Toner, two-component developer, and replenishing developer

Abstract

To provide a toner that prevents a reduction in image density even when continuous image output is performed in a low humidity environment.SOLUTION: A toner has a toner particle containing resin. The resin contains polyrotaxane. The polyrotaxane has (i) a plurality of cyclic molecules and (ii) a chain molecule clathrated in an opening in the cyclic molecule in a skewered manner, and (iii) the chain molecule has two or more blocking groups to prevent the cyclic molecule from being separated from the chain molecule.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to toner, two-component developer, and replenishment developer. [Background technology]

[0002] To obtain high-quality images regardless of the environment, toners used in electrophotographic image forming apparatuses are required to have high electrostatic stability in various environments. For example, Patent Document 1 discloses that the electrostatic stability of toner can be improved by incorporating an acrylic polymer having a specific unit into the toner. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2013-97292 [Patent Document 2] WO01 / 083566 [Patent Document 3] Japanese Patent Publication No. 2017-31258 [Non-patent literature]

[0004] [Non-Patent Document 1] "polym.Eng.Sci., 14(2), 147-154(1974)" [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] One aspect of this disclosure aims to provide a toner that does not easily reduce image density even when continuous image output is performed in a low-humidity environment.

[0006] Furthermore, other aspects of this disclosure are toward providing a two-component developer having the toner relating to this disclosure.

[0007] Another aspect of the present disclosure is directed to providing a replenishing developer having the toner according to the present disclosure. **Means for Solving the Problems**

[0008] According to one aspect of the present disclosure, there is provided a toner having toner particles containing a resin, wherein the resin contains a polyrotaxane, and the polyrotaxane (i) has a plurality of cyclic molecules, (ii) has a chain molecule inclusively inserted into the ring of the cyclic molecule in a skewer-like manner, and has (iii) two or more blocking groups for preventing the cyclic molecule from detaching from the chain molecule. There is provided a toner characterized by the above.

[0009] According to another aspect of the present disclosure, there is provided a two-component developer containing a toner and a magnetic carrier, wherein the toner is the toner according to the present disclosure. There is provided a two-component developer characterized by the above. <oo00088>

[0010] According to another aspect of the present disclosure, there is provided a replenishing developer containing a toner and a magnetic carrier, wherein the toner is the toner according to the present disclosure. There is provided a replenishing developer characterized by the above. **Advantages of the Invention**

[0011] According to one aspect of the present disclosure, it is possible to provide a toner in which the image density is less likely to decrease even when continuous image output is performed in a low-humidity environment.

[0012] According to another aspect of the present disclosure, it is possible to provide a two-component developer having the toner according to the present disclosure.

[0013] According to another aspect of the present disclosure, it is possible to provide a replenishing developer having the toner according to the present disclosure. [Modes for carrying out the invention]

[0014] In this disclosure, unless otherwise specified, the expressions "greater than or equal to XX and less than or equal to XX" or "XX to XX" refer to a numerical range that includes the lower and upper limits.

[0015] <Background leading to the invention> Recent image forming apparatuses are required to be less prone to image defects even in harsh environments. One example of such image defects is the phenomenon in which toner tends to overcharge in low-humidity environments, leading to a decrease in the density of the formed image. Various studies have been conducted to address this decrease in image density, but the inventors believe there is still room for improvement. Therefore, the inventors focused on the overcharging of toner in low-humidity environments and considered it necessary to investigate how to reduce the overcharging of toner by improving the materials contained in the toner particles, thereby making it less likely for the decrease in image density to occur in low-humidity environments.

[0016] Based on the above idea, the inventors investigated toner particles containing various materials in order to obtain a toner that does not easily reduce image density in low humidity environments. As a result, they found that toner particles containing polyrotaxane are effective in realizing a toner with the above-mentioned characteristics.

[0017] Because the cyclic molecules contained in polyrotaxanes can rotate and move along the chain molecules, polyrotaxanes are materials with high molecular mobility. The inventors believe that by incorporating such a material with high molecular mobility into toner particles, the charges generated within the toner particles will move more easily, thereby making it easier to dissipate excess charges within the toner particles. As a result, the inventors hypothesize that excessive charging of the toner will be less likely to occur even in low-humidity environments, and a decrease in image density will be less likely to occur.

[0018] <Polyrotaxane> The resin according to this disclosure contains a polyrotaxane. The polyrotaxane according to this disclosure has (i) a plurality of cyclic molecules and (ii) a chain-like molecule that is skewered and enclosed around the rings of the cyclic molecules, and (iii) the chain-like molecule has two or more chelating groups that prevent the cyclic molecules from detaching from the chain-like molecule.

[0019] Generally, molecular aggregates in which a chain molecule penetrates the inside of a cyclic molecule and a bulky molecule is attached to the end of the axis, thereby binding the cyclic molecule to the chain molecule, are called rotaxanes. Molecular aggregates in which many cyclic molecules are linked together on a single chain molecule are called polyrotaxanes. The cyclic molecules are not bonded to the chain molecule, can rotate on the chain molecule, and can move along the chain molecule.

[0020] The polyrotaxane content is preferably 0.2% by mass or more and 30.0% by mass or less relative to the total mass of resin contained in the toner particles. A content of 0.2% by mass or more is thought to allow for sufficient release of excess charge, resulting in less fluctuation in image density. Therefore, 0.2% by mass or more is preferred, and 1.0% by mass or more is more preferred. Furthermore, a content of 30.0% by mass or less is thought to make it less likely for excess charge to escape from the toner, resulting in less image fogging. Therefore, 30.0% by mass or less is preferred, 20.0% by mass or less is more preferred, and 10.0% by mass or less is even more preferred.

[0021] The polyrotaxanes disclosed herein can be manufactured by methods already known, such as those described in Patent Documents 2 and 3, or they can be obtained and used as commercially available products (product name: CELUM Superpolymer, manufactured by ASM).

