Toner

Abstract

To provide a toner that has both of low-temperature fixability and heat-resistant storageability and also has high tinting power.SOLUTION: A toner contains a binder resin and a colorant. The binder resin is a resin meeting one of following conditions (A) and (B): (A) it contains a crystalline resin having a unit (a) represented by the formula (1), and a resin having a sulfide structure; and (B) it contains a crystalline resin having a sulfide structure, and also having a unit (a) represented by the formula (1). The colorant is any one selected from carbon black, titanium black, copper phthalocyanine, copper phthalocyanine derivative, anthraquinone compound, azo pigment and condensed multicyclic compound. The peak temperature at the maximum endothermic peak of the toner exists in a range of 50°C or more and 70°C or less, and the endothermic quantity at the maximum endothermic peak is 30 J / g or more and 70 J / g or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to toner used in electrophotography and electrostatic recording. [Background technology]

[0002] In recent years, energy conservation has become a major technical challenge in electrophotographic equipment, and significant reductions in the amount of heat required for the fuser are being considered. In particular, there is a growing need for so-called "low-temperature fixing" toners, which enable fixing with lower energy consumption. One method to enable fixing at low temperatures is to lower the glass transition temperature (Tg) of the binder resin in the toner. However, lowering Tg leads to a decrease in the heat resistance of the toner, so it is considered difficult to achieve both low-temperature fixing and heat resistance with this method. Therefore, in order to achieve both low-temperature fixability and heat-resistant storage of toner, a method of using crystalline vinyl resin as a binder resin is being considered. Amorphous resins, which are commonly used as binder resins for toner, do not show a clear endothermic peak in differential scanning calorimeter (DSC) measurements, but when crystalline resin components are included, an endothermic peak appears in DSC measurements. Crystalline vinyl resin has the property that it hardly softens until its melting point due to the regular arrangement of side chains within the molecule. Furthermore, the crystals melt rapidly at the melting point, and a rapid decrease in viscosity occurs as a result. For this reason, it is attracting attention as a material that has excellent sharp-melt properties and can achieve both low-temperature fixability and heat-resistant storage. Typically, crystalline vinyl resin has long-chain alkyl groups as side chains in the main chain skeleton, and the crystallinity of the resin is exhibited by the crystallization of the long-chain alkyl groups in the side chains. On the other hand, toners with high coloring power are required to improve the image quality of color images. In response to this, various studies are being conducted on the binder resins and colorants contained in the toner. Patent Document 1 provides a positively charged toner that has excellent low-temperature fixing properties, heat resistance for storage, durability, and electrostatic properties. Furthermore, Patent Document 2 provides a toner for developing electrostatic images that has good low-temperature fixing properties and whose fixing properties do not deteriorate even after storage at high temperatures. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-219648 [Patent Document 2] Japanese Patent Publication No. 2017-37245 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] While the positively charged toner described in Patent Document 1 did indeed show improvements in low-temperature fixability and heat-resistant storage, there was still room for improvement in achieving both low-temperature fixability and high colorability. Similarly, the electrostatic image developing toner described in Patent Document 2 also had room for improvement in achieving both low-temperature fixability and high colorability. Therefore, the object of the present invention is to provide a toner that achieves low-temperature fixability, heat resistance for storage, and high coloring power simultaneously. [Means for solving the problem]

[0005] The present invention, which solves the above problems, is a toner having toner particles containing a binder resin and a colorant, The binder resin is a resin that satisfies at least one of the following requirements (A) and (B): (A) A crystalline resin having a unit (a) represented by the following formula (1), and a resin having a sulfide structure; (B) A crystalline resin having a sulfide structure and a unit (a) represented by the following formula (1)

[0006] [ka] [In formula (1), R 1represents a hydrogen atom or a methyl group, and n represents an integer of 16 or more and 30 or less. The colorant is any colorant selected from the group consisting of carbon black, titanium black, copper phthalocyanine, copper phthalocyanine derivatives, anthraquinone compounds, azo pigments, and condensed polycyclic compounds. When the toner is measured with a differential scanning calorimeter, the peak temperature of the maximum endothermic peak exists in the range of 50°C or more and 70°C or less. The present invention relates to a toner characterized in that the heat absorption amount of the maximum endothermic peak is 30 J / g or more and 70 J / g or less.

Effects of the Invention

[0007] According to the present invention, a toner having both low-temperature fixing property, heat-resistant storage property, and high coloring power can be provided.

Modes for Carrying Out the Invention

[0008] The description of "○○ or more and ×× or less" or "○○ to ××" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified.

[0009] "(Meth)acrylate" is an expression including both acrylate and methacrylate, and "(meth)acrylic acid" is an expression including both acrylic acid and methacrylic acid.

[0010] When numerical ranges are described stepwise, the upper limit and the lower limit of each numerical range can be arbitrarily combined.

[0011] A monomer unit is a unit (unit) constituting a polymer (polymer, resin), and refers to the reacted form of a monomer (polymerizable monomer). For example, one section of the carbon-carbon bond in the main chain where vinyl monomers in the polymer are polymerized is one monomer unit. A vinyl monomer can be represented by the following formula (Z), and a vinyl monomer unit is a constituent unit of the polymer and is the reacted form of the monomer represented by the following formula (Z). Also, the monomer unit may be simply referred to as "unit".

[0012] [ka]

[0013] Crystalline resins refer to resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements using resin, toner particles, or toner as the measurement sample.

[0014] To achieve both low-temperature fixation and heat-resistant storage, the entire binder resin must be crystalline. This requires that the long-chain alkyl groups present as side chains in the main chain skeleton of the binder resin crystallize sufficiently. Therefore, a high content of long-chain alkyl groups is necessary, and the resulting melting point must be within a range sufficient to ensure heat-resistant storage.

[0015] On the other hand, in order to achieve high colorability, it is necessary that colorants such as pigments are uniformly dispersed within the toner particles.

[0016] Colorants such as carbon black, titanium black, copper phthalocyanine, copper phthalocyanine derivatives, anthraquinone compounds, azo pigments, and condensed polycyclic compounds generally possess polar groups. In contrast, crystalline resins containing unit (a) tend to have a low polarity structure. Therefore, the affinity between crystalline resins containing unit (a) and colorants tends to be low, leading to a problem of reduced dispersibility of the colorant and low coloring power.

[0017] Therefore, after diligent research, the inventors discovered that by including a resin having a sulfide structure in the binder resin, the dispersibility of the colorant in the toner particles can be improved and the coloring power enhanced due to the high polarity based on the sulfur atoms in the sulfide structure, leading to the present invention.

[0018] The toner of the present invention will be described in detail below.

[0019] The binder resin contained in the toner particles according to the present invention is a resin that satisfies at least one of the following conditions (A) and (B). (A) Contains a crystalline resin having a unit (a) represented by the above formula (1), and a resin having a sulfide structure. (B) Contains a crystalline resin having a sulfide structure and a unit (a) represented by the above formula (1).

[0020] In unit (a), having a long-chain alkyl group (alkyl group with 16 to 30 carbon atoms) as a side chain in the binder resin, the binder resin becomes crystalline, resulting in a toner with excellent low-temperature fixation and heat-resistant storage properties. Furthermore, the binder resin becomes a crystalline resin that exhibits a clear endothermic peak in DSC measurements.

[0021] Unit (a) can be incorporated into the binder resin by vinyl polymerization of a (meth)acrylic acid ester having a linear alkyl group with 16 to 30 carbon atoms as a polymerizable monomer.

[0022] Examples of (meth)acrylic acid esters having an alkyl group with 16 to 30 carbon atoms include cecil (meth)acrylate, stearyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, hexacosyl (meth)acrylate, octacosyl (meth)acrylate, and myricyl (meth)acrylate.

[0023] Among these, (meth)acrylic acid esters having an alkyl group with 18 to 30 carbon atoms are more preferred from the viewpoint of low-temperature fixation and heat-resistant storage of the toner, and stearyl (meth)acrylic acid and behenyl (meth)acrylic acid are even more preferred.

[0024] That is, in formula (1), the number of carbon atoms (n) is 16 or more and 30 or less, more preferably 18 or more and 30 or less, and even more preferably 18 or more and 22 or less. Also, R 1It is preferably hydrogen.

[0025] The polymerizable monomers that form unit (a) (hereinafter also referred to as monomer (a)) and unit (a) may be used individually or in combination of two or more types.

[0026] It is preferable that the content of unit (a) in the crystalline resin is 40.0% by mass or more and 80.0% by mass or less.

[0027] If the content is 40.0% by mass or more, the crystallinity is improved, and a toner with excellent low-temperature fixability and heat-resistant storage properties can be obtained. 45.0% by mass or more is more preferable.

[0028] If the content is 80.0% by mass or less, the pigment dispersibility is more easily improved, and a toner with higher coloring power can be obtained. 75.0% by mass or less is preferred, and 60.0% by mass or less is more preferred.

[0029] Furthermore, the content of unit (a) is the sum of the content of all units represented by the above formula (1).

[0030] Next, we will explain the requirements (A) and (B) that the above-mentioned binder resin must satisfy.

[0031] First, as mentioned above, the "crystalline resin having unit (a)" in provision (A) can be incorporated into the binder resin by vinyl polymerization of a (meth)acrylic acid ester having an alkyl group with 16 to 30 carbon atoms with other polymerizable monomers.

[0032] On the other hand, the "resin having a sulfide structure" in provision (A) can be obtained by adding mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, and 2,2,4,6,6-pentamethylheptan-4-thiol; or thiuram disulfides such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, N,N'-dimethyl-N,N'-diphenyl thiuram disulfide, and N,N'-dioctadecyl-N,N'-diisopropyl thiuram disulfide to a polymerizable monomer and performing vinyl polymerization.

[0033] Furthermore, a "sulfide structure" is a structure represented by RSR, in which organic groups R are bonded to both sides of a sulfur atom. In this invention, a "resin having a sulfide structure" is a resin that has a structure represented by RSR, in which at least one of the organic groups R bonded to the sulfur atom is a polymer, and the whole can be considered a resin.

[0034] In this invention, it is necessary for the structure to have a sulfide structure in order to disperse uniformly in the binder resin and to interact with the colorant from a polarity standpoint. Similarly, when a sulfonic acid group was introduced instead of a sulfide structure as a functional group containing a sulfur element, although it had polarity, the polarity was too high, resulting in a tendency for the colorant to aggregate and a decrease in coloring power.

[0035] The additives, mercaptans and / or thiuram disulfides, can be added before polymerization begins or during polymerization. The amount added is preferably 0.01 parts by mass to 10 parts by mass, and more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of polymerizable monomer.

[0036] Next, the "crystalline resin having a sulfide structure and a unit (a) represented by formula (1)" of specification (B) can be obtained by adding a polymerizable monomer of a (meth)acrylic acid ester having an alkyl group with 16 to 30 carbon atoms, and the above-mentioned additives, mercaptans and / or thiuram disulfides, and then performing vinyl polymerization.

