Toner and method for manufacturing the same

Abstract

To provide a toner capable of maintaining excellent charge amount over a long term in high humidity / high temperature environment.SOLUTION: A toner includes toner particles including resins A and B. The resin A is a vinyl based resin having a sulfonic acid based group, and the resin B is a polyester resin. In the analysis of the toner particles in the depth direction by time-of-flight type secondary ion mass spectrometry, when setting: a depth of which the abundance ratio of the resin A in a depth to 10 nm from the surface of the toner particle is the maximum to DA (nm); the abundance ratio of the resin A in the depth DA to CAS(%); the abundance ratio of the resin B in the depth DA to CBS(%); the abundance ratio of the resin A in a depth of 75 nm to CA75(%); and the abundance ratio of the resin B in a depth of 75 nm to CB75, CAS, CA75, CBS and CB75 show a specific relation.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a toner used in recording methods that utilize electrophotography, electrostatic recording, and toner jet recording, and a method for producing the toner. [Background technology]

[0002] In recent years, the environments in which electrophotographic image formation methods are used are expanding beyond temperature- and humidity-controlled environments such as offices to include uncontrolled environments such as outdoors. Electrophotography creates images by transporting charged toner using a potential difference. Temperature and humidity conditions affect the amount of charge that the toner can hold, so research is underway to develop toner that can maintain a stable charge even when the temperature and humidity change.

[0003] As a means for controlling the charge amount of toner, a charge control resin (hereinafter also referred to as "CCR") having a charge site in the resin is generally blended into the toner. Patent Document 1 discloses a suspension polymerization toner that contains a vinyl resin having a sulfonic acid group as a charge control resin and a monoester compound as a softener. Furthermore, Patent Document 2 discloses an emulsion aggregation toner containing a polyester resin having sulfonic acid groups. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-070835 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-267298 Summary of the Invention [Problem to be solved by the invention]

[0005] However, it has been found that the toner described in Patent Document 1 is prone to a decrease in charge amount when stored in a high-temperature, high-humidity environment. Therefore, when forming an image after storing the toner in a high-temperature, high-humidity environment for a long period of time, such as during a long vacation, the toner needs to be charged by a sequence such as pre-rotation, which leads to a decrease in First Print Output Time (FPOT). Similarly, the toner described in Patent Document 2 is also prone to a decrease in charge amount when stored in a high-temperature, high-humidity environment. Thus, toners having CCR have a problem in that the charge amount decreases after storage in a high-temperature, high-humidity environment, and further improvement is required.

[0006] The present disclosure provides a toner capable of maintaining a good charge amount for a long period of time even in a high-temperature, high-humidity environment, and a method for producing the toner. [Means for solving the problem]

[0007] The present disclosure provides a toner having toner particles containing resin A and resin B, the resin A is a vinyl resin having at least one sulfonic acid group selected from the group consisting of a sulfonic acid group, a sulfonate salt group, and a sulfonate ester group, Resin B is a polyester resin, In a depth direction analysis of the toner particles by time-of-flight secondary ion mass spectrometry, The depth at which the abundance ratio of the resin A is maximum within a depth of 10 nm from the surface of the toner particle is defined as DA (nm), The abundance ratio of the resin A at the depth DA calculated from the spectrum at the depth DA is CA S (%), and the abundance ratio of resin B at depth DA is CB S (%)year, The abundance ratio of the resin A at a depth of 75 nm calculated from the spectrum at a depth of 75 nm is CA 75 (%), and the abundance ratio of resin B at a depth of 75 nm is CB 75 When set to (%), CA Sis 40.0 to 85.0, CA S / CA 75 is 1.5 to 5.0, CB S / CB 75 is 1.5 to 5.0, CA S / CB S is 1.0 to 6.0, (CA S / CB S ) / (CA 75 / CB 75 ) is 0.5 to 3.0. [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide a toner that can maintain a good charge amount for a long period of time even in a high-temperature, high-humidity environment. DETAILED DESCRIPTION OF THE INVENTION

[0009] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0010] A "monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, in the case of a vinyl resin, one section of carbon-carbon bond in the main chain formed by polymerizing a vinyl monomer in the polymer is considered to be one unit. A vinyl monomer can be represented by the following formula (C): [ka]

[0011] [In formula (C), R A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R B represents an optional substituent.]

[0012] The present disclosure provides a toner having toner particles containing resin A and resin B, the resin A is a vinyl resin having at least one sulfonic acid group selected from the group consisting of a sulfonic acid group, a sulfonate salt group, and a sulfonate ester group, Resin B is a polyester resin, In a depth direction analysis of the toner particles by time-of-flight secondary ion mass spectrometry, The depth at which the abundance ratio of the resin A is maximum within a depth of 10 nm from the surface of the toner particle is defined as DA (nm), The abundance ratio of the resin A at the depth DA calculated from the spectrum at the depth DA is CA S (%), and the abundance ratio of resin B at depth DA is CB S (%)year, The abundance ratio of the resin A at a depth of 75 nm calculated from the spectrum at a depth of 75 nm is CA 75 (%), and the abundance ratio of resin B at a depth of 75 nm is CB 75 When set to (%), CA S is 40.0 to 85.0, CA S / CA 75 is 1.5 to 5.0, CB S / CB 75 is 1.5 to 5.0, CA S / CB S is 1.0 to 6.0, (CA S / CB S ) / (CA 75 / CB 75 ) is 0.5 to 3.0.

[0013] The present inventors speculate as follows about the reason why the toner can maintain a good charge amount for a long period of time even in a high-temperature, high-humidity environment. Toners having toner particles containing a charge control resin (CCR) are capable of retaining charge at the charging sites in the CCR. Toner particles generally have a charge on their surface, and conventional toners containing CCR have generally been designed to have the CCR unevenly distributed on the surface of the toner particles. However, when the charge is only on the surface of the toner particles, in environments susceptible to moisture, such as high temperature and humidity, the charge on the surface of the toner particles leaks due to the influence of moisture, and the charge amount easily decreases.

[0014] On the other hand, if CCR is distributed inside the toner particles as well, it becomes possible to retain charge inside the toner particles. However, if the charge on the surface of the toner particles is lost, the charge inside the toner particles cannot be transferred to the surface of the toner particles, and therefore the charge inside the toner particles cannot be effectively utilized. Due to these factors, the charge amount of the toner having the conventional CCR decreases in a high temperature and high humidity environment.

[0015] Therefore, the inventors of the present invention have considered that the above-mentioned problems can be solved if the charge held by the CCR inside the toner particle can be transferred to the surface of the toner particle after distributing the CCR on the surface and inside of the toner particle. In order to transfer the charge held by the CCR inside the toner particle, it is considered necessary to transport the charge from one charged site to another. As a result of extensive research, the present inventors have found that when a vinyl resin having a sulfonic acid group as a charging site is used as the CCR, the ester bond in the polyester resin can transport charge. They have also found that controlling the concentration gradient of the CCR and polyester resin from the vicinity of the surface to the interior of the toner particles makes it possible to effectively move the charge inside the toner particles toward the surface of the toner particles.

[0016] More specifically, it is necessary that the concentrations of the CCR and polyester resin are high at the surface of the toner particles and in the vicinity thereof (up to a depth of 10 nm from the surface) and have a concentration gradient such that the concentration decreases toward the center of the toner particles. In this case, if the gradients of the concentration gradients of the CCR and polyester resin are similar, the charge held by the charged portion of the CCR inside the toner particles can be effectively transferred toward the surface of the toner particles. The charging site and the charge transport site each have a concentration gradient from the interior of the toner particle toward the surface of the toner particle, and when comparing the surface direction of the toner particle from a point of the gradient with the center direction of the toner particle, the charge retention ability and charge transport ability increase toward the surface direction of the toner particle. This generates a driving force that moves the charge toward the surface of the toner particle, making it easier to move the charge effectively.

[0017] However, if the concentration gradient of the CCR and that of the polyester resin differ significantly, a mismatch occurs in the ratio of charging sites to charge transport sites, preventing smooth charge transfer to the surface of the toner particles. Therefore, it is necessary to control the relationship so that the concentration gradient of the CCR and that of the polyester resin do not deviate too much. In this way, in addition to providing a concentration gradient of the CCR and polyester resin such that the concentration decreases from the surface toward the center of the toner particle, the relationship between these concentration gradients is controlled. This allows the charge inside the toner particles to be effectively transferred toward the surface of the toner particles.

[0018] The parameters related to the concentration gradient will be explained in detail below. In the depth direction analysis of toner particles by time-of-flight secondary ion mass spectrometry, the depth at which the abundance ratio of resin A is maximum from the surface of the toner particle to a depth of 10 nm is defined as DA (nm). The abundance ratio of resin A at depth DA calculated from the spectrum at depth DA is defined as CA. S (%), and the abundance ratio of resin B at depth DA is CB S(%). The abundance ratio of resin A at a depth of 75 nm calculated from the spectrum at a depth of 75 nm is CA 75 (%), and the abundance ratio of resin B at a depth of 75 nm is CB 75 (%).

[0019] At this time, CA S (%) is 40.0 to 85.0. CA S represents the amount of CCR present near the surface of the toner particle (up to a depth of 10 nm from the surface). S The charge amount of the toner falls within an appropriate range by adjusting the ratio to 40.0 to 85.0, preferably 50.0 to 80.0, and more preferably 60.0 to 75.0. By increasing the amount of CCR contained in the toner particles, CA S In addition, by reducing the amount of CCR contained in the toner particles, the CA S can be made smaller.