[0022] The polyrotaxanes of this disclosure are not particularly limited in terms of the number of cyclic molecules (inclusion amount) that penetrate a single linear molecule. The inclusion amount can be controlled by the molar ratio of linear molecules to cyclic molecules used in the production of the polyrotaxane.

[0023] <Cyclic molecule> The cyclic molecules of the polyrotaxane can be used without particular limitation, as long as they have a cyclic structure that can encapsulate chain molecules and through which chain molecules can pass.

[0024] Examples of cyclic molecules in this disclosure include cyclodextrins, crown ethers, benzocrowns, dibenzocrowns, dicyclohexanocrowns and their derivatives or modified forms. Among these, cyclodextrins are preferred because they readily encapsulate chain molecules. That is, it is preferable that the cyclic molecule is a molecule having a cyclodextrin skeleton. More preferably, it is a molecule having at least one cyclodextrin skeleton selected from the group consisting of α-cyclodextrin skeleton, β-cyclodextrin skeleton, and γ-cyclodextrin skeleton. Furthermore, the above cyclic molecule may be used individually, or two or more may be used in combination.

[0025] In this disclosure, a molecule having a cyclodextrin skeleton is treated as a cyclodextrin molecule, or a molecule having a structure synthesized when a derivatization reaction is carried out on the hydroxyl group of a cyclodextrin molecule.

[0026] <Side chains bound to cyclodextrin> Preferably, the cyclic molecule of the polyrotaxane is a molecule having a cyclodextrin skeleton, and the molecule having the cyclodextrin skeleton has a cyclodextrin and a side chain bonded to the cyclodextrin. Here, the side chain bonded to the cyclodextrin in this disclosure is treated as a substructure introduced when a derivatization reaction is carried out on the hydroxyl group of the cyclodextrin. The side chain may have a linear structure or a branched structure. Furthermore, it is more preferable that the side chain has a polymer structure, and more preferably a polyester structure or a vinyl polymer structure. Examples of polyester structures include polymer structures formed by the condensation of a diol and a dicarboxylic acid, and polycaprolactone structures. A vinyl polymer structure is a polymer structure formed by the polymerization of vinyl monomers, and an example is a styrene-methyl methacrylate polymer structure.

[0027] The weight-average molecular weight of the cyclodextrin skeleton molecule having the aforementioned side chains is preferably between 1,000 and 50,000. It has been found that being within this range makes it less likely for image density to decrease and image flicker to occur. The weight-average molecular weight is preferably 1,000 or more, and more preferably 2,500 or more. Furthermore, it is thought that a weight-average molecular weight of 50,000 or less makes it less likely for the molecular mobility of the cyclic molecule to be too small. More preferably it is 30,000 or less, more preferably 20,000 or less, and even more preferably 10,000 or less.

[0028] Molecules having a cyclodextrin skeleton that satisfy the above weight-average molecular weight can be produced, for example, by introducing a polyester structure to the hydroxyl group of cyclodextrin. They can also be produced by a vinyl polymerization reaction between a cyclodextrin derivative having a vinyl polymerizable double bond and a vinyl monomer.

[0029] The molecular weight of a cyclic molecule can be measured using analytical instruments such as GPC after the cyclic molecule has been isolated. To isolate a cyclic molecule, the first step is to remove the end-binding groups of the polyrotaxane. For example, in the case of polyrotaxanes with end-binding groups bonded by amide or carbonyl groups, this can be achieved by heating under acidic or basic conditions to induce hydrolysis. Subsequently, the cyclic molecule can be isolated by conventional methods such as reprecipitation, filtration, centrifugation, or membrane separation.

[0030] <chain molecule> The chain-like molecules of the polyrotaxane are not particularly limited, as long as they can penetrate the cyclic molecule in a skewer-like manner, are enclosed by the cyclic molecule, and allow the cyclic molecule to rotate, slide, or move freely. The length of the chain-like molecules is also not particularly limited. Furthermore, it is preferable that the chain-like molecules are linear molecules. In this disclosure, a linear molecule is defined as a molecule whose main chain does not have branching.

[0031] The chain molecule is preferably at least one selected from the group consisting of polyalkylenes, polyesters, polyethers, polyamides, and polyacrylics, and among these, polyethers are more preferable. That is, it is preferable that the chain molecule is a molecule having a polyether chain. More preferably, it is a molecule having a polyalkylene glycol chain, and even more preferably, it is a molecule having a polyethylene glycol chain.

[0032] <Blocking group> The above-described chain molecule has two or more chapping groups at its ends to prevent the detachment of the cyclic molecule. The chapping groups of the polyrotaxane are not particularly limited as long as they can prevent the detachment of the cyclic molecule. Examples of chapping groups in this disclosure include bulky groups that physically prevent the detachment of the cyclic molecule, and ionic groups that provide electrical prevention. Specifically, examples include dinitrophenyl groups, adamantyl groups, trityl groups, and pyrenyl groups. Cyclodextrins and fluoresceins, which are introduced as substituents at the ends of the chain molecule, are also specific examples. Derivatives and modified forms of the above may also be used.

[0033] <Conjugated polyrotaxane> The two or more polyrotaxanes may be bonded by forming chemical bonds between each of their respective cyclic molecules.

[0034] That is, the polyrotaxane includes a conjugated polyrotaxane formed by the bonding of a first polyrotaxane and a second polyrotaxane. The first polyrotaxane and the second polyrotaxane may be bonded together by a chemical bond between the cyclic molecule of the first polyrotaxane and the cyclic molecule of the second polyrotaxane.

[0035] Furthermore, multiple cyclic molecules within a single polyrotaxane may be bonded together by chemical bonds.

[0036] In this disclosure, a chemical bond may be a single bond or a bond involving various atoms or molecules (a bond involving a linking group).

