Toner, method for manufacturing the same, process cartridge, and image forming apparatus

Abstract

This product provides a toner that achieves both high-speed fixing performance in the fixing process and control and suppression of image gloss degradation. [Solution] The toner contains a binder resin containing a styrene-acrylic copolymer, a block copolymer A having styrene units and specific olefin units, and an ester wax B having a specific structure.

Description

[Technical Field]

[0001] The present invention relates to a toner used in recording methods utilizing electrophotography, electrostatic recording, and toner jet recording, and to a method for manufacturing the same, and further to a process cartridge and image forming apparatus using the toner. [Background technology]

[0002] In image formation using electrophotography technology, low-temperature fixing techniques are being investigated to save energy and increase printing speed. As one method for achieving low-temperature fixing, a technique that is being widely studied involves adding a plasticizer that is easily compatible with the binder resin to the toner, thereby lowering the fixing temperature as the plasticizer becomes compatible with the binder resin during fixing. Specific examples of plasticizers include crystalline resins such as crystalline polyester resins, and crystalline low-molecular-weight materials such as ester waxes. In particular, when styrene-acrylic resin is used as the binder resin, it is known that excellent low-temperature fixing effect can be obtained by using ester wax as a plasticizer, and research is being widely conducted to improve low-temperature fixing performance by controlling the position and dispersion state of ester wax in the toner. Patent Document 1 discloses a toner using a resin containing ester wax and isoprene units for the purpose of improving the dispersibility of ester wax in the toner. On the other hand, the structure of ester waxes has also been studied, and it is known that ester compounds of diols and aliphatic carboxylic acids, and ester compounds of dicarboxylic acids and aliphatic alcohols, have excellent compatibility with styrene-acrylic resins and are effective in improving low-temperature fixability. Patent document 2 discloses a toner that uses styrene-acrylic resin as the binder resin and an ester compound of diols and aliphatic carboxylic acids as the plasticizer. [Prior art documents] [Patent Documents]

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the toner of Patent Document 1 has a problem in fixing property in a high-speed fixing process because of its low compatibility with the binder resin of ester wax. On the other hand, although the toner of Patent Document 2 is excellent in fixing property in a high-speed fixing process, the gloss of the image tends to be high, and it is difficult to control the gloss even when it is desired to suppress the gloss. In addition, when the output image is stored under specific conditions, it has been clarified that there are problems such as the gloss of the image decreases due to the precipitation of an ester compound on the image surface, or the contact portion is contaminated with the ester compound when contacting the image. Thus, there has been a demand for a toner that can achieve both fixing property in a high-speed fixing process and control of image gloss and suppression of gloss reduction. The present invention solves the above problems and provides a toner that achieves both fixing property in a high-speed fixing process, control of image gloss, and suppression of reduction of image gloss.

Means for Solving the Problems

[0005] The present invention is a toner having toner particles containing a binder resin, a block copolymer A, and an ester wax B, the binder resin contains a styrene-acrylic copolymer, the content of the styrene-acrylic copolymer in the binder resin is 50% by mass or more, the block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment, and the polyolefin segment has an olefin unit C represented by any one of the following formulas (1) to (4),

[0006] [ka] The ester wax B is compatible at 100°C with 15.0 parts by mass or more of 100 parts by mass of styrene-n-butyl acrylate copolymer α having the following composition. • Styrene-n-butyl acrylate copolymer α: A copolymer of 75 parts by mass of styrene monomer and 25 parts by mass of n-butyl acrylate monomer (weight-average molecular weight Mw is 29,000 or more and 31,000 or less) The present invention relates to a toner characterized in that the ester wax B is an ester compound having the structure of formula (5) or formula (6) below.

[0007] [ka] (In formula (5), R 1 and R 3 Each independently represents an n-alkyl group with 13 to 21 carbon atoms, and R 2 This represents an alkylene group with 2 to 8 carbon atoms.

[0008] [ka] (In formula (6), R 4 and R 6 Each independently represents an n-alkyl group with 14 to 22 carbon atoms, and R 5 (This indicates a single bond or an alkylene group having 1 to 6 carbon atoms.) Furthermore, the present invention relates to a method for producing toner having toner particles containing a binder resin, a block copolymer A, and an ester wax B, The binder resin contains a styrene-acrylic copolymer, The content of the styrene-acrylic copolymer in the binder resin is 50% by mass or more. The block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment, and the polyolefin segment has an olefin unit C represented by any of the above formulas (1) to (4). The ester wax B is compatible at 100°C with 15.0 parts by mass or more of styrene-n-butyl acrylate copolymer α having the above composition, The ester wax B is an ester compound having the structure of formula (5) or formula (6) above, The present invention relates to a method for producing toner, characterized by having a cooling step in which the toner particles are cooled in an aqueous medium from a temperature above the melting point of the ester wax B to a temperature below the glass transition temperature (Tg) of the binder resin at a rate of 1°C / second or more. Furthermore, the present invention relates to a process cartridge that can be attached to and detached from an image forming apparatus, The process cartridge is Toner and, A toner container for storing the toner, It has, The present invention relates to a process cartridge characterized by having the toner having the above configuration. Furthermore, the present invention relates to toner and A toner carrier that holds the toner, Electrostatic latent image carrier, A charging means for charging the surface of the electrostatic latent image carrier with a charging member, An electrostatic latent image forming means for forming an electrostatic latent image on a charged electrostatic latent image carrier, Development: Using the toner to develop the electrostatic latent image and form a toner image on the electrostatic latent image carrier. means and A transfer means for transferring the toner image onto a recording medium, Fixing means for fixing the toner image transferred onto the recording medium onto the recording medium, An image forming apparatus comprising, The present invention relates to an image forming apparatus characterized in that the toner is a toner having the above-described configuration. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a toner that achieves both high fixing performance in a high-speed fixing process, control of image gloss, and suppression of the decrease in image gloss. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 is a schematic diagram of an image forming apparatus. [Modes for carrying out the invention]

[0011] In this invention, unless otherwise specified, the expressions "greater than or equal to XX and less than or equal to XX" or "XX to XX" that represent a numerical range mean a numerical range that includes the lower and upper limits, which are the endpoints.

[0012] [Features of the present invention] The toner of the present invention is a toner having toner particles containing a binder resin, a block copolymer A, and an ester wax B, The binder resin contains a styrene-acrylic copolymer, The content of the styrene-acrylic copolymer in the binder resin is 50% by mass or more. The block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment, and the polyolefin segment has an olefin unit C represented by any of the following formulas (1) to (4).

[0013] [ka]

[0014] The ester wax B is compatible at 100°C with 15.0 parts by mass or more of 100 parts by mass of styrene-n-butyl acrylate copolymer α having the following composition. • Styrene-n-butyl acrylate copolymer α: A copolymer of 75 parts by mass of styrene monomer and 25 parts by mass of n-butyl acrylate monomer (weight-average molecular weight Mw is 29,000 or more and 31,000 or less) The toner is characterized in that the ester wax B is an ester compound having the structure of formula (5) or formula (6) below.

[0015] [ka] (In formula (5), R 1 and R 3 each independently represent an n-alkyl group having 13 to 21 carbon atoms, and R 2 represents an alkylene group having 2 to 8 carbon atoms.)

[0016] [Chemical formula] (In formula (6), R 4 and R 6 each independently represent an n-alkyl group having 14 to 22 carbon atoms, and R 5 represents a single bond or an alkylene group having 1 to 6 carbon atoms.)

[0017] In the toner of the present invention, the reason for achieving both the fixing property in a high-speed fixing process and the suppression of the decrease in image gloss is not clear, but the present inventors presume as follows.

[0018] Generally, the effect of improving the fixing property of a plasticizer is more excellent as the compatibility of the plasticizer with the binder resin is higher. And the compatibility of the plasticizer with the binder resin is affected by the affinity between the plasticizer and the binder resin and the molecular weight of the plasticizer. Tendency is that the compatibility becomes higher as the affinity is high and the molecular weight of the plasticizer is small.

[0019] The ester wax B having the structure of the above formula (5) or the structure of formula (6) is a bifunctional ester compound having two ester bonds in the structure. The bifunctional ester compound has a higher polarity compared to a monofunctional ester compound having an equivalent molecular weight and is close to the polarity of the styrene acrylic resin. Therefore, it has a high affinity with the styrene acrylic resin. Also, it has a lower molecular weight compared to a tetrafunctional ester compound or a hexafunctional ester compound having an equivalent melting point. Thus, when using a styrene acrylic resin as the binder resin, a high effect of improving the fixing property can be obtained.

[0020] Ester wax B having the structure of formula (5) or formula (6) above exhibits excellent fixability as described above, but due to its high compatibility, it tends to remain in a compatible state with the binder resin in the image immediately after fixation without crystallizing. The ester wax that remains in a compatible state without crystallizing gradually crystallizes under the influence of ambient temperature. Although ester compounds have a high affinity for styrene-acrylic resin, they are more hydrophobic than styrene-acrylic resin, and therefore have a high affinity for air, which is also hydrophobic. As a result, when crystallization occurs, crystals tend to grow toward the image surface. Furthermore, due to their structural characteristics, ester waxes having the structure of formula (5) or formula (6) above tend to form large crystals when crystallizing. Therefore, it is assumed that the ester compound remaining in a compatible state in the image formed large crystals on the image surface, reducing the smoothness of the image surface and causing a decrease in gloss.

[0021] The block copolymer A used in this invention has an olefin unit C with high affinity for ester wax B and a polystyrene segment with high affinity for styrene-acrylic resin. Therefore, immediately after image formation, the polystyrene segment can be uniformly dispersed in the image due to the interaction between the polystyrene segment and the styrene-acrylic resin. Furthermore, by crystallizing ester wax B starting from the polyolefin segment, the precipitation of ester wax B on the image surface can be suppressed, while reducing the amount of ester wax B remaining in a compatible state in the image. In addition, when the ester wax B remaining in a compatible state crystallizes, it interacts with both ester wax B and the styrene-acrylic resin, making it possible to retain ester wax B in the image. It is assumed that the decrease in gloss can be suppressed by the above two actions.

[0022] In addition, block copolymer A functions as a thermoplastic elastomer. A thermoplastic elastomer exhibits a pseudo-crosslinked state at low temperatures due to cohesive forces between blocks, while at high temperatures the molecular chains unwind and the crosslinked structure is eliminated. Therefore, during heating in the fixing process, block copolymer A's molecular chains unwind, increasing its degree of freedom, while after fixing, it forms a pseudo-crosslinked structure, thereby stabilizing the gloss of the image. This is expected to enable control over gloss.