[0020] CA S / CA 75 is 1.5 to 5.0. CA S / CA 75 represents the ratio of the amount of CCR near the surface of the toner particle to the amount of CCR at a depth of 75 nm from the surface of the toner particle. By arranging the CCR in a concentration gradient from the surface of the toner particle to the depth direction, the concentration is higher at the surface of the toner particle and decreases as the depth increases, CA S / CA 75 It is possible to control the charge within a suitable range, thereby enabling the toner to retain charge not only on the surface but also inside.

[0021] Specifically, CA can be obtained by increasing the polarity of the sulfonic acid group in CCR or by increasing the amount of sulfonic acid group. S / CA 75 In addition, the CA can be increased by lowering the polarity of the sulfonic acid group in the CCR or by reducing the amount of sulfonic acid group.S / CA 75 can be made smaller. CA S / CA 75 is 1.5 to 5.0, preferably 2.0 to 5.0, and more preferably 3.0 to 4.5.

[0022] Also, CA 75 (%) is preferably 12.0 to 32.0, and more preferably 14.0 to 27.0.

[0023] Also, CB S / CB 75 is 1.5 to 5.0. CB S / CB 75 represents the ratio of the amount of polyester resin present near the surface of the toner particle to the amount of polyester resin present at a depth of 75 nm from the surface of the toner particle. By arranging the polyester resin in a concentration gradient from the surface of the toner particle to the depth direction, the concentration is higher at the surface of the toner particle and decreases as the depth increases, CB S / CB 75 It is possible to control the charge density within a suitable range, thereby enabling the charge held inside the toner particles to move. Specifically, the pH value of the polyester resin can be increased by increasing the pH during the heat treatment process described below or by increasing the acid value of the polyester resin. S / CB 75 In addition, by lowering the pH in the heat treatment step described later or by lowering the acid value of the polyester resin, the CB S / CB 75 can be made smaller. CB S / CB 75 is 1.5 to 5.0, preferably 1.5 to 4.0, and more preferably 2.0 to 3.5.

[0024] CB S (%) is preferably 14.0 to 50.0, and more preferably 15.0 to 37.0. CB75 (%) is preferably 5.0 to 35.0, and more preferably 7.0 to 15.0.

[0025] Also, CA S / CB S is 1.0 to 6.0. CA S / CB S represents the ratio of the amount of CCR present near the surface of the toner particle to the amount of polyester resin present. S / CB S By setting CA to 1.0 to 6.0, the toner charge amount will be in an appropriate range. S / CB S is preferably 1.5 to 5.5, and more preferably 2.0 to 5.0. By controlling the ratio of CCR to polyester resin and lowering the pH in the heat treatment process described later, CA S / CB S In addition, by controlling the ratio of CCR to polyester resin and by increasing the pH in the heat treatment process described later, the CA S / CB S can be made smaller.

[0026] Also, (CA S / CB S ) / (CA 75 / CB 75 ) is 0.5 to 3.0. (CA S / CB S ) / (CA 75 / CB 75 ) represents the relationship between the ratio of the amount of CCR present near the surface of the toner particle to the amount of polyester resin present, and the ratio of the amount of CCR present at a depth of 75 nm from the surface of the toner particle to the amount of polyester resin present. S / CB S ) / (CA 75 / CB 75) is in the above range, it indicates that the relationship between the amount of CCR and the amount of polyester resin present does not deviate significantly between the vicinity of the surface of the toner particle and the depth of 75 nm. By arranging the CCR and polyester resin with the same concentration gradient from the surface of the toner particles to the depth direction, S / CB S ) / (CA 75 / CB 75 ) can be controlled within a preferred range. S / CA 75 , C.B. S / CB 75 and CA S / CB S By controlling (CA S / CB S ) / (CA 75 / CB 75 ) can be controlled. (CA S / CB S ) / (CA 75 / CB 75 ) is 0.5 to 3.0, preferably 1.0 to 3.0, and more preferably 1.5 to 2.5.

[0027] Next, raw materials that can be used for the toner will be described below. The toner contains toner particles. The toner particles contain resin A and resin B. The toner particles preferably contain resin C.

[0028] <Resin A> Resin A is a vinyl resin having at least one sulfonic acid group selected from the group consisting of a sulfonic acid group, a sulfonate salt group, and a sulfonate ester group. Preferably, it is a vinyl resin having at least one sulfonic acid group selected from the group consisting of a sulfonic acid group and a sulfonate ester group. Any known vinyl resin having a sulfonic acid group can be used without any particular limitation. In particular, it is preferable that Resin A is a copolymer of a monomer mixture containing a vinyl monomer having a sulfonic acid group (hereinafter referred to as a sulfonic acid group-containing monomer) described below and a styrene monomer and / or a (meth)acrylic acid ester monomer described below.

[0029] The sulfonic acid group concentration of Resin A is preferably 0.05 to 0.50 mmol / g, and more preferably 0.10 to 0.30 mmol / g. When the sulfonic acid group concentration of Resin A is within the above range, it becomes easier to set the parameters relating to the concentration gradient within the above range. In addition, the charge amount of the toner can be controlled within a suitable range. Furthermore, it is preferable that Resin A is an amorphous resin. By using an amorphous resin, it is easy to maintain the electrical conductivity of Resin A low, which prevents charge from leaking outside the toner. Therefore, it is possible to control the charge amount of the toner within a more suitable range.

[0030] The sulfonic acid group can be represented by -SO3H. The sulfonate group is a salt of a monovalent cation of a sulfonic acid group. The monovalent cation is Li + , Na + , K. + and quaternary ammonium cations. Examples of the quaternary ammonium cation include tetramethylammonium cation and ethyltrimethylammonium cation. Examples of the sulfonate group include alkylsulfonyl groups having 1 to 6 carbon atoms, such as methanesulfonyl, ethanesulfonyl, and hexanesulfonyl.

[0031] <Monomers containing sulfonic acid groups> The sulfonic acid group-containing monomer used in Resin A is not particularly limited, and any known sulfonic acid group-containing monomer can be used. Specific examples include the following: vinyl sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-acrylamidomethylsulfonic acid, 2-acrylamidoethylsulfonic acid, 2-acrylamidobenzenesulfonic acid, 4-acrylamidobenzenesulfonic acid, and 2-acrylamido-5-methoxybenzenesulfonic acid, as well as their methyl esters, ethyl esters, isopropyl esters, lithium salts, sodium salts, and potassium salts. Examples of esters include alkyl (preferably C1-C3) esters of styrenesulfonic acid, such as ethyl p-styrenesulfonate. These sulfonic acid group-containing monomers can be used alone or in combination of two or more.

[0032] Resin A preferably contains a monomer unit of at least one monomer selected from the group consisting of the sulfonic acid group-containing monomers. More preferably, it contains a monomer unit of 2-acrylamido-2-methylpropanesulfonic acid. The content of the monomer unit of the sulfonic acid group-containing monomer in Resin A is preferably 0.5 to 15.0 mass%, more preferably 1.2 to 12.0 mass%.

[0033] <Styrene-based monomers> The styrene-based monomer used in Resin A is not particularly limited and any conventionally known styrene-based monomer can be used. Specific examples include styrene and α-methylstyrene. Resin A preferably contains a styrene-based monomer unit. The content of the styrene-based monomer unit in Resin A is preferably 60.0 to 95.0 mass %, more preferably 75.0 to 90.0 mass %.

[0034] <(Meth)acrylic acid ester monomer> There are no particular limitations on the (meth)acrylic acid ester monomer used in Resin A, and any known (meth)acrylic acid ester monomer can be used. Specific examples include the following acrylic acid esters such as methyl acrylate and n-butyl acrylate (n-butyl acrylate); and methacrylic acid esters such as methyl methacrylate, 2-hydroxyethyl methacrylate, t-butyl methacrylate, and 2-ethylhexyl methacrylate.

[0035] Preferably, it is a (meth)acrylic acid alkyl ester having an alkyl group with 1 to 8 carbon atoms (more preferably 2 to 6). More preferably, it is n-butyl acrylate. Preferably, Resin A has a monomer unit based on a (meth)acrylic acid ester monomer. The content ratio of the monomer unit based on a (meth)acrylic acid ester monomer in Resin A is preferably The content is preferably 2.0 to 20.0 mass %, and more preferably 8.0 to 15.0 mass %.

[0036] <Other vinyl monomers> In addition to the above-mentioned sulfonic acid group-containing monomer, styrene monomer, and (meth)acrylic acid ester monomer, other known vinyl monomers may be used in Resin A. That is, Resin A may have monomer units of vinyl monomers other than sulfonic acid group-containing monomers, styrene monomers, and (meth)acrylic acid ester monomers.

[0037] Specific examples include monofunctional monomers having one polymerizable unsaturated bond in the molecule, such as unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid; unsaturated dicarboxylic acid anhydrides such as maleic anhydride; nitrile-based vinyl monomers such as acrylonitrile; halogen-containing vinyl monomers such as vinyl chloride; and nitro-based vinyl monomers such as 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 trimethylolpropane tri(meth)acrylate.

[0038] <Resin B> As the resin B, any known polyester resin can be used without any particular limitations. The polyester resin is preferably a condensation polymer of an acid component and an alcohol component. In particular, it is preferably a condensation polymer of a monomer mixture containing a dicarboxylic acid having a structure in which a carboxy group is directly bonded to an aromatic ring, and a diol. A structure in which a carboxy group is directly bonded to an aromatic ring forms a wide conjugated structure including the aromatic ring from the ester bond site, and charge transfer is likely to occur via the π electron cloud that spreads across the conjugated structure. This makes it possible to further improve charge mobility.