[0037] The above-mentioned conjugated polyrotaxanes can be obtained, for example, by reacting a polyrotaxane having a cyclic molecule containing a hydroxyl group, such as cyclodextrin, with a compound such as 1,4-butanediol diglycidyl ether.

[0038] <Toner and toner particles> The toner relating to this disclosure is a toner having toner particles. Preferably, the weight-average particle size (D4) of the toner particles is 3.0 to 10.0 μm. Preferred embodiments of the toner and toner particles relating to this disclosure are described below.

[0039] <Resin A> The resin according to this disclosure preferably contains a resin different from polyrotaxane (hereinafter also referred to as resin A). Resin A differs from the polyrotaxane described above in that it does not have a polyrotaxane structure in its molecule. Furthermore, it is preferable that resin A is contained in the toner particles at a concentration of 50.0% by mass or more, more preferably 70.0% by mass or more, more preferably 90.0% by mass or more, and even more preferably 95.0% by mass or more. The resin according to this disclosure may also be a binder resin.

[0040] Resin A is not particularly limited, but examples include the following polymers and resins.

[0041] Monopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene.

[0042] Styrene-based copolymers such as styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylate methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, and styrene-acrylonitrile-indene copolymer. Among these, styrene-acrylic resins such as styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylate methyl copolymer, and styrene-acrylonitrile copolymer are more preferred.

[0043] Polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin.

[0044] Among them, it is preferable that resin A contains at least one resin selected from the group consisting of styrene acrylic resin, polyester resin, silicone resin, and fluororesin. More preferably, it is at least one resin selected from the group consisting of styrene acrylic resin and polyester resin.

[0045] Also, from the viewpoint of being less likely to reduce the image density and less likely to cause image fogging, it is preferable that resin A satisfies the following relationship. That is, taking the SP value of resin A as SPa (J / cm 3 ) 1 / 2 and the SP value of the side chain in the molecule having the above-mentioned cyclodextrin skeleton as SPb (J / cm 3 ), it is preferable to satisfy the following formula (1). 1 / 2 When |SPb - SPa| ≦ 2.0 (J / cm 3 ) 1 / 2 ···(1)

[0046] The SP value is calculated from the following formula (2). SP value (J / cm 3 ) 1 / 2 = √(Ev / v) = √(ΣΔei / ΣΔvi) ···(2) (The abbreviations in formula (2) are as follows. ·Ev: Evaporation energy (J / mol), ·v: Molar volume (cm 3 / mol), ·Δei: Evaporation energy of each atom or atomic group, ·Δvi: Molar volume of each atom or atomic group)

[0047] The SP value of resin A can be calculated by determining the SP value of each monomer unit that makes up resin A, multiplying these by their mol% content in resin A, and then summing them up. For example, if resin A is composed of a single monomer unit, the SP value of that monomer unit is considered to be the SP value of resin A. If resin A is composed of two types of monomer units (in a 50:50 molar ratio), the SP values ​​of the two monomer units are calculated separately, and their average value is considered to be the SP value of resin A. Similarly, if the side chain has a polymer portion, the SP value of the side chain is calculated using the monomer units that make up the polymer portion and their molar ratio.

[0048] It is believed that satisfying the above formula (1) increases the compatibility between the side chains of the cyclic molecule and resin A. In addition, the values ​​of the evaporation energy and molar volume in the above formula (2) are those given in the table described in Non-Patent Document 1.

[0049] <Various additives> Toner may contain one or more additives selected from colorants, waxes, charge control agents, developers, and inorganic fine particles, as needed. The various additives used in toner are described in detail below.

[0050] <wax> Examples of waxes include the following:

[0051] Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; Oxides of hydrocarbon waxes such as polyethylene oxide wax, or block copolymers thereof; Waxes primarily composed of fatty acid esters, such as carnauba wax; Deoxidized carnauba wax and other fatty acid esters, some or all of which have been deoxidized.

[0052] Among these, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, and fatty acid ester waxes such as carnauba wax are preferred from the viewpoint of toner's low-temperature fixability and resistance to hot offset.

[0053] In this disclosure, hydrocarbon waxes are more preferred from the viewpoint of the toner's resistance to hot offset.

[0054] The wax content in the toner particles is preferably 1.0 part by mass or more and 20.0 parts by mass or less per 100 parts by mass of resin in the toner particles. When the wax content is within the above range, the resistance to hot offset at high temperatures is further improved.

[0055] Furthermore, from the viewpoint of toner storage properties and resistance to hot offset, it is preferable that the peak temperature of the endothermic peak originating from wax in the endothermic curve measured by a differential scanning calorimetry (DSC) with toner as the measurement sample is between 50°C and 110°C.

[0056] <Coloring agent> As colorants, known yellow colorants, magenta colorants, cyan colorants, and black colorants can be used. Examples of black colorants include carbon black, or a black color produced by mixing yellow colorants, magenta colorants, and cyan colorants. In addition, pigments or dyes may be used alone as colorants, or dyes and pigments may be used in combination.

[0057] The amount of colorant in the toner particles is preferably 0.1 parts by mass or more and 30.0 parts by mass or less per 100 parts by mass of resin in the toner particles.

[0058] <Magnetic material> The toner described herein may be either a magnetic toner or a non-magnetic toner, but when used as a magnetic toner, it is preferable to use magnetic iron oxide as the magnetic material contained in the toner particles. Examples of magnetic iron oxide include magnetite, magnetite, and ferrite.

[0059] The magnetic material content in the toner particles is preferably 25 parts by mass or more and 95 parts by mass or less, and more preferably 30 parts by mass or more and 45 parts by mass or less, per 100 parts by mass of resin in the toner particles.

[0060] <Static components> It is preferable that the toner contains a charged component. The charged component is preferably at least one selected from the group consisting of a charge control agent and a polar resin.