[0023] [Constituent materials and physical properties of the toner of this invention] Next, the materials that can be used in the toner of the present invention will be described in detail below.

[0024] <Block Copolymer A> The block copolymer A of the present invention is a block copolymer having a polyolefin segment containing an olefin unit C and a polystyrene segment.

[0025] Block copolymer A is not particularly limited in terms of the number of polymer blocks or their bonding configuration, as long as it contains one or more polyolefin segments and polystyrene segments containing olefin units C. Specific examples of block copolymer A of the present invention are as follows. In the following examples, S represents a polystyrene segment, O represents a polyolefin segment containing olefin units C, and n represents an integer of 2 or more. (a) Styrene-olefin copolymer represented as SO (b) Styrene-olefin-styrene copolymer represented as SOS (c) Olefin-styrene-olefin copolymer represented as OSO (d) Styrene-olefin-styrene-olefin block copolymers represented as SOSO (e) A mixture of block copolymers obtained by arbitrarily combining two or more of the above (a) to (d).

[0026] However, the block copolymer A of the present invention is not limited to (a) to (e) above. Suitable block copolymers in the present invention include (a), (b), and (e) above, which are mixtures of block copolymers obtained by combining (a) and (b).

[0027] The olefin unit C contained in the polyolefin segment of the present invention has the structure of the following structural formulas (1), (2), (3), or (4). The following structural formulas are characterized by having branching in the structure. As a result, the aggregation of olefin units C is reduced, which relatively increases the interaction between olefin units C and ester wax B, thus providing an excellent effect in suppressing gloss reduction.

[0028] [ka]

[0029] In particular, the structures of structural formula (1) or structural formula (2) are preferred because the cohesiveness between units is further reduced, and the structure of structural formula (1) is more preferred because it has superior affinity with ester wax B.

[0030] In addition to the olefin unit C described above, the polyolefin segment may also contain other olefin units. Specifically, examples include olefin-derived olefin units such as ethylene, propylene, butene, and butadiene. Within the polyolefin segment, the bonding form between the olefin unit C and the other olefin units is not particularly limited; they may form blocks or be randomly bonded. The polyolefin segment is substantially composed of olefin unit C and other olefin units. Specifically, 90% or more by mass consists of olefin unit C and other olefin units. More preferably, 98% or more by mass consists of olefin unit C and other olefin units, and even more preferably, it consists only of olefin unit C and other olefin units.

[0031] Polystyrene segments consist substantially of styrene units. Specifically, 98% or more by mass are styrene units. It is more preferable that they consist solely of styrene units. Other units that can be used include styrene derivative units derived from styrene derivatives such as vinyltoluene and α-methylstyrene; unsaturated fatty acid units derived from unsaturated fatty acids such as acrylic acid and methacrylic acid; acrylic ester units derived from acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, and dimethylaminoethyl acrylate; and methacrylic ester units derived from methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and dimethylaminoethyl methacrylate.

[0032] Block copolymer A can be produced by conventional methods. For example, a method for producing such a block copolymer involves sequentially polymerizing styrene and isoprene using anionic living polymerization to form polymer blocks, and then, if necessary, reacting them with a coupling agent to perform coupling. Structures of structural formula (2) or (4) can be obtained by hydrogenating the resulting block copolymer under appropriate conditions.

[0033] In the present invention, commercially available block copolymers can also be used. Examples of commercially available block copolymers include those with trade names "Septon" and "Hybrar" (manufactured by Kuraray Co., Ltd.), "Quintac" (manufactured by Nippon Zeon Co., Ltd.), "JSR-SIS" (manufactured by JSR Corporation), "Vector" (manufactured by DEXCO Polymers), and "Asaprene," "Toughprene," and "Toughtech" (manufactured by Asahi Kasei Chemicals Corporation).

[0034] The content of olefin units C in block copolymer A is preferably 50% by mass or more, more preferably 50% by mass or more and 95% by mass or less, even more preferably 60% by mass or more and 90% by mass or less, even more preferably 70% by mass or more and 85% by mass or less, and particularly preferably 73% by mass or more and 80% by mass or less.

[0035] The content of styrene units in block copolymer A is preferably 50% by mass or less, more preferably 5% by mass or more and 50% by mass or less, even more preferably 10% by mass or more and 40% by mass or less, even more preferably 15% by mass or more and 30% by mass or less, and particularly preferably 20% by mass or more and 27% by mass or less. When the styrene unit content is within the above range, the effect as a thermoplastic elastomer is enhanced, and the gloss control effect is further enhanced.

[0036] The styrene unit content in block copolymer A can be measured by known methods. For example, the styrene unit content in block copolymer A can be measured by measuring the refractive index of block copolymer A using an Abbe refractometer in accordance with JIS K 7142.

[0037] The weight-average molecular weight (Mw) of block copolymer A is not particularly limited, but is preferably 60,000 to 350,000, and more preferably 80,000 to 250,000. When the weight-average molecular weight (Mw) of block copolymer A is 60,000 to 350,000, the toner exhibits excellent heat resistance for storage and good low-temperature fixation.

[0038] The content of block copolymer A is preferably 2 to 10 parts by mass, more preferably 2 to 8 parts by mass, and even more preferably 3 to 7 parts by mass, per 100 parts by mass of binder resin.

[0039] <Ester wax B> The ester wax B of the present invention is compatible with 15.0 parts by mass or more of 100 parts by mass of styrene-n-butyl acrylate copolymer α having the following composition at 100°C. Since the binder resin of the present invention contains 50% by mass or more of styrene-acrylic copolymer, a high compatibility with styrene-n-butyl acrylate copolymer α indicates that it is compatible with the binder resin in large quantities and rapidly during fixing. Therefore, such an ester wax exhibits excellent low-temperature fixability. The compatibility of ester wax B with 100 parts by mass of styrene-n-butyl acrylate copolymer α having the following composition at 100°C is 15.0 parts by mass or more, preferably 25.0 parts by mass or more, and more preferably 35.0 parts by mass or more. • Styrene-n-butyl acrylate copolymer α: A copolymer of 75 parts by mass of styrene monomer and 25 parts by mass of n-butyl acrylate monomer (weight-average molecular weight Mw is 29,000 or more and 31,000 or less)

[0040] The ester wax B of the present invention is an ester compound having the structure of formula (5) or formula (6) below, and preferably an ester compound having the structure of formula (7) below.

[0041] [ka] (In formula (5), R 1 and R 3 Each independently represents an n-alkyl group with 13 to 21 carbon atoms, and R 2 This represents an alkylene group with 2 to 8 carbon atoms.

[0042] [ka] (In formula (6), R 4 and R 6 Each independently represents an n-alkyl group with 14 to 22 carbon atoms, and R 5 (This indicates a single bond or an alkylene group having 1 to 6 carbon atoms.)

[0043] [ka] (In formula (7), R 7 and R 9 Each independently represents an n-alkyl group with 17 to 21 carbon atoms, and R 8 (This indicates an alkylene group with 2 carbon atoms.)

[0044] Specific examples of compounds include, but are not limited to, ester compounds having the structures of formulas (5) and (7) above, such as ethylene glycol distearate and ethylene glycol dibehenate; ester compounds having the structure of formula (5) above, such as ethylene glycol dimyristate, ethylene glycol dipalmitate, butanediol distearate, and hexanediol distearate; and ester compounds having the structure of formula (6) above, such as distearyl adipate.

[0045] Furthermore, regarding the relationship between the olefin unit C and the ester wax B, the solubility parameter of the olefin unit C is defined as SPc(J / cm²). 3 ) 0.5 The solubility parameter of the ester wax B is set to SPb (J / cm²). 3 ) 0.5 In this case, it is preferable that the SPb-SPc value is between 1.50 and 3.00. When the SPb-SPc value is within the above range, the interaction between the ester wax B and the olefin unit C is within an appropriate range, and the effect of controlling the gloss and suppressing the decrease in gloss is further enhanced.

[0046] The solubility parameter of ester wax B is 17.8 (J / cm³). 3 ) 0.5 More than 18.5(J / cm 3 ) 0.5 Preferably, it is 18.0 (J / cm²). 3 ) 0.5 More than 18.3(J / cm 3 ) 0.5 The following is more preferable:

[0047] The solubility parameter (SP value) was determined as follows, following the calculation method proposed by Fedors.

[0048] For atoms or groups of atoms in the molecular structure of ester wax B or olefin unit C, the evaporation energy (Δei) (J / mol) and molar volume (Δvi) (cm³) are determined from the table in "Polym.Eng.Sci.,14(2),147-154(1974)". 3 Determine the value of (per mole) and calculate it using the following formula. SP value = (ΣΔei / ΣΔvi) 1 / 2

[0049] The molecular weight of ester wax B is preferably 500 to 1000, and more preferably 550 to 800. When the molecular weight of ester wax B is within the above range, it becomes easier to adjust its compatibility with the binder resin to a suitable range.

[0050] The melting point of ester wax B is preferably 60°C to 90°C, more preferably 65°C to 85°C, and even more preferably 70°C to 80°C. When the melting point of ester wax B is within the above range, the storage life of the toner can be improved while maintaining the low-temperature fixability of the toner.

[0051] <Other waxes> In addition to the ester wax B described above, other waxes may be added to the toner of the present invention for purposes such as imparting release properties.

[0052] Other waxes include paraffin wax, microcrystalline wax, petroleum-based hydrocarbon waxes such as petrolatum and their derivatives, montan wax and its derivatives, hydrocarbon waxes and their derivatives produced by the Fischer-Tropsch process, monofunctional ester waxes such as behenyl behenate, stearyl stearate, palmityl palmitate (esters of monohydric alcohols and aliphatic carboxylic acids), or esters of monohydric carboxylic acids and aliphatic alcohols; Trifunctional ester waxes, such as esters of trivalent alcohols and aliphatic carboxylic acids, or esters of trivalent carboxylic acids and aliphatic alcohols, like glycerol tribehenate; Tetrafunctional ester waxes, such as esters of tetravalent alcohols and aliphatic carboxylic acids, like pentaerythritol tetrastearate and pentaerythritol tetrapalmitate, or esters of tetravalent carboxylic acids and aliphatic alcohols; Hexafunctional ester waxes, such as esters of hexavalent alcohols and aliphatic carboxylic acids, including dipentaerythritol hexastearate and dipentaerythritol hexapalmitate, or esters of hexavalent carboxylic acids and aliphatic alcohols; Esters of polyhydric alcohols and aliphatic carboxylic acids, such as polyglycerol behenates, or esters of polyhydric carboxylic acids and aliphatic alcohols; Natural ester waxes such as carnauba wax and rice wax; Ester waxes, such as those mentioned above. Examples include polyolefin hydrocarbon waxes such as polyethylene and polypropylene and their derivatives, and natural waxes such as carnauba wax and candelilla wax and their derivatives. Derivatives also include oxides, block copolymers with vinyl monomers, and graft-modified products.