[0039] The ester group concentration of Resin B is preferably 2.0 to 10.0 mmol / g, and more preferably 3.0 to 8.0 mmol / g. When the ester group concentration of Resin B is in the above range, it becomes easier to set the parameters related to the concentration gradient within the above range, and it is also possible to control the charge mobility in the toner particles within a suitable range. The acid value of Resin B is preferably 1.0 to 30.0 mgKOH / g, more preferably 2.0 to 20.0 mgKOH / g, and even more preferably 3.0 to 1.0 mgKOH / g.

[0040] Furthermore, it is preferable that Resin B is an amorphous resin. By using an amorphous resin, it is easy to maintain low electrical conductivity of Resin B as a whole, and charge leakage to the outside of the toner via a path different from the expected charge transfer is suppressed. Therefore, it is possible to control the charge amount of the toner within a more suitable range. An amorphous resin is a resin that does not have a clear endothermic peak in differential scanning calorimetry.

[0041] <Dicarboxylic acid> There are no particular limitations on the dicarboxylic acid used in Resin B. Any known dicarboxylic acid can be used. Among them, it is preferable to use a dicarboxylic acid having a structure in which a carboxy group is directly bonded to an aromatic ring, as described above. Specific examples include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc. Also usable are alkyl dicarboxylic acids or anhydrides thereof such as succinic acid, adipic acid, sebacic acid, and azelaic acid; succinic acid or anhydrides thereof substituted with an alkyl or alkenyl group having 6 to 18 carbon atoms; and unsaturated dicarboxylic acids or anhydrides thereof such as fumaric acid, maleic acid, citraconic acid, and itaconic acid.

[0042] In addition to the dicarboxylic acid, a trivalent or higher carboxylic acid compound may be used in combination, and examples thereof include trimellitic acid, trimellitic anhydride, and pyromellitic acid. The content of aromatic dicarboxylic acid monomer units in Resin B is preferably 30 to 60 mol %, more preferably 40 to 55 mol %.

[0043] <Diol> The diol used in Resin B is not particularly limited and may be a conventionally known diol. Specific examples include the following: ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, cyclohexanedimethanol, butenediol, octenediol, cyclohexenedimethanol, hydrogenated bisphenol A, or a bisphenol derivative represented by formula (A); a hydrogenated product of a compound represented by formula (A) below, a diol represented by formula (B) below, or a diol of a hydrogenated product of a compound of formula (B). [ka]

[0044] In formula (A), R is an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x+y is 2-10. [ka]

[0045] As the dihydric alcohol component, the alkylene oxide adduct of bisphenol A is particularly preferred, as it is excellent in charging characteristics and environmental stability and is well-balanced in other electrophotographic characteristics. In the case of this compound, the average number of moles of alkylene oxide added is preferably 2 or more and 10 or less in terms of fixability and durability of the toner.

[0046] Resin B preferably has a monomer unit of an alkylene oxide adduct of bisphenol A and a monomer unit of ethylene glycol. The content of the monomer unit of the alkylene oxide adduct of bisphenol A in the resin B is preferably 30 to 60 mol %, more preferably 40 to 55 mol %.

[0047] Of the resins constituting the toner, the content of resin A is preferably 0.1 to 5.0% by mass, and more preferably 0.3 to 2.0% by mass. Of the resins constituting the toner, the content of Resin B is preferably 1.0 to 20.0% by mass, and more preferably 2.0 to 10.0% by mass.

[0048] <Resin C> The toner particles preferably contain a resin C. The resin C is a vinyl resin having no sulfonic acid group. The resin C is preferably a vinyl resin having a monomer unit represented by the following formula (1). [ka]

[0049] (In formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents a straight-chain alkyl group having 10 to 14 carbon atoms) Resin C preferably accounts for 50% by mass or more of the resins constituting the toner, preferably 80 to 99% by mass, and more preferably 90 to 98% by mass. Resin C may be a binder resin.

[0050] <Monomers forming the monomer unit of formula (1)> The polymerizable monomer forming the monomer unit represented by formula (1) is not particularly limited, and known polymerizable monomers can be used. Specific examples include the following acrylic acid esters and methacrylic acid esters, such as decyl acrylate, decyl methacrylate, lauryl acrylate, lauryl methacrylate, myristyl acrylate, and myristyl methacrylate. Among these, it is preferable to use lauryl acrylate or lauryl methacrylate. The content of the monomer unit of formula (1) in Resin C is preferably 1.0 to 15.0 mass %, more preferably 4.0 to 10.0 mass %.

[0051] <Other monomers> As the monomer used for Resin C, in addition to the monomer that forms the unit of the above-mentioned formula (1), monomers such as styrene-based monomers, (meth)acrylic acid ester-based monomers and other monomers listed in the section on Resin A can be used without any particular restrictions. Preferably, Resin C has a styrene monomer unit. The content of the styrene monomer unit in Resin C is preferably 60.0 to 90.0 mass %, more preferably 75.0 to 85.0 mass %. Preferably, Resin C has a monomer unit based on a (meth)acrylic acid ester monomer. The (meth)acrylic acid ester monomers described above for Resin A can be used. The content of monomer units based on a (meth)acrylic acid ester monomer in Resin C is preferably 5.0 to 25.0 mass %, more preferably 10.0 to 20.0 mass %.

[0052] <Other resins> The toner particles may contain a binder resin other than Resin A, Resin B, and Resin C. The resin may be any known resin without any particular limitations. Specific examples include polyurethane resin and polyamide resin.

[0053] <Plasticizer> It is preferable to use a plasticizer in the toner particles. The plasticizer is not particularly limited, and known waxes used in toners such as those described below can be used. It is preferable that the toner particles contain an ester wax.

[0054] The ester wax is preferably at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the formula (5), and a compound represented by the formula (6). The compound represented by the formula (6) is more preferred. [ka]

[0055] In formula (4), formula (5) and formula (6), R 31 and R 41 each independently represents an alkylene group having 2 to 8 carbon atoms, and R 32 , R 33 , R 42 , R 43 , R 51 and R 52 are each independently a linear alkyl group having 14 to 24 carbon atoms (more preferably 16 to 24).

[0056] Specific examples of the ester wax include esters of monohydric alcohols and aliphatic carboxylic acids, such as behenyl behenate, stearyl stearate, behenyl behenate, stearyl stearate, and palmityl palmitate, or esters of monohydric carboxylic acids and aliphatic alcohols; and esters of dihydric alcohols and aliphatic carboxylic acids, such as ethylene glycol distearate, dibehenyl sebacate, and hexanediol dibehenate, or esters of dihydric carboxylic acids and aliphatic alcohols.

[0057] Esters of trihydric alcohols and aliphatic carboxylic acids, such as glycerin tribehenate, or esters of trihydric carboxylic acids and aliphatic alcohols; esters of tetrahydric alcohols and aliphatic carboxylic acids, such as pentaerythritol tetrastearate and pentaerythritol tetrapalmitate, or esters of tetrahydric carboxylic acids and aliphatic alcohols; esters of hexahydric alcohols and aliphatic carboxylic acids, such as dipentaerythritol hexastearate and dipentaerythritol hexapalmitate, or esters of hexahydric carboxylic acids and aliphatic alcohols; esters of polyhydric alcohols and aliphatic carboxylic acids, such as polyglycerin behenate, or esters of polyhydric carboxylic acids and aliphatic alcohols; and natural ester waxes, such as carnauba wax and rice wax. These can be used alone or in combination.

[0058] The content of the plasticizer is preferably 1.0 to 50.0 parts by mass, more preferably 5.0 to 30.0 parts by mass, relative to 100.0 parts by mass of the binder resin (for example, resin C).

[0059] In the depth direction analysis of toner particles by time-of-flight secondary ion mass spectrometry, the abundance ratio CW of ester wax at depth DA S (%) is preferably 10 or less, more preferably 0 to 5, even more preferably 0 to 3, still more preferably 0 to 1, and particularly preferably 0. CW S The fact that CW is in the above range indicates that there is little ester wax on the surface of the toner particles. S When the surface roughness is in the above range, the adhesion of the toner to the drum is reduced, and the transferability is improved. Ester wax has low affinity with polyester resin. S can be reduced by increasing the amount of polyester resin present on the surface by increasing the pH in the heat treatment step or by increasing the amount of polyester resin.

[0060] <Inorganic fine particles> (magnetic material) The toner particles preferably contain inorganic fine particles. The toner particles more preferably contain inorganic fine particles that have been hydrophobized. The hydrophobized inorganic fine particles function as charge retention sites within the toner particles, further enhancing the charge retention performance within the toner particles.

[0061] Examples of inorganic fine particles include oxides of metals such as Fe, Si, Ti, Sn, Zn, Al, and Ce, and known fine particles can be used. Hydrophobic treatment can be achieved by covering the surface of inorganic fine particles with a treatment agent having an alkyl group. The inorganic fine particles are preferably surface-treated with a treating agent having an alkyl group with 4 to 20 carbon atoms (preferably 4 to 14, more preferably 6 to 12). For example, the inorganic fine particles are preferably inorganic fine particles having an alkyl group with 4 to 20 carbon atoms (preferably 4 to 14, more preferably 6 to 12) on the surface.

[0062] The hydrophobic treatment agent is not particularly limited as long as it contains an alkyl group, and examples thereof include silane coupling agents, alkyl-modified silicones, and titanium coupling agents. The hydrophobic treatment agent is preferably a silane coupling agent. Silane coupling agents will be described later.