[0061] Examples of charge control agents include negative charge control agents and positive charge control agents. Examples of negative charge control agents include the following:

[0062] Salicylate metal compounds, naphthoate metal compounds, dicarboxylic acid metal compounds, polymeric compounds with sulfonic acid or carboxylic acid as a side chain. Polymeric compounds with sulfonate salts or sulfonic acid esters as a side chain. Polymeric compounds with carboxylate salts or carboxylic acid esters as a side chain. Boron compounds, urea compounds, silicon compounds, calixarenes, etc.

[0063] When toner particles contain a charge control agent, the charge control agent may be added internally to the toner particles or externally.

[0064] The amount of charge control agent in the toner particles is preferably 0.2 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of resin in the toner particles.

[0065] A polar resin is a resin that readily undergoes triboelectric charging and readily transfers electric charge. Examples of polar resins include those containing ether bonds, ester bonds, amide bonds, etc., or those containing polar groups such as carboxyl groups, sulfonic acid groups, and hydroxyl groups. Specifically, examples include polyester resins, polyether resins, polyamide resins, and styrene-acrylic resins containing carboxyl groups, sulfonic acid groups, and hydroxyl groups, as well as hybrid resins that combine these. Furthermore, vinyl polymer units in vinyl resins and hybrid resins may have a crosslinked structure formed by crosslinking with a crosslinking agent having two or more vinyl groups.

[0066] <External additives> The toner of this disclosure may contain external additives to improve the toner's fluidity and adjust the amount of triboelectric charge. Preferred external additives of inorganic fine particles include silicon dioxide (silica), aluminum oxide (alumina), titanium dioxide (titania), strontium titanate, and calcium carbonate. Examples of external additives other than inorganic fine particles include resin fine particles such as vinyl resins, polyesters, and silicone resins.

[0067] These inorganic and resin particles function to control the charge properties of the toner and act as fluidity and cleaning aids.

[0068] <Developer> The toner of this disclosure may be mixed with a magnetic carrier and used as a two-component developer. Known magnetic particles such as magnetite particles, ferrite particles, and magnetic material-dispersed resin particles can be used as the magnetic carrier.

[0069] The carrier core preferably has a volume-average particle size (D50) of 20 μm or more and 80 μm or less, which allows for uniform coating of the coating resin, prevents carrier adhesion, and allows for an appropriate density of the developer magnetic brush for obtaining high-quality images.

[0070] The method for coating the carrier core surface with the coating resin is not particularly limited and can be carried out by known methods. For example, there is a so-called immersion method in which the carrier core and the coating resin solution are stirred while the solvent is evaporated to coat the carrier core surface with the coating resin. Specifically, examples include a universal mixer / stirrer (manufactured by Fuji Powdal Co., Ltd.) and a Nauter mixer (manufactured by Hosokawa Micron Corporation). Another method involves spraying the coating resin solution from a spray nozzle while forming a fluidized bed to coat the carrier core surface with the coating resin. Specifically, examples include a Spiracoater (manufactured by Okada Seikou Co., Ltd.) and a Spiraflow (manufactured by Freund Industrial Co., Ltd.). There is also a method of dry coating the magnetic carrier core with the coating resin in granular form. Specifically, examples include processing methods using equipment such as a hybridizer (manufactured by Nara Machine Works Co., Ltd.), Mechanofusion (manufactured by Hosokawa Micron Corporation), Highflex Gral (manufactured by Fukae Powtech Co., Ltd.), and Theta Composer (manufactured by Tokuju Kogyo Co., Ltd.).

[0071] <Method for manufacturing toner particles> The toner particles of this disclosure can be manufactured using known methods for manufacturing toner particles, such as the melt-kneading method, the emulsification-coagulation method, and the dissolution-suspension method.

[0072] The following describes the toner manufacturing procedure using the grinding method.

[0073] In the raw material mixing process, predetermined amounts of materials that constitute the toner particles, such as resin, release agent, colorant, crystalline polyester, and other components such as charge control agents as needed, are weighed, blended, and mixed. Examples of mixing equipment include double-con mixers, V-type mixers, drum-type mixers, super mixers, Henschel mixers, Nauta mixers, and Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.).

[0074] Next, the mixed materials are melt-kneaded to disperse wax and other substances into the resin. In this melt-kneading process, batch-type kneaders such as pressure kneaders and Banbury mixers, or continuous kneaders can be used, and single-screw or twin-screw extruders are the mainstream due to their advantage of being able to produce continuously. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Iron Works, Ltd.), the twin-screw extruder (manufactured by KCK Co., Ltd.), the Co-kneader (manufactured by Buss Co., Ltd.), and the Nidex (manufactured by Nippon Coke Industries Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water in a cooling process.

[0075] Next, the cooled resin composition is pulverized to the desired particle size in a pulverization process. In the pulverization process, for example, it is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further finely pulverized using a fine pulverizer such as a Cryptron system (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Industries Co., Ltd.), or an air jet type pulverizer.

[0076] Subsequently, the materials are classified as needed using classifiers or sieves such as the inertial classifier Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), the centrifugal classifier Turboplex (manufactured by Hosokawa Micron Corporation), the TSP separator (manufactured by Hosokawa Micron Corporation), and the Faculty (manufactured by Hosokawa Micron Corporation).

[0077] Methods for external additive processing include using mixing equipment such as double-con mixers, V-type mixers, drum-type mixers, super mixers, Henschel mixers, Nauta mixers, Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.), and Novilta (manufactured by Hosokawa Micron Corporation) as external additive machines to stir and mix. In this case, external additives other than silica fine particles, such as fluidizing agents, may be added as needed.

[0078] Next, we will explain the methods for measuring each of the physical properties related to this disclosure.

[0079] <Various measurement methods> <Measurement of weight-average particle size (D4) of toner particles> The weight-average particle size (D4) of toner particles is measured using the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method with a 100 μm aperture tube, and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data, with an effective measurement channel count of 25,000. The measurement data is then analyzed and calculated.

[0080] The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to a concentration of approximately 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

[0081] Before performing measurements and analysis, configure the dedicated software as described above.