[0037] The binding resin, (A) A crystalline resin having a unit (a) represented by the above formula (1), and a resin having a sulfide structure, or (B) A crystalline resin having a sulfide structure and having a unit (a) represented by the above formula (1), This makes it possible to achieve a balance between low-temperature fixation, heat resistance, and coloring power.

[0038] Furthermore, of the above provisions (A) and (B), satisfying provision (B) is preferable from the viewpoint of significantly improving the coloring power. This is because the binder resin has a sulfide structure and a crystalline resin having unit (a), which makes it easier to increase the polarity of the entire crystalline resin, allowing it to interact with the polar groups in the colorant at a high frequency, thereby improving the dispersibility of the colorant and obtaining high coloring power.

[0039] If the binder resin satisfies specification (A), it is preferable that the content of crystalline resin having unit (a) in the binder resin is 50.0% by mass or more. A content of crystalline resin having unit (a) of 50.0% by mass or more makes it easier to improve low-temperature fixation and heat-resistant storage properties.

[0040] Furthermore, if the binder resin satisfies specification (B), it is preferable that the content of unit (a) and crystalline resin having a sulfide structure in the binder resin be 50.0% by mass or more. In this case as well, having a content of unit (a) and crystalline resin having a sulfide structure of 50.0% by mass or more makes it easier to improve low-temperature fixation and heat-resistant storage properties.

[0041] The colorants of the present invention are selected from carbon black, titanium black, copper phthalocyanine, copper phthalocyanine derivatives, anthraquinone compounds, azo pigments, and condensed polycyclic compounds.

[0042] It is hypothesized that the hydroxyl groups, alkoxy groups, carboxyl groups, aldehyde groups, ketone groups, imino groups, amino groups, and azo groups contained in these colorants interact with the polar parts of the sulfide structure, allowing the colorants to be uniformly dispersed in the binder resin, thereby achieving the coloring power of the present invention.

[0043] By selecting the above-mentioned colorants, the colorants interact with the binder resin that satisfies the requirements of (A) and / or (B) above, thereby improving the coloring power.

[0044] Examples of copper phthalocyanine compounds, their derivatives, and anthraquinone compounds include CI Pigment Blue 2, 3, 6, 15, 15:1, 15:2, 15:3, 15:4, 16, 17:1, and 60.

[0045] Examples of azo pigments and condensed polycyclic compounds include CI Pigment Yellow 3, 12, 13, 14, 15, 17, 62, 65, 73, 74, 83, 93, 97, 120, 138, 155, 180, 181, 185, 186, and 213.

[0046] Other examples include CI Pigment Red 31, 48, 57:1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 149, 150, 163, 170, 184, 185, 187, 202, 206, 207, 209, 237, 238, 251, 254, 255, 269 and CI Pigment Violet 19.

[0047] The colorants are preferably carbon black, CI pigment red 31, 122, 150; CI pigment yellow 74, 155; and CI pigment blue 15, 15:3.

[0048] On the other hand, when toner is measured with a differential scanning calorimeter (DSC), the peak temperature of the maximum endothermic peak is in the range of 50°C to 70°C. The presence of an endothermic peak in toner indicates that the toner contains crystalline components. A maximum endothermic peak temperature of 50°C or higher results in a toner with excellent storage properties and durability, while a peak temperature of 70°C or lower results in a toner with excellent low-temperature fixing properties and coloring ability.

[0049] Therefore, the peak temperature of the maximum endothermic peak is located within the above range, which allows the toner to achieve both low-temperature fixability, heat resistance for storage, and coloring power. More preferably, the range is 55°C to 70°C.

[0050] Furthermore, the heat absorption amount at the maximum endothermic peak of the toner of the present invention is 30 J / g or more and 70 J / g or less. This heat absorption amount indicates the amount of crystalline components in the toner. If it is 30 J / g or more, the amount of crystalline components is high, resulting in a toner with excellent low-temperature fixing and heat-resistant storage properties. If it is 70 J / g or less, the pigment dispersibility is improved, resulting in a toner with excellent coloring power.

[0051] It is preferable that the amount of heat absorbed at the maximum endothermic peak is between 40 J / g and 60 J / g.

[0052] The binder resin preferably contains monomer units derived from macromonomers. Macromonomers refer to polymers having polymerizable functional groups (for example, unsaturated groups such as carbon-carbon double bonds) at their ends.

[0053] The macromonomer preferably has an acryloyl group or a methacryloyl group at the end of its molecular chain. A methacryloyl group is more preferred due to its ease of copolymerization.

[0054] The number-average molecular weight (Mn) of the monomer units derived from the macromonomer is preferably 1,000 or more and 20,000 or less.

[0055] Note that the polymerizable monomers that produce unit (a) and unit (b) described below do not belong to the definition of macromonomers described above, and are polymerizable monomers with a number average molecular weight of less than 1,000.

[0056] Furthermore, the content of monomer units derived from macromonomers in the binder resin is preferably 0.01% by mass or more and 5.00% by mass or less, and more preferably 0.10% by mass or more and 1.00% by mass or less, based on the binder resin.

[0057] When the content ratio of monomer units derived from macromonomers is within the above range, the effects described later can be sufficiently obtained, and heterogeneity during polymerization can be easily suppressed.

[0058] When monomer units derived from macromonomers are present, branching of long linear molecular chains occurs within the molecular chain. These long linear molecular chains then self-aggregate, making it easier to adopt a microphase separation structure. As a result, unit (a) becomes more easily oriented, and crystalline regions are more easily retained. This improves heat resistance, storage durability, and overall longevity.

[0059] In particular, when the number-average molecular weight of the monomer units derived from the macromonomer is between 1,000 and 20,000, the branched structural portion (also called the grafted structural portion) is more mobile, and a microphase separation structure is easily formed.

[0060] Furthermore, components that constitute the long linear molecular chains (polymer portion) include styrene, styrene derivatives, methacrylic acid esters, acrylic acid esters, acrylonitrile, and methacrylonitrile. The polymer portion can be a polymer obtained by polymerizing these individually or two or more of them; or one having a polysiloxane skeleton.

[0061] It is preferable that the macromonomer is at least one selected from the group consisting of (meth)acrylic acid ester polymers having an acryloyl group or a methacryloyl group at the end of the molecular chain. In this case, in the monomer unit derived from the macromonomer, the (meth)acrylic acid ester polymer exists as a branched molecular chain, which increases cohesiveness and makes it easier to retain crystalline parts.

[0062] It is preferable that the crystalline resin has, in addition to unit (a), unit (b) that satisfies the following requirements. When the SP value of unit (a) is SPa and the SP value of unit (b) is SPb, the following equation (2) is satisfied. 3.0≦(SPb-SPa)≦25.0 (2)

[0063] By satisfying equation (2) above, the crystallinity of the crystalline resin is less likely to decrease, and the melting point is easier to maintain. This makes it easier to achieve both low-temperature fixability and heat-resistant storage. Furthermore, durability is also easier to improve. The inventors of this invention speculate as follows:

[0064] Unit (a) is incorporated into a crystalline resin, and the alkyl groups of unit (a), which form the side chains of the crystalline resin, aggregate to form domains, thereby exhibiting crystallinity. Normally, the incorporation of other units tends to inhibit crystallization, resulting in reduced crystallinity. However, in the present invention, because SPb-SPa is within the range of formula (2) above, during crystallization, unit (a) and unit (b) act to repel each other, allowing for good crystallization of each and maintaining high crystallinity.

[0065] Therefore, it becomes easier to achieve both low-temperature fixation and heat-resistant storage. Furthermore, durability also tends to improve.

[0066] Furthermore, if unit (a) contains (meth)acrylic acid esters having two or more alkyl groups with 16 to 30 carbon atoms, SPa represents a value calculated according to the molar ratio of each unit.

[0067] On the other hand, if unit (b) consists of two or more polymerizable monomers, SPb represents the SP value of the unit derived from each polymerizable monomer, and SPb-SPa is determined for the unit derived from each polymerizable monomer.

[0068] The content of unit (b) satisfying formula (2) above in the crystalline resin is preferably 20.0% by mass or more. A content of unit (b) of 20.0% by mass or more facilitates the sharp melting properties of the crystalline resin and improves low-temperature fixation. Furthermore, the crystallinity is less likely to deteriorate, and the melting point is easier to maintain, resulting in improved heat resistance and durability. If there are two or more types of unit (b) satisfying formula (2) above in the crystalline resin, the proportion of unit (b) shall be the total mass of those units.

[0069] Examples of polymerizable monomers (b) that form unit (b) include polymerizable monomers that satisfy formula (2) above, among the polymerizable monomers listed below.

[0070] Monomer (b) may be used alone or in combination of two or more types.

[0071] Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc.

[0072] Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0073] Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by known methods.

[0074] Monomers having a urethane group: For example, monomers obtained by reacting an alcohol having 2 to 22 carbon atoms and having an ethylenically unsaturated bond (such as 2-hydroxyethyl methacrylate, vinyl alcohol, etc.) with an isocyanate having 1 to 30 carbon atoms by known methods, and Monomers, etc., obtained by reacting an alcohol having 1 to 26 carbon atoms with an isocyanate having 2 to 30 carbon atoms and having an ethylenically unsaturated bond, using a known method.

[0075] Monomers having a urea group: For example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (n-butylamine, t-butylamine, propylamine, isopropylamine, etc.), secondary amines (di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cycloxylamine, etc.] with an isocyanate having 2 to 30 carbon atoms and having an ethylenically unsaturated bond, by known methods.

[0076] Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate.

[0077] In addition, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octoate can also be used as monomer (b).

[0078] In particular, the unit represented by the following formula (3) is preferred.

[0079] [ka] [R in equation (3)] 2 [This represents a hydrogen atom or a methyl group.]

[0080] By including the unit shown in formula (3) above, the crystallization of the crystalline resin is less likely to be inhibited, and in addition, the melting point tends to be higher, improving low-temperature fixability and heat resistance. Furthermore, because it has a highly polar nitrile group, it interacts easily with the colorant of the present invention, improving the dispersibility of the colorant and thus improving the coloring power.

[0081] Preferably, methacrylonitrile is used to obtain the unit shown in formula (3). Using methacrylonitrile improves the low-temperature fixability, heat resistance, and coloring ability mentioned above, and also makes it easier to suppress fogging. This is thought to be because the electron-donating methyl group is in close proximity to the nitrile group, which increases charge retention and suppresses charge leakage during the electrophotographic process.

[0082] The crystalline resin may contain one or more other units in addition to units (a) and (b). For example, it is preferable that the units be derived from polymerizable monomers such as the following. (Meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; styrenes such as styrene and α-methylstyrene.

[0083] In particular, using ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, or styrene is preferable because it allows for appropriate control of the toner's elasticity.

[0084] The acid value of the crystalline resin is preferably 5.0 mg KOH / g or less. If there are units that impart an acid value to the crystalline resin, the crystallization of unit (a) is easily inhibited. Therefore, by having an acid value of 5.0 mg KOH / g or less, the crystallinity of the crystalline resin can be ensured, and the low-temperature fixability and heat-resistant storage properties tend to be better. More preferably, it is 3.0 mg KOH / g or less, and even more preferably, 0 mg KOH / g.

[0085] The toner particles preferably have a core-shell structure, with the core containing a binder resin and the shell being an amorphous resin. Having the binder resin in the core makes it easier to disperse the polar portion of the sulfide structure, a characteristic of the present invention, throughout the toner particles, improving the dispersibility of the colorant in the toner particles and thus improving the coloring power. Furthermore, having an amorphous resin for the shell is preferable because it tends to improve electrostatic properties and durability.

[0086] It is preferable that the amorphous resin constituting the shell (hereinafter sometimes referred to as resin S) contains 1.0% by mass or more and 30.0% by mass or less of the unit (c) shown in formula (4).

[0087] [ka] [In formula (4), R 3 [where m represents a hydrogen atom or methyl group, and m represents an integer between 10 and 24.]

[0088] Unit (c) has a long-chain alkyl group (alkyl group with 10 to 24 carbon atoms) that has a similar structure to the side chain of unit (a) which exhibits the crystallinity of the crystalline resin. This makes the crystalline resin and resin S more compatible, and the interaction between the long-chain alkyl groups makes it easier for the crystals of the crystalline resin and resin S to adhere to each other. As a result, the adhesion between the core and the shell is improved, and durability is enhanced. In addition, because the crystalline resin and resin S are more compatible, the coating properties of the shell resin S are improved, the electrostatic charge is stabilized, and initial fogging is more easily suppressed.

[0089] Furthermore, it is preferable that the resin S does not show a clear endothermic peak in DSC measurement, i.e., is an amorphous resin, and that its glass transition temperature TgS is between 30°C and 90°C.

[0090] Because resin S is amorphous, it is easier to suppress deterioration in durability, thus improving durability. If the TgS is 30°C or higher, the heat resistance for storage is improved, and if it is 90°C or lower, the low-temperature fixing properties are improved.

[0091] Unit (c) can be incorporated into resin S by vinyl polymerization of a (meth)acrylic acid ester having an alkyl group with 10 to 24 carbon atoms as a polymerizable monomer.

[0092] Examples of (meth)acrylic acid esters having an alkyl group with 10 to 24 carbon atoms (m) include (meth)acrylic acid esters having a linear alkyl group with 10 to 24 carbon atoms [(meth)acrylic acid decyl (meth)acrylate, (meth)acrylate hendecyl (meth)acrylate, (meth)acrylate lauryl (meth)acrylate, (meth)acrylate tridecyl (meth)acrylate, (meth)acrylate tetradecyl (meth)acrylate, (meth)acrylate pentadecyl (meth)acrylate, (meth)acrylate cetyl (meth)acrylate, (meth)acrylate heptadecyl (meth)acrylate, (meth)acrylate stearyl (meth)acrylate, (meth)acrylate nonadecyl (meth)acrylate, (meth)acrylate eicosyl (meth)acrylate, (meth)acrylate heneicosyl (meth)acrylate, (meth)acrylate behenyl (meth)acrylate, (meth)acrylate lignoceryl (meth)acrylate, (meth)acrylate ceryl (meth)acrylate, (meth)acrylate octacosyl (meth)acrylate, (meth)acrylate myricyl (meth)acrylate, etc.].

[0093] Of these, it is preferable that the absolute value |nm| of the difference between the number of carbon atoms n of the long-chain alkyl group in unit (a) and the number of carbon atoms m of the long-chain alkyl group in unit (c) is 10 or less.

[0094] When n and m are close together, the interaction between long-chain alkyl groups becomes stronger, improving the adhesion between the crystalline resin and resin S, thus facilitating uniform coating, suppressing initial clouding, and improving durability. More preferably, |nm| is 5 or less, and even more preferably |nm| is 0.

[0095] Resin S may be used as a single unit (c) or as a combination of two or more units.

[0096] The content of unit (c) in resin S is preferably 1.0% by mass or more and 30.0% by mass or less. If the content is 1.0% by mass or more, the crystalline resin and resin S blend well together, and adhesion is improved, making it easier to obtain a toner with excellent durability and fogging suppression. If it is 30.0% by mass or less, the uniform coating of the shell is improved, and durability is improved. Preferably it is 1.0% by mass or more and 25.0% by mass or less, and more preferably 5.0% by mass or more and 20.0% by mass or less. The content of unit (c) is the sum of the content of all units shown in formula (4) above. The same applies when there are multiple monomers (c).

[0097] Resin S may contain, in addition to unit (c), one or more other units that do not satisfy the above conditions. Examples of polymerizable monomers that form other units include unit (b) as exemplified in the crystalline resin and monomers of other units.

[0098] The content of resin S in the toner particles is preferably 1.0% by mass or more and 20.0% by mass or less. When the content is 1.0% by mass or more and 20.0% by mass or less, initial fogging suppression, durable fogging suppression, and durability are improved. More preferably it is 2.0% by mass or more and 15.0% by mass or less, and even more preferably 3.0% by mass or more and 8.0% by mass or less.

[0099] Furthermore, it is preferable that the resin S has a weight-average molecular weight (MwS) of tetrahydrofuran (THF) soluble content measured by gel permeation chromatography (GPC) of 10,000 to 20,000. An MwS of 10,000 or more results in high elasticity of the resin S, making it easier to improve durability. An MwS of 20,000 or less improves the uniformity of the shell coating, making it easier to suppress fogging.

[0100] The acid value Av of resin S is preferably 5.0 mg KOH / g or more and 30.0 mg KOH / g or less. A value of 5.0 mg KOH / g or more improves the shell's coating properties and thus enhances its durability. More preferably, it is 10.0 mg KOH / g or more and 30.0 mg KOH / g or less.

[0101] The toner of the present invention may also contain vinyl resins, polyesters, polyurethanes, epoxy resins, etc., which are not included in the resins that constitute the present invention.

[0102] Polymerizable monomers that constitute vinyl resins not included in the present invention include those other than those that constitute unit (a) or (b) among those described above. Two or more types may be used in combination as needed.

[0103] Polyesters can be obtained by the condensation polymerization reaction of a divalent or greater polycarboxylic acid and a polyhydric alcohol.

[0104] Examples of polycarboxylic acids include the following compounds.

[0105] Dibasic acids such as succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, malonic acid, and dodecenylsuccinic acid, and their anhydrides or lower alkyl esters, as well as aliphatic unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid. 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and their anhydrides or lower alkyl esters. These may be used individually or in combination of two or more.

[0106] Examples of polyhydric alcohols include the following compounds:

[0107] Alkylene glycols (ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol); alkylene ether glycols (polyethylene glycol and polypropylene glycol); alicyclic diols (1,4-cyclohexanedimethanol); bisphenols (bisphenol A); alkylene oxide (ethylene oxide and propylene oxide) adducts of alicyclic diols. The alkyl portions of alkylene glycols and alkylene ether glycols may be linear or branched. In the present invention, branched alkylene glycols can also be preferably used. Furthermore, glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol, etc. These may be used individually or in combination of two or more.

[0108] Furthermore, monohydric acids such as acetic acid and benzoic acid, and monohydric alcohols such as cyclohexanol and benzyl alcohol may be used as needed to adjust the acid value and hydroxyl value.

[0109] The method for producing polyester is not particularly limited, but examples include the transesterification method and the direct polycondensation method.

[0110] Polyurethane is obtained by the reaction of a diol component with a diisocyanate component.

[0111] Examples of diisocyanate components include: aromatic diisocyanates with 6 to 20 carbon atoms (excluding carbon atoms in the NCO group; the same applies hereinafter), aliphatic diisocyanates with 2 to 18 carbon atoms, alicyclic diisocyanates with 4 to 15 carbon atoms, and modified products of these diisocyanates (modified products containing urethane groups, carbodiimide groups, allophanate groups, urea groups, biuret groups, uretoidone groups, uretoimine groups, isocyanurate groups, or oxazolidone groups; hereinafter also referred to as "modified diisocyanates"), as well as mixtures of two or more of these.

[0112] Examples of aromatic diisocyanates include: m- and / or p-xylylene diisocyanate (XDI) and α,α,α',α'-tetramethylxylylene diisocyanate.

[0113] Other examples of aliphatic diisocyanates include: ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), and dodecamethylene diisocyanate.

[0114] Examples of alicyclic diisocyanates include: isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4'-diisocyanate, cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate.

[0115] Among these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, with XDI, IPDI, and HDI being particularly preferred.

[0116] In addition to the diisocyanate components mentioned above, isocyanate compounds with three or more functionalities can also be used.

[0117] The diol components that can be used in polyurethane are the same as the divalent alcohols that can be used in polyester as mentioned above.

[0118] The toner may contain wax as a release agent, and there are no particular restrictions; any known wax can be used. Preferably, it is a hydrocarbon wax or an ester wax. By using a hydrocarbon wax or an ester wax, effective release properties can be ensured.

[0119] There are no particular limitations on hydrocarbon waxes, but examples include the following:

[0120] Aliphatic hydrocarbon waxes: low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymers, Fischer-Tropsch waxes, or waxes obtained by oxidation or acid addition of these materials.

[0121] Here, an ester wax is defined as any molecule having at least one ester bond, and either natural or synthetic ester waxes may be used.

[0122] There are no particular limitations on ester waxes, but examples include the following: Esters of monohydric alcohols and monocarboxylic acids, such as behenyl behenate, stearyl stearate, and palmityl palmitate; Esters of divalent carboxylic acids and monoalcohols, such as dibehenyl sebacate; Esters of dihydric alcohols such as ethylene glycol distearate and hexanediol dibehenate with monocarboxylic acids; Esters of trihydric alcohols such as glycerol tribehenate and monocarboxylic acids; Esters of tetrahydric alcohols such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate with monocarboxylic acids; Esters of hexahydritol alcohols such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate with monocarboxylic acids; Esters of polyfunctional alcohols such as polyglycerin behenates and monocarboxylic acids; natural ester waxes such as carnauba wax and rice wax;

[0123] Among these, esters of hexavalent alcohols and monocarboxylic acids, such as dipentaerythritol hexastearate, dipentaerythritol hexapalmitate, and dipentaerythritol hexabéhenate, are preferred.

[0124] The wax used in this invention may be a hydrocarbon wax or an ester wax used alone, a hydrocarbon wax and an ester wax used in combination, or a mixture of two or more types of each wax used.

[0125] The toner may optionally contain one or more additives selected from colorants other than the colorant according to the present invention, magnetic materials, charge control agents, and fluidizers, and the colorant is selected from the viewpoint of hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner particles.

[0126] If the coloring agent is not magnetic particles, it is preferable that the coloring agent is contained in an amount of 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the resin component. If magnetic particles are used as the coloring agent, it is preferable that the amount added is 40.0 parts by mass or more and 150.0 parts by mass or less per 100.0 parts by mass of the resin component.

[0127] The charge control agent can be used without any particular limitations. Examples of negative charge control agents include: monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds.