[0063] The coating treatment is preferably carried out using 4 to 20 parts by mass, more preferably 5 to 15 parts by mass, of the treating agent per 100 parts by mass of inorganic fine particles. The method for treating the surface of inorganic fine particles is not particularly limited as long as it is a treatment method that usually uses a surface hydrophobic treatment agent.For example, examples include a wet method in which the powder to be treated is dispersed in a solvent such as water or an organic solvent using a mechanochemical mill such as a ball mill or a sand grinder, and then the hydrophobic treatment agent is mixed, and the solvent is removed and dried; a dry method in which the powder to be treated and the hydrophobic treatment agent are mixed using a Henschel mixer or a super mixer, and then dried; and a method in which the powder to be treated is brought into contact with the surface hydrophobic treatment agent in a high-speed airflow such as a jet mill to treat the powder.

[0064] Furthermore, the hydrophobized inorganic fine particles are preferably magnetic, since the magnetic particles can transport electric charges, thereby further increasing the mobility of electric charges inside the toner particles.

[0065] Magnetic materials include magnetic iron oxides such as magnetite, maghemite, ferrite, and other metal oxides; metals such as Fe, Co, Ni, or alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof.

[0066] Among these, magnetite is preferred, and its shape may be polyhedral, octahedral, hexahedral, spherical, needle-like, or flaky. However, hexahedral and spherical shapes, which have a small contact area between magnetic particles, are preferred in terms of increasing image density because they suppress aggregation. The number average particle size of the primary particles of the magnetic material is preferably 50 nm or more and 500 nm or less, more preferably 100 nm or more and 300 nm or less, and even more preferably 150 nm or more and 250 nm or less.

[0067] The content of the magnetic material is preferably 35 to 100 parts by mass, more preferably 45 to 95 parts by mass, relative to 100 parts by mass of the binder resin (for example, resin C). The content of magnetic material in toner particles can be measured using a thermal analyzer TGA Q5000IR manufactured by PerkinElmer, Inc. The measurement method involves heating the toner from room temperature to 900°C at a temperature increase rate of 25°C / min in a nitrogen atmosphere, and the mass loss from 100°C to 750°C is taken as the mass of the components excluding the magnetic material from the toner, and the remaining mass is taken as the amount of magnetic material.

[0068] Examples of methods for producing the magnetic material include the following. An aqueous solution containing ferrous hydroxide is prepared by adding an equivalent or greater amount of alkali such as sodium hydroxide to an aqueous solution of ferrous salt. While maintaining the pH of the prepared solution at pH 7 or higher, air is blown into the solution, and the solution is heated to 70°C or higher to carry out an oxidation reaction of the ferrous hydroxide, first producing seed crystals that will become the core of the magnetic material.

[0069] Next, an aqueous solution containing 1 equivalent of ferrous sulfate based on the amount of alkali added previously is added to the slurry containing the seed crystals. While maintaining the pH of the solution between 5 and 10, air is blown in to promote the ferrous hydroxide reaction, growing magnetic iron oxide particles around the seed crystals as cores. By selecting the desired pH, reaction temperature, and stirring conditions, the shape and magnetic properties of the magnetic material can be controlled. As the oxidation reaction progresses, the pH of the solution shifts toward the acidic side, but it is preferable not to allow the pH of the solution to fall below 5. The magnetic iron oxide particles obtained in this manner are filtered, washed, and dried using standard methods to obtain a magnetic material.

[0070] Although the hydrophobic treatment of the magnetic material is not particularly limited, it is preferable to use a hydrophobic treatment agent having a relatively large carbon number, as shown in the general formula (I) described below.Furthermore, it is preferable that the magnetic material has been subjected to a surface treatment using a treatment device described below. This allows the hydrophobic treatment agent to react uniformly with the particle surfaces of the magnetic material, thereby making it possible to develop high hydrophobicity. The magnetic material is preferably a magnetic material that has been hydrophobized using an alkyltrialkoxysilane coupling agent as a hydrophobizing agent represented by the following formula (I). That is, the magnetic material is preferably a product that has been surface-treated with a hydrophobizing agent represented by the following formula (I). C p H 2p+1 -Si-(OC q H 2q+1 )3(I) In formula (I), p represents an integer of 4 to 20 (preferably 4 to 14, more preferably 6 to 12), and q represents an integer of 1 to 3 (preferably 1 or 2).

[0071] In the above formula, when p is 4 or more, sufficient hydrophobicity can be imparted, while when p is 20 or less, the surface of the magnetic material can be uniformly treated and coalescence of the magnetic material can be suppressed, which is preferable. Examples include n-butyltrimethoxysilane, iso-butyltrimethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, and n-decyltrimethoxysilane.

[0072] The SP value of the hydrophobic treatment agent when bonded to the magnetic material is preferably 8.00 or more and 9.00 or less, more preferably 8.20 or more and 8.90 or less, and even more preferably 8.40 or more and 8.80 or less. When the hydrophobic treatment agent is an alkyltrialkoxysilane coupling agent, the bonding form with the magnetic material surface is assumed to be such that one functional group forms a bond with the magnetic material surface, and the remaining two functional groups are condensed with functional groups possessed by another hydrophobic treatment agent molecule. Even when the number of functional groups is different, one functional group will bond with the magnetic material surface in the same way. The unit of SP value is (cal / cm 3 ) 0.5 is.

[0073] Furthermore, the difference between the SP value of the hydrophobic treatment agent when bonded to the magnetic material and the SP value of the plasticizer is preferably 0.30 or less, more preferably 0.25 or less, and even more preferably 0.20 or less. When the difference between the SP value of the hydrophobic treatment agent when bonded to the magnetic material and the SP value of the plasticizer is within the above range, the vicinity of the magnetic material is easily plasticized during the fixing process. Therefore, the mobility of the magnetic material during the fixing process is improved, and the magnetic material is more uniformly dispersed on the image. Therefore, the image density is further improved.

[0074] The method for the hydrophobic treatment is not particularly limited, but the following method is preferred. It is preferable to carry out the hydrophobic treatment in a dry manner using a wheel-type kneader or a mixing mill, in order to uniformly react the hydrophobic treatment agent with the particle surface of the magnetic material to develop high hydrophobicity, while at the same time leaving some of the hydroxyl groups on the particle surface of the magnetic material without completely hydrophobizing them. As the wheel-type kneader, a Mixmuller, a Multimul, a Stotts mill, a counter-flow kneader, an Eirich mill, etc. can be used, and it is preferable to use a Mixmuller. When a wheel-type mixer or a kneading machine is used, three actions can be exerted: compression, shearing, and spatula action.

[0075] The compression action presses the hydrophobic treatment agent present between the magnetic particles onto the surface of the magnetic material, increasing adhesion and reactivity with the particle surface. The shear action applies shear force to both the hydrophobic treatment agent and the magnetic material, stretching the hydrophobic treatment agent and breaking up the magnetic material particles to break up agglomerations. Furthermore, the spatula action allows the hydrophobic treatment agent present on the magnetic particle surface to be spread evenly as if stroking with a spatula. By continuously and repeatedly exerting the above three effects, the surfaces of the magnetic particles can be hydrophobized evenly while breaking down the particles one by one without causing them to re-aggregate.

[0076] Normally, hydrophobic treatment agents having a relatively large number of carbon atoms, as represented by formula (I), tend to be difficult to treat uniformly at the molecular level on the particle surface of a magnetic material because the molecules are large and bulky. However, treatment by the above-mentioned method is preferred because it enables stable treatment.

[0077] <Coloring agent> The toner particles may further contain a colorant in addition to the magnetic particles described above. As the colorant, known pigments and dyes of black, yellow, magenta, cyan, and other colors, magnetic materials, etc., can be used without any particular limitation. Examples of black colorants include black pigments such as carbon black. Examples of yellow colorants include yellow pigments and yellow dyes such as monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, benzimidazolone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples include CI Pigment Yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, and 185, and CI Solvent Yellow 162.

[0078] Examples of magenta colorants include magenta pigments and magenta dyes such as monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, 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, and 269 , CI Pigment Violet 19, etc.

[0079] Examples of cyan colorants include cyan pigments and cyan dyes such as copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specific examples include CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66. The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin (for example, resin C).

[0080] <Release agent> The toner particles may contain a known wax as a release agent in addition to the plasticizer. Specifically, examples include petroleum waxes and their derivatives, such as paraffin wax, microcrystalline wax, and petroleum waxes represented by petrolactam, montan wax and its derivatives, hydrocarbon waxes and their derivatives produced by the Fischer-Tropsch process, polyolefin waxes and their derivatives, such as polyethylene, and natural waxes and their derivatives, such as carnauba wax and candelilla wax. The derivatives also include oxides, block copolymers with vinyl monomers, and graft-modified products. 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; vegetable waxes; and animal waxes. These may be used alone or in combination.

[0081] Among these, polyolefin, hydrocarbon wax produced by the Fischer-Tropsch method, or petroleum wax is preferred because it tends to improve the developability and transferability. These waxes may contain an antioxidant to the extent that it does not affect the effects of the present invention. The content of these waxes is preferably 1.0 part by mass or more and 30.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin (for example, resin C).

[0082] The melting point of the wax is preferably 30°C or higher and 120°C or lower, and more preferably 60°C or higher and 100°C or lower. By using wax having the above-described thermal properties, the releasing effect is efficiently exhibited and a wider fixing area is ensured.

[0083] <Charge control agent> The toner particles may contain a charge control agent in addition to the above-mentioned resin A. As the charge control agent, any known charge control agent can be used without any particular limitation. Specific examples of the negative charge control agent include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, and dicarboxylic acids, or polymers or copolymers having metal compounds of the aromatic carboxylic acids; polymers or copolymers other than Resin A having sulfonic acid groups, sulfonate salt groups, or sulfonate ester groups; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, and calixarenes.