[0082] In the "Change Standard Measurement Method (SOM)" screen of the dedicated software mentioned above, 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). Press the Threshold / Noise Level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the box for flushing the aperture tube after measurement.

[0083] 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 to 2 μm or more and 60 μm or less.

[0084] The specific measurement methods are as follows (1) to (7).

[0085] (1) Pour approximately 200 ml of the above 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 dirt and air bubbles from inside the aperture tube.

[0086] (2) Place approximately 30 ml of the above electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker. Add approximately 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass 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.

[0087] (3) Two oscillators with an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and a predetermined amount of deionized water is placed in the water tank of an ultrasonic dispersion system "Ultrasonic Dispersion System Tetora150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120 W. Approximately 2 ml of the above Contaminon N is added to this water tank.

[0088] (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.

[0089] (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) above with ultrasound, add approximately 10 mg of toner particles to the electrolytic aqueous solution in small amounts and disperse them. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate.

[0090] (6) Using a pipette, add the electrolytic aqueous solution (5) containing the dispersed toner particles to the round-bottom beaker (1) placed in the sample stand, adjusting the concentration to approximately 5%. Continue measuring until the number of particles reaches 50,000.

[0091] (7) Analyze the measurement data using the dedicated software attached to the device to calculate the weight average particle size (D4). When set to graph / volume% in the dedicated software, the "average diameter" on the analysis / volume statistical value (arithmetic mean) screen is the weight average particle size (D4).

[0092] <Measurement of the volume average particle size (D50) of particles> For the measurement of the volume average particle size (D50), for example, it is possible to perform the measurement by attaching a sample feeder for dry measurement "One Shot Dry Type Sample Conditioner Turbotrac" (manufactured by Nikkiso Co., Ltd.). The control is automatically performed on the software. The particle size is the 50% particle size (D50) which is the cumulative value of the volume average. The control and analysis are performed using the attached software (version 10.3.3 - 202D). The measurement conditions are as follows. · SetZero time: 10 seconds · Measurement time: 10 seconds · Number of measurements: 1 time · Particle refractive index: 1.81% · Particle shape: non - spherical · Measurement upper limit: 1408 μm · Measurement lower limit: 0.243 μm · Measurement environment: 23°C, 50% RH <Measurement of weight average molecular weight by GPC> The molecular weight distribution of the sample is measured by gel permeation chromatography (GPC) as follows.

[0093] First, dissolve the sample in tetrahydrofuran (THF) over 24 hours at room temperature. Then, filter the obtained solution through a solvent - resistant membrane filter "Maechori Disk" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in THF is about 0.8 mass%. Using this sample solution, perform the measurement under the following conditions. · Device: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation) · Column: 7 - series of Shodex KF - 801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK) • Eluent: Tetrahydrofuran (THF) ·Flow rate: 1.0ml / min Oven temperature: 40.0℃ • Sample injection volume: 0.10 ml For calculating the molecular weight of the sample, a molecular weight calibration curve prepared 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. [Examples]

[0094] The present disclosure will be described in more detail below with reference to examples, but the disclosure is not limited to these examples. First, the preparation of the polyrotaxanes used in each example will be described.

[0095] <Preparation of Polyrotaxane A1> The following materials were added to a reaction vessel equipped with a stirrer, condenser, and thermometer, and then mixed uniformly. • Polyrotaxane 1 10.0g (see below) (Polyrotaxane 1: Celmu Superpolymer SA1305P-20 (trade name), manufactured by ASM. The chain molecule has a polyethylene glycol structure, with an adamantyl group at the end of the chain molecule, and multiple α-cyclodextrins with polycaprolactone structures in the side chains as cyclic molecules. In addition, it has an acrylic skeleton at the end of the side chain, and therefore possesses a vinyl polymerizable carbon-carbon double bond.) ·1.0N-NaOH aqueous solution 40mL • 1,4-Butanediol diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.2 mL The mixture was stirred at 23°C for 24 hours to obtain a linked polyrotaxane in which cyclic molecules were crosslinked. Next, after isolation, 600.0 g of xylene, 150.0 g of styrene, 50.0 g of methyl methacrylate, and 1.5 g of the initiator t-butyl peroxypivalate were added, and polymerization was carried out for 3 hours while maintaining a temperature of 90°C with a stirring motor to obtain the reaction product. The obtained reaction product was washed and dried to obtain polyrotaxane A1, in which cyclodextrins were chemically bonded to each other, and side chains having a polycaprolactone structure and a styrene-methyl methacrylate polymer structure were bonded to the cyclodextrins.

[0096] <Preparation of Polyrotaxane A2> The following materials were added to a reaction vessel equipped with a stirrer, condenser, and thermometer, and then uniformly stirred. • Polyrotaxane 2 10.0g (see below) (Polyrotaxane 2: Celmu Superpolymer SM1305P-20 (trade name), manufactured by ASM. The chain molecule has a polyethylene glycol structure, with an adamantyl group at the end of the chain molecule, and multiple α-cyclodextrins with polycaprolactone structures as side chains as cyclic molecules. In addition, it has a methacrylic skeleton at the end of the side chain, and therefore possesses a vinyl polymerizable carbon-carbon double bond.) ·1.0N-NaOH aqueous solution 40mL • 1,4-Butanediol diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.2 mL

[0097] The mixture was stirred at 23°C for 24 hours to obtain a linked polyrotaxane in which cyclic molecules were crosslinked. Next, after isolation, 600.0 g of xylene, 250.0 g of styrene, 75.0 g of methyl methacrylate, and 1.5 g of the initiator t-butyl peroxypivalate were added, and polymerization was carried out for 5 hours while maintaining a temperature of 90°C with a stirring motor to obtain the reaction product. The obtained reaction product was washed and dried to obtain polyrotaxane A2, in which cyclodextrins were chemically bonded to each other, and side chains having a polycaprolactone structure and a styrene-methyl methacrylate polymer structure were bonded to the cyclodextrins.