[0053] Other examples include alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid, or their acid amides, esters, and ketones; hydrogenated castor oil and its derivatives; plant waxes; and animal waxes. These can be used alone or in combination.

[0054] <Binding resin> The binder resin of the present invention contains 50% by mass or more of a styrene-acrylic copolymer. Preferably, it contains 90% by mass or more.

[0055] As the styrene-acrylic copolymer, any conventionally known styrene-acrylic copolymer can be used without particular limitations, as long as it is a copolymer of a monomer composition containing styrene and at least one acrylic monomer selected from acrylic acid and its derivatives, and methacrylic acid and its derivatives. In particular, the styrene unit content is preferably 60% to 90% by mass, and more preferably 70% to 80% by mass, relative to the entire styrene-acrylic copolymer. Furthermore, the acrylic unit content is preferably 10% to 40% by mass, and more preferably 20% to 30% by mass.

[0056] Examples of acrylic monomers include acrylic acid esters such as methyl acrylate and n-butyl acrylate (n-butyl acrylate); methacrylic acid esters such as methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate; acrylic acid, methacrylic acid, etc. Among these, it is preferable to use an acrylic acid ester or a methacrylic acid ester, more preferable to use n-butyl acrylate or methyl methacrylate, and even more preferable to use n-butyl acrylate.

[0057] In addition to the styrene and acrylic monomers mentioned above, the styrene-acrylic copolymer of the present invention can use conventionally known polymerizable monomers without any particular limitations. Specifically, examples include monofunctional monomers having one polymerizable unsaturated bond in the molecule, such as aromatic monomers like α-methylstyrene and vinyltoluene; unsaturated dicarboxylic acids like maleic acid; unsaturated dicarboxylic acid anhydrides like maleic anhydride; nitrile vinyl monomers like acrylonitrile; halogen-containing vinyl monomers like vinyl chloride; and nitro vinyl monomers like nitrostyrene; as well as polyfunctional monomers having multiple polymerizable unsaturated bonds in the molecule, such as divinylbenzene, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, and trimethylolpropanetri(meth)acrylate.

[0058] Furthermore, using macromonomers as part of the polymerizable monomer allows for a good balance between the storage properties and low-temperature fixability of the resulting toner. Macromonomers are oligomers or polymers with polymerizable carbon-carbon unsaturated double bonds at the ends of their molecular chains, and a number-average molecular weight of typically 1,000 to 30,000, indicating high reactivity. It is preferable that the macromonomer yields a polymer with a glass transition temperature (Tg) higher than that of the polymer obtained by polymerizing monovinyl monomers. The macromonomer is used in amounts of preferably 0.03 to 5 parts by mass, and more preferably 0.05 to 1 part by mass, per 100 parts by mass of monovinyl monomer.

[0059] Furthermore, in addition to the styrene-acrylic copolymer described above, conventionally known binder resins can be used as the binder resin of the present invention without any particular limitations. Specifically, examples include polyester resins, vinyl resins, polyurethane resins, and polyamide resins.

[0060] <Coloring agent> The toner of the present invention may contain a colorant. The colorant can be any conventionally known black, yellow, magenta, and cyan pigments and dyes, magnetic materials, etc., without any particular limitations.

[0061] Examples of black colorants include black pigments such as carbon black.

[0062] Examples of yellow colorants include yellow pigments and dyes such as monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, benzimidazolon compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.

[0063] Specifically, examples include CI Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185, and CI Solvent Yellow 162.

[0064] Examples of magenta colorants include magenta pigments and dyes such as monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolon compounds, thioindigo compounds, and perylene compounds.

[0065] Specifically, examples include CI Pigment Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, and CI Pigment Violet 19.

[0066] Examples of cyanide colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and cyanide pigments and dyes such as basic dye lake compounds.

[0067] Specifically, examples include CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.

[0068] The coloring agent content is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100.0 parts by mass of the binder resin.

[0069] Furthermore, toner can be made magnetic by incorporating a magnetic material. In this case, the magnetic material can also serve as a colorant.

[0070] Examples of magnetic materials include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and alloys and mixtures thereof of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium.

[0071] When a magnetic material is used as a coloring agent, the magnetic material content is preferably 20.0 parts by mass or more and 120.0 parts by mass or less per 100.0 parts by mass of the binder resin.

[0072] <Static control agent> Other additives that can be used to improve the chargeability of the toner include positively or negatively charged charge control agents.

[0073] The charge control agent is not particularly limited as long as it is one that is generally used as a charge control agent for toner. However, among charge control agents, positively charged or negatively charged resins are preferred because they can impart stable charge properties (charge stability) to the toner particles.

[0074] Examples of positively charged charge control agents include nigrosine dyes, quaternary ammonium salts, triaminotriphenylmethane compounds, and imidazole compounds, as well as polyamine resins as preferred charge control resins, and quaternary ammonium group-containing copolymers and quaternary ammonium base-containing copolymers. Among these, the use of quaternary ammonium group-containing copolymers or quaternary ammonium base-containing copolymers is more preferred.

[0075] Examples of negatively charged charge control agents include azo dyes containing metals such as Cr, Co, Al, and Fe, metal salicylate compounds and alkylsalicylate compounds, and preferably used charge control resins such as sulfonic acid group-containing copolymers, sulfonic acid base-containing copolymers, carboxylic acid group-containing copolymers and carboxylic acid base-containing copolymers.

[0076] The weight-average molecular weight (Mw) of the charge-controlled resin is measured by gel permeation chromatography (GPC) using tetrahydrofuran and is in the range of 5,000 to 30,000 in polystyrene equivalent, preferably in the range of 8,000 to 25,000, and more preferably in the range of 10,000 to 20,000.

[0077] Furthermore, the copolymerization ratio of monomers having functional groups such as quaternary ammonium groups and sulfonic acid bases in the electrostatically controlled resin is in the range of 0.5% by mass or more and 12% by mass or less, preferably in the range of 1.0% by mass or more and 6% by mass or less, and more preferably in the range of 1.5% by mass or more and 3% by mass or less.

[0078] In the present invention, it is desirable to use the charge control agent in a ratio of 0.01 parts by mass to 10 parts by mass, preferably 0.03 parts by mass to 8 parts by mass, per 100 parts by mass of the binder resin. When the amount of charge control agent added is 0.01 parts by mass to 10 parts by mass, the risk of fogging and the risk of printing smudges are both small.

[0079] <External Additives> The toner of the present invention may contain external additives. There are no particular restrictions on the external additives used; conventionally known external additives can be used.

[0080] External additives include raw silica nanoparticles such as wet-process silica and dry-process silica, or surface-treated silica nanoparticles obtained by surface-treating these raw silica nanoparticles with treatment agents such as silane coupling agents, titanium coupling agents, and silicone oil; metal oxide nanoparticles such as titanium oxide nanoparticles, aluminum oxide nanoparticles, and zinc oxide nanoparticles, or metal oxide nanoparticles obtained by hydrophobizing metal oxides; fatty acid metal salts such as zinc stearate, calcium stearate, and zinc stearate; metal complexes of aromatic carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, and dicarboxylic acid; clay minerals such as hydrotalcite; and fluorine-based resin nanoparticles such as vinylidene fluoride nanoparticles and polytetrafluoroethylene nanoparticles.

[0081] The content of external additives is preferably 0.1 parts by mass or more and 5.0 parts by mass or less per 100.0 parts by mass of toner particles.

[0082] <Domain of ester wax B> In the toner of the present invention, ester wax B domains are present in the cross-section of the toner particles observed with a scanning transmission electron microscope, and the average number of such domains is preferably 100 or more per cross-section of the toner particle, more preferably 150 or more, and even more preferably 200 or more. Furthermore, when the average major axis of the domains is denoted as r1, r1 is preferably 1.00 μm or less, more preferably 0.50 μm or less, and even more preferably 0.30 μm or less. By controlling the state of the ester wax B domains to the above conditions, the ester wax B quickly becomes compatible with the binder resin during the fixing process, improving fixing performance in high-speed processes. In addition, the deposition of ester wax B on the toner surface during toner storage is suppressed, improving the storage life of the toner.

[0083] <Storage modulus of toner particles> The toner of the present invention has a storage modulus G'(100) of toner particles at 100°C, determined by dynamic viscoelasticity measurement, which is 1.0 × 10⁻⁶. 4 Pa or more 1.0×10 5 It is preferable that it is Pa or less. More preferably 1.2 × 10 4 Pa or more 8.0×10 4 The Pa is less than or equal to the Pa. Furthermore, the storage modulus G'(60) of the toner particles at 60°C, as determined by dynamic viscoelasticity measurement, is 1.0 × 10⁻⁶. 7 Pa or more 1.5×10 8 It is preferable that it is Pa or less. More preferably 1.2 × 10 7 Pa or more 1.0×10 8 It is Pa or less. The combination of block copolymer A and ester wax B of the present invention makes it possible to lower G'(60) while maintaining preservation properties. In addition, the ratio of G'(60) to G'(100), G'(60) / G'(100), is 1.0 × 10⁻⁶. 2 The above 1.5 × 10 3The following is preferable: By ensuring that the storage modulus of the toner particles satisfies the above range and relationship, a similar fixing state can be obtained over a wide temperature range. Therefore, the occurrence of gloss differences (uneven gloss) due to the temperature difference between the leading and trailing edges of the paper during fixing can be suppressed.

[0084] [Method for obtaining toner according to the present invention] Next, the method for obtaining the toner of the present invention will be described in detail below.

[0085] <Method for manufacturing toner particles> The method for producing toner particles of the present invention is not particularly limited, and methods such as suspension polymerization, dissolution-suspension, emulsification-coagulation, and pulverization can be used. Among these, suspension polymerization is preferred.