[0084] On the other hand, examples of the positive charge control agent include the following: quaternary ammonium salts, polymeric compounds having quaternary ammonium salts in the side chains; guanidine compounds; nigrosine compounds; and imidazole compounds. The content of the charge control agent is preferably 0.01 parts by mass or more and 5.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin (for example, resin C).

[0085] <External additives> The toner may also contain external additives. As the external additive, any known external additive can be used without any particular limitation. Specific examples include the following: raw silica fine particles such as wet-process silica and dry-process silica, or surface-treated silica fine particles obtained by surface-treating such raw silica fine particles with a treating agent such as a silane coupling agent, a titanium coupling agent, or silicone oil; strontium titanate fine particles; and resin fine particles such as vinylidene fluoride fine particles and polytetrafluoroethylene fine particles.

[0086] Organic-inorganic composite fine particles may also be used. The organic-inorganic composite fine particles preferably have a structure in which resin particles are used as base particles and inorganic fine particles such as silica fine particles are present on the surface of the base particles. It is more preferable that at least a portion of the inorganic fine particles is embedded in the resin particles.

[0087] Examples of the resin particles include polymers of alkoxysilane compounds containing a (meth)acrylic group, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyltriethoxysilane.

[0088] A method for forming a composite using resin particles and silica fine particles is described in, for example, International Publication No. 2013 / 063291. For example, the alkoxysilane compound is mixed with a dispersion of silica fine particles, and the alkoxysilane compound is polymerized in the presence of the silica fine particles.

[0089] The content of inorganic fine particles in the organic-inorganic composite fine particles is preferably 40% by mass to 80% by mass, more preferably 50% by mass to 75% by mass, and even more preferably 55% by mass to 70% by mass. The number average particle size of the primary particles of the inorganic fine particles in the organic-inorganic composite fine particles is preferably 5 nm to 60 nm, and more preferably 10 nm to 30 nm.

[0090] The organic-inorganic composite fine particles may be surface-treated by hydrophobic treatment or silicone oil treatment. Hydrophobicity can be imparted by chemical treatment with an organosilicon compound that reacts with or physically adsorbs to silica. A preferred method is to treat silica produced by vapor phase oxidation of a silicon halide compound with an organosilicon compound.

[0091] The content of the external additive is preferably 0.1 parts by mass or more and 5.0 parts by mass or less with respect to 100.0 parts by mass of the toner particles. The external additive preferably contains silica fine particles, strontium titanate fine particles, and organic-inorganic composite fine particles. The external addition of external additives may be carried out using a known mixer such as a Henschel mixer. When multiple external additives are used, the toner particles and organic-inorganic composite fine particles may be mixed in the first mixing step, and then silica fine particles and strontium titanate fine particles may be mixed in the second mixing step.

[0092] Next, a method for obtaining the toner will be described in detail below. <Production of toner particles> The method for producing toner particles is not particularly limited, and can be a suspension polymerization method, a solution suspension method, an emulsion aggregation method, a pulverization method, etc. Among these, the suspension polymerization method and the solution suspension method are preferred because they make it easy to control the state of existence of resin A and resin B in the toner particles within a suitable range.

[0093] The method for producing toner particles preferably includes a heat treatment step in which a toner particle precursor containing resin A and resin B is treated in an aqueous medium at a temperature of 95 to 120°C and a pH range of 7.5 to 10.0 for 10 minutes or longer. The heat treatment step facilitates extraction of resin B to the surface of the toner particles, making it easier to achieve the effects of the present invention. The heat treatment step can be conducted using an aqueous medium containing the toner particle precursor obtained in the polymerization step and, if necessary, the subsequent distillation step. The temperature in the heat treatment step is more preferably 97 to 115° C., and even more preferably 97 to 100° C. The pH in the heat treatment step is more preferably 7.8 to 9.5, and even more preferably 7.8 to 8.5. The time for the heat treatment step is more preferably 20 minutes or more, more preferably 20 to 120 minutes, and even more preferably 30 to 60 minutes. The toner particle precursor preferably contains inorganic fine particles such as the above-mentioned magnetic material.

[0094] As an example, a method for obtaining toner particles (toner particle precursors) by suspension polymerization will be described below. First, a polymerizable monomer capable of producing a binder resin (e.g., resin C), resin A, resin B, and various additives such as inorganic fine particles (magnetic materials) as needed are mixed, and a polymerizable monomer composition in which the above materials are dissolved or dispersed is prepared using a disperser. The various additives include colorants, release agents, plasticizers, charge control agents, polymerization initiators, and chain transfer agents. Examples of the dispersing machine include a homogenizer, a ball mill, a colloid mill, and an ultrasonic dispersing machine.

[0095] Next, the polymerizable monomer composition is introduced into an aqueous medium containing a dispersion aid such as a poorly water-soluble inorganic dispersion stabilizer as needed, and droplets of the polymerizable monomer composition are prepared using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser (granulation process). Thereafter, the polymerizable monomer in the droplets is polymerized to obtain toner particle precursors (polymerization step).

[0096] The polymerization initiator may be mixed when the polymerizable monomer composition is prepared, or may be mixed into the polymerizable monomer composition immediately before forming droplets in the aqueous medium. Alternatively, the compound may be added in a state dissolved in the polymerizable monomer or another solvent, if necessary, during or after the granulation of the droplets, that is, immediately before the start of the polymerization reaction. After obtaining a binder resin by polymerizing the polymerizable monomer, a distillation step may be carried out as necessary to remove the remaining polymerizable monomer, thereby obtaining a dispersion of toner particle precursors. The polymerization and distillation steps are preferably followed by the heat treatment step described above.

[0097] After the heat treatment step, it is preferable to carry out a crystallization control step. In the crystallization control step, the dispersion liquid after the heat treatment step is maintained at a temperature that facilitates crystallization of the crystalline material, preferably about 40 to 65°C (more preferably 50 to 60°C). The maintenance time is, for example, 0.5 to 5 hours (preferably 1 to 3 hours). Thereafter, if necessary, the mixture is filtered, washed, dried, classified, etc. by known methods to obtain toner particles.

[0098] When the binder resin is obtained by an emulsion aggregation method, a suspension polymerization method, or the like, any known monomer can be used as the polymerizable monomer without any particular limitation. Specific examples thereof include the vinyl monomers listed in the section on binder resins.

[0099] As the polymerization initiator, any known polymerization initiator can be used without any particular limitation. Specific examples include the following: Hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propanol Pionil, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid tert-hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetic acid, tert-butyl permethoxyacetate, per-N-(3-toluyl)palmitate tert-butylbenzoyl peroxide, t-butylperoxy 2-ethylhexanoate peroxide-based polymerization initiators typified by t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, and the like; azo- or diazo-based polymerization initiators typified by 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, and the like; and the like.

[0100] A dispersing aid may be used in the aqueous medium. As the dispersing aid, known dispersion stabilizers, surfactants, etc. can be used. Specific examples of dispersion stabilizers include the following: inorganic dispersion stabilizers such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina; and organic dispersion stabilizers such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch. Examples of surfactants include anionic surfactants such as alkyl sulfate ester salts, alkylbenzene sulfonate salts, and fatty acid salts; nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxypropylene alkyl ethers; and cationic surfactants such as alkylamine salts and quaternary ammonium salts. Among these, it is preferable to contain an inorganic dispersion stabilizer, and it is more preferable to contain a dispersion stabilizer containing a phosphate such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, or aluminum phosphate.

[0101] Next, the measurement methods for each physical property will be described in detail below. <Measuring method of ion amount (secondary ion mass / secondary ion charge number (m / z)) by time-of-flight secondary ion mass spectrometry (TOF-SIMS) (CA S , C.B. S , CA 75 , C.B. 75 , C.W. S Measurement) To measure the ion amount (peak intensity) using TOF-SIMS, nanoTOFII manufactured by ULVAC-PHI, Inc. was used. The analysis conditions are as follows. Sample preparation: Toner particles separated from the toner using the method described below are attached to an indium sheet. Sample preparation: None Primary ion: Bi3 ++ ion Accelerating voltage: 30 kV Charge neutralization mode: On Measurement mode: Negative Raster: 300 × 300 μm 2 Mass range: m / z 0.5 ~ 1850 Measurement time: 30s

[0102] TOF-SIMS is typically a surface analysis method, and data in the depth direction is approximately 1 nm. Therefore, the internal strength of toner particles is measured by sputtering the toner with argon gas cluster ions and scraping the surface. The sputtering conditions were as follows: Accelerating voltage: 5 kV Current: 4.9nA Raster: 800 × 800 μm 2 Irradiation time: 4s The depth was measured in advance by sputtering a PMMA film under the same conditions to confirm the relationship with irradiation time, and it was confirmed that 75 nm was removed in 120 seconds. In the toner of the present disclosure, the intensity at 75 nm from the surface of the toner particle was the value of the amount of ions measured when sputtering was performed 30 times under the above conditions.

[0103] From the spectra obtained by measuring the standards of Resin A, Resin B, and ester wax, peaks specific to each material are selected, and the peak intensities at each depth are compared with the peak intensities of the standards to calculate the abundance ratio of each material at each depth. The depth at which the abundance ratio of resin A is maximum between the depth of 0 nm (the surface of the toner particle) and 10 nm is defined as DA (nm), and the abundance ratio of resin A at the depth DA is defined as CA. S (%), and the abundance ratio of resin B at depth DA is CB S (%), and the proportion of ester wax at depth DA is CW S (%). The abundance ratio of resin A at a depth of 75 nm is CA 75 (%), the proportion of resin B at a depth of 75 nm is CB 75 (%). Specifically, the abundance ratio (%) is the ratio of the peak intensity of each material in the toner when the peak intensity measured for the standard is set to 100. If multiple peaks are selected, the average of the peak intensity ratios is used. If each material is available, the material is used as the standard. If it is difficult to obtain the materials, resin A and resin B separated from the toner by the method described below may be used as the standard.