[0098] <Preparation of Polyrotaxane A3> The following materials were added to a reaction vessel equipped with a stirrer, condenser, and thermometer, and then uniformly stirred. • Polyrotaxane 2 10.0g (as described above) ·1.0N-NaOH aqueous solution 40mL • 1,4-Butanediol diglycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.2 mL By stirring at 23°C for 24 hours, a polyrotaxane was obtained in which cyclic molecules were crosslinked. Next, after isolation, 600.0 g of xylene, 300.0 g of styrene, 100.0 g of methyl methacrylate, and 1.5 g of the initiator t-butyl peroxypivalate were added, and polymerization was carried out for 8 hours while maintaining a temperature of 90°C with a stirring motor to obtain the reaction product. By washing and drying the obtained reaction product, polyrotaxane A3 was obtained in which cyclodextrins were chemically bonded to each other, and side chains having a polycaprolactone structure and a styrene-methyl methacrylate polymer structure were bonded to the cyclodextrins.

[0099] <Preparation of Polyrotaxane A4> The following materials were added to a reaction vessel equipped with a stirrer, condenser, and thermometer, and then stirred. • Methacrylic acid 5.0g Methyl methacrylate 45.0g • Styrene 150.0g Xylene 600.0g t-butyl peroxypivalate 1.5g Polymer 1 was obtained by reacting the above at a temperature of 60°C for 24 hours. Next, after removing the solvent by distillation, 10.0 g of the above polyrotaxane 2 and 40 mL of concentrated sulfuric acid (98% by mass) were added and mixed uniformly. Then, the mixture was stirred at a temperature of 100°C for 1 hour to obtain a polyrotaxane in which the hydroxyl group of the cyclic molecule and the carboxyl group in polymer 1 were esterified.

[0100] Next, after isolation, 600.0 g of xylene, 300.0 g of styrene, 100.0 g of methyl methacrylate, and 1.5 g of the initiator t-butyl peroxypivalate were added, and polymerization was carried out for 8 hours while maintaining a temperature of 90°C with a stirring motor to obtain the reaction product. By washing and drying the obtained reaction product, polyrotaxane A4 was obtained, in which side chains having a polycaprolactone structure and a styrene-methyl methacrylate polymer structure are bonded to cyclodextrin.

[0101] <Preparation of Polyrotaxane A5> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 600.0 g of xylene, 10.0 g of the above-mentioned polyrotaxane 2, 150.0 g of styrene, 50.0 g of methyl methacrylate, and 1.5 g of the initiator t-butyl peroxypivalate were added. Polymerization was then carried out for 3 hours while maintaining a temperature of 90°C with the stirrer running to obtain the reaction product. By washing and drying the obtained reaction product, polyrotaxane A5 was obtained, in which side chains having a polycaprolactone structure and a styrene-methyl methacrylate polymer structure are bonded to cyclodextrin.

[0102] <Preparation of Polyrotaxane A6> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 600.0 g of xylene, 10.0 g of the polyrotaxane 3 listed below, and 15.0 g of epoxy-modified silicone resin (ES1001N; manufactured by Shin-Etsu Chemical Co., Ltd.) were added. (Polyrotaxane 3: Celmu Superpolymer SH1310P, manufactured by ASM. The chain molecule has a polyethylene glycol structure, with an adamantyl group at the end of the chain molecule, and multiple α-cyclodextrins with polycaprolactone structures in their side chains as cyclic molecules. It also has hydroxyl groups at the ends of the side chains.) Subsequently, the reaction product was obtained by maintaining a temperature of 60°C while rotating a stirrer. By washing and drying the obtained reaction product, polyrotaxane A6 was obtained, in which side chains having a polycaprolactone structure and a silicone polymer structure are bonded to cyclodextrin.

[0103] <Preparation of Polyrotaxane A7> Polyrotaxane A7 was prepared using the polyrotaxane 2 mentioned above.

[0104] <Preparation of Polyrotaxane A8> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 1200.0 g of xylene, 10.0 g of the above-mentioned polyrotaxane 2, 1000.0 g of styrene, 350.0 g of methyl methacrylate, and 1.5 g of the initiator t-butyl peroxypivalate were added. Polymerization was then carried out for 24 hours while maintaining a temperature of 90°C with the stirrer running to obtain the reaction product. By washing and drying the obtained reaction product, polyrotaxane A8 was obtained, in which side chains having a polycaprolactone structure and a styrene-methyl methacrylate polymer structure are bonded to cyclodextrin.

[0105] <Preparation of Polyrotaxane A9> Polyrotaxane A9 was prepared using the above-mentioned polyrotaxane 3.

[0106] <Preparation of Polyrotaxane A10> In a reaction vessel equipped with a stirrer, condenser, and thermometer, 1200.0 g of xylene, 10.0 g of the above-mentioned polyrotaxane 2, 1000.0 g of styrene, 500.0 g of methyl methacrylate, and 1.5 g of the initiator t-butyl peroxypivalate were added. Polymerization was then carried out for 24 hours while maintaining a temperature of 90°C with the stirrer running to obtain the reaction product. The obtained reaction product was washed and dried to obtain polyrotaxane A10 in which α-cyclodextrin was encapsulated.

[0107] <Preparation of Polyrotaxane A11> Add 2,2,6,6-tetramethyl-1-piperodinyloxy radical (TEMPO) (6.4 × 10) to 100 mL of pure water. -4 After adding (mol) of sodium bromide, the pH was adjusted to 10-11. -4 (mol), sodium hypochlorite (10 mL), n=35,000 (Aldrich) polyethylene glycol (PEG) (7.0 × 10-4 (mol) was added and stirred at room temperature for 10-15 minutes.