[0128] Examples of positive charge control agents include quaternary ammonium salts, polymeric compounds having quaternary ammonium salts in their side chains, guanidine compounds, pyridine compounds, nigrosine compounds, and imidazole compounds.

[0129] The charge control agent is preferably contained in an amount of 0.01 parts by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the resin component. More preferably, it is contained in an amount of 0.5 parts by mass or more and 10.0 parts by mass or less.

[0130] Examples of external additives include: inorganic fine particles selected from the group consisting of silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of composite oxides include silica-aluminum fine particles and strontium titanate fine particles.

[0131] The external additive is preferably contained in an amount of 0.01 parts by mass or more and 8.0 parts by mass or less per 100 parts by mass of toner particles, and more preferably in an amount of 0.1 parts by mass or more and 4.0 parts by mass or less.

[0132] Toner particles may be manufactured by any of the conventionally known methods, such as suspension polymerization, emulsification and agglutination, dissolution and suspension, or pulverization, as long as they are within the scope of the present configuration. Among these, suspension polymerization is preferred as it is easier to uniformly disperse the polar portion of the sulfide structure in the binder resin, and the following manufacturing method is preferred.

[0133] I will now describe the suspension polymerization method in detail.

[0134] For example, the pre-synthesized resin S is added to a mixture of polymerizable monomers that produce the binder resin of the present invention, and an additive that can introduce a sulfide structure into the resin, such as the colorant, mercaptans, and / or thiuram disulfides of the present invention, is added thereto. In addition, if necessary, a polymerizable monomer composition to which other materials such as wax, charge control agents, and crosslinking agents are added is uniformly dissolved or dispersed to prepare a polymerizable monomer composition.

[0135] Subsequently, the polymerizable monomer composition is dispersed in an aqueous medium using a stirrer or the like to prepare suspended particles of the polymerizable monomer composition. Then, the polymerizable monomers contained in the particles are polymerized with an initiator or the like to obtain suspension polymerization toner particles.

[0136] After polymerization is complete, the toner particles should be filtered, washed, and dried by known methods, and external additives may be added as needed to obtain toner.

[0137] Known polymerization initiators can be used as the polymerization initiator. Examples include azo-based or diazo-based polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; and peroxide-based polymerization initiators such as benzoyl peroxide, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0138] In addition, known chain transfer agents and polymerization inhibitors may be used.

[0139] The aqueous medium may contain an inorganic or organic dispersion stabilizer. Known dispersion stabilizers can be used as the dispersion stabilizer.

[0140] Examples of inorganic dispersion stabilizers include phosphates such as hydroxyapatite, tricalcium phosphate, dicalcium phosphate, magnesium phosphate, aluminum phosphate, and zinc phosphate; carbonates such as calcium carbonate and magnesium carbonate; metal hydroxides such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide; sulfates such as calcium sulfate and barium sulfate; calcium metasilicate; bentonite; silica; and alumina.

[0141] On the other hand, examples of organic dispersion stabilizers include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, polyacrylic acid and its salts, and starch.

[0142] When using inorganic compounds as dispersion stabilizers, commercially available compounds may be used as is, but to obtain finer particles, the inorganic compounds may be generated in an aqueous medium before use. For example, in the case of calcium phosphate such as hydroxyapatite or tricalcium phosphate, it is preferable to mix the aqueous phosphate solution with the aqueous calcium salt solution under high stirring.

[0143] The aqueous medium may contain a surfactant. Known surfactants can be used as the surfactant. Examples include anionic surfactants such as sodium dodecylbenzene sulfate and sodium oleate; cationic surfactants; amphoteric surfactants; and nonionic surfactants.

[0144] [Various measurement methods] The following describes various measurement methods, etc.

[0145] <Method for measuring the content ratio of various units in resin> The measurement of the content ratio of various units in the resin is 1 The procedure is performed using H-NMR under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: 30℃ Sample: Place 50 mg of the sample to be measured into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve in a constant temperature bath at 40°C to prepare the sample.

[0146] obtained 1 The H-NMR chart is analyzed to identify the structure of each unit. Here, as an example, the measurement of the content of unit (a) in a crystalline resin is described. 1In the 1H-NMR chart, select a peak that is independent of the peaks attributed to the components of other units from among the peaks attributed to the components of unit (a), and calculate the integral value S1 of this peak. For the other units contained in the resin, calculate the integral values in the same manner respectively.

[0147] When the units constituting the crystalline resin are unit (a) and one other unit, the content ratio of unit (a) is determined as follows using the above integral value S1 and the integral value S2 of the peak of the other unit. Here, n1 and n2 are the number of hydrogens in the components to which the peaks focused on for each site are attributed. Content ratio of unit (a) (mol%) = {(S1 / n1) / ((S1 / n1)+(S2 / n2))}×100

[0148] Even when there are two or more other units, the content ratio of unit (a) can be calculated in the same manner.

[0149] When a polymerizable monomer that does not contain a hydrogen atom in components other than the vinyl group is used, 13 using 13C-NMR, set the measured nucleus to 13 13C, perform the measurement in single pulse mode, 1 and calculate in the same manner as with 1H-NMR.

[0150] Multiply the ratio (mol%) of each unit calculated by the above method by the molecular weight of each unit to convert the content ratio of each unit to mass%.

[0151] Also, when measuring NMR using the toner as a sample, the peaks of resins other than wax and crystalline resin may overlap and independent peaks may not be observed. As a result, the content ratio of each unit in the binder resin may not be calculated. In that case, the binder resin' can be manufactured by performing the same production without using wax or other resins, and it can be analyzed by regarding it as a crystalline resin. The measurement is also performed using the same method for the above resin S.

[0152] <Method for measuring the weight-average molecular weight (Mw) of resins> The weight-average molecular weight (Mw) of the resin is measured by gel permeation chromatography (GPC) as follows:

[0153] First, the sample is dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the resulting solution is filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain the sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8% by mass. This sample solution is then used for measurement under the following conditions. Equipment: HLC8120 GPC (Detector: RI) (Manufactured by Tosoh Corporation) Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 series, 7-car set (manufactured by Showa Denko) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL

[0154] When calculating the molecular weight of the sample, standard polystyrene resin (for example, product name "TSK S Standard Polystyrene F-850, F-450, F-288, F-128, F-8 0, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-25 A molecular weight calibration curve created using "00, A-1000, A-500" (manufactured by Tosoh Corporation) was used. To use.

[0155] <Method for measuring maximum endothermic peak temperature and heat absorption amount> The melting point and heat absorption of the toner or resin are measured using a DSC Q2000 (TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃

[0156] The temperature correction for the device's detection unit uses the melting points of indium and zinc, while the heat of fusion of indium is used for heat quantity correction.

[0157] Specifically, approximately 5 mg of the sample is accurately weighed, placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference. The temperature is raised to 180°C at a rate of 10°C / min. Then, the peak temperature and endothermic value are calculated from each peak.

[0158] When using toner as a sample, if the maximum endothermic peak (usually an endothermic peak thought to originate from the crystalline resin) does not overlap with other endothermic peaks such as those of the mold release agent, the temperature at that endothermic peak can be treated as the maximum endothermic peak temperature of the toner, and the amount of heat absorbed can be calculated.

[0159] On the other hand, if other endothermic peaks, such as those of release agents, overlap with the maximum endothermic peak, it is necessary to subtract the endothermic peak originating from the release agent.

[0160] For example, by the following method, the endothermic peak originating from the mold release agent can be subtracted to obtain the endothermic peak originating from the binder resin.

[0161] First, a separate DSC measurement is performed on the release agent alone to determine its endothermic properties. Next, the release agent content in the toner is determined. The release agent content in the toner can be measured using known structural analysis methods. Then, the amount of heat absorbed by the release agent is calculated from the release agent content in the toner, and this amount is subtracted from the endothermic peak obtained from the measurement.

[0162] If the release agent is highly compatible with the binder resin component, it is necessary to calculate and subtract the amount of heat absorbed by the release agent after multiplying the release agent content by the compatibility ratio. The compatibility ratio is calculated by dividing the amount of heat absorbed obtained when the molten mixture of the resin component and the release agent are molten and mixed in the same ratio as the release agent content by the theoretical amount of heat absorbed calculated from the heat absorbed by the molten mixture and the heat absorbed by the release agent alone, which have been determined in advance.

[0163] The amount of heat absorbed is calculated using DSC analysis software, ranging from a temperature 20.0°C below the corresponding endothermic peak Tp to a temperature 10.0°C above Tp.

[0164] <Measurement of glass transition temperature> The glass transition temperature (Tg) is measured using a differential scanning calorimetry analyzer "Q2000" (TA Instruments) in accordance with ASTM D3418-82. The temperature correction for the instrument's detection unit uses the melting points of indium and zinc, and the heat correction uses the heat of fusion of indium.

[0165] Specifically, approximately 2 mg of the sample is accurately weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and measurements are taken at a heating rate of 10°C / min within the measurement temperature range of -10 to 200°C. During the measurement, the temperature is raised to 200°C, then lowered to -10°C, and then raised again. The specific heat change is obtained in the temperature range of 30°C to 100°C during this second heating process. The intersection point of the line midway between the baseline before and after the specific heat change and the differential heat curve is defined as the glass transition temperature (Tg).

[0166] <Measurement of weight-average particle size (D4) of toner> The weight-average particle size (D4) of the toner is calculated as follows. The measuring device used is the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), a precision particle size distribution analyzer using the pore electrical resistance method equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the included dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed using 25,000 effective measurement channels.

[0167] The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to a concentration of 1.0%, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.).

[0168] Before performing measurements and analysis, configure the dedicated software as follows.

[0169] In the dedicated software's "Change Standard Measurement Method (SOMME)" 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 "Standard Particle 10.0 μm" (manufactured by Beckman Coulter, Inc.). Press the "Measure Threshold / Noise Level Button" to automatically set the threshold and noise level. Also, set the current to 1,600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement".

[0170] In the dedicated software's "Pulse to Particle Size Conversion Settings" screen, set the bin spacing to logarithmic particle size, the particle size bins to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

[0171] The specific measurement method is as follows: (1) Place 200.0 mL of electrolytic solution into a 250 mL round-bottom glass beaker specifically designed for the Multisizer 3, set it on the sample stand, and stir the mixture with the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Tube Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Place 30.0 mL of the electrolytic solution into a 100 mL flat-bottomed glass beaker. Add 0.3 mL of a diluted solution of "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.) diluted three times by mass with deionized water as a dispersant. (3) Prepare an "Ultrasonic Dispersion System Tetra150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120W, which incorporates two oscillators with an oscillation frequency of 50kHz, with their phases shifted by 180 degrees. Add 3.3L of deionized water to the water tank of the ultrasonic disperser, and add 2.0mL of Contaminon N to this water tank. (4) Place the beaker from (2) above into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) above with ultrasound, add 10 mg of toner particles to the electrolytic aqueous solution in small amounts and disperse them. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate. (6) Using a pipette, add the electrolytic aqueous solution (5) containing the dispersed toner particles to the round-bottom beaker (1) placed in the sample stand, adjusting the concentration to 5%. Continue measuring until the number of particles reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is calculated. Note that the "Average Diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen when the dedicated software is set to Graph / Volume % is the weight-average particle size (D4).

[0172] <Measurement of Acid Value of Resin> The acid value is the weight (mg) of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of resin A in this invention is measured in accordance with JIS K 0070-1992, and specifically, it is measured according to the following procedure.

[0173] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add deionized water to make a total volume of 100 mL, and obtain a phenolphthalein solution.

[0174] Dissolve 7 g of special grade potassium hydroxide in 5 mL of water and add ethyl alcohol (95 vol%) to make 1 L. Place the solution in an alkali-resistant container, taking care not to allow it to come into contact with carbon dioxide, etc., and leave it for 3 days. After that, filter the solution to obtain potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the above potassium hydroxide solution is determined by taking 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the above phenolphthalein solution, titrating with the above potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. The above 0.1 mol / L hydrochloric acid should be prepared in accordance with JIS K 8001-1998.

[0175] (2) Operation (A) Main examination 2.0 g of melt-kneaded and pulverized toner sample is accurately weighed into a 200 mL Erlenmeyer flask, and 100 mL of a toluene / ethanol (2:1) mixture is added. The mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and the sample is titrated with the potassium hydroxide solution. The endpoint of the titration is when the indicator turns a pale pink color for 30 seconds. (B) Blank test The titration procedure is the same as described above, except that no sample is used (i.e., only a mixed solution of toluene / ethanol (2:1) is used).

[0176] (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(C - B) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (mL), C: addition amount of potassium hydroxide solution in this test (mL), f: factor of potassium hydroxide solution, S: sample (g).

[0177] <Calculation method of SP value> SPa and SPb were determined as follows according to the calculation method proposed by Fedors.

[0178] For the atoms or atomic groups in the molecular structure in the state where the double bonds of each polymerizable monomer are cleaved by polymerization, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) were obtained from the table described in "polym. Eng. Sci., 14(2), 147 - 154(1974)", and (4.184 × ΣΔei / ΣΔvi) 0.5 was taken as the SP value (J / cm 3 ) 0.5 and so on.

[0179] The SP value, SPA, and SPB of the resin were obtained by calculating the evaporation energy (Δei) and molar volume (Δvi) of the units constituting the resin for each unit, calculating the product with the molar ratio (j) of each unit in the resin, respectively, and dividing the sum of the evaporation energies of each unit by the sum of the molar volumes, and calculating according to the following formula (6). Formula (6) SPs = {(Σj × ΣΔei) / (Σj × ΣΔvi)} 1 / 2

[0180] As described above, the SP value was calculated for each resin.

[0181] The unit of the SP value is 1 (J / cm 3 ) 0.5 = 2.045 (cal / cm 3 ) 0.5 and can be converted to the unit of (cal / cm 3 ) 0.5 by this.

[0182] [Configurations included in embodiments of the present invention] This embodiment includes the following configuration. (Configuration 1) A toner having toner particles containing a binder resin and a colorant, The binder resin is a resin that satisfies at least one of the following requirements (A) and (B): (A) A crystalline resin having a unit (a) represented by the above formula (1), and a resin having a sulfide structure; (B) Contains a crystalline resin having a sulfide structure and a unit (a) represented by the above formula (1); The coloring agent is one of the coloring agents selected from the group consisting of carbon black, titanium black, copper phthalocyanine, copper phthalocyanine derivatives, anthraquinone compounds, azo pigments, and condensed polycyclic compounds. When the toner was measured with a differential scanning calorimeter, the peak temperature of the maximum endothermic peak was in the range of 50°C to 70°C. A toner characterized in that the heat absorption of the maximum endothermic peak is 30 J / g or more and 70 J / g or less. (Configuration 2) The toner according to Configuration 1, wherein the colorant is selected from the group consisting of carbon black, CI pigment red 31, CI pigment red 122, CI pigment red 150, CI pigment yellow 74, CI pigment yellow 155, CI pigment blue 15, and CI pigment blue 15:3. (Configuration 3) The toner according to Configuration 1 or 2, wherein the binder resin satisfies the requirements of (A), and the content of crystalline resin having unit (a) represented by formula (1) in the binder resin is 50.0% by mass or more. (Configuration 4) The toner according to claim 1, wherein the binder resin is a resin that satisfies the provision (B). (Configuration 5) The toner according to any one of Configurations 1 to 4, wherein the content of a crystalline resin having a sulfide structure and having a unit (a) represented by formula (1) in the binder resin is 50.0% by mass or more. (Configuration 6) The toner according to any one of Configurations 1 to 5, wherein the content of unit (a) in the crystalline resin is 40.0% by mass or more and 80.0% by mass or less. (Configuration 7) The binder resin contains monomer units derived from macromonomers, The toner according to any one of configurations 1 to 6, wherein the number-average molecular weight of the monomer units derived from the macromonomer is 1,000 or more and 20,000 or less. (Configuration 8) The toner according to Configuration 7, wherein the monomer unit derived from the macromonomer has a (meth)acrylic acid ester polymer portion. (Configuration 9) The crystalline resin has unit (b) in addition to unit (a), SP value of unit (a) ((J / cm 3 ) 0.5 ) is SPa, and the SP value of the unit (b) is (J / cm 3 ) 0.5 When SPb is defined as SPa, the toner according to any of configurations 1 to 8 satisfies the following formula (2). 3.0≦(SPb-SPa)≦25.0 (2) (Configuration 10) The toner according to Configuration 9, wherein unit (b) is the unit represented by formula (3) above. (Configuration 11) The toner according to any one of Configurations 1 to 10, wherein the toner particles have a core-shell structure, the core has the binder resin, and the shell is an amorphous resin. (Configuration 12) The toner according to Configuration 11, wherein the amorphous resin has 1.0% by mass or more and 30.0% by mass or less of the unit (c) represented by the above formula (4). (Configuration 13) The toner according to Configuration 11 or 12, wherein the acid value Av of the amorphous resin is 5.0 mg KOH / g or more and 30.0 mg KOH / g or less. (Configuration 14) The toner particles are the toner described in any of Configurations 1 to 13, which is a suspension polymerization toner. [Examples]

[0183] The present invention will be described in detail below with reference to examples, but these examples are not intended to limit the present invention in any way. In the following formulations, parts are by mass unless otherwise specified.

[0184] <Example of resin S1 manufacturing> The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. solvent: • Toluene 100.0 parts monomer: • Styrene 64.0 parts Behenyl acrylate 18.0 parts • Acrylonitrile 15.0 parts • Methacrylic acid 3.0 parts • Polymerization initiator: t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) 5.0 parts The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain resin S1 for the shell. The physical properties of resin S1 are shown in Table 1.

[0185] <Manufacturing examples of resins S2-S10> Resins S2 to S10 were obtained in the same manner as the production method for resin S1, except that the polymerizable monomer and the amount of polymerizable monomer added were changed as shown in Table 1. The physical properties of resins S2 to S10 are shown in Table 1.

[0186] <Example of resin S11 manufacturing> A pressurized reaction vessel equipped with a reflux tubing, a stirrer, a thermometer, a nitrogen inlet tube, a dropping device, and a vacuum device, solvent: • Methanol 250 copies 2-Butanone 150 copies 2-propanol 100 units monomer: • Styrene 85 parts Butyl acrylate 12 parts 2-Acrylamide-2-methylpropanesulfonic acid 3 parts (Hereafter referred to as "AMPS") The mixture was heated to reflux temperature while stirring after adding the additive. A solution of 0.28 parts of tert-butylperoxy-2-ethylhexanoate, a polymerization initiator, diluted with 20 parts of 2-butanone was added dropwise over 30 minutes, and the mixture was stirred for a further 5 hours to initiate polymerization.

[0187] After removing the polymerization solvent under reduced pressure, the resulting polymer was coarsely ground to a particle size of 100 μm or less using a cutter mill equipped with a 150-mesh screen. The resulting resin S11 had a Tg of approximately 70°C. The physical properties of resin S11 are shown in Table 1.

[0188] [Table 1]

[0189] <Example of Toner 1 manufacturing> [Toner manufacturing by suspension polymerization method] (Preparation of toner particles 1) The following materials were added to an attritor (manufactured by Nippon Coke Co., Ltd.). • Methacrylonitrile 29.91 parts • Styrene 6.98 parts • Ethyl methacrylate 12.96 parts • 0.3 parts of polymethyl methacrylate having a methacryloyl group at the terminal end (Macromonomer, manufactured by Toagosei Co., Ltd., AA-6, Mn: 6,000) • Coloring agent (carbon black) 8.0 parts A dispersion of raw materials was obtained by dispersing 5 mm diameter zirconia beads at 200 rpm for 2 hours.

[0190] Meanwhile, 735.0 parts of deionized water and 16.0 parts of trisodium phosphate dodecahydrate were added to a container equipped with a high-speed stirring device homomixer (manufactured by Primix) and a thermometer, and the temperature was raised to 60°C while stirring at 12,000 rpm. Subsequently, a calcium chloride aqueous solution, prepared by dissolving 9.0 parts of calcium chloride dihydrate in 65.0 parts of deionized water, was added to the above container, and the mixture was stirred at 12,000 rpm for 30 minutes while maintaining a temperature of 60°C, thereby obtaining an aqueous medium in which a dispersion stabilizer containing hydroxyapatite was dispersed in water.

[0191] Next, the above raw material dispersion was transferred to a container equipped with a stirring device and a thermometer, and heated to 60°C while stirring at 100 rpm. The following materials were then added. Behenyl acrylate 49.85 parts ·Resin S1 3.8 parts t-dodecyl mercaptan 1.0 part • Wax (Dipentaerythritol Hexastearate) 9.0 parts After stirring at 100 rpm for 30 minutes while maintaining a temperature of 60°C, 5.0 parts of t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV) were added as a polymerization initiator and stirred for another minute. This mixture was then added to an aqueous medium being stirred at 12,000 rpm using the high-speed stirring device described above. Stirring was continued at 12,000 rpm for 20 minutes while maintaining a temperature of 60°C using the high-speed stirring device described above to obtain a granulated liquid.

[0192] The granulated liquid described above was transferred to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, and heated to 70°C while stirring at 150 rpm under a nitrogen atmosphere. The polymerization reaction was carried out at 150 rpm for 12 hours while maintaining the temperature at 70°C to obtain a toner particle dispersion.

[0193] The obtained toner particle dispersion was cooled to 45°C while stirring at 150 rpm, and then heat-treated for 5 hours while maintaining the temperature at 45°C. After the heat treatment, it was cooled to 30°C, and while maintaining stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the above-mentioned dispersion stabilizer. Then, the solid components were filtered off, thoroughly washed with deionized water, and vacuum-dried at 30°C for 24 hours to obtain toner particles 1 containing binder resin 1.

[0194] Furthermore, binder resin 1' was obtained in the same manner as the method for producing toner particles 1 described above, except that carbon black, resin S1, and wax were not used. The weight-average molecular weight (Mw) of binder resin 1' was 56,000, the melting point was 63°C, and the acid value was 0.0 mgKOH / g. NMR analysis of binder resin 1' revealed that it contained 49.8% by mass of units derived from behenyl acrylate, 29.9% by mass of units derived from methacrylonitrile, 7.0% by mass of units derived from styrene, 13.0% by mass of units derived from ethyl methacrylate, and 0.3% by mass of units derived from polymethyl methacrylate having a methacryloyl group at the end.

[0195] Furthermore, it was confirmed by combustion ion chromatography that the sulfur element derived from the mercaptan was present in the binder resin 1' in the prescribed amount. The measurement conditions for combustion ion chromatography were as follows: Equipment: Combustion device (AQF-100) Mitsubishi Chemical Analytec, Ion chromatograph (ICS-2000), Thermo Fisher Scientific. Sample amount: approximately 20 mg Combustion conditions: AQF: Inlet: 900℃ Outlet: 1000℃ Gas: Ar / O2: 200ml / min O2: 400ml / min Ar: 150ml / min ABC:1st 120mm,120sec 2nd 140mm,160sec 3rd 150mm,150sec End 360sec Cool Time 30sec Boat Speed: 10mm / sec GA-100: Absorption volume: 10ml Absorbent solution: H2O2 30 ppm, internal standard PO4 1 ppm Analytical conditions: Column: AS-17 Temperature: 35℃ Fluid delivery conditions: 0 → 15 minutes KOH 1 mmol → 40 mmol gradient

[0196] Under the above measurement conditions, a calibration curve was created using standard samples, and the sulfur element in the resin was quantified.

[0197] Furthermore, since the binder resin 1 and binder resin 1' contained in toner 1 are manufactured in the same manner, it was determined that they have equivalent physical properties.

[0198] To 100.0 parts of toner particles, 2.0 parts of silica microparticles (hydrophobized with hexamethyldisilazane, number-average particle size of primary particles: 10 nm) were added as an external additive and mixed using an FM mixer (manufactured by Nippon Coke Industries Co., Ltd.) at 3000 rpm for 15 minutes to obtain toner 1. The SP values ​​related to this invention are shown in Table 3. The physical properties of toner 1 are shown in Table 4.

[0199] <Manufacturing examples for toners 2-29, 35, and 36> In the manufacturing example of toner 1, toner particles 2-29, 35, and 36 were obtained by following all the same procedures except for changing the type and amount of materials used as shown in Table 2.

[0200] Furthermore, toners 2-29, 35, and 36 were obtained by performing the same external addition as toner 1. The SP values ​​related to the present invention are shown in Table 3. The physical properties of the toners are shown in Table 4.

[0201] <Example of Toner 30 Manufacturing> [Toner manufacturing using emulsification and coagulation method] (Preparation of polymer dispersion 1) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Toluene 100.00 copies • Monomer composition 100.00 parts Behenyl acrylate 50.00 parts Methacrylonitrile 30.00 units Styrene 7.00 units Ethyl methacrylate 13.00 parts t-dodecyl mercaptan 1.0 part t-butyl peroxypivalate 5.0 parts A monomer solution was prepared by mixing the above components. An aqueous surfactant solution was prepared by dissolving 10 parts of anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK) in 1130 parts of deionized water. This surfactant solution and the monomer solution were then placed in a two-necked flask and emulsified by stirring at a rotation speed of 10,000 r / min using a homogenizer (manufactured by IKA Corporation: Ultra-Turrax T50).

[0202] Subsequently, the flask was purged with nitrogen, and the contents were heated in a water bath with slow stirring until they reached 70°C, thereby initiating polymerization.

[0203] After continuing the reaction for 8 hours, the reaction solution was cooled to room temperature, and the concentration was adjusted with deionized water to obtain an aqueous dispersion of polymer fine particles 1 with a concentration of 20% by mass (polymer dispersion 1).

[0204] The 50% particle size (D50) of polymer microparticle 1, based on its volume distribution, was measured using a dynamic light scattering particle size analyzer, NanoTrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and was found to be 0.40 μm.

[0205] (Preparation of resin dispersion 1 for shells) • Toluene (manufactured by Wako Pure Chemical Industries) 300 copies ·Resin S1 100 parts The above materials were weighed, mixed, and dissolved at 90°C.

[0206] Separately, 5.0 parts sodium dodecylbenzenesulfonate and 10.0 parts sodium laurate were added to 700 parts deionized water and heated to 90°C until dissolved.

[0207] Next, the toluene solution and the aqueous solution were mixed and stirred at 7000 rpm using a high-speed stirring device TK Robomix (manufactured by Primix). Furthermore, the mixture was emulsified at a pressure of 200 MPa using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Machinery Industry). After that, toluene was removed using an evaporator, and the concentration was adjusted with deionized water to obtain an aqueous dispersion of shell resin dispersion 1 with a concentration of 20% by mass.

[0208] The 50% particle size (D50) of the volume distribution of the resin dispersion 1 for shells was measured using a dynamic light scattering particle size analyzer NanoTrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and was found to be 0.40 μm.

[0209] (Preparation of wax dispersion 1) Fischer Tropush Wax 100.00 units (Manufactured by Nippon Seiro Co., Ltd.: HNP-51, Melting point: 74℃) • Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku) 5.00 parts • Ion-exchanged water: 395.00 units The above materials were weighed, placed in a mixing container equipped with a stirring device, heated to 90°C, and then circulated through a CreaMix W Motion (manufactured by M-Technique) for a dispersion treatment of 60 minutes. The dispersion treatment conditions were as follows: • Rotor outer diameter 3cm • Clearance 0.3mm • Rotor rotation speed: 19,000 r / min Screen rotation speed: 19000 r / min After dispersion treatment, the wax dispersion 1 with a concentration of 20% by mass of wax fine particles 1 was obtained by cooling to 40°C under cooling treatment conditions of rotor rotation speed 1000 r / min, screen rotation speed 0 r / min, and cooling rate 10°C / min.

[0210] The 50% particle size (D50) of wax microparticle 1, based on its volume distribution, was measured using a dynamic light scattering particle size analyzer, NanoTrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and was found to be 0.15 μm.

[0211] (Preparation of Colorant Dispersion Liquid 1) · 50.00 parts of colorant (Yellow Pigment PY74) · 7.50 parts of anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) · 442.50 parts of ion-exchanged water The above materials were weighed and mixed, and then dispersed for 1 hour using a high-pressure impact disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain Colorant Dispersion Liquid 1 with a concentration of 10% by mass of Colorant Fine Particles 1 in which the colorant was dispersed.

[0212] When the 50% particle size (D50) based on the volume distribution of Colorant Fine Particles 1 was measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.20 μm.

[0213] (Manufacture of Toner 30) · 400.00 parts of Polymer Dispersion Liquid 1 · 225.00 parts of Wax Dispersion Liquid 1 · 300.00 parts of Colorant Dispersion Liquid 1 · 160.00 parts of ion-exchanged water Each of the above materials was put into a round stainless steel flask and mixed. Subsequently, it was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultraturrax T50 (manufactured by IKA). After adding a 1.0% nitric acid aqueous solution and adjusting the pH to 3.0, it was heated to 58 °C while appropriately adjusting the rotation speed such that the mixture was stirred using a stirring blade in a water bath for heating.

[0214] The volume average particle size of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III. When aggregated particles with a volume average particle size of about 6.0 μm were formed, the pH was adjusted to 9.0 using a 5% sodium hydroxide aqueous solution.

[0215] Thereafter, it was heated to 75 °C while continuing stirring. Then, the aggregated particles were fused by holding at 75 °C for 1 hour.

[0216] Thereafter, 64.00 parts (solid content 4.00 parts) of the resin dispersion liquid for shell was added, and the aggregated particles were fused by holding at 75 °C for 1 hour.

[0217] Thereafter, it was cooled to 50 °C and held for 3 hours to promote the crystallization of the polymer.

[0218] Thereafter, it was cooled to 25 °C, filtered and solid-liquid separated, and then washed with ion-exchanged water.

[0219] After completion of the washing, drying was performed using a vacuum dryer to obtain toner particles 30 having a weight average particle diameter (D4) of 6.2 μm.

[0220] External addition similar to that in Example 1 was performed on the toner particles 30 to obtain toner 30. The SP values related to the present invention are shown in Table 3. The physical properties of the toner are shown in Table 4.

[0221] <Production Examples of Toners 31 to 34> (Preparation of Polymer Dispersion Liquid 2) In a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, the following materials were charged under a nitrogen atmosphere. · Toluene 100.00 parts · Monomer composition 100.00 parts ·· Behenyl acrylate 50.00 parts ·· Methacrylonitrile 30.00 parts ·· Styrene 7.00 parts ·· Ethyl methacrylate 13.00 parts · t-Dodecyl mercaptan 1.0 part · t-Butyl peroxypivalate 5.0 parts Each of the above components was mixed to prepare a monomer solution. An anionic surfactant (Neogen RK manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) ①0 parts was dissolved in 1130 parts of ion-exchanged water, and the surfactant aqueous solution and the monomer solution were charged into a two-necked flask and stirred at a rotation speed of 10,000 r / min using a homogenizer (Ultra Turrax T50 manufactured by IKA) for emulsification.

[0222] Note: There seems to be a formatting issue in the original text where "①0 parts" is likely a typo. It should probably be "10 parts". This has been noted in the translation for clarity.Subsequently, the flask was purged with nitrogen, and the contents were heated in a water bath with slow stirring until they reached 70°C, thereby initiating polymerization.

[0223] After continuing the reaction for 8 hours, the reaction solution was cooled to room temperature, and the concentration was adjusted with deionized water to obtain an aqueous dispersion of polymer fine particles 2 with a concentration of 20% by mass (polymer dispersion 2).

[0224] The 50% particle size (D50) of polymer microparticles 2, based on the volume distribution, was measured using a dynamic light scattering particle size analyzer, NanoTrac UPA-EX150 (manufactured by Nikkiso), and was found to be 0.40 μm.

[0225] (Preparation of polymer dispersion 3) The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Toluene 100.00 copies • Monomer composition 100.00 parts Styrene 75.00 units Butyl acrylate 25.00 parts t-dodecyl mercaptan 1.0 part t-butyl peroxypivalate 5.0 parts A monomer solution was prepared by mixing the above components. An aqueous surfactant solution was prepared by dissolving 10 parts of anionic surfactant (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK) in 1130 parts of deionized water. This surfactant solution and the monomer solution were then placed in a two-necked flask and emulsified by stirring at a rotation speed of 10,000 r / min using a homogenizer (manufactured by IKA Corporation: Ultra-Turrax T50).

[0226] Subsequently, the flask was purged with nitrogen, and the contents were heated in a water bath with slow stirring until they reached 70°C, thereby initiating polymerization.

[0227] After continuing the reaction for 8 hours, the reaction solution was cooled to room temperature, and the concentration was adjusted with deionized water to obtain an aqueous dispersion of polymer fine particles 3 with a concentration of 20% by mass (polymer dispersion 3).

[0228] When the 50% particle size (D50) based on the volume distribution of the polymer microparticles 3 was measured using a dynamic light scattering particle size distribution analyzer NanoTrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.40 μm.

[0229] Toner particles 31 were obtained in the same manner as in the production example of toner 30, except that 400 parts of the polymer dispersion 1 were changed to 208 parts of the polymer dispersion 2 and 192 parts of the polymer dispersion 3.

[0230] Toner particles 32 were obtained in the same manner as in the production example of toner 30, except that 400 parts of the polymer dispersion 1 were changed to 192 parts of the polymer dispersion 2 and 208 parts of the polymer dispersion 3.

[0231] Toner particles 33 were obtained in the same manner as in the preparation of the polymer dispersion 3 in the production example of toner 30, except that t-dodecyl mercaptan was not used.

[0232] Toner particles 34 were obtained in the same manner as in the preparation of the polymer dispersion 2 in the production example of toner 30, except that t-dodecyl mercaptan was not used.

[0233] Furthermore, external additives similar to those of toner 1 were added to obtain toners 31 to 34. The SP values related to the present invention are shown in Table 3. The physical properties of the toners are shown in Table 4.

[0234] <Production Examples of Comparative Toners 1, 2, 5, and 6> Comparative toner particles 1, 2, 5, and 6 were obtained in the same manner as in the production example of toner 1, except that the types and amounts of the materials used were changed as shown in Table 2.

[0235] Furthermore, external additives similar to those of toner 1 were added to obtain comparative toners 1, 2, 5, and 6. The SP values related to the present invention are shown in Table 3. The physical properties of the toners are shown in Table 4.

[0236] <Production Example of Comparative Toner 3> Comparative toner particles 3 were obtained by preparing polymer dispersions 2 and 3 in the manufacturing example of toner 31, in the same manner as above, except that t-dodecyl mercaptan was not used.

[0237] Furthermore, a comparative toner 3 was obtained by performing the same external additive procedure as for toner 1. The SP values ​​related to the present invention are shown in Table 3. The physical properties of the toner are shown in Table 4.

[0238] <Example of manufacturing for comparative toner 4> (Synthesis of crystalline polyester resin 1) 281 parts of dodecanediol and 283 parts of 1,6-hexanediol were placed in a reaction vessel equipped with a stirrer, thermometer, condenser, and nitrogen gas inlet. After replacing the reaction vessel with dry nitrogen gas, 0.1 parts of Ti(OBu)4 were added, and the reaction was carried out with stirring at approximately 180°C for 8 hours under a nitrogen gas flow. Further, 0.2 parts of Ti(OBu)4 were added, the temperature was raised to approximately 220°C, and the reaction was carried out with stirring for 6 hours. Then, the pressure inside the reaction vessel was reduced to 1333.2 Pa, and the reaction was carried out under reduced pressure to obtain crystalline polyester resin 1. The number-average molecular weight (Mn) of crystalline polyester resin 1 was 5500, the weight-average molecular weight (Mw) was 18000, and the melting point (Tc) was 67°C.

[0239] (Preparation of crystalline resin fine particle dispersion (C1)) Thirty parts of the above-mentioned crystalline polyester resin 1 were melted and transferred in its molten state to the emulsifying disperser "Cavitron CD1010" (manufactured by Eurotech Co., Ltd.) at a transfer rate of 100 parts per minute. Simultaneously with the transfer of this molten crystalline polyester resin 1, a dilute ammonia solution with a concentration of 0.37% by mass, prepared by diluting 70 parts of reagent ammonia solution with ion-exchanged water in an aqueous solvent tank, was transferred to the emulsifying disperser "Cavitron CD1010" (manufactured by Eurotech Co., Ltd.) at a transfer rate of 0.1 liters per minute while being heated to 100°C in a heat exchanger. The emulsifying disperser "Cavitron CD1010" (manufactured by Eurotech Co., Ltd.) was operated at a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm². 2By operating under these conditions, a crystalline resin fine particle dispersion (C1) of crystalline polyester resin 1 with a solid content of 30 parts was prepared. At this time, the volume-based median diameter of the particles contained in the crystalline resin fine particle dispersion (C1) was 200 nm.

[0240] (Preparation of amorphous resin fine particle dispersion (X1)) (1) First-stage polymerization In a 5L reaction vessel equipped with a stirrer, temperature sensor, cooling tube, and nitrogen introduction device, 8 parts sodium dodecyl sulfate and 3000 parts deionized water were charged, and the internal temperature was raised to 80°C while stirring at a stirring speed of 230 rpm under a nitrogen atmosphere. After raising the temperature, 10 parts potassium persulfate dissolved in 200 parts deionized water was added, and the liquid temperature was raised again to 80°C. A monomer mixture with the following composition was added dropwise over 1 hour, and polymerization was carried out by heating and stirring at 80°C for 2 hours to prepare a dispersion of resin fine particles (x1). Styrene 480 copies n-butyl acrylate 250 units Methacrylic acid 68 parts

[0241] (2) Second stage polymerization A 5L reaction vessel equipped with a stirrer, temperature sensor, cooling tube, and nitrogen introduction device was charged with a solution prepared by dissolving 7 parts of sodium polyoxyethylene(2) dodecyl ether sulfate in 3000 parts of deionized water. After heating to 98°C, 80 parts (in terms of solid content) of a dispersion of resin fine particles (x1) and a solution prepared by dissolving monomers and a release agent with the following composition at 90°C were added. The mixture was then mixed and dispersed for 1 hour using a mechanical disperser "CLEARMIX" (manufactured by M-Technique Co., Ltd.) with a circulation path to prepare a dispersion containing emulsion particles (oil droplets). Styrene (St) 285 parts n-butyl acrylate (BA) 95 parts Methacrylic acid (MAA) 20 parts n-octyl-3-mercaptopropionate 8 parts Release agent: Behenyl behenate (melting point 73°C) 190 parts Next, an initiator solution prepared by dissolving 6 parts potassium persulfate in 200 parts deionized water was added to this dispersion, and polymerization was carried out by heating and stirring the system at 84°C for 1 hour to prepare a dispersion of resin fine particles (x2).

[0242] (3) Third-stage polymerization Furthermore, 400 parts of deionized water were added to the resin fine particle dispersion (x2), and after thorough mixing, a solution of 11 parts of potassium persulfate dissolved in 400 parts of deionized water was added, and a monomer mixture consisting of the following composition was added dropwise over 1 hour under a temperature of 82°C. After the dropwise addition was completed, polymerization was carried out by heating and stirring for 2 hours, and then cooled to 28°C to prepare an amorphous resin fine particle dispersion (X1) consisting of vinyl resin (styrene-acrylic resin 1). Styrene (St) 308 parts n-butyl acrylate (BA) 147 parts Behenyl acrylate 143 parts Acrylic acid (AA) 52 parts n-octyl-3-mercaptopropionate 8 parts When the physical properties of the obtained amorphous resin fine particle dispersion (X1) were measured, the volume-based median diameter of the amorphous resin fine particles was 220 nm, the glass transition temperature (Tg) was 46 °C, and the weight-average molecular weight (Mw) was 32,000.

[0243] (Preparation of colorant particle dispersion [Bk]) A dispersion of colorant microparticles [Bk] was prepared by dissolving 90 parts of sodium dodecyl sulfate in 1600 parts of deionized water with stirring, and gradually adding 420 parts of carbon black "Regal 330R" (manufactured by Cabot Corporation) to this solution while stirring, and then dispersing the mixture using a stirring device "Creamix" (manufactured by M-Technique Corporation). The volume-based median diameter of the colorant microparticles in the dispersion of colorant microparticles [Bk] was measured using an electrophoretic light scattering photometer "ELS-800" (manufactured by Otsuka Electronics Co., Ltd.) and was found to be 120 nm.

[0244] (Preparation of amorphous resin fine particle dispersion for shells (S1)) The raw material monomers and radical polymerization initiators for the following addition polymerization resin (styrene-acrylic resin: StAc), which contain both reactive monomers, were placed in a dropper funnel. 80 parts of styrene n-butyl acrylate 20 parts Acrylic acid 10 parts Polymerization initiator (di-t-butyl peroxide) 16 parts Furthermore, the raw material monomers for the polycondensation resin (amorphous polyester resin) described below were placed in a four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, and heated to 170°C to dissolve them. Bisphenol A propylene oxide 2 molar adduct 285.7 parts Terephthalic acid 66.9 parts Fumaric acid 47.4 parts Next, the raw material monomers for the addition polymerization resin were added dropwise over 90 minutes under stirring, and after 60 minutes of aging, unreacted addition polymerization monomers were removed under reduced pressure (8 kPa).

[0245] Subsequently, 0.4 parts of Ti(OBu)4 were added as an esterification catalyst, the temperature was raised to 235°C, and the reaction was carried out under normal pressure (101.3 kPa) for 5 hours, followed by a further reaction under reduced pressure (8 kPa) for 1 hour.

[0246] Next, after cooling to 200°C, the reaction was carried out under reduced pressure (20 kPa) until the desired softening point was reached. Then, the solvent was removed to obtain the shell resin (s1) as an amorphous resin. The obtained shell resin (s1) had a glass transition temperature (Tg) of 60°C and a weight-average molecular weight (Mw) of 30,000.

[0247] 100 parts of the obtained shell resin (s1) were dissolved in 400 parts of ethyl acetate (manufactured by Kanto Chemical Co., Ltd.), and mixed with 638 parts of a pre-prepared 0.26 mass% sodium lauryl sulfate solution. The mixture was ultrasonically dispersed for 30 minutes at V-LEVEL 300 μA using an ultrasonic homogenizer "US-150T" (manufactured by Nippon Seiki Seisakusho Co., Ltd.) while stirring. Then, the mixture was heated to 40°C and the ethyl acetate was completely removed under reduced pressure for 3 hours using a diaphragm vacuum pump "V-700" (manufactured by BUCHI Co., Ltd.) while stirring to prepare an amorphous resin fine particle dispersion for shells (S1) with a solid content of 13.5 mass%. At this time, the median diameter of the particles contained in the amorphous resin fine particle dispersion for shells (S1) was 160 nm by volume.

[0248] (Preparation of comparative toner particles 4) In a reaction vessel equipped with a stirrer, temperature sensor, and cooling tube, 288 parts by mass (based on solid content) of amorphous resin fine particle dispersion (X1) and 2000 parts of deionized water were added. Then, a 5 mol / liter sodium hydroxide aqueous solution was added to adjust the pH to 10 (measurement temperature 25°C).

[0249] To the amorphous resin microparticle dispersion (X1) after pH adjustment, 30 parts by mass (solid content equivalent) of colorant microparticle dispersion [Bk] was added. Next, an aqueous solution of 30 parts magnesium chloride dissolved in 60 parts ion-exchanged water was added as a flocculant over 10 minutes at 30°C under stirring. The temperature of this mixture was raised to 80°C, and 40 parts of crystalline resin microparticle dispersion (C1) of crystalline polyester resin 1 were added over 10 minutes to promote flocculation. The particle size of the associated particles was measured using a "Coulter Multisizer 3" (manufactured by Beckman Coulter). When the median diameter by volume reached 6.0 μm, 37 parts (solid content equivalent) of amorphous resin microparticle dispersion (S1) for shells were added over 30 minutes. When the supernatant of the reaction solution became clear, an aqueous solution of 190 parts sodium chloride dissolved in 760 parts ion-exchanged water was added to stop particle growth. Furthermore, by heating and stirring at 80°C, particle fusion was promoted, and when the average circularity of the toner reached 0.945 using the FPIA-2100 (Sysmex Corporation) (with 4000 HPF detections), it was cooled to 30°C at a cooling rate of 2.5°C / min.

[0250] Next, the toner cake was separated into solid and liquid components, dehydrated, and then redispersed in deionized water. This process was repeated three times for washing, and the resulting toner was dried at 40°C for 24 hours to obtain comparative toner particles 4.

[0251] Furthermore, a comparative toner 4 was obtained by performing the same external additive procedure as with toner 1. The physical properties of the toners are shown in Table 4.

[0252] [Table 2-1]

[0253] [Table 2-2]

[0254] [Table 3]

[0255] [Table 4]

[0256] [Examples 1-36, Comparative Examples 1-6] Evaluation tests were conducted on toners 1-36 and comparative toners 1-6. The evaluation method and evaluation criteria of the present invention are described below.

[0257] <Evaluation of toner's low-temperature fixing properties> To evaluate the low-temperature fixing properties of the toner, a modified laser beam printer (product name: LBP-7700C, manufactured by Canon) was used as the image forming apparatus. The modifications to the machine included enabling operation even without the fuser and allowing the fixing temperature to be freely set. The paper used for outputting the images was white paper (product name: Fox River Bond (90g / m²)). 2 ), FOX RIVER Corporation.

[0258] First, the toner was removed from the cartridge, cleaned with compressed air, and then 300g of toner was filled into the cartridge. The cartridge was then left for 48 hours in an environment of 25°C and 40% RH. Under these conditions, it was installed in the cyan station of the printer, while dummy cartridges were installed in the other positions. The evaluation was then carried out under the same conditions as above.

[0259] Next, using the image forming apparatus described above with the fuser removed, an unfixed image of the image pattern was output by transferring a 10mm x 10mm square image to nine points, which are the intersections of lines dividing the long and short sides of the paper into four equal parts. The amount of toner on the paper was 0.80 mg / cm². 2 That's what I decided.

[0260] Using the removed fuser, the process speed was set to 250 mm / s, and the initial temperature was set to 90°C. The temperature was then sequentially increased by 5°C at each temperature, and the unfixed image was fixed at each temperature to obtain the fixed image. A 50 g / cm³ coating was applied to the obtained fixed image. 2 A load was applied, and five back-and-forth rubs were performed using Lenz Cleaning Paper “dusper(R)” (Ozu Paper Co. Ltd). The image density was measured before and after rubbing, and the temperature at which the decrease in image density after rubbing compared to the image density before rubbing became 20% or less was defined as the fixing start temperature. This value was used to evaluate the low-temperature fixing performance of the toner. If the fixing start temperature was 120°C or lower, it was judged that the effects of the present invention were obtained. The evaluation results are shown in Table 5.

[0261] (Evaluation Criteria) A: Fixation start temperature is 100°C or lower B: Fixation start temperature is between 105°C and 110°C. C: Fixing start temperature is between 115°C and 120°C. D: Fixing start temperature is 125°C or higher

[0262] <Evaluation of toner's heat resistance and storage properties> 6g of toner was placed in a 100mL poly cup and left for 10 days in an environment with a temperature of 50°C and a humidity of 20%RH. The degree of aggregation of the toner 1 after this period was measured as follows.

[0263] As the measuring device, a "Powder Tester" (manufactured by Hosokawa Micron Corporation) was used, with a digital display vibration meter "DigiVibro MODEL 1332A" (manufactured by Showa Sokki Co., Ltd.) connected to the side of the vibration table. Then, on the vibration table of the Powder Tester, sieves with a mesh size of 38 μm (400 mesh), 75 μm (200 mesh), and 150 μm (100 mesh) were stacked in that order from bottom to top. The measurements were performed in a 23°C, 60% RH environment using the following procedure. (1) The vibration amplitude of the vibration table was pre-adjusted so that the displacement value of the digital display vibration meter was 0.60 mm (peak-to-peak). (2) The toner that had been left for 10 days as described above was then left for 24 hours in an environment of 23°C and 60% RH, and 5g of the toner was weighed and gently placed on the top sieve with a mesh size of 150μm. (3) After vibrating the sieves for 15 seconds, the mass of toner remaining on each sieve was measured, and the degree of cohesion (%) was calculated using the following formula. A score of C or higher was considered good. The evaluation results are shown in Table 5. Degree of aggregation (%) = {(Sample mass on a sieve with a mesh size of 150 μm (g)) / 5 (g)} × 100 +{(Sample mass on a sieve with a mesh size of 75 μm (g)) / 5 (g)} × 100 × 0.6 +{(Sample mass on a sieve with a mesh size of 38 μm (g)) / 5 (g)} × 100 × 0.2

[0264] (Evaluation Criteria) A: Cohesion level is 19% or less B: Cohesion level between 20% and 24% C: Cohesion level between 25% and 29% D: Cohesion level of 30% or higher

[0265] <Evaluation of coloring power> The toner cartridge was left in a normal temperature and humidity environment (temperature 23°C, relative humidity 50%) for 24 hours.

[0266] After leaving the toner cartridge for 24 hours, it was installed in the LBP9600C, and the amount of toner on the evaluation paper was 0.45 mg / cm². 2 A solid image was output, and its image density was measured and evaluated using a color reflectance densitometer (X-RITE 404A: manufactured by X-Rite Co.).

[0267] Furthermore, images with a print ratio of 1.0% were printed out up to 3000 times on A4 paper in landscape orientation. After printing 3000 copies, solid images were printed in the same manner, and their image density was measured and evaluated using a color reflectance densitometer. A score of C or higher was considered good. The evaluation results are shown in Table 5.

[0268] (Evaluation Criteria) A: Image density is 1.40 or higher B: Image density is between 1.35 and 1.39 C: Image density is between 1.20 and 1.34. D: Image density is 1.19 or less

[0269] <Evaluation of fog suppression> Under low temperature and low humidity conditions (15°C, 10%RH), 3000 printouts of an image with a 1% print density in horizontal lines were tested. After the test was completed, the images were left for 48 hours, and then the reflectance (%) of the non-image areas of the printed images was measured using a "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.).

[0270] The obtained reflectance was evaluated using the following criteria, with the percentage obtained by subtracting it from the reflectance (%) of unused printout paper (standard paper) measured in the same manner. A smaller value indicates better suppression of image fringing. The evaluation was performed in gloss paper mode using plain paper (HP Brochure Paper 200g, Glossy, manufactured by HP, 200g / m²). 2 The evaluation was conducted using [a specific method / tool]. A score of C or higher was considered good. The evaluation results are shown in Table 5.

[0271] (Evaluation Criteria) A: 1.0% or less B: 1.1% or more and 3.0% or less C: 3.1% or more and 5.0% or less D: 5.1% or more

[0272] [Table 5]

Claims

1. A toner having toner particles containing a binder resin and a colorant, The binder resin is a resin that satisfies at least one of the following requirements (A) and (B): (A) A crystalline resin having a unit (a) represented by the following formula (1) and a resin having a sulfide structure: (B) A crystalline resin having a sulfide structure and a unit (a) represented by the following formula (1): 【Chemical 1】 [In formula (1), R 1 represents a hydrogen atom or a methyl group, and n represents an integer of 15 or more and 29 or less. the colorant is any colorant selected from the group consisting of carbon black, titanium black, copper phthalocyanine, copper phthalocyanine derivatives, anthraquinone compounds, azo pigments, and condensed polycyclic compounds; When the toner is measured with a differential scanning calorimeter, the peak temperature of the maximum endothermic peak is in the range of 50° C. or more and 70° C. or less, The toner is characterized in that the endothermic amount of the maximum endothermic peak is 30 J / g or more and 70 J / g or less.

2. 2. The toner of claim 1, wherein the colorant is selected from the group consisting of carbon black, C.I. Pigment Red 31, C.I. Pigment Red 122, C.I. Pigment Red 150, C.I. Pigment Yellow 74, C.I. Pigment Yellow 155, C.I. Pigment Blue 15, and C.I. Pigment Blue 15:

3.

3. 2. The toner according to claim 1, wherein the binder resin satisfies the requirement of (A), and the content of the crystalline resin having the unit (a) represented by formula (1) in the binder resin is 50.0% by mass or more.

4. 2. The toner according to claim 1, wherein the binder resin is a resin that satisfies the requirement (B).

5. 5. The toner according to claim 4, wherein the content of the crystalline resin having a sulfide structure and having the unit (a) represented by formula (1) in the binder resin is 50.0% by mass or more.

6. 2. The toner according to claim 1, wherein the content of the unit (a) in the crystalline resin is 40.0% by mass or more and 80.0% by mass or less.

7. the binder resin contains a monomer unit derived from a macromonomer, 2. The toner according to claim 1, wherein the number average molecular weight of the monomer unit derived from the macromonomer is 1,000 or more and 20,000 or less.

8. 8. The toner according to claim 7, wherein the monomer unit derived from the macromonomer has a (meth)acrylic acid ester polymer moiety.

9. the crystalline resin has a unit (b) in addition to the unit (a), The SP value of the unit (a) ((J / cm 3 ) 0.5 ) is SP, the SP value of the unit (b) ((J / cm 3 ) 0.5 2. The toner according to claim 1, wherein when SPb is SPa, SPa and SPb satisfy the following formula (2): 3.0≦(SPb-SPa)≦25.0 (2)

10. 10. The toner according to claim 9, wherein the unit (b) is a unit represented by the following formula (3): 【Chemistry 2】 [In formula (3), R 2 represents a hydrogen atom or a methyl group.

11. 2. The toner according to claim 1, wherein the toner particles have a core-shell structure, the core containing the binder resin, and the shell containing an amorphous resin.

12. 12. The toner according to claim 11, wherein the amorphous resin contains the unit (c) represented by formula (4) in an amount of 1.0% by mass or more and 30.0% by mass or less. 【Chemistry 3】 [In formula (4), R 3 represents a hydrogen atom or a methyl group, and m represents an integer of 9 or more and 23 or less.

13. 12. The toner according to claim 11, wherein the acid value Av of the amorphous resin is 5.0 mgKOH / g or more and 30.0 mgKOH / g or less.

14. 2. The toner according to claim 1, wherein the toner particles are suspension polymerization toner.

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