[0104] The peaks specific to each material are selected as follows: Resin A: Select a peak specific to the sulfonic acid group. In the case of Resin A-1 in the examples, m / z = 80 (SO3 - Select the peaks at 206 (corresponding to the monomer unit) and 206 (corresponding to the monomer unit). Resin B: Select the peaks derived from the dicarboxylic acid or diol of the polyester resin. In the case of Resin B-1 in the examples, select the peaks at m / z = 76, 120, 121 (corresponding to the terephthalic acid moiety) and 211 (corresponding to the bisphenol A moiety). Ester wax: Select the peaks derived from the carboxylic acid or alcohol that make up the ester. In the case of behenyl stearate, select the peaks at m / z = 265, 285 (corresponding to the stearic acid moiety) and 592 (corresponding to behenyl stearate).

[0105] <Separation of Resin A, Resin B, and Resin C from Toner> The chloroform-soluble portion of the toner particles is used as the sample. The sample is adjusted with chloroform so that the toner particle concentration is 0.1% by mass, and the solution is filtered through a 0.45 μm PTFE filter before measurement. The gradient polymer LC measurement conditions are as follows: Equipment: UlTIMATE3000 (Thermo Fisher Scientific) Mobile phase: A chloroform (HPLC), B acetonitrile (HPLC) Gradient: 2 min (A / B = 0 / 100) → 25 min (A / B = 100 / 0) (The gradient of the mobile phase change was made linear.) Flow rate: 1.0mL / min Injection: 0.1% by mass x 20μL Column: Tosoh TSKgel ODS (4.6 mm diameter x 150 mm x 5 μm) Column temperature: 40℃ Detector: Corona Charged Aerosol Detector (Corona-CAD) (Therm Fisher Scientific) In this measurement, components with higher solubility in acetonitrile elute earlier, so resin A elutes first, followed by resin B and resin C. The peaks corresponding to each resin are confirmed, and fractionation is carried out at that timing to collect fractions containing resin A, resin B, and resin C. The fractions are then dried and concentrated to obtain samples of resin A component, resin B component, and resin C component.

[0106] <Analysis of the structures (each monomer unit) of Resin A, Resin B, and Resin C separated from toner> Using samples of resin component A, resin component B, and resin component C, the composition ratio and mass ratio are measured by nuclear magnetic resonance spectroscopy (NMR) as follows. 1 mL of deuterated chloroform is added to 20 mg samples of resin component A and resin component B, and the proton NMR spectrum of the dissolved resin is measured. The molar and mass ratios of each monomer are calculated from the obtained NMR spectrum, and the content of each monomer unit can be determined. For example, in the case of a styrene-acrylic copolymer, the composition ratio and mass ratio can be calculated based on the peak at around 6.5 ppm derived from the styrene monomer and the peak at around 3.5-4.0 ppm derived from the acrylic monomer. From the obtained proportions of the monomer units, the sulfonic acid group concentration in resin A and the ester group concentration in resin B are calculated. The following equipment and measurement conditions can be used for nuclear magnetic resonance spectroscopy (NMR). NMR device: JEOL RESONANCE ECX500 Observed nucleus: proton Measurement mode: Single pulse

[0107] <Measurement of sulfonic acid group concentration of resin A> Specifically, the calculation is as follows: The ratio of the monomer units was calculated using the method described above, and the ratio R of the monomer units having sulfonic acid groups was calculated. S (mass%) and mass number W S From the (g / mol) the sulfonic acid group concentration is calculated based on the following formula: Sulfonic acid group concentration (mmol / g) = (R S / 100)×1000 / W S

[0108] <Measurement of ester group concentration of resin B> Specifically, the calculation is as follows: The ratio of the monomer units was calculated using the method described above, and the mass number W of the alcohol monomer was calculated. AL (g / mol) and number of functional groups N AL (When multiple types of mass number and functional group are used, the arithmetic mean is used) and the mass number W of the acid monomer AC (g / mol) and number of functional groups N AC (When multiple types of mass number and number of functional groups are used, the arithmetic mean is used.) From these values, the ester group concentration is calculated based on the following formula. Ester group concentration (mmol / g) = 1000 × ((N AL +N AC ) / 2) / (W AL +W AC )

[0109] <Wax molecular weight measurement by mass spectrometry> Separation of wax from toner Although the measurement can be performed with the toner as it is, it is more preferable to carry out a separation operation. The toner is dispersed in ethanol, which is a poor solvent for the toner, and the temperature exceeds the melting point of the wax. The temperature is raised to the specified temperature. Pressure may be applied at this time if necessary. This operation causes the wax to exceed its melting point and is melted and extracted into the ethanol. The wax can be separated from the toner by heating, and if pressure is applied, by performing solid-liquid separation while still under pressure. The extracted liquid is then dried and solidified to obtain the wax.

[0110] Wax identification and molecular weight measurement by pyrolysis GCMS Mass spectrometer: ThermoFisherScinetific ISQ GC equipment: ThermoFisher Scientific FocusGC Ion source temperature: 250℃ Ionization method: EI Mass range: 50-1000 m / z Column: HP-5MS [30 m] Pyrolysis device: Japan Analysis Industry Co., Ltd. JPS-700

[0111] A small amount of the wax separated by extraction and 1 μL of tetramethylammonium hydroxide (TMAH) are added to a pyrofoil at 590°C. The sample is subjected to pyrolysis GCMS measurement under the above conditions, and peaks are obtained for the alcohol and carboxylic acid components derived from the ester compound. Due to the action of TMAH, a methylating agent, the alcohol and carboxylic acid components are detected as methylated products. The structure of the wax can be identified by analyzing the peaks obtained.

[0112] (Separation of toner particles from toner) The toner particles are separated from the toner by the following procedure: The obtained toner particles can be used for each measurement method.

[0113] (For non-magnetic toner) A concentrated sucrose solution was prepared by adding 160 g of sucrose (Kishida Chemical) to 100 mL of ion-exchanged water and dissolving it in a hot water bath. A centrifuge tube was charged with 31 g of the concentrated sucrose solution and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) to prepare a dispersion. 1 g of toner was added to the dispersion, and any clumps of toner were broken up using a spatula or similar tool. The centrifuge tube is placed in an Iwaki Sangyo KM Shaker (model V.SX) and shaken at 350 strokes per minute for 20 minutes. After shaking, the solution is transferred to a 50 mL glass tube for a swing-out rotor and centrifuged at 3,500 rpm for 30 minutes. After centrifugation, the toner particles are in the top layer of the glass tube, and external additives such as silica microparticles are in the aqueous solution below. The toner particles in the top layer are collected and filtered, then washed with 2 L of ion-exchanged water heated to 40°C, and the washed toner particles are taken out.

[0114] (For magnetic toner) A dispersion medium was prepared by adding 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) to 100 mL of ion-exchanged water. Five grams of toner was added to this dispersion medium and dispersed for five minutes using an ultrasonic disperser (AS ONE Corporation VS-150). The mixture was then placed in an Iwaki Sangyo Co., Ltd. "KM Shaker" (model: V.SX) and shaken at 350 strokes per minute for 20 minutes. The toner particles are then restrained using a neodymium magnet. The restrained toner particles are collected and washed with 2 L of ion-exchanged water heated to 40°C. The washed toner particles are then collected.

[0115] <Separation of inorganic fine particles contained in toner particles and analysis of the structure of the processing agent> 100 mg of toner particles separated from the toner using the above method are added to 10 mL of chloroform, and the binder resin is dissolved by homogenizing for 10 minutes. The inorganic particles are then recovered by centrifugation. This process is repeated several times to separate the inorganic particles. The obtained magnetic material is subjected to pyrolysis GCMS under the following conditions. The measurement results reveal the pyrolysis products of the surface treatment agent, and the carbon number of the surface treatment agent is determined from the main component. The pyrolysis products are detected as alkyl substituents of the surface treatment agent, or their double bond modifications, alkylsilanes, etc.

[0116] Mass spectrometer: ThermoFisherScinetific ISQ GC equipment: ThermoFisher Scientific FocusGC Ion source temperature: 250℃ Ionization method: EI Mass range: 50-1000 m / z Column: HP-5MS [30 m] Pyrolysis device: Japan Analysis Industry Co., Ltd. JPS-700

[0117] <Measurement of the number average particle size of primary particles of magnetic material> The particle size of the magnetic material is measured using a scanning electron microscope "S-4800" (product name; manufactured by Hitachi, Ltd.). The separated magnetic material is observed, and the particle size is determined by measuring the long diameter of the primary particles of the magnetic material in a field of view magnified up to 200,000 times. The observation magnification is adjusted appropriately depending on the size of the magnetic material.

[0118] <Confirmation that Resin A, Resin B, and Resin C separated from the toner are amorphous resins> Whether resin A, resin B, resin C, etc. are amorphous resins can be confirmed by the presence or absence of a clear endothermic peak using the following method. The endothermic peak measured by differential scanning calorimetry (DSC) is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments). The temperature correction of the device detection part uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. Specifically, 3 mg of the sample is accurately weighed, placed in an aluminum pan, and measured under the following conditions using an empty aluminum pan as a reference. Heating rate: 10 °C / min Measurement start temperature: 30 °C Measurement end temperature: 180 °C Measurement is performed at a heating rate of 10 °C / min within the measurement range of 30 to 180 °C. Heat up to 180 °C once and hold for 10 minutes, then cool down to 30 °C, and then heat up again. In the second heating process, confirm the endothermic peak of the sample from the temperature-endothermic quantity curve in the temperature range of 30 °C to 180 °C.