[0108] Subsequently, 10 ml of ethanol was added, the pH was adjusted to 2, and dichloromethane extraction was performed by adding 100 ml of dichloromethane in three separate additions. The obtained dichloromethane extract was dried under reduced pressure, dissolved in ethanol at 40-50°C, and stored frozen overnight. The PEG (PEG-COOH) with carboxylic acid end groups was recovered by centrifugation. The obtained PEG-COOH was freeze-dried.

[0109] The PEG-COOH (8.6 × 10) synthesized above -5 (mol) and α-cyclodextrin (1.2 × 10 -2 The compound (mol) was dissolved in 100 mL of pure water and left to stand in a freezer overnight. The resulting white paste-like compound was then freeze-dried to obtain a powdered inclusion complex.

[0110] The following materials were dissolved in 100 mL of anhydrous dimethylformamide and reacted at 4°C for 24 hours. • Synthesized inclusion complex 14g Adamantanamine 1.1 × 10 -3 mol Benzotriazole-1-yloxy-trisdimethylaminophosphonium salt 1.1 × 10 -3 mol Ethylisopropylamine 1.2 × 10 -3 mol Subsequently, the material was washed twice each with a dimethylformamide / methanol solution (1:1, v / v) and methanol. Further washing was performed with a solution of 80 mL of anhydrous dimethyl sulfoxide and 800 mL of pure water, and the material was freeze-dried to obtain polyrotaxane A11 with encapsulated α-cyclodextrin.

[0111] <Example 1> <Example of manufacturing of binder resin 1> In an autoclave reaction vessel equipped with a thermometer and stirrer, 300.0 parts xylene and 15.0 parts polypropylene were added and thoroughly dissolved. After nitrogen purging, a mixed solution of 69.0 parts styrene, 4.5 parts cyclohexyl methacrylate, 3.5 parts methacrylic acid, 8.0 parts behenyl acrylate, and 250.0 parts xylene was added dropwise at 180°C for 3 hours and polymerization was carried out. The mixture was then maintained at this temperature for another 30 minutes to remove the solvent and obtain binder resin 1, a styrene-acrylic resin composition. The SP value of binder resin 1 was calculated using the method described above and was found to be 10.2 (J / cm²). 3 ) 1 / 2 That was the case.

[0112] <Example of Toner 1 manufacturing> • Binding resin 1 98.0 parts Fischer-Tropsch wax (melting point 90°C) 6.0 parts • Polyrotaxane A1 2.0 parts CI Pigment Blue 15:3 4.0 parts The above materials were pre-mixed in a Henschel mixer, and then melt-kneaded at 160°C using a twin-screw extruder.

[0113] The resulting mixture was cooled, coarsely ground in a hammer mill, and then finely ground in a turbo mill. The obtained finely ground material was classified using a multi-part classifier utilizing the Coanda effect to obtain toner particles 1 with a weight-average particle size (D4) of 6.0 μm.

[0114] For every 100 toner particles, hydrophobically treated silica microparticles (with a specific surface area of ​​140 m² due to nitrogen adsorption as measured by the BET method) 2 2.0 parts of ( / g) were added externally and mixed, then sieved through a mesh with a mesh opening of 150 μm to obtain toner 1.

[0115] <Example of two-component developer manufacturing> The above toner 1 and magnetic carrier were mixed using a V-type mixer (product name: V-10, Tokuju Seisakusho Co., Ltd.) for 0.5 seconds, so that the toner concentration was 9% by mass. -1The mixture was then mixed under conditions of 5 minutes to obtain a two-component developer. The magnetic carrier used was a magnetic ferrite carrier (volume-average particle size (D50): 35 μm) whose surface was coated with acrylic resin.

[0116] <Example of manufacturing of replacement developer> The above toner 1 and the above magnetic ferrite carrier were mixed using a V-type mixer (product name: V-10, Tokuju Seisakusho Co., Ltd.) for 0.5 seconds until the toner concentration reached 90% by mass. -1 The mixture was then mixed under conditions of 5 minutes to obtain a replenishment developer.

[0117] <Rating> First, a modified full-color copier (product name: imagePRESS C10000VP, manufactured by Canon) was used as the image forming apparatus. The modification to the copier was to allow adjustment of the development bias.

[0118] Furthermore, during image formation, the developer in the cyan-colored developer unit was replaced with the two-component developer obtained above, and the developer in the cyan-colored replenishment developer container was replaced with the replenishment developer obtained above. The reason for using both the two-component developer and the replenishment developer in this evaluation is that using both is the normal procedure when using the image forming apparatus described above.

[0119] Using the above apparatus, an image output durability test of 30,000 images was conducted under normal temperature and low humidity conditions (23°C / 5%RH, hereafter referred to as N / L environment) and under high temperature and high humidity conditions (30°C / 80%RH, hereafter referred to as H / H environment), and the following evaluations were performed before and after this image output durability test.

[0120] During the durability test, the same development and transfer conditions as the first sheet were used (without calibration). The print ratio of the output image was set to 30%, and the development bias was adjusted so that the initial image density was 1.55. The paper used for evaluation was A4 size plain copy paper (product name: CF-C081, basis weight: 81.4 g / m²). 2 (Canon Marketing Japan Inc.) was used.

[0121] <Evaluation of image density> After the durability test in the N / L environment described above, three solid images were printed on the entire surface of an A3-sized sheet of paper. For the third image, the density of the output image was measured at five points using a spectrophotometer (product name: 500 series, X-Rite), and the average of these five points was taken as the image density after durability. The image density was evaluated by the retention rate of the image density after durability compared to the initial image density of 1.55. The results are shown in Table 2.

[0122] Since a higher retention rate of the image density is considered to indicate less change in the carrier's charge, we determined that the effects of this disclosure were achieved when the retention rate of the image density was 80% or higher.

[0123] <Evaluation of overlap> The following evaluations were conducted before and after the durability test in the above H / H environment.