[0086] The following describes in detail the method for obtaining toner using suspension polymerization.

[0087] (Process 1: Granulation process) A polymerizable monomer composition containing a polymerizable monomer, a colorant, block copolymer A, and ester wax B is dispersed in an aqueous medium containing a dispersion stabilizer, a polymerization initiator is added, and then droplet formation of the polymerizable monomer composition is performed. The method of droplet formation is not particularly limited, but for example, it is performed using a device capable of strong stirring, such as an (in-line type) emulsifying disperser (manufactured by Taiheiyo Kiko Co., Ltd., product name: Milder) or a high-speed emulsifying disperser (manufactured by Primix Corporation, product name: TK Homomixer MARK II).

[0088] Examples of polymerization initiators include potassium persulfate and persulfates such as ammonium persulfate; azo compounds such as 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide), 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobisisobutyronitrile; and organic peroxides such as di-t-butyl peroxide, benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylbutanoate, diisopropyl peroxydicarbonate, di-t-butyl peroxyisophthalate, and t-butyl peroxyisobutyrate. These can be used individually or in combination of two or more. Among these options, organic peroxides are preferred because they reduce the amount of residual polymerizable monomers and offer excellent print durability.

[0089] Among organic peroxides, peroxyesters are preferred because they have good initiator efficiency and can reduce the amount of residual polymerizable monomers, and non-aromatic peroxyesters, i.e., peroxyesters without aromatic rings, are more preferred.

[0090] The polymerization initiator may be added after the polymerizable monomer composition has been dispersed in an aqueous medium but before droplet formation, as described above, or it may be added to the polymerizable monomer composition before it is dispersed in the aqueous medium.

[0091] The amount of polymerization initiator added to the polymerization of the polymerizable monomer composition is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.3 parts by mass or more and 15 parts by mass or less, and particularly preferably 1 part by mass or more and 10 parts by mass or less, per 100 parts by mass of monomer.

[0092] In this invention, an aqueous medium refers to a medium whose main component is water.

[0093] In the present invention, it is preferable to include a dispersion stabilizer in the aqueous medium. Examples of dispersion stabilizers include inorganic compounds such as sulfates such as barium sulfate and calcium sulfate; carbonates such as barium carbonate, calcium carbonate, and magnesium carbonate; phosphates such as calcium phosphate; metal oxides such as aluminum oxide and titanium oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and ferric hydroxide; and organic compounds such as water-soluble polymers such as polyvinyl alcohol, methylcellulose, and gelatin; anionic surfactants; nonionic surfactants; and amphoteric surfactants.

[0094] The above-mentioned dispersion stabilizers can be used individually or in combination of two or more. The amount of dispersion stabilizer added is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.2 parts by mass or more and 10 parts by mass or less, per 100 parts by mass of polymerizable monomer.

[0095] Among the above-mentioned dispersion stabilizers, inorganic compounds, particularly colloids of poorly water-soluble metal hydroxides, are preferred. By using inorganic compounds, especially colloids of poorly water-soluble metal hydroxides, the particle size distribution of toner particles can be narrowed, and the amount of residual dispersion stabilizer after washing can be reduced. As a result, the resulting toner can reproduce images clearly and does not worsen environmental stability.

[0096] (Step 2: Polymerization step) As in step 1, droplet formation is performed, the resulting aqueous dispersion medium is heated to initiate polymerization, and an aqueous dispersion of resin particles containing a binder resin, a colorant, block copolymer A, and ester wax B is formed.

[0097] The polymerization temperature of the polymerizable monomer composition is preferably 50°C or higher, and more preferably 60 to 95°C. The polymerization reaction time is preferably 1 to 20 hours, and more preferably 2 to 15 hours.

[0098] In order to carry out polymerization while stably dispersing droplets of the polymerizable monomer composition, the polymerization reaction may proceed while carrying out dispersion treatment by stirring, following step 1 above.

[0099] The resin particles may be used as is or with the addition of external additives as toner, but it is preferable to use so-called core-shell type (or "capsule type") resin particles, which are obtained by using the resin particles as a core layer and creating a shell layer different from the core layer on the outside. Core-shell type resin particles allow for a balance between lowering the fixing temperature and preventing aggregation during storage by coating a core layer made of a material with a lower softening point with a material with a higher softening point.

[0100] There are no particular restrictions on the method for producing core-shell type toner particles using the resin particles described above, and they can be produced by conventionally known methods. In situ polymerization and phase separation methods are preferred from the viewpoint of production efficiency.

[0101] The following describes a method for producing core-shell type resin particles by in situ polymerization.

[0102] Core-shell type resin particles can be obtained by adding a polymerizable monomer (polymerizable monomer for shells) and a polymerization initiator to an aqueous medium in which toner particles are dispersed, and then polymerizing them.

[0103] For the shell polymerizable monomer, the same monomers as those mentioned above can be used. Among these, monomers that yield polymers with a Tg exceeding 80°C, such as styrene, acrylonitrile, and methyl methacrylate, are preferably used individually or in combination of two or more.

[0104] Polymerization initiators used for polymerizing polymerizable monomers for shells include persulfate metal salts such as potassium persulfate and ammonium persulfate; azo-based initiators such as 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)propionamide) and 2,2'-azobis-(2-methyl-N-(1,1-bis(hydroxymethyl)2-hydroxyethyl)propionamide); and other water-soluble polymerization initiators. These can be used individually or in combination of two or more. The amount of polymerization initiator is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass, per 100 parts by mass of polymerizable monomers for shells.

[0105] The polymerization temperature of the shell layer is preferably 50°C or higher, and more preferably 60 to 95°C. The polymerization reaction time is preferably 1 to 20 hours, and more preferably 2 to 15 hours.

[0106] (Step 3: Volatile component removal step) A volatile component removal step may be performed to remove unreacted polymerizable monomers and other substances from the resin particle dispersion after the polymerization process is complete. The volatile component removal step is performed by heating and stirring the resin particle dispersion in a stirring tank equipped with a stirring means. The heating conditions during the volatile component removal step are adjusted as appropriate, taking into account the vapor pressure of the components to be removed, such as polymerizable monomers. The volatile component removal step can be performed under atmospheric pressure or reduced pressure.

[0107] (Process 4: Cooling process) Before sending the resin particle dispersion, after the volatile component removal process has been completed, to the next process, it is advisable to perform a cooling process to lower the liquid temperature. The state of the ester wax B can be altered depending on the conditions of the cooling process.

[0108] The conditions for cooling can be determined by the starting temperature, cooling rate, and ending temperature.

[0109] The cooling start temperature is preferably any temperature higher than the crystallization temperature of ester wax B in the binder resin. When the cooling start temperature is within this range, fine crystal nuclei of ester wax B are generated starting from the olefin unit C by cooling, and domains of ester wax B grow using these nuclei, thus promoting the formation of fine domains.

[0110] Furthermore, a cooling rate of 1°C / second or higher is more preferable. When the cooling rate is within this range, the hardening of the binder resin during cooling is sufficiently fast, so even with materials that tend to form plate-like crystals, such as ester wax B, the orientational growth of crystals is inhibited, and domains close to spherical can be formed. As a result, even if crystallization of ester wax B occurs during toner storage, the deposition of wax on the toner surface can be suppressed because there is little anisotropy in the crystallization.

[0111] The cooling start temperature is preferably above the melting point of ester wax B. When the cooling start temperature is within this range, the formation of coarse domains in ester wax B can be suppressed. It is more preferable that the cooling start temperature is 10°C or more higher than the melting point of ester wax B.

[0112] The cooling termination temperature is preferably below the glass transition temperature (Tg) of the binder resin. When the cooling termination temperature is within this range, the growth of wax domains can be suppressed by the curing of the binder resin.

[0113] Furthermore, the state of wax domains can be confirmed by observing a cross-section of the toner particle using a scanning transmission electron microscope.

[0114] (Process 5: High-temperature processing process) Before sending the resin particle dispersion, which has completed the cooling process, to the next process, it is advisable to perform a high-temperature treatment process to improve the crystallinity of ester wax B in the resin particles. Performing a high-temperature treatment process after the cooling process increases the crystallinity of ester wax B, thereby improving the shelf life of the toner.

[0115] The temperature of the high-temperature processing step is preferably above the glass transition temperature (Tg) of the binder resin. When the temperature of the high-temperature processing step is within the above range, the mobility of the ester wax B remaining in the compatible state increases, and crystallization is promoted.

[0116] (Post-processing: washing, filtration, dewatering, drying, and classification) Toner particles are obtained by performing washing, filtering, dehydration, drying, and classification processes on the aqueous dispersion of resin particles produced by the above process, according to standard methods.

[0117] In the above cleaning method, when an inorganic compound is used as a dispersion stabilizer, it is preferable to dissolve and remove the dispersion stabilizer in water by adding an acid or alkali to the aqueous dispersion of toner particles. When a colloid of poorly water-soluble inorganic hydroxide is used as a dispersion stabilizer, it is preferable to add an acid to adjust the pH of the aqueous dispersion of toner particles to 6.5 or below. As the acid to be added, inorganic acids such as sulfuric acid, hydrochloric acid, and nitric acid, as well as organic acids such as formic acid and acetic acid, can be used, but sulfuric acid is particularly preferred due to its high removal efficiency and low burden on manufacturing equipment.

[0118] The dehydration and filtration methods are not particularly limited and can be any of the known methods. For example, centrifugal filtration, vacuum filtration, and pressure filtration can be used. Similarly, the drying method is not particularly limited and can be any of the various methods used.

[0119] <Toner manufacturing method> When adding an external additive to toner particles to produce toner (toner product), there are no particular restrictions on the mixer used to add the external additive to the toner particles; any known mixer, whether dry or wet, can be used. Examples include the FM mixer (manufactured by Nippon Coke Industries Co., Ltd.), the Super Mixer (manufactured by Kawata Co., Ltd.), the Nobilta (manufactured by Hosokawa Micron Corporation), and the Hybridizer (manufactured by Nara Machinery Co., Ltd.). To control the coating state of the external additive, the rotation speed, processing time, and water temperature and volume of the jacket of the above-mentioned external additive device can be adjusted to prepare the toner.

[0120] Furthermore, sieving devices used to separate coarse particles after external addition include the Ultrasonic (manufactured by Koei Sangyo Co., Ltd.), Resona Sieve, Gyro Shifter (manufactured by Tokuju Kogyo Co., Ltd.), Vibrasonic System (manufactured by Dalton Co., Ltd.), Soniclean (manufactured by Shinto Kogyo Co., Ltd.), Turbo Screener (manufactured by Turbo Kogyo Co., Ltd.), and Micro Shifter (manufactured by Makino Sangyo Co., Ltd.).

[0121] [Method for measuring physical properties] The following describes the methods for measuring the physical properties of toner and each material.

[0122] <Identification of ester wax B in toner> (1) Method for separating wax from toner First, the melting point of the wax in the toner is measured using a thermal analyzer (DSC Q2000, manufactured by TA Instruments Japan Co., Ltd.). 3.0 mg of the toner sample is placed in an aluminum pan (KIT NO. 0219-0041) sample container, which is then placed on a holder unit and set in an electric furnace. Under a nitrogen atmosphere, the sample is heated from 30°C to 200°C at a heating rate of 10°C / min, and the DSC curve is measured using a differential scanning calorimeter (DSC) to calculate the melting point of the wax in the toner sample.

[0123] Next, the toner is dispersed in ethanol, which is a poor solvent for toner, and the temperature is raised to a level above the melting point of the wax. Pressure may be applied as needed during this process. Through this operation, the wax above its melting point is melted and extracted into the ethanol. If heating and pressurization are applied, solid-liquid separation can be performed while maintaining the pressurized state to separate the wax from the toner. The extracted liquid is then dried and solidified to obtain the wax.

[0124] (2) Identification of waxes by pyrolysis GC-MS The specific conditions for identifying waxes by pyrolysis GC-MS are shown below. Mass spectrometer: ThermoFisherScinetific ISQ GC system: ThermoFisher Scientific FocusGC Ion source temperature: 250℃ Ionization method: EI Mass range: 50-1000 m / z Column: HP-5MS [30m] Pyrolysis apparatus: JPS-700, manufactured by Nippon Analytical Industry Co., Ltd.

[0125] A small amount of wax separated by extraction and 1 μL of tetramethylammonium hydroxide (TMAH) are added to pyrofoil heated to 590°C. The prepared sample is subjected to thermal decomposition GC-MS analysis under the above conditions to obtain peaks derived from the wax. If the wax is an ester compound, peaks for the alcohol component and the carboxylic acid component are obtained separately. Due to the action of the methylating agent TMAH, the alcohol component and the carboxylic acid component are detected as methylated products. By analyzing the obtained peaks and identifying the structure of the wax, the molecular weight can also be obtained.

[0126] <Method for measuring melting point> The melting point of crystalline materials (crystalline resins or waxes) is measured using a differential scanning calorimeter (DSC) Q2000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃

[0127] 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.

[0128] Specifically, 5 mg of the sample is accurately weighed, placed in an aluminum pan, and measured once. An empty aluminum pan is used as a reference. The peak temperature of the maximum endothermic peak at that time is defined as the melting point.

[0129] <Separation of block copolymer A> The chloroform-soluble portion of toner particles is used as the sample. The sample is prepared by adjusting the concentration of toner particles in chloroform to 0.1% by mass, and the solution is filtered through a 0.45 μm PTFE filter before being used for measurement. The gradient polymer LC measurement conditions are shown below. Equipment: UlTIMATE3000 (manufactured by Thermo Fisher Scientific) Mobile phase: A. Chloroform (HPLC), B. Acetonitrile (HPLC) Gradient: 2 min (A / B=0 / 100) → 25 min (A / B=100 / 0) (Note that the gradient of the mobile phase change was made to be a straight line.) Flow rate: 1.0mL / min Injection: 0.1% by mass x 20μL Column: Tosoh TSKgel ODS (4.6mmφ x 150mm x 5μm) Column temperature: 40℃ Detector: Corona Charged Particle Detector (Corona-CAD) (manufactured by Thermo Fisher Scientific)

[0130] In the time-intensity graph obtained from the measurement, the resin components can be separated into two peaks depending on their polarity. Subsequently, by repeating the above measurement and sampling at the time of the trough of each peak, it is possible to separate them into two types of resin. In this measurement, components with higher solubility in acetonitrile elute earlier. Therefore, the binder resin and block copolymer A elute in that order. By identifying the peaks corresponding to each resin and sampling at that timing, fractions containing the binder resin and block copolymer A are collected. After drying and concentration, the sample of block copolymer A is obtained. Note that even for toner particles containing components other than the binder resin and block copolymer A, it is possible to collect each fraction by performing the same procedure.

[0131] If the toner contains a release agent, it is necessary to separate the release agent from the toner. The release agent is separated by recycled HPLC, which separates components with a molecular weight of 2000 or less as the release agent. The measurement method is as follows. First, a chloroform solution of the toner is prepared using the method described above. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshoridisk" (manufactured by Tosoh Corporation) with a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in chloroform is 1.0 mass%. This sample solution is used for measurement under the following conditions. ·Equipment: LC-Sakura NEXT (manufactured by Nippon Analytical Industry Co., Ltd.) • Columns: JAIGEL2H, 4H (manufactured by Nippon Analytical Engineering Co., Ltd.) • Eluent: Chloroform ·Flow rate: 10.0mL / min Oven temperature: 40.0℃ • Sample injection volume: 1.0 mL

[0132] To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0133] From the molecular weight curve obtained in this way, components with a molecular weight of 2000 or less are repeatedly separated, and the release agent is removed from the toner.

[0134] <Identification of olefin unit C in block copolymer A, confirmation of block structure, and measurement of content ratio> Identification of olefin unit C in block copolymer A, confirmation of block structure, and measurement of content ratio are performed. 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.

[0135] obtained 1 The H-NMR chart is analyzed to identify the structure of each monomer unit. 1 In the 1H-NMR chart, a peak is selected from among the peaks attributed to the components of olefin unit C, independent of the peaks attributed to the components of other monomer units, and the integral value S1 of this peak is calculated. The integral values ​​are similarly calculated for each of the other monomer units contained in block copolymer A.

[0136] If the monomer units constituting block copolymer A are olefin unit C and one other monomer unit, the content of olefin unit C is determined as follows using the integral value S1 and the integral value S2 of the peak of the other monomer unit. Note that n1 and n2 are the number of hydrogen atoms in the constituent element to which the peak of interest belongs for each part. Olefin unit C content (mol%) = {(S1 / n1) / ((S1 / n1)+(S2 / n2))}×100

[0137] The same method can be used to calculate the content ratio of olefin unit C even when there are two or more other monomer units.

[0138] If a polymerizable monomer is used in which no hydrogen atoms are present in any component other than the vinyl group, 13 The atomic nuclei were measured using C-NMR. 13 Let C be used, and the measurement will be performed in single-pulse mode. 1The same calculation is performed using 1H-NMR. The percentage (mol%) of each monomer unit calculated by the above method is multiplied by the molecular weight of each monomer unit to convert the content of each monomer unit into mass%.

[0139] The fact that block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment was obtained by the above method. 13 This can be confirmed by the ratio of peaks originating from carbon atoms between olefin units, peaks originating from carbon atoms between styrene units, and peaks originating from carbon atoms between styrene units and olefin units in the 1C-NMR chart. As an example, equation (8) shows carbon atoms between olefin units, equation (9) shows carbon atoms between styrene units, and equation (10) shows carbon atoms between styrene units and olefin units. In equations (8) to (10), the carbon atoms indicated by arrows correspond to the carbon atoms mentioned above.

[0140] Specifically, the integral value of the peak originating from carbon atoms between olefin units (S II ) and the integral value of the peak originating from the bond between the styrene unit and the olefin unit (S SI The ratio value (S) II / S SI ) is 10 or more, and the integral value of the peak originating from carbon atoms between styrene units (S SS ) and the integral value of the peak originating from the bond between the styrene unit and the olefin unit (S SI The ratio value (S) SS / S SI When the value is 5 or greater, it is determined that block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment.

[0141] Furthermore, regarding the fact that the polyolefin segment contains olefin unit C, 13 This can be determined from the peak positions on the C-NMR chart.

[0142] [ka]

[0143] <Observation of a cross-section of toner particles using a scanning transmission electron microscope> The ester wax B domains in toner particles are confirmed by observing a cross-section of the toner particles using a scanning transmission electron microscope.

[0144] In cross-sectional images of toner particles obtained using a scanning transmission electron microscope, ester wax B is observed as domains. By measuring the number and shape of these ester wax B domains, the state of the ester compound is identified.

[0145] The procedure for observing the cross-section of toner particles is as follows:

[0146] Toner particles are embedded in a visible light-curable embedding resin (product name: D-800, manufactured by Nisshin EM Co., Ltd.) and then cut to a thickness of 70 nm using an ultrasonic ultramicrotome (product name: UC7, manufactured by Leica Microsystems K.K.).

[0147] From the obtained thin section samples, 10 samples are arbitrarily selected in which the diameter of the toner particle cross-section is within the weight-average particle size (D4) ± 2.0 μm.

[0148] The selected thin section samples are stained for 15 minutes in a RuO4 gas atmosphere at 500 Pa using a vacuum staining device (product name: VSC4R1H, manufactured by Philgen Co., Ltd.). Subsequently, STEM images are created using the scanning mode of a scanning transmission electron microscope (product name: JEM2800, manufactured by JEOL Ltd.).

[0149] The STEM probe size is 1 nm, and the image size is 1024 x 1024 pixels. STEM images are acquired under the following conditions. Brightfield image Detector Control panel Contrast: 1425 Brightness: 3750 Image Control Panel Contrast: 0.0 Brightness: 0.5 Gammma: 1.00

[0150] The obtained STEM images were binarized (with a threshold of 120 / 255 levels) using the image processing software "Image-Pro Plus (Media Cybernetics)" to clearly distinguish between the ester wax B domain and the binder resin region.

[0151] When the binarization threshold is set to 210, the white areas represent the ester wax B domain.

[0152] <Identification of the domain of ester wax B> In toners containing release agents, the domains of the release agent may appear white in STEM images, similar to the domains of ester wax B. In such cases, the domains should be identified using the following procedure.

[0153] If crystalline materials are available as raw materials, their crystal structures are observed in the same manner as the method for observing the cross-section of toner particles using a ruthenium-stained transmission electron microscope described above, and images of the lamellar structures of the crystals of the release agent and ester wax B are obtained. By comparing these images with the lamellar structures of the domains in the cross-section of the toner particles, if the lamellar spacing is less than 10% error, the raw materials forming the domains in the cross-section of the toner particles can be identified.

[0154] <Method for calculating the average number of domains and average length of domains in ester compounds> In the STEM images of the cross-sections of the 10 selected toner particles, the number of ester wax B domains in each particle is counted, and the average value of these counts is taken as the average number of domains.

[0155] Furthermore, in the STEM images of the cross-sections of the 10 selected toner particles, the maximum diameter of all domains contained in each is measured, and the average value of these measurements is defined as the average major axis r1 (μm) of the domains.

[0156] <Method for measuring G'(60) and G'(100) of toner particles> Toner particles were sandwiched between a pair of 8mmφ plates (parallel plates or cross-hatch plates) under a 20g load (the colored resin particles were uniformly arranged over the 8mmφ area and sandwiched between the pair of plates under a 20g load). This was used as the measurement sample, and dynamic viscoelasticity was determined using a rotating planar rheometer dynamic viscoelasticity measuring device (product name "ARES-G2", manufactured by TA Instruments Co., Ltd.) under the conditions of a measurement frequency of 24Hz, a load of 20g, and a heating rate of 5°C / min in the range of 45 to 150°C.

[0157] <Method for measuring the glass transition temperature (Tg) of binder resins> The glass transition temperature (Tg) of the binder resin is measured using a differential scanning calorimetry analyzer "Q1000" (TA Instruments) in accordance with ASTM D3418-82. The temperature correction of the instrument's detection unit uses the melting points of indium and zinc, and the heat correction uses the heat of fusion of indium. Specifically, 5 mg of toner is accurately weighed and placed in an aluminum pan, with an empty aluminum pan used as a reference. Measurements are taken within the measurement range of 30 to 200°C at a heating rate of 1°C / min. During this heating process, a change in specific heat is obtained in the temperature range of 40°C to 100°C. 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) of the binder resin.

[0158] <Method for measuring weight-average particle size (D4) and number-average particle size (D1)> The weight-average particle size (D4) and number-average particle size (D1) of toner, toner particles, or toner matrix particles (hereinafter also referred to as toner, etc.) are calculated as follows.

[0159] 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.

[0160] Setting measurement conditions and analyzing measurement data are performed using the included dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). Measurements are performed using 25,000 effective measurement channels.

[0161] 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.).

[0162] Before performing measurements and analysis, configure the dedicated software as follows.

[0163] 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".

[0164] 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.

[0165] 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 or the like to the electrolytic aqueous solution little by little and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank as appropriate so that it is between 10°C and 40°C. (6) Using a pipette, add the electrolytic aqueous solution (5) containing the dispersed toner, etc., 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 to calculate the weight-average particle size (D4) and the number-average particle size (D1). Note that when the dedicated software is set to graph / volume %, the "Average Diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen is the weight-average particle size (D4). When the dedicated software is set to graph / number %, the "Average Diameter" on the "Analysis / Number Statistics (Arithmetic Mean)" screen is the number-average particle size (D1).

[0166] [Image forming apparatus] Figure 1 is a diagram showing a schematic configuration of an example of an image forming apparatus according to one aspect of the present disclosure. The overall configuration of the image forming apparatus will be described with reference to Figure 1. However, the components, dimensions, arrangement, etc. in this example configuration should be changed as appropriate and do not limit the scope of this invention. Figure 1 is a schematic cross-sectional view of an image forming apparatus 100, which is a laser printer capable of forming monochrome (black single-color) images using an electrophotographic method.

[0167] The image forming apparatus 100 has a rotatable drum-shaped (cylindrical) photoreceptor (photosensitive drum) 11 as an electrostatic latent image carrier. When the image forming operation is started, the photoreceptor 11 is rotated in the direction of arrow A1 (clockwise direction) in the figure by the driving force transmitted from the drive motor, which is a drive source constituting the driving means.

[0168] The surface of the rotating photoreceptor 11 is uniformly charged to a predetermined potential with a predetermined polarity, which is the normal polarity of the toner, by a charging roller 21, which is a roller-type charging member acting as a charging means. The charging roller 21 has its surface (outer surface) in contact with the surface (outer surface) of the photoreceptor 11 to form a charged portion N2.

[0169] The charging roller 21 is pressed against the surface of the photoreceptor 11 with a predetermined pressure by springs at both ends in the direction of the rotation axis of a conductive support. The charging roller 21 rotates in conjunction with the rotation of the photoreceptor 11. During the charging process, a predetermined charging voltage (charging bias) is applied to the charging roller 21 at a predetermined timing from a charging power supply, which is a charging voltage application means (charging voltage application unit). The uniformly charged surface (non-image area) of the photoreceptor 11 becomes dark potential.

[0170] The surface of the charged photoreceptor 11 is scanned and exposed by an exposure device (laser exposure unit) 131, which acts as an exposure means (electrostatic image forming means), and an electrostatic latent image (electrostatic image) is formed on the photoreceptor 11. The exposure device 131 scans the surface of the photoreceptor 11 with a laser beam along the main scanning direction of the photoreceptor 11 (approximately parallel to the rotation axis direction of the photoreceptor 11) according to the image information (image data) to perform exposure. The exposure device 131 also repeats exposure along the main scanning direction along the sub-scanning direction (approximately parallel to the movement direction of the surface of the photoreceptor 11) in time with the image information. As a result, an electrostatic latent image is formed on the photoreceptor 11. The exposed surface of the photoreceptor 11, which is the exposed area (image area), becomes bright.

[0171] The electrostatic latent image formed on the photoreceptor 11 is developed (visualized) by a developing device (developing unit) 2, which is a developing means, when toner T is supplied as a developer, and a toner image (toner image, developer image) is formed on the photoreceptor 11. In this disclosure, a one-component toner is used as the developer contained in the developing device 2. Details of the toner are as described above.

[0172] The developing device 2 has a developing roller 31 as a toner carrier (developing member). During development, the surface (outer surface) of the developing roller 31 comes into contact with the surface (outer surface) of the photoreceptor 11 to form a developing section N1. Also during development, a predetermined developing voltage (developing bias) is applied to the developing roller 31 at a predetermined timing from a developing power supply, which is a developing voltage application means (developing voltage application section). Toner charged with the same polarity as the charging polarity of the photoreceptor 11 adheres to the exposed section (image section) on the photoreceptor 11, where the absolute value of the potential has decreased after uniform charging treatment and exposure (reverse developing method).

[0173] Development is performed by the potential difference (development contrast) formed between the development voltage applied to the developing roller 31 and the bright potential on the photoreceptor 11; therefore, a predetermined development voltage is applied to the developing roller 31. It is assumed that the surface potential formed on the surface of the developing roller 31 and the magnitude of the development voltage applied to the developing roller 31 are approximately the same. The developing roller 31 rotates in the direction of arrow A2 in the figure (counterclockwise) opposite to the direction of the photoreceptor 11 (the direction of movement at the contact point is forward). The developing device 2 will be further explained later.

[0174] Opposite the photoreceptor 11 is a transfer roller 111, which is a roller-type transfer member serving as a transfer means. The transfer roller 111 is pressed toward the photoreceptor 11, forming a transfer portion (transfer nip) N3, which is the contact area between the photoreceptor 11 and the transfer roller 111. The toner image formed on the photoreceptor 11 is transferred in the transfer portion N3 onto the recording material R, which is held and transported between the photoreceptor 11 and the transfer roller 111 by the action of the transfer roller 111. During transfer, a predetermined transfer voltage (transfer bias) is applied to the transfer roller 111 at a predetermined timing from a transfer power supply, which serves as a transfer voltage application means (transfer voltage application unit).

[0175] A sheet-like recording material (transfer material, recording medium, sheet) R, such as paper, is supplied from the paper feeding unit (feeding unit) 181 to the transfer unit N3. The paper feeding unit 181 may have a cassette as a recording material storage unit, transport rollers as transport members, etc. The recording material R is transported to the transfer unit N3 in timing with the toner image on the photoreceptor 11.

[0176] The recording material R onto which the toner image has been transferred is transported to a fixing device 121, which serves as a fixing means. The fixing device 121 applies heat and pressure to the recording material R carrying the unfixed toner image to fix (melt and solidify) the toner image to the recording material R. The recording material R with the fixed toner image is discharged (output) from the paper discharge unit (discharge unit) 191 and loaded onto a tray 192 located on the top of the image forming apparatus 100.

[0177] In this configuration example, the photoreceptor 11, the charging roller 21 acting as a process means on the photoreceptor 11, and the developing device 2 form a process cartridge 1 that can be attached to and detached from the image forming apparatus 100 as a single unit. The transfer roller 111, exposure device 131, fixing device 121, pre-exposure means 6, control unit 141 for controlling the developing device 2, and various power supplies are attached to the image forming apparatus 100. The image forming apparatus and process cartridge may have a cleaning blade (not shown) for cleaning the toner on the surface of the photoreceptor 11.

[0178] [Process Cartridge] Next, we will further explain process cartridge 1 in this configuration example.

[0179] The process cartridge 1 comprises a developing device (developing unit) 2 and a photoreceptor unit 3. The developing device 2, as will be described in detail later, includes a developing roller 31, a supply roller 32, a developing blade 33, and a developing container 36 which also serves as a developer container. The developing container 36 also serves as a developing frame that supports the developing roller 31, the supply roller 32, and the developing blade 33.

[0180] The photoreceptor unit 3 has a photoreceptor 11 and a charging roller 21, which are supported by each. The developing device 2 and the photoreceptor unit 3 are coupled such that the developing device 2 can pivot relative to the photoreceptor unit 3 about a rotation axis that is substantially parallel to the rotation axis direction of the photoreceptor 11. More specifically, the developing container (developing frame) 36 of the developing device 2 and the photoreceptor support container (photoreceptor unit frame) 61 of the photoreceptor unit 3 are pivotably coupled, thereby integrating the process cartridge 1.

[0181] As a result, the developing device 2 can move between a contact position where the developing roller 31 is in contact with the photoreceptor 11 and a separation position where the developing roller 31 is separated from the photoreceptor 11. By configuring the developing device 2 to be able to move between the contact position and the separation position, unnecessary wear of the developing device 2 and the photoreceptor 11 is suppressed. In other words, in the separation position, the rotation of the developing roller 31 and the supply roller 32 is stopped by stopping the drive of the developing device 2, thereby suppressing toner consumption, and wear of the charge transport layer is suppressed because the photoreceptor 11 no longer comes into contact with the developing roller 31.

[0182] [Developing equipment] Next, the developing device (developing unit) 2 in this configuration example will be further explained. The developing device 2 has a developing roller 31 as a developing agent carrier (developing member) that carries and transports toner as a developing agent and supplies toner to the electrostatic latent image formed on the surface of the photoreceptor 11 to develop the electrostatic latent image. The developing device 2 also has a supply roller (supply stripping roller) 32 as a developing agent supply member (developing agent supply stripping member) that supplies toner to the developing roller 31 and also strips the toner from the developing roller 31. The supply roller 32 rotates in the direction of arrow A3.

[0183] Furthermore, the developing device 2 has a developing blade 33 as a regulating member that restricts the amount of toner supplied onto the developing roller 31 to a predetermined amount. The developing device 2 also has a developing container 36 that forms a toner storage section (toner container) 37 inside. One component of the developing agent, toner, is stored inside the toner storage section 37.

[0184] [Configurations included in embodiments of the present invention] This embodiment includes the following configuration. (Composition 1) A toner having toner particles containing a binder resin, block copolymer A and ester wax B, The binder resin contains a styrene-acrylic copolymer, The content of the styrene-acrylic copolymer in the binder resin is 50% by mass or more. The block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment, and the polyolefin segment has an olefin unit C represented by any of the above formulas (1) to (4). The ester wax B is compatible at 100°C with 15.0 parts by mass or more of styrene-n-butyl acrylate copolymer α having the above composition, • Styrene-n-butyl acrylate copolymer α: A copolymer of 75 parts by mass of styrene monomer and 25 parts by mass of n-butyl acrylate monomer (weight-average molecular weight Mw is 29,000 or more and 31,000 or less) A toner characterized in that the ester wax B is an ester compound having the structure of formula (5) or formula (6) described above. (Configuration 2) The toner according to Configuration 1, wherein the olefin unit C is a unit of either formula (1) or (2). (Configuration 3) The toner according to claim 1 or 2, wherein the ester wax B is an ester compound having the structure of formula (7) above. (Configuration 4) The solubility parameter of the olefin unit C is set to SPc (J / cm 3 ) 0.5 The solubility parameter of the ester wax B is set to SPb (J / cm²). 3 ) 0.5 In this case, the toner described in any of configurations 1 to 3, where the SPb-SPc value is between 1.50 and 3.00. (Configuration 5) The toner according to any one of Configurations 1 to 4, wherein domains of the ester wax B are present in the cross-section of the toner particles as observed by a scanning transmission electron microscope, the average number of such domains is 100 or more per cross-section of the toner particles, and when the average major axis of the domains is r1 (μm), r1 is 1.00 or less. (Composition 6) A method for producing toner having toner particles containing a binder resin, block copolymer A and ester wax B, The binder resin contains a styrene-acrylic copolymer, The content of the styrene-acrylic copolymer in the binder resin is 50% by mass or more. The block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment, and the polyolefin segment has an olefin unit C represented by any of the above formulas (1) to (4). The ester wax B is compatible at 100°C with 15.0 parts by mass or more of styrene-n-butyl acrylate copolymer α having the above composition, The ester wax B is an ester compound having the structure of formula (5) or formula (6) above, A method for producing toner, characterized by comprising a cooling step of cooling the toner particles in an aqueous medium from a temperature above the melting point of the ester wax B to a temperature below the glass transition temperature (Tg) of the binder resin at a rate of 1°C / second or more. (Configuration 7) The toner manufacturing method according to Configuration 6, wherein the toner manufacturing method comprises a high-temperature processing step of processing at a temperature equal to or greater than the Tg of the binder resin after the cooling step. (Composition 8) A process cartridge that can be attached to and detached from an image forming apparatus, The process cartridge is Toner and, A toner container for storing the toner, It has, The process cartridge is characterized in that the toner is the toner described in any of configurations 1 to 5. (Composition 9) Toner and, A toner carrier that holds the toner, Electrostatic latent image carrier, A charging means for charging the surface of the electrostatic latent image carrier with a charging member, An electrostatic latent image forming means for forming an electrostatic latent image on a charged electrostatic latent image carrier, Development: Using the toner to develop the electrostatic latent image and form a toner image on the electrostatic latent image carrier. means and A transfer means for transferring the toner image onto a recording medium, Fixing means for fixing the toner image transferred onto the recording medium onto the recording medium, An image forming apparatus comprising, The image forming apparatus is characterized in that the toner is the toner described in any of configurations 1 to 5. [Examples]

[0185] The present invention will be specifically described by the following examples. However, this does not limit the present invention in any way. The toner and the method for manufacturing the toner are described below. Unless otherwise specified, all "parts" in the examples and comparative examples are based on mass.

[0186] [Examples of toner manufacturing] <Toner 1> (Process 1: Granulation process) • Styrene: 77 parts • n-butyl acrylate: 23 parts • Carbon black (manufactured by Mitsubishi Chemical Corporation, product name: #25B): 7 parts • Divinylbenzene: 0.6 parts t-dodecyl mercaptan: 1.2 parts • Polymethacrylate macromonomer (manufactured by Toa Gosei Chemical Co., Ltd., product name: AA6, Tg=94℃): 0.3 parts The above materials were mixed and wet-ground using a media-type wet grinder.

[0187] • Electrostatic charge control resin (manufactured by Fujikura Chemical Co., Ltd., product name: Acrybase FCA-207P, styrene / acrylic resin): 1 part · Block copolymer A-1 (manufactured by Kuraray Co., Ltd., trade name: Hybrar 5125, containing the structure of formula (1) as the olefin unit C): 5 parts · Ester wax B-1 (ethylene glycol distearate: melting point 76°C): 15 parts Thereafter, the above materials were added and mixed to obtain a polymerizable monomer composition.

[0188] On the other hand, in a stirring tank, at room temperature, an aqueous solution prepared by dissolving 7.4 parts of magnesium chloride (water-soluble polyvalent metal salt) in 250 parts of ion-exchanged water was gradually added with stirring to an aqueous solution prepared by dissolving 4.1 parts of sodium hydroxide (alkali metal hydroxide) in 50 parts of ion-exchanged water to prepare a magnesium hydroxide colloid (water-insoluble metal hydroxide colloid) dispersion.

[0189] On the other hand, 2 parts of methyl methacrylate (Tg = 105°C) and 65 parts of ion-exchanged water as the polymerizable monomer for the shell were finely dispersed using an ultrasonic emulsifier to obtain an aqueous dispersion of the polymerizable monomer for the shell.

[0190] The particle size of the droplets of the polymerizable monomer for the shell was such that D90 was 1.6 μm.

[0191] The polymerizable monomer composition was introduced into the magnesium hydroxide colloid dispersion obtained above, stirred until the droplets were stabilized, and 6 parts of t-butyl peroxyisobutyrate (manufactured by NOF Corporation, trade name: Perbutyl IB) was added thereto as a polymerization initiator. Then, using an in-line emulsifying disperser (manufactured by Taihei Kiko Co., Ltd., trade name: Mildar), high-shear stirring was performed at a rotational speed of 15,000 rpm, and dispersion was carried out while circulating to form droplets of the polymerizable monomer composition.

[0192] (Step 2: Polymerization step) Next, 1 part of sodium tetraborate decahydrate was added to the aqueous dispersion of the droplet-formed polymerizable monomer composition, and it was put into a reactor equipped with a stirring blade. The temperature was raised to 85 °C to carry out a polymerization reaction. After the polymerization conversion rate reached almost 100%, the aqueous dispersion of the polymerizable monomer for the shell and 0.3 parts of 2,2'-azobis(2-methyl-N-(2-hydroxyethyl)-propionamide) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: VA-086, water-soluble), as a polymerization initiator for the shell, were added to the reactor. Further, the polymerization was continued for 4 hours to obtain a resin particle dispersion.

[0193] In addition, in the above process, resin particle formation was carried out except for carbon black, charge control resin, block copolymer A-1, and ester wax B-1, and the glass transition temperature of the obtained resin particles (corresponding to the binder resin) was measured. The glass transition temperature was 53 °C.

[0194] (Step 3: Volatile component removal step) While continuing stirring, the temperature of the resin particle dispersion was raised to 100 °C, and the volatile component removal step was carried out while holding for 2 hours.

[0195] (Step 4: Cooling step) Subsequently, a cooling step was carried out to cool the resin particle dispersion to 40 °C at a rate of 4.0 °C / second.

[0196] (Step 5: High-temperature treatment step) Thereafter, the temperature of the resin particle dispersion was raised to 55 °C, and the high-temperature treatment step was carried out while holding for 3 hours. Thereafter, the temperature was lowered to 25 °C to obtain a toner particle dispersion.

[0197] (Post-process: Filtration, washing, and drying process) The toner particle dispersion was washed with dilute sulfuric acid (25 °C, 10 minutes) to make the pH 4.5 or less. Next, after separating water by filtration, 200 parts of fresh ion-exchanged water was added to re-slurry, and the water washing treatment (washing, filtration, and dehydration) was repeated several times at room temperature (25 °C). After the obtained solid content was separated by filtration, vacuum drying was carried out to obtain toner particles 1.

[0198] To 100 parts of the toner particles obtained as described above, 1 part of hydrophobically treated silica fine particles (number average primary particle diameter: 7 nm) and 1 part of hydrophobically treated silica fine particles (number average primary particle diameter: 35 nm) were added as external additives, and using a high-speed stirrer (manufactured by Mitsui Mining Co., Ltd., trade name: Henschel Mixer), they were mixed and stirred to perform an external addition treatment, thereby obtaining Toner 1. The physical properties of Toner Particles 1 and Toner 1 are shown in Table 4.

[0199] <Toner 2 to 24> Toner 2 to 24 were obtained in the same manner as in the production example of Toner 1, except that the raw materials containing the block copolymer A described in Table 1 and the ester wax B described in Table 2 and the production conditions were changed to those described in Table 3. The physical properties of Toner Particles 2 to 24 and Toner 2 to 24 are shown in Table 4.

[0200]

Table 1

[0201]

Table 2

[0202]

Table 3

[0203]

Table 4

[0204] [Examples 1 to 18, Comparative Examples 1 to 6] Using the above Toner 1 to 24, evaluations were conducted in the combinations shown in Table 5. The evaluation results are shown in Table 5.

[0205] Hereinafter, the evaluation method and evaluation criteria of the present invention will be described.

[0206] As the image forming apparatus, a modified Canon LBP-712Ci laser printer was used, with the process speed adjustable from 50 mm / sec to 300 mm / sec and the fixing temperature adjustable from 140°C to 220°C. A Canon 040H (black) toner cartridge was also used as the processing device. The original toner was removed from the cartridge, cleaned with compressed air, and then filled with 165 g of the toner of the present invention. The yellow, magenta, and cyan stations were each evaluated by removing the original toner and inserting yellow, magenta, and cyan cartridges with the toner level detection mechanism disabled.

[0207] <Gross decline> Under normal temperature and humidity conditions (25°C / 50%RH, hereafter referred to as N / N environment), BROCHURE PAPER 150g GLOSSY paper (HP Corporation: 150g / m²) was tested. 2 Using this method, the process speed was adjusted to 70 mm / sec and the fixing temperature to 200°C, resulting in a toner load of 0.50 mg / cm². 2 Ten solid black images were output.

[0208] The image gloss of the center of the 10th image, both horizontally and vertically, was measured using a gloss meter. Subsequently, the image was stored in a high-temperature, high-humidity environment (30°C / 80%RH) for 30 days. The gloss was then measured again, and the gloss decrease was evaluated from the difference in gloss before and after storage. A handheld gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used. For gloss measurement, the light projection angle and light reception angle were both set to 75°. A: Gross decrease is 2 or less B: Gross decrease is greater than 2 and less than or equal to 5 C: Gross decrease is greater than 5 and less than or equal to 10 D: Gross decrease exceeds 10

[0209] <Glossy unevenness> The gloss was measured at the center of the 10th image in the horizontal direction, at a point 2 cm from the top edge of the image in the vertical direction, and at the center of the image in the horizontal direction, and at a point 2 cm from the bottom edge of the image. The difference in gloss between the top and bottom edges was used to evaluate the unevenness of the gloss. A: Gross difference is 1 or less B: Gross difference greater than 1 and less than or equal to 2 C: Gross difference is greater than 2 and less than or equal to 5 D: Gross difference exceeds 5

[0210] <Low-temperature fixation> Under normal temperature and humidity conditions (25°C / 50%RH, hereafter referred to as N / N environment), high-whiteness paper GF-C081 (manufactured by Canon: 81.4g / m²) was tested. 2 Using a process speed of 300 mm / sec and a fixing temperature of 220°C, the toner load is 0.50 mg / cm². 2 Ten solid black images were printed. Next, the fixing temperature was lowered in 5°C increments until a white patch appeared on the tenth image, and the results were evaluated. The low-temperature fixing performance was evaluated based on the temperature at which the white patch appeared. A: The temperature at which the white areas occurred was below 150°C. B: The temperature at which white spots occurred was between 155°C and 170°C. C: The temperature at which white spots occurred was between 175°C and 195°C. D: The temperature at which white spots occurred was 200°C or higher.

[0211] <Blocking resistance> 5g of toner was weighed into a poly cup and stored in an environment of 55°C / 10%RH for 72 hours. Subsequently, the blocking resistance was evaluated based on the aggregation state of the toner according to the following evaluation criteria. A: No change is observed compared to before storage. B: Some aggregation is observed, but it loosens when vibration is applied. C: Some aggregation is observed, but it can be broken down by crushing it with a spatula. D: Aggregation is observed, and it does not break apart even when crushed with a spatula.

[0212] <Wax seepage> The wettability of the toner was evaluated using a wettability tester. Next, 5g of toner was weighed into a poly cup and stored in an environment of 40°C / 95%RH for 30 days. Afterward, the wettability was measured again, and wax seepage was evaluated based on the difference in wettability before and after storage. The wettability tester used was the powder wettability tester "WET-100P" (manufactured by Lesca Co., Ltd.). Wettability was measured using the following procedure. A large change in wettability suggests that wax has seeped onto the toner surface.

[0213] [Procedure for measuring wettability] A fluororesin-coated spindle-shaped rotor, 25 mm long and with a maximum diameter of 8 mm, is placed in a cylindrical glass container with a diameter of 5 cm and a thickness of 1.75 mm. 60.0 mL of distilled water is added to the cylindrical glass container and treated with an ultrasonic disperser for 5 minutes to remove air bubbles and other impurities. 0.1 g of toner is accurately weighed and added to this to prepare the sample solution. While stirring the spindle-shaped rotor in the cylindrical glass container at a speed of 300 rpm using a magnetic stirrer, methanol is continuously added to the sample solution at a dropping rate of 0.8 mL / min through the powder wettability tester. The transmittance is measured using light at a wavelength of 780 nm, and a methanol dropping transmittance curve is created. From the obtained methanol dropping transmittance curve, the methanol concentration (TA) when the transmittance is 50% is read. The methanol concentration (TA; volume %) is calculated as (volume of methanol in the cylindrical glass container / volume of methanol and water mixture in the cylindrical glass container) × 100. A: Change in wettability is 3% or less B: Change in wettability is greater than 3% but less than or equal to 5%. C: Change in wettability is greater than 5% but less than or equal to 10%. D: Change in wettability exceeds 10%

[0214] [Table 5] [Explanation of Symbols]

[0215] 1: Process cartridge, 2: Developing device (developing means), 11: Photoreceptor (electrostatic latent image carrier), 21: Charging roller (charging means), 31: Developing roller (toner carrier), 37: Toner storage section (toner container), 100: Image forming apparatus, 111: Transfer roller (transfer means), 121: Fixing device (fixing means), 131: Exposure device (electrostatic latent image forming means), R: Recording material (recording medium), T: Toner

Claims

1. A toner having toner particles containing a binder resin, block copolymer A, and ester wax B, The binder resin contains a styrene-acrylic copolymer, The content of the styrene-acrylic copolymer in the binder resin is 50% by mass or more. The block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment, and the polyolefin segment has an olefin unit C represented by any of the following formulas (1) to (4). 【Chemistry 1】 The ester wax B is compatible at 100°C with 15.0 parts by mass or more of 100 parts by mass of styrene-n-butyl acrylate copolymer α having the following composition. • Styrene-n-butyl acrylate copolymer α: A copolymer of 75 parts by mass of styrene monomer and 25 parts by mass of n-butyl acrylate monomer (weight-average molecular weight Mw is 29,000 or more and 31,000 or less) A toner characterized in that the ester wax B is an ester compound having the structure of formula (5) or formula (6) below. 【Chemistry 2】 (In formula (5), R 1 and R 3 Each independently represents an n-alkyl group having 13 to 21 carbon atoms, and R 2 (This represents an alkylene group with 2 to 8 carbon atoms.) 【Transformation 3】 (In formula (6), R 4 and R 6 Each independently represents an n-alkyl group having 14 to 22 carbon atoms, and R 5 (This represents a single bond or an alkylene group having 1 to 6 carbon atoms.)

2. The toner according to claim 1, wherein the olefin unit C is a unit of either formula (1) or (2).

3. The toner according to claim 1 or 2, wherein the ester wax B is an ester compound having the structure of the following formula (7). 【Chemistry 4】 (In formula (7), R 7 and R 9 each independently represents an n-alkyl group having 17 to 21 carbon atoms, and R 8 represents an alkylene group having 2 carbon atoms.)

4. The solubility parameter of the olefin unit C is set to SPc (J / cm²). 3 ) 0.5 The solubility parameter of the ester wax B is set to SPb (J / cm²). 3 ) 0.5 The toner according to claim 1 or 2, wherein the value of SPb-SPc is 1.50 or more and 3.00 or less.

5. The toner according to claim 1 or 2, wherein domains of the ester wax B are present in the cross-section of the toner particles as observed by a scanning transmission electron microscope, the average number of such domains is 100 or more per cross-section of the toner particles, and when the average major axis of the domains is r1 (μm), r1 is 1.00 or less.

6. A method for producing toner having toner particles containing a binder resin, block copolymer A, and ester wax B, The binder resin contains a styrene-acrylic copolymer, The content of the styrene-acrylic copolymer in the binder resin is 50% by mass or more. The block copolymer A is a block copolymer having a polyolefin segment and a polystyrene segment, and the polyolefin segment has an olefin unit C represented by any of the following formulas (1) to (4). 【Transformation 5】 The ester wax B is compatible at 100°C with 15.0 parts by mass or more of 100 parts by mass of styrene-n-butyl acrylate copolymer α having the following composition. • Styrene-n-butyl acrylate copolymer α: A copolymer of 75 parts by mass of styrene monomer and 25 parts by mass of n-butyl acrylate monomer (weight-average molecular weight Mw is 29,000 or more and 31,000 or less) The ester wax B is an ester compound having the structure of formula (5) or formula (6) below, A method for producing toner, characterized by comprising a cooling step of cooling the toner particles in an aqueous medium from a temperature above the melting point of the ester wax B to a temperature below the glass transition temperature (Tg) of the binder resin at a rate of 1°C / second or more. 【Transformation 6】 (In formula (5), R 1 and R 3 Each independently represents an n-alkyl group having 13 to 21 carbon atoms, and R 2 (This represents an alkylene group with 2 to 8 carbon atoms.) 【Transformation 7】 (In formula (6), R 4 and R 6 Each independently represents an n-alkyl group having 14 to 22 carbon atoms, and R 5 (This represents a single bond or an alkylene group having 1 to 6 carbon atoms.)

7. The toner manufacturing method according to claim 6, further comprising a high-temperature processing step of processing the binder resin at a temperature equal to or greater than the Tg of the binder resin after the cooling step.

8. A process cartridge that can be attached to and detached from an image forming apparatus, The process cartridge is Toner and, A toner container for storing the toner, It has, A process cartridge characterized in that the toner is the toner described in claim 1 or 2.

9. Toner and, A toner carrier that holds the toner, Electrostatic latent image carrier, A charging means for charging the surface of the electrostatic latent image carrier with a charging member, An electrostatic latent image forming means for forming an electrostatic latent image on a charged electrostatic latent image carrier, Development: Using the toner to develop the electrostatic latent image and form a toner image on the electrostatic latent image carrier. means and A transfer means for transferring the toner image onto a recording medium, Fixing means for fixing the toner image transferred onto the recording medium onto the recording medium, An image forming apparatus comprising, The image forming apparatus is characterized in that the toner is the toner described in claim 1 or 2.

Images