[0119] <Calculation of SP value> The SP value is obtained as follows according to the calculation method proposed by Fedors. For each atom or atomic group in the molecular structure, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm 3 / mol) are obtained from the table described in "Polym. Eng. Sci., 14(2), 147-154(1974)". Specifically, the evaporation energy (Δei) and molar volume (Δvi) of the alkyl group are obtained respectively, and the evaporation energy is divided by the molar volume and calculated from the following formula. SP value = {(Σj × ΣΔei) / (Σj × ΣΔvi)} 0.5

[0120] <Measurement method of weight average particle diameter (D4) and number average particle diameter (D1)> The weight average particle diameter (D4) and number average particle diameter (D1) of toner, toner particles, or toner mother particles (hereinafter also referred to as toner, etc.) are calculated as follows. The measuring device used is a precision particle size distribution measuring device using the narrow hole electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube. The measurement conditions and data analysis were performed using the dedicated software "Beckman Coulter The measurement was performed using a Beckman Coulter Multisizer 3 Version 3.51 system. The effective number of measurement channels was 25,000. The aqueous electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of 1.0%, for example, "ISOTON II" (manufactured by Beckman Coulter, Inc.). Before performing measurements and analysis, the dedicated software is set up as follows. On the "Change Standard Measurement Method (SOMME)" screen of the dedicated software, 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 Particles 10.0 μm" (Beckman Coulter, Inc.). Press the "Threshold / Noise Level Measurement 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." On the "Pulse to particle size conversion setting" screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

[0121] The specific measurement method is as follows. (1) Pour 200.0 mL of electrolyte solution into a 250 mL round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture Tube Flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) 30.0 mL of the electrolyte solution is placed in a 100 mL flat-bottom glass beaker. 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 ion-exchanged water is added as a dispersant. (3) Prepare an ultrasonic disperser "Ultrasonic Dispersion System Tetra150" (manufactured by Nikkaki Bios Co., Ltd.) with an electrical output of 120 W and two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees. Place 3.3 L of ion-exchanged water in the ultrasonic disperser's water tank and add 2.0 mL of Contaminon N to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is being irradiated with ultrasonic waves, 10 mg of toner or the like is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion process, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, add the electrolytic solution (5) containing dispersed toner particles to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to 5%. Then, measure the particle count until it reaches 50,000 particles. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight-average particle size (D4) and number-average particle size (D1) are calculated. 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 weight-average particle size (D4). "Average diameter" is the number average particle diameter (D1).

[0122] <Method for measuring molecular weight> The molecular weight of a resin such as a polyester resin is measured by gel permeation chromatography (GPC) as follows. First, the polyester resin is dissolved in tetrahydrofuran (THF) at room temperature. The resulting solution is then filtered through a solvent-resistant membrane filter "Maesholidisc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is 0.8% by mass. Measurements are performed using this sample solution under the following conditions. Equipment: High-speed GPC equipment "HLC-8220GPC" [manufactured by Tosoh Corporation] Column: LF-604 in two columns Eluent:THF Flow rate: 0.6ml / min Oven temperature: 40°C Sample injection volume: 0.020 ml To calculate the molecular weight of a sample, a molecular weight calibration curve prepared using standard polystyrene resins (for example, trade names "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.

[0123] <Measurement of glass transition temperature (Tg)> The glass transition temperature (Tg) is measured using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments) in accordance with ASTM D3418-82.

[0124] <Measurement of the acid value of resin> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of sample. The acid value of the binder resin is measured in accordance with JIS K 0070-1992. [Example]

[0125] The present invention will be described in more detail below with reference to the following examples, which, however, are not intended to limit the scope of the present invention. In the formulations of the examples and comparative examples, "parts" and "%" are all by mass unless otherwise specified.

[0126] <(Resin A-1) Production Example of Sulfonic Acid Group-Containing Vinyl Resin 1> Styrene 85.0 parts n-Butyl acrylate (n-BA) 11.0 parts 2-acrylamido-2-methylpropanesulfonic acid (AMPS) 4.0 parts The above materials were dissolved in 60.0 parts of dimethylformamide, stirred for 1.0 hour while bubbling with nitrogen, and then heated to 110°C. To this reaction solution, a mixture of 3.0 parts of tert-butylperoxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name Perbutyl I) and 37.0 parts of toluene was added dropwise as an initiator. The reaction was continued for 4.0 hours at 110°C. The mixture was then cooled and added dropwise to 1000.0 parts of methanol to obtain a precipitate. The resulting precipitate was dissolved in 120.0 parts of tetrahydrofuran and then added dropwise to 1800 parts of methanol to obtain a white precipitate. The precipitate was then filtered and dried under reduced pressure at 90°C to obtain a sulfonic acid group-containing vinyl resin 1.

[0127] <(Resins A-2 to A-4) Production Examples of Sulfonic Acid Group-Containing Vinyl Resins 2 to 4> Sulfonic acid group-containing vinyl resins 2 to 4 (resins A-2 to A-4) were prepared in the same manner as in the production example of sulfonic acid group-containing vinyl resin 1, except that the raw materials used were changed to those shown in Table 1 below. 4) was obtained. As the sulfonic acid ester, ethyl p-styrenesulfonate was used. [Table 1] The values ​​for each monomer in the table indicate the number of parts. The sulfonic acid group concentration is in mmol / g.

[0128] <(Resin B-1) Production Example of Polyester Resin 1> A reaction vessel equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with 45 mol% of terephthalic acid (TPA), 5 mol% of trimellitic acid (TMA), 45 mol% of bisphenol A-propylene oxide 2-mol adduct (BisA-PO 2-mol adduct), and 5 mol% of ethylene glycol (EG), and then 1.5 parts of dibutyltin catalyst per 100 parts of the total amount of monomers was added. Next, the temperature was quickly raised to 180°C under normal pressure in a nitrogen atmosphere, and then polycondensation was carried out by distilling off water while heating from 180°C to 210°C at a rate of 10°C / hour. After reaching 210°C, the pressure inside the reaction vessel was reduced to 5 kPa or less, and polycondensation was carried out under conditions of 210°C and 5 kPa or less to obtain polyester resin 1. The polyester resin 1 had a weight average molecular weight (Mw) of 12,000, a glass transition temperature (Tg) of 70°C, and an acid value of 6.7 mgKOH / g.

[0129] <(Resins B-2 to B-6) Production Examples of Polyester Resins 2 to 6> Polyester resins 2 to 6 (resins B-2 to B-6) were obtained in the same manner as in the production example for polyester resin 1, except that the raw materials used were changed to those shown in Table 2 below. [Table 2] The numerical values ​​for each monomer in the table indicate mol%.

[0130] <Production example of magnetic fine particle 1> A 1.0 equivalent amount of caustic soda solution (containing 1% by mass of sodium hexametaphosphate converted to P relative to Fe) was mixed into a ferrous sulfate aqueous solution to obtain a solution containing ferrous hydroxide. A solution was prepared. While maintaining the aqueous solution at pH 9, air was blown into the solution to carry out an oxidation reaction at 80°C, and a slurry liquid for producing seed crystals was prepared. Next, an aqueous solution of ferrous sulfate was added to the slurry in an amount of 1.0 equivalent to the initial alkali amount (sodium content of caustic soda). The pH of the slurry was maintained at 8, and the oxidation reaction was allowed to proceed while blowing in air. At the end of the oxidation reaction, the pH was adjusted to 6, and the slurry was washed with water and dried to obtain magnetic iron oxide, which was spherical magnetite particles with a number-average particle size of the primary particles of 200 nm.

[0131] 10.0 kg of the magnetic iron oxide was placed in a Simpson Mixmuller (manufactured by Shin-Nitto Kogyo Co., Ltd., model MSG-0L) and crushed for 30 minutes. Thereafter, 95 g of n-decyltrimethoxysilane was added as a silane coupling agent to the device, and the device was operated for 1 hour to hydrophobize the particle surfaces of the magnetic iron oxide with the silane coupling agent, thereby obtaining magnetic microparticles 1. The physical properties of magnetic microparticles 1 are shown in Table 3.

[0132] <Production Examples of Magnetic Microparticles 2 to 4> Magnetic microparticles 2 to 4 were obtained in the same manner as in the production example of magnetic microparticle 1, except that the raw materials used were changed to those shown in Table 3. [Table 3] The average primary particle size is the number-average particle size of the primary particles. The SP value of the treatment agent is the SP value in a state in which it is bonded to the magnetic material, and is expressed in units of (cal / cm 3 ) 0.5 is.

[0133] <Production example of organic-inorganic composite particles> In a 250 mL four-neck round-bottom flask equipped with a propeller stirrer, water bath, and thermometer, add 15 nm The colloidal silica dispersion, methacryloxypropyl-trimethoxysilane (MPS), and ion-exchanged water were added and stirred, with the amount of colloidal silica adjusted to 67.0% by mass in the organic-inorganic composite fine particles. The water bath was adjusted to 65°C, and the mixture was stirred at 120 rpm for 30 minutes under a nitrogen atmosphere. After 3 hours, the radical initiator 2,2'-azobisisobutylene dissolved in 10 mL of ethanol was added. Nitronitrile was added so that the amount was 1% by mass or less based on the MPS, and the temperature was raised to 75°C, followed by polymerization for 5 hours. After the polymerization was completed, 3 mL (2.3 g, 0.014 mol) of 1,1,1,3,3,3-hexamethyldisilazane (HMDZ) was added to the mixture, and the mixture was treated for 3 hours. The final mixture was filtered through a sieve to remove agglomerates, and then dried overnight at 120°C. The dried product was crushed to obtain the desired organic-inorganic composite particles. The number-average particle diameter of the organic-inorganic composite particles was 106 nm.