[0124] Ten 00h images were printed, and the average reflectance Dr (%) of the image portion on the 10th image was measured using a reflectometer ("REFLECTOMETER MODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.). The same measurement was also performed on the non-image portion, and the average reflectance Ds (%) on the paper was measured. Then, the above Dr (%) and Ds (%) were substituted into the following formula to calculate the haze (%). The results are shown in Table 2. If the calculated value was 1.0% or less both before and after the durability test, it was judged that the effect of this disclosure was obtained. Coverage (%) = Dr(%) - Ds(%)

[0125] <Examples 2-18 and Comparative Example 1> As shown in Table 1, the same procedure as in Example 1 was followed to prepare toners 2-19, except for changes in the type and amount of materials. Then, two-component developers and replenishment developers were prepared in the same manner and evaluated. The evaluation results are shown in Table 2.

[0126] [Table 1]

[0127] In Table 1, the molecular weight and SP values ​​of the cyclic molecules were calculated using the method described above. SPb is the SP value of the side chain bound to the cyclodextrin in the polyrotaxane, and SPa is the SP value of the binder resin.

[0128] Furthermore, the preparation of binder resin 2 and binder resin 3 in Table 1 is shown below.

[0129] <Adjustment of binding resin 2> • Bisphenol A ethylene oxide (2.2 molar adduct): 50.0 mol% • Bisphenol A propylene oxide (2.2 molar adduct): 50.0 mol% Terephthalic acid: 90.0 mol% • Trimellitus anhydride: 10.0 mol% 100 parts by mass of the material in the above proportions were added to a 5-liter autoclave along with 500 ppm titanium tetrabutoxide and mixed.

[0130] A reflux condenser, moisture separator, N2 gas inlet tube, thermometer, and stirring device were attached to the autoclave, and a condensation polymerization reaction was carried out at 230°C while introducing N2 gas into the autoclave. After the reaction was complete, the mixture was removed from the container, cooled, and pulverized to obtain binder resin 2. The SP value of binder resin 2 was calculated using the method described above and was found to be 10.7 (J / cm²). 3 ) 1 / 2 That was the case.

[0131] <Preparation of binding resin 3> A solution consisting of 79 parts by mass of styrene, 19 parts by mass of n-butyl acrylate, 2.0 parts by mass of 2-hydroxyethyl methacrylate, 2.2 parts by mass of n-octyl mercaptan, and 75 parts by mass of xylene solvent was prepared by uniformly dissolving 4 parts by mass of di-t-butyl peroxide. This solution was continuously supplied to a 5 L reactor at a rate of 800 mL / hour, maintaining the temperature inside the vessel at 180°C and an internal pressure of 5 kg / cm². 2 The polymerization reaction was carried out by holding the material in the solution. Subsequently, vinyl polyol 1-1 was obtained by removing the xylene solvent.

[0132] In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 40 parts by mass of vinyl polyol 1-1, 9 parts by mass of isophorone diisocyanate, and 50 parts by mass of ethyl acetate were added and reacted at 110°C for 6 hours to obtain binder resin 3. The SP value of binder resin 3 was calculated using the method described above and was found to be 10.0 (J / cm²). 3 ) 1 / 2 That was the case.

[0133] [Table 2]

Claims

1. 1. A toner having toner particles containing a resin, the resin contains polyrotaxane, The polyrotaxane is (i) a plurality of cyclic molecules; (ii) a chain molecule that is skewered and included in the ring of the cyclic molecule; and (iii) The chain molecule has two or more blocking groups that prevent the cyclic molecule from being detached from the chain molecule. A toner characterized by:

2. 2. The toner according to claim 1, wherein the cyclic molecule is a molecule having a cyclodextrin skeleton.

3. 3. The toner according to claim 2, wherein the weight average molecular weight of the molecule having a cyclodextrin skeleton is 1,000 to 50,000.

4. 4. The toner according to claim 2, wherein the molecule having a cyclodextrin skeleton comprises a cyclodextrin and a side chain bonded to the cyclodextrin.

5. 5. The toner according to claim 4, wherein the side chain has a polyester structure or a vinyl polymer structure.

6. 6. The toner according to claim 5, wherein the polyester structure is a polycaprolactone structure.

7. The content of the polyrotaxane is 0.2% by mass or more and 30.0% by mass or less with respect to the total mass of the resin contained in the toner particles. The toner according to any one of claims 1 to 6.

8. the resin contains a resin A different from the polyrotaxane, the mass ratio of the resin A is 50.0 mass% or more with respect to the total mass of the resins contained in the toner particles, the cyclic molecule is a molecule having a cyclodextrin skeleton, the weight-average molecular weight of the molecule having a cyclodextrin skeleton is 1,000 to 50,000; the molecule having a cyclodextrin skeleton comprises a cyclodextrin and a side chain attached to the cyclodextrin; The SP value of the side chain is SPb (J / cm ３ ) １／２ The SP value of the resin A is SPa (J / cm ３ ) １／２ When this is the case, the following formula (1) is satisfied. |SPb-SPa|≦2.0...(1) The toner according to any one of claims 1 to 7.

9. 9. The toner according to claim 8, wherein the resin A is a styrene-acrylic resin or a polyester resin.

10. the polyrotaxane includes a first polyrotaxane and a second polyrotaxane; the polyrotaxane includes a bound polyrotaxane formed by binding the first polyrotaxane and the second polyrotaxane; The first polyrotaxane and the second polyrotaxane are bonded to each other by forming a chemical bond between a cyclic molecule of the first polyrotaxane and a cyclic molecule of the second polyrotaxane. The toner according to any one of claims 1 to 9.

11. 11. The toner according to claim 1, wherein the chain molecule is a molecule having a polyalkylene glycol chain.

12. A two-component developer containing a toner and a magnetic carrier, The toner is the toner according to any one of claims 1 to 11. A two-component developer.

13. A replenishment developer containing a toner and a magnetic carrier, The toner is the toner according to any one of claims 1 to 11. A replenishment developer characterized by: