for example, increasing the SP values ​​of the binder 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 binder resin and wax or decreasing the melting point of the 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.

[0031] <Crystalline resin> The crystalline resin has a first monomer unit (hereinafter also simply referred to as the first monomer unit) represented by the following formula (1): The crystalline resin is preferably a crystalline vinyl resin. 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. TIFF0007757375000004.tif56153

[0032] In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R 1represents an alkyl group having 18 to 36 carbon atoms. 1 is preferably an alkyl group having a carbon number of 18 to 30. In addition, the alkyl group preferably has a linear structure.

[0033] The first monomer unit has R in the side chain. 1 The presence of this moiety 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 more improved. The content of the mer unit is preferably 30.0 to 80.0 mass %, more preferably 40.0 to 75.0 mass %, and even more preferably 45.0 to 65.0 mass %.

[0034] 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 structure in the side chains of crystalline vinyl resins enhances interaction with wax (described below), which tends to increase the storage modulus G' at the temperature P1.

[0035] 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.

[0036] Examples of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group having 18 to 36 carbon atoms [stearyl (meth)acrylate, 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.].

[0037] 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.

[0038] 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.

[0039] 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. TIFF0007757375000005.tif67153

[0040] 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.

[0041] 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. 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate amide, 2-hydroxypropyl (meth)acrylate amide.

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] By using such polymerizable monomers in combination, drum fusion can be further suppressed, even when printing a large amount of material at high speed over a long period of time in a high-temperature, high-humidity environment, and higher quality print products can be obtained, achieving a higher level of low-temperature fixability. This is thought to be due to the fact that the monomer structure described above allows the coexistence of a component with a low SP value that is highly compatible with wax and a component with a high SP value that is poorly compatible with wax.

[0047] 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. On the other hand, the third monomer unit has a polar hydroxy group at a position distant from the main chain, and therefore, after the toner is melted, the storage modulus is less likely to be high compared to a resin having a polar group directly bonded to the main chain of the crystalline vinyl resin.

[0048] When the second monomer unit and the third monomer unit coexist, the storage modulus of the toner is maintained at an appropriate level, and drum fusion is further suppressed even when printing a large amount of material at high speed over a long period of time in a high-temperature, high-humidity environment, thereby producing higher quality print products and achieving a higher level of low-temperature fixability.

[0049] 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. The content of monomer units other than the first, second and third monomer units in the crystalline resin is preferably 10.0 to 60.0 mass %, more preferably 20.0 to 40.0 mass %.

[0050] 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.

[0051] 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, Acetylacetone Peroxides, ketone peroxides such as 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 peroxyisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butyl peroxyazelate.

[0052] 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, even more 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 0 mgKOH / g to 75 mgKOH / g, further preferably 0 mgKOH / g to 20 mgKOH / g, and particularly preferably 0 mgKOH / g.

[0053] <Amorphous resin> The toner contains an amorphous resin as a binder resin in addition to a crystalline resin. The content of the amorphous resin in the binder resin is not particularly limited, but is preferably 25% by mass to 65% by mass, more preferably 30% by mass to 50% by mass, and even more preferably 35% by mass to 45% by mass. As the amorphous resin, known amorphous resins can be used, for example, the following:

[0054] 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.

[0055] More preferably, the resin is an amorphous polyester resin. That is, the amorphous resin is preferably an amorphous polyester resin. By using an amorphous polyester resin, the crystallinity of the wax is increased, and the storage modulus of the toner is maintained more appropriately. Therefore, even when a large amount of printing is performed at high speed for a long period of time under a high-temperature and high-humidity environment, drum fusion is suppressed, a higher quality print product can be obtained, and low-temperature fixability can be achieved at a higher level. .

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the aforementioned polyhydric alcohol and polycarboxylic acid are simultaneously charged and polymerized via 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 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] Among them, acrylic acid or acrylic acid such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate are preferred. It is preferable to use a monomer which is a condensation product of methacrylic acid and an alcohol having 6 to 22 carbon atoms.

[0068] 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.

[0069] In addition to the above, various polymerizable monomers capable of vinyl polymerization may be used in combination with the vinyl resin as needed. 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.

[0070] 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.

[0071] 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.

[0072] 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, and 3,4-dichlorostyrene. , m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, 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, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate Preferably, the polymer is a polymer of a polymerizable monomer containing at least one selected from the group consisting of methyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, 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.

[0073] 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.

[0074] 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.

[0075] 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 Ketone peroxides such as 2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, and di-tert-butyl peroxide. oxide, 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-butylperoxyisobutyrate, tert-butylperoxyneodecanoate, tert-butylperoxy-2- Ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisophthalate, tert-butylperoxyallyl carbonate, tert-amylperoxy-2-ethylhexanoate, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate.

[0076] The vinyl resin and polyester resin used to form the hybrid resin in which the vinyl resin and the polyester resin are bonded can be the same as the vinyl resin and polyester resin used as the amorphous resin described above.

[0077] 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").

[0078] 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.

[0079] 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.

[0080] 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.

[0081] The binder resin contained in the toner contains a crystalline resin and an amorphous resin, and when a cross section of the toner is observed using a transmission electron microscope, a domain matrix structure consisting of a matrix containing a crystalline resin and a domain containing an amorphous resin is observed.

[0082] The inclusion of a crystalline resin in the matrix provides excellent low-temperature fixability. Furthermore, the inclusion of an amorphous resin in the domains allows the amorphous resin domains to function as fillers. The domain-matrix structure of the toner particles allows the crystallized wax to interact with the domains in the matrix. This allows the toner to maintain a moderate viscoelasticity even when the temperature exceeds the melting point of the binder resin, making it less likely for the toner to fuse to the photoreceptor drum surface even when heated by frictional heat in the cleaning section of the photoreceptor drum during long-term use in a high-temperature, high-humidity environment. By appropriately changing the composition of the crystalline resin and the amorphous resin, the toner particles can have a domain matrix structure.

[0083] Furthermore, when observing the cross section of the toner with a transmission electron microscope, the number-average diameter of the domains is preferably 0.05 to 3.00 μm, more preferably 0.10 to 1.00 μm. When the number-average diameter of the domains is within the above range, the amorphous resin is likely to act as a filler when the toner is melted, and is likely to interact with the crystallized wax, which is preferable. As a result, the toner is likely to be easily absorbed into the cleaning of the photosensitive drum during long-term use in a high-temperature and high-humidity environment. Even if the temperature rises due to frictional heat in the area, the toner is less likely to fuse to the surface of the photosensitive drum.

[0084] The number-average diameter of the domains can be controlled by the composition of the monomers constituting the crystalline resin, the composition of the monomers constituting the amorphous resin, the manufacturing conditions of the toner particles, etc. Specifically, the number-average diameter of the domains can be increased, for example, by making the SP values ​​of the crystalline resin and the amorphous resin more distant from each other, or by increasing the kneading intensity of the crystalline resin and the amorphous resin during manufacturing. The number-average diameter of the domains can be decreased, for example, by making the SP values ​​of the crystalline resin and the amorphous resin more similar to each other, or by decreasing the kneading intensity of the crystalline resin and the amorphous resin during manufacturing.

[0085] Furthermore, when observing the cross section of the toner using a transmission electron microscope, the domains preferably account for 30 to 65 area % of the total area of ​​the matrix and domains, and more preferably 35 to 45 area %. Within this range, the toner maintains its strength in the temperature range of 50 to 70°C, while achieving a sufficiently low viscosity in a molten state at 80 to 120°C, ensuring low-temperature fixability. The area ratio can be controlled by the ratio of the crystalline resin and amorphous resin added.

[0086] <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.

[0087] <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.

[0088] 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; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid, and stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol. Esters with alcohols such as ethyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacamide; m-xylene bisstearic acid amide, N,N'-distearic acid amide Aromatic bisamides such as 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 or acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds with hydroxy groups obtained by hydrogenating vegetable oils and fats.

[0089] The wax is preferably a hydrocarbon wax, more preferably a Fischer-Tropsch wax. The melting point of the wax is preferably 90°C or higher, more preferably 90 to 105°C, and even more preferably 90 to 95°C. When the wax contains a 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. Therefore, even if the toner is heated by frictional heat in the cleaning section of the photoreceptor drum during long-term use in a high-temperature, high-humidity environment, the toner is less likely to fuse to the surface of the photoreceptor drum. The wax content is preferably 2.0 to 30.0 parts by mass, more preferably 5.0 to 20.0 parts by mass, and even more preferably 7.0 to 12.0 parts by mass, relative to 100 parts by mass of the binder resin.

[0090] In toner, the SP value of the crystalline resin (J / cm 3 ) 0.5 is defined as SP1, and the SP value of the amorphous resin (J / cm 3 ) 0.5 is SP2, and the SP value of the wax (J / cm 3 ) 0.5 When SP3 is defined as SP1, SP2, and SP3, it is preferable that SP1, SP2, and SP3 satisfy the following formula: 2.5≦|SP2-SP1| 2.5≦|SP3-SP1|

[0091] Here, the SP value is an abbreviation for solubility parameter, which is a value that serves as an index of solubility, and is calculated according to the method proposed by Fedors. The unit of the SP value in this disclosure is (J / cm 3 ) 0.5 However, 1 (cal / cm 3 ) 0.5 =2.045×10 3 (J / cm 3 ) 0.5 by (cal / cm 3 ) 0.5 can be converted into units of

[0092] In a toner having a matrix domain structure, if the absolute difference between SP2 and SP1 is 2.5 or more, the domains are less compatible with the matrix, and the filler effect of the domains is more fully exhibited. Furthermore, if the absolute difference between SP3 and SP1 is 2.5 or more, the wax is less compatible with the matrix, and the wax is more likely to crystallize. Therefore, during long-term use in a high-temperature, high-humidity environment, the viscoelasticity of the toner is less likely to decrease when the temperature rises due to frictional heat in the cleaning section of the photosensitive drum.

[0093] It is more preferable that |SP2-SP1| is 2.5 to 5.0. It is more preferable that |SP3-SP1| is 2.5 to 4.0. SP1 is preferably 19.0 to 22.0, more preferably 19.0 to 21.0. SP2 is preferably 22.0 to 26.0, more preferably 23.0 to 25.0. SP3 is preferably 16.0 to 18.0, more preferably 16.5 to 17.5.

[0094] <Inorganic filler particles> The toner particles preferably contain inorganic filler particles, and the content of the inorganic filler particles in the toner particles is preferably 5 to 20 parts by mass, and more preferably 5 to 15 parts by mass, per 100 parts by mass of the binder resin. By satisfying the above range, it is possible to further increase the viscoelasticity of the toner when the temperature rises due to frictional heat in the cleaning section of the photosensitive drum during durable use in a high-temperature, high-humidity environment, and the toner is less likely to fuse to the drum surface.

[0095] The filler particles are preferably treated with a fatty acid. 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. As a result, the viscoelasticity of the toner can be increased when the temperature rises due to frictional heat in the cleaning section of the photosensitive drum during endurance use in a high-temperature, high-humidity environment, and melting to the drum surface does not occur.

[0096] Preferable inorganic filler particles to be added to the toner 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 preferable from the viewpoint of interaction with the crystalline resin.

[0097] 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.

[0098] <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.

[0099] 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.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] <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.

[0105] 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.

[0106] 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.

[0107] <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.

[0108] 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.

[0109] <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, in that stable images can be obtained over a long period of time. More preferably, it is a toner. 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.

[0110] 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.

[0111] <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.

[0112] The toner manufacturing method is a melt-kneading step of melt-kneading a mixture containing a binder resin having a crystalline resin and an amorphous resin, and a wax; and It is preferable to have an annealing step in which the melt-kneaded product obtained after the melt-kneading step is kept at 40 to 60° C. for 30 minutes or more.

[0113] 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.).

[0114] <Melting and kneading process> Next, the mixed materials are melt-kneaded to disperse wax and other materials in a binder resin containing a crystalline resin and an amorphous resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Single- or twin-screw extruders are commonly used due to their advantage of 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 Ko-Kneader (manufactured by Buss Co., Ltd.), and a Kneadex (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.

[0115] 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.

[0116] <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.

[0117] <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.

[0118] <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.

[0119] <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.

[0120] <Annealing process> The melt-kneaded product obtained after the melt-kneading step is preferably annealed to promote the crystal growth of the wax in the toner. Annealing is preferably performed after the cooling step. By promoting the crystal growth of the wax, it becomes easier to satisfy 0.70≦ΔH(T) / ΔH(W)≦0.90.

[0121] Specifically, the melt-kneaded product obtained after the melt-kneading step is preferably kept at 40 to 60° C. for 30 minutes or more (preferably 30 to 120 minutes, more preferably 40 to 60 minutes). It is more preferable to keep it at 40 to 50° C. Furthermore, from the viewpoint of controlling the exposure state of the wax on the toner particle surface after the melt-kneading step, it is more preferable to anneal the product.

[0122] The methods for measuring various physical properties of the toner and raw materials are described below. <Measurement of minimum value P1, minimum value P2, and toner storage modulus G'> 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 25 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).

[0123] The measurement is carried out under the following conditions: (1) Use parallel plates with a diameter of 25 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 performed at a temperature ramp rate of 2.0°C / min between 40°C and 150°C. The measurement is performed under the following automatic adjustment mode settings. Measurement is performed in automatic strain adjustment mode (Auto Strain). (5) Set the maximum applied strain to 40.0%. (6) Set the maximum torque (Max Allowed Torque) to 150.0 g·cm and the minimum torque (Min Allowed Torque) to 0.2 g·cm. (7) Set the strain adjustment to 20.0% of the current strain. The measurement is performed in the auto tension adjustment mode. (8) Set Auto Tension Direction to Compression. (9) Set the initial static force to 10.0 g and the auto tension sensitivity to 40.0 g. (10) The operating condition of the auto tension is a sample modulus of 1.0 × 10 3 Pa or more.

[0124] The storage modulus G' measurement results obtained in the above measurements 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 temperature-storage modulus curve is obtained by smoothly connecting the plotted points. Next, the slope of the obtained temperature-storage modulus curve is calculated, and a differential curve obtained by differentiating the common logarithm LogG' with respect to temperature is graphed. From the obtained differential curve, a minimum value P1 in the range of 50 to 70°C and a minimum value P2 in the range of 80 to 120°C are obtained. In addition, the storage modulus G' at the temperature of P1 and the storage modulus G' at the temperature of P2 are obtained. If there are multiple minimum values ​​in the above temperature range, the smallest one is selected as minimum value P1 or P2.

[0125] If it is difficult to smoothly connect the temperature-storage modulus plot, three or five measured values ​​may be smoothed to make it easier to connect the plot. Three-point smoothing means that the smoothing is performed using the average value of three points, consisting of a certain measurement point and one point before and one point after it.

[0126] <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.

[0127] 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

[0128] 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.

[0129] 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 electron microscope) (TEM-EDX). A cross-sectional image of the toner is obtained, and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen.

[0130] 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.

[0131] 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.

[0132] 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.

[0133] 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.

[0134] Thereafter, binarization processing is performed, and the domain particle diameters present in the toner cross-sectional image are measured. 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 domain. The crystalline resin and amorphous resin samples may be those separated from the toner by the method described below.

[0135] <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).

[0136] (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, it is as follows.

[0137] 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.

[0138] 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. In this case, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A linear function 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 molding 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 calculated from the calibration curve.

[0139] <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.

[0140] obtained 1From 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.

[0141] 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)...+(S x / n x ))}×100 Content of third monomer unit (mol%)= {(S3 / n3) / ((S1 / n1)+(S2 / n2)+(S3 / n3)...+(S x / n x ))}×100

[0142] 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%.

[0143] <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℃

[0144] 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.

[0145] <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.

[0146] 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

[0147] <Method for measuring weight average particle size (D4) of toner (particles)> The weight-average particle size (D4) of the toner (particles) was measured using a precision particle size distribution analyzer, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube and using the attached dedicated software, "Beckman Coulter Multisize Using the "Beckman Coulter r 3 Version 3.51" (manufactured by Beckman Coulter), measurements are taken 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:

[0148] In the dedicated software's "Change Standard Measurement Method (SOM) screen," set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using a "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the "Flush aperture tube after measurement" box. In the dedicated software's "Pulse to particle size conversion setting screen," set the bin spacing to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less. The specific measurement method is as follows.

[0149] (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).

[0150] <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.

[0151] 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.

[0152] 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.

[0153] 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.

[0154] In the examples, a flow-type particle image analyzer that had undergone calibration work by Sysmex Corporation and had received a calibration certificate issued by Sysmex Corporation was used. Measurements were performed under the measurement and analysis conditions at the time of receiving the calibration certificate, except that the analyzed particle diameter was limited to 1.985 μm or more and less than 39.69 μm in terms of equivalent circle diameter.

[0155] <Calculation method of SP value> The SP values of the crystalline resin, amorphous resin, and 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 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.

Examples

[0156] The basic configuration and features of the present disclosure have been described above. Hereinafter, the present disclosure will be specifically described based on examples. However, the present disclosure is not limited thereto. Unless otherwise specified, parts and % are based on mass.

[0157] <Production example of crystalline resin 1> · Solvent: 100.0 parts of toluene · Monomer composition: 100.0 parts (The monomer composition is a mixture of behenyl acrylate, styrene, acrylonitrile, and 2-hydroxyethyl acrylate shown below in the following proportions.) (50.0 parts of behenyl acrylate) (30.0 parts of styrene) (15.0 parts of acrylonitrile) (5.0 parts of 2-hydroxyethyl acrylate) · Polymerization initiator: 0.5 part [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 (Tp) of the obtained crystalline resin 1 was 61°C.

[0158] <Production Examples of Crystalline Resins 2 to 10> Crystalline resins 2 to 10 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.

[0159] <Production Example of Crystalline Resin 11> The above materials were weighed and placed in a reaction vessel equipped with dodecanediol (50 mol%), sebacic acid (50 mol%), a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After the atmosphere in the flask was replaced with nitrogen gas, the temperature was gradually raised with stirring, and the mixture was allowed to react for 3 hours at 140°C while stirring. Tin 2-ethylhexanoate was added at 0.5% relative to the monomer, 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 11 was obtained.

[0160] [Table 1] The abbreviations in Table 1 are as follows: Regarding the parts in Table 1, dodecanediol and cebasil The number of parts of phosphate is in parts by mole. BEA: Behenyl acrylate STA: stearyl acrylate MYA: Myricyl acrylate St: styrene ACN: Acrylonitrile MCN: methacrylonitrile HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 2-hydroxypropyl methacrylate

[0161] <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: 71.4 parts (50.0 mol parts) Terephthalic acid: 14.7 parts (25.0 mol parts) Adipic acid: 5.2 parts (10.0 mol parts) Fumaric acid: 4.1 parts (15.0 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 Thereafter, 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 150°C. The reaction was then stopped by lowering the temperature (second reaction step), and amorphous resin 1 was obtained.

[0162] <Production examples of amorphous resins 2 and 3> Amorphous resins 2 and 3 were obtained by carrying out the reaction in the same manner as in the production example of amorphous resin 1, except that the monomers and the parts by mass thereof were changed as shown in Table 2.

[0163] <Production Example of Amorphous Resin 4> An autoclave was charged with 50.0 parts of xylene, and after replacing the atmosphere with nitrogen, the autoclave was heated to 185°C in a sealed state with stirring. A mixed solution of 28.0 parts of styrene, 7.0 parts of n-butyl acrylate, 18.0 parts of acrylonitrile, and 1.5 parts of di-tert-butyl peroxide and 20.0 parts of xylene was continuously added dropwise to the autoclave for 3 hours to polymerize while controlling the temperature inside the autoclave at 185° C. The temperature was maintained for another 1 hour to complete the polymerization, and the solvent was removed to obtain amorphous resin 4.

[0164] [Table 2] The abbreviations in Table 2 are as follows. Note that the values ​​for St, BA, and AN in Table 2 are not parts by mol but parts by mass. The unit of the SP value is (J / cm 3 ) 0.5 is. BPA-EO: Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane BPA-PO: Polyoxypropylene (2.0)-2,2-bis(4-hydroxyphenyl)propane TPA: Terephthalic acid FA: Fumaric acid SA: succinic acid AA: Adipic acid PE: Polyethylene AN: Acrylonitrile BA: butyl acrylate St: styrene

[0165] <Production Example of Toner Particle 1> ·Crystalline resin 1: 60 parts Amorphous resin 1: 40 parts Wax: 10 parts (Fischer-Tropsch A; melting point 92°C) Colorant 1: 5 parts (Cyan pigment manufactured by Dainichi Seika Chemicals: Pigment Blue 15:3) Inorganic filler: 10 parts (Calcium carbonate, number average particle size 0.3 μm, fatty acid (stearic acid) treated) The above materials were mixed in a Henschel mixer (FM-75 model, manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotation speed of 20 s -1 After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at 120°C with a screw rotation speed of 250 rpm and a discharge temperature of 130°C. The resulting kneaded material was rolled and cooled using a drum flaker (MBD30-30, manufactured by Nippon Coke Co.). The cooling water temperature was set to 50°C, and conditions were set so that the thickness of the resin composition after rolling would be 1.0 mm. The rolled resin composition was then held at 50°C for 45 minutes for annealing. 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 product. The resulting coarsely crushed product was then finely crushed using a mechanical crusher (T-250, manufactured by Freund Turbo Corporation).

[0166] 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.

[0167] <Production Examples of Toner Particles 2 to 35> Toner particles 2 to 35 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 3 and 4. [Table 3]

[0168] [Table 4] Regarding annealing, "after tonerization" means that annealing was performed after the toner particles were obtained. This indicates that...

[0169] [Table 5] In the table, the domain size is the number-average diameter of the domains.

[0170] <Toner 1 manufacturing example> 100 parts of toner particles 5.0 parts of external additive particles for toner 1 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.

[0171] <Toner 2-35 manufacturing example> Toners 2 to 35 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 35, respectively. In the obtained toners 1 to 35, the content ratio of the first monomer unit in the crystalline resin and the content ratio of the inorganic filler particles were measured by the above-mentioned method, and it was confirmed that they matched the amount added during toner production.

[0172] <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.

[0173] 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.

[0174] <Manufacturing 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.

[0175] <Production examples of two-component developers 2 to 35> In the production example of two-component developer 1, toners 2 to 35 were used to obtain two-component developers 2 to 35, respectively. [Table 6] In the table, G' is the storage modulus G' at the temperature of the minimum value. For example, the notation 10^6 is 10 6 This means that The wax crystallinity change rate is the value of "ΔH(T) / ΔH(W)". The domain area % is the ratio of the area occupied by the domain to the total area of ​​the matrix and domain.

[0176] 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).

[0177] The evaluation was carried out based on the following evaluation methods, and the results are shown in Table 5. ·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 humidity: 15°C / 10%RH (hereinafter referred to as "L / L") Fixing temperature: 140℃ Process speed: 400mm / sec

[0178] 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

[0179] [Drum fusion] <Print durability test (evaluation of image whiteout and image smearing)> The image forming apparatus used was a modified Canon Inc. imageRUNNER ADVANCE C5560 II full-color copier. After a durability image output test of 100,000 sheets in a high temperature and high humidity environment (temperature 30°C / relative humidity 80%, hereinafter referred to as H / H environment), evaluation was performed using the following method. During the 100,000-sheet continuous paper feed time, the sheets were fed under the same development and transfer conditions (no calibration) as for the first sheet. For the durability image, the image print ratio was set to 20%, and the development bias was adjusted so that the initial image density was 1.45. The evaluation paper was plain copy paper CS-680 (A4, basis weight 68 g / m) for the durability image output of 100,000 sheets. 2 (sold by Canon Marketing Japan Inc.) was used.

[0180] After printing 100,000 images under the above conditions, a halftone image with an image density of 0.800 was printed using an X-Rite color reflection densitometer (500 series, manufactured by X-Rite). If image bleeding or blank spaces occur due to toner fusion on the photosensitive drum surface, the image dots become smaller and the image density decreases, so measurements were taken at 10 locations to confirm the difference in image density (the difference between the maximum and minimum values). The evaluation was carried out according to the following criteria, and the results are shown in Table 7. Rank AA: Image density difference less than 0.025 Rank A: Image density difference 0.025 or more and less than 0.050 Rank B: Image density difference 0.050 or more and less than 0.075 Rank C: Image density difference 0.075 or more and less than 0.100 Rank D: Image density difference 0.100 or more

[0181] [Hot offset resistance] ·Paper:CS-064(64.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on paper: 0.08mg / cm 2 (Adjusted by DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power) Evaluation image: A 2cm x 20cm image placed on the long edge of the A4 paper with a 2mm margin from the leading edge of the paper. Test environment: Normal temperature and low humidity: Temperature 23°C / Humidity 5% RH (hereinafter referred to as "N / L") Fixing temperature: 100°C, increasing in 5°C increments Process speed: 300mm / sec The above evaluation image was output, and the hot offset resistance was evaluated according to the following criteria at the highest fixing temperature at which no hot offset occurred. (Evaluation criteria) A: 140℃ or higher B: 130℃ or higher but lower than 140℃ C: 120℃ or higher but lower than 130℃ D: 100℃ or higher but lower than 120℃ E: Less than 100℃

[0182] <Examples 2 to 28 and Comparative Examples 1 to 7> Evaluations of low temperature fixability, drum fusion, and hot offset resistance were carried out in the same manner as in Example 1, except that two-component developers 2 to 35 were used instead of two-component developer 1. The evaluation results are shown in Table 7.

[0183] [Table 7]

Claims

1. A toner having toner particles containing a binder resin having a crystalline resin and an amorphous resin, and a wax, 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 crystalline resin has a first monomer unit represented by the following formula (1): In a differential curve obtained by differentiating a temperature-storage modulus curve obtained by measuring the viscoelasticity of the toner, the horizontal axis being temperature and the vertical axis being common logarithm LogG' of the storage modulus G', It has a minimum value P1 in the range of 50 to 70 ° C., and the minimum value P1 is −0.50 to −0.20, It has a minimum value P2 in the range of 80 to 120 ° C., and the minimum value P2 is −0.20 to −0.03; The storage modulus G' of the toner at the temperature at which the minimum value P1 is reached is 5.0×10 ５ ~2.0 x 10 ７ Pa, The storage modulus G' of the toner at the temperature at which the minimum value P2 is reached is 1.0×10 ２ ~1.0 x 10 ４ a toner comprising: 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.

2. In measuring the heat absorption amount of the toner using a differential scanning calorimeter, the total heat absorption amount J / g per 1 g of wax derived from the wax is defined as ΔH(T), In the measurement of the endothermic heat of the wax, when the total endothermic heat J / g per 1 g of wax derived from the wax is defined as ΔH(W), 2. The toner according to claim 1, wherein ΔH(T) and ΔH(W) satisfy the relationship 0.70≦ΔH(T) / ΔH(W)≦0.

90.

3. 3. The toner according to claim 1, wherein the content of the first monomer unit in the crystalline resin is 30.0% by mass or more based on the mass of all monomer units in the crystalline resin.

4. 3. The toner according to claim 1, wherein the amorphous resin is an amorphous polyester resin.

5. When a cross section of the toner is observed using a transmission electron microscope, 3. The toner according to claim 1, wherein the number average diameter of the domains is 0.05 to 3.00 μm.

6. When a cross section of the toner is observed using a transmission electron microscope, 3. The toner according to claim 1, wherein the domains occupy 30 to 65 area % of the total area of ​​the matrix and the domains.

7. The toner according to claim 1 or 2, wherein the crystalline resin contains a second monomer unit represented by the following formula (2) and a third monomer unit represented by the following formula (3): In formula (2), R ２ represents a hydrogen atom or a methyl group. In formula (3), X represents —O— or —NH—, and R ４ represents a hydrogen atom or a methyl group, R ３ represents an alkylene group having 2 to 6 carbon atoms.

8. The wax is a hydrocarbon wax, 3. The toner according to claim 1, wherein the wax has a melting point of 90° C. or higher.

9. The SP value (J / cm ３ ) ０．５ is defined as SP1, and the SP value (J / cm ３ ) ０．５ is defined as SP2, and the SP value of the wax (J / cm ３ ) ０．５ When SP3 is used, The SP1, the SP2, and the SP3, 2.5≦|SP2-SP1| 2.5≦|SP3-SP1| The toner according to claim 1 or 2, which satisfies the relationship:

10. the toner particles contain inorganic filler particles, 3. The toner according to claim 1, wherein the content of the inorganic filler particles in the toner particles is 5 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

11. The toner of claim 10, wherein the inorganic filler particles are fatty acid treated.

12. 3. The method for producing the toner according to claim 1 or 2, The manufacturing method comprises: a melt-kneading step of melt-kneading a mixture containing the binder resin having the crystalline resin and the amorphous resin, and the wax; and an annealing step of holding the melt-kneaded product obtained after the melt-kneading step at 40 to 60°C for 30 minutes or more; A method for producing a toner comprising the steps of:

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