[0134] <Preparation example of colorant dispersion> The following materials were mixed and stirred with zirconia beads (3 / 16 inch) in an attritor (manufactured by Mitsui Mining Co., Ltd.) at 200 rpm for 3 hours, and the beads were separated to obtain a colorant dispersion. Styrene 37.5 parts Colorant: Nipex 35 (carbon black manufactured by Orion Engineered Carbons) 7.5 copies

[0135] <Toner 1 manufacturing example> <Preparation of aqueous medium> 11.2 parts of sodium phosphate (12-hydrate) were added to a reaction vessel containing 390.0 parts of ion-exchanged water, and the mixture was kept at 65°C for 1.0 hour while purging with nitrogen. A TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to stir the mixture at 12,000 rpm. While maintaining stirring, an aqueous calcium chloride solution prepared by dissolving 7.4 parts of calcium chloride (dihydrate) in 10.0 parts of ion-exchanged water was added all at once to the reaction vessel to prepare an aqueous medium containing a dispersion stabilizer. Furthermore, 1.0 mol / L of hydrochloric acid was added to the aqueous medium in the reaction vessel to adjust the pH to 5.3, thereby preparing an aqueous medium.

[0136] <Example of toner particle production> (Preparation of Polymerizable Monomer Composition) Styrene: 79.0 parts n-Butyl acrylate: 15.0 parts Lauryl acrylate: 6.0 parts Hexanediol diacrylate: 0.5 parts Polyester resin 1 (resin B-1): 3.0 parts Sulfonic acid group-containing vinyl resin 1 (resin A-1): 1.0 part ·Magnetic fine particles 1: 70.0 parts Release agent (hydrocarbon wax, melting point: 79°C): 5.0 parts Plasticizer (behenyl stearate): 20.0 parts The above materials were kept at 65°C and uniformly dissolved and dispersed at 500 rpm using a TK homomixer to prepare a polymerizable monomer composition.

[0137] (granulation process) While maintaining the temperature of the aqueous medium at 70°C and the rotation speed of the stirrer at 12,500 rpm, the polymerizable monomer composition was added to the aqueous medium, and 8.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. Granulation was continued for 10 minutes while maintaining the stirring speed at 12,500 rpm.

[0138] (Polymerization process) The high-speed stirring device was changed to a stirrer equipped with a propeller stirring blade, and polymerization was carried out for 5.0 hours while stirring at 200 rpm and maintaining the temperature at 70°C. The temperature was then raised to 85°C and heated for 2.0 hours to carry out the polymerization reaction, thereby obtaining a resin particle dispersion liquid containing toner particle precursors.

[0139] (Distillation process) While maintaining stirring at 200 rpm, the resin particle dispersion after the polymerization step was heated to 98°C and heated for 3.0 hours to carry out a distillation step to remove residual monomers, thereby obtaining a precursor dispersion in which toner particle precursors are dispersed in an aqueous medium.

[0140] (Heat treatment process) While stirring the precursor dispersion at 200 rpm, a 1.0 mol / L aqueous sodium carbonate solution was added to the resin particle dispersion after the distillation process to adjust the pH to 8.1. The dispersion was then subjected to a heat treatment at 98°C for 40 minutes.

[0141] (Crystallization control process) After the heat treatment step, the dispersion was cooled to 40°C at a rate of 10°C / min. The temperature was then increased to 55°C and maintained at 55°C for 2.0 hours while stirring to carry out a crystallization control step. The temperature was then decreased to 25°C.

[0142] (filtration, washing, drying, classification processes) The pH of the dispersion after the crystallization control process was adjusted to 1.5 with 1.0 mol / L hydrochloric acid and stirred for 1.5 hours to dissolve the dispersion stabilizer. The resin particles were then filtered and washed three times with ion-exchanged water to remove ions adhering to the surface of the resin particles. The particles were then dried in a dryer maintained at 40°C for three days to remove moisture. The resulting powder was classified using an air classifier to obtain toner particles 1. The number average particle diameter (D1) of toner particles 1 was 6.8 μm, and the weight average particle diameter (D4) was 7.4 μm.

[0143] (External addition process) Toner particles 1: 100.0 parts ·Organic-inorganic composite fine particles: 0.5 part The above materials were mixed and subjected to external addition mixing treatment by mixing at 2970 rpm for 9 minutes using a Henschel mixer FM10C (Nippon Coke Engineering Co., Ltd. (formerly Mitsui Miike Chemical Engineering Co., Ltd.)). Hydrophobic silica particles (treated with dimethyl silicone oil) 0.5 parts Strontium titanate microparticles (stearic acid treatment) 0.3 parts Next, the above materials were added and mixed at 2970 rpm for 5 minutes to obtain Toner 1.

[0144] <Toner 16 manufacturing example> Toner 16 was produced in the same manner as in Production Example of Toner 1, except that the raw material in the preparation step of the polymerizable monomer composition in Production Example of Toner 1 was changed from 79.0 parts of styrene to 38.5 parts of styrene, the magnetic fine particles and plasticizer were omitted, and 45.0 parts of colorant dispersion was added. In addition, n-butyl acrylate and lauryl acrylate were also changed as shown in Table 4.

[0145] <Toner 17 manufacturing example> Toner 17 was produced in the same manner as in the production example of Toner 16, except that 20.0 parts of plasticizer was added and the conditions of the heat treatment step were changed to those shown in Table 4.

[0146] <Toner 23 manufacturing example> A pulverized toner was produced by the following method. Polyester resin 1 (resin B-1): 30.0 parts Sulfonic acid group-containing vinyl resin 1 (resin A-1): 70.0 parts Colorant: Nipex 35 (carbon black manufactured by Orion Engineered Carbons) 7.5 copies Release agent (hydrocarbon wax, melting point: 79°C): 5.0 parts The above materials were premixed in a Henschel mixer FM10C (Nippon Coke Engineering Co., Ltd. (formerly Mitsui Miike Chemical Engineering Co., Ltd.)) and then melt-kneaded using a twin-screw kneader (Model PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) to obtain a kneaded mixture. The resulting kneaded mixture was cooled, coarsely pulverized using a hammer mill (manufactured by Hosokawa Micron Corporation), and then pulverized using a mechanical pulverizer (Model T-250, manufactured by Turbo Kogyo Co., Ltd.) to obtain a finely pulverized powder. The resulting finely pulverized powder was classified using a multi-division classifier (Model EJ-L-3, manufactured by Nittetsu Mining Co., Ltd.) utilizing the Coanda effect to obtain toner particles. The resulting toner particles were subjected to the external addition process in the same manner as in the production example of Toner 1 to produce Toner 23.

[0147] <Production examples of toners 2-15, 18-22> Toners 2 to 15 and 18 to 22 were obtained in the same manner as in Production Example of Toner 1, except that the raw materials were changed to those shown in Table 4. The physical properties of Toners 1 to 23 are shown in Tables 5 and 6. [Table 4] In the table, the values ​​for styrene, BA, and LA indicate the number of parts. The treatment temperature, treatment pH, and treatment time indicate the conditions for the heat treatment step. The abbreviations are as follows: BS: Behenyl stearate LA: Lauryl acrylate BA: butyl acrylate

[0148] [Table 5] The columns for Resin A and Resin B were marked Y if the respective resins were included, and N if they were not.

[0149] [Table 6] The column for inorganic fine particles was marked with Y if inorganic fine particles were included, and N if they were not included. The column for long-chain alkyl treatment indicates the number of carbon atoms in the alkyl group of the surface treatment agent for the magnetic material. The magnetic material column was marked Y if magnetic fine particles were included, and N if they were not included. In the table, "surface wax amount" is the ratio of ester wax present at depth DA. S (%). In the column for resin C, if resin C was included, it was marked Y, and if it was not, it was marked N. The long-chain acrylate is a monomer unit represented by formula (1) 2 The number of carbon atoms in the alkyl group corresponding to the formula is shown.

[0150] [Examples 1 to 17, Comparative Examples 1 to 6] The above toners 1 to 23 were used to carry out the evaluations shown in Table 7. Toners 1 to 17 were used in Examples 1 to 17, respectively, and toners 18 to 23 were used in Comparative Examples 1 to 6, respectively. The evaluation results are shown in Table 7.

[0151] The evaluation method and evaluation criteria are explained below. The image forming device used was a commercially available laser printer LBP-712Ci (Canon) modified to eliminate the warm-up operation and set the process speed to 300 mm / sec, and a commercially available process cartridge, toner cartridge 040H (black) (Canon) was used. The product toner was removed from the inside of the cartridge, which was then cleaned with an air blower, and 165 g of the toner to be evaluated was then filled into the cartridge. The yellow, magenta and cyan cartridges were inserted into each of the yellow, magenta and cyan stations with the product toner removed and the remaining toner amount detection mechanism disabled, and the evaluation was carried out.

[0152] <Transferability> The image forming apparatus and toner cartridge were left in a high temperature and high humidity environment (32.5°C / 80% RH: hereinafter referred to as HH environment) for 48 hours. Then, 10 density check images (solid images) were printed consecutively, and the image density of the 10th image was confirmed. The image density was confirmed using X-RITE (manufactured by X-Rite Corporation). A: Image density 1.50 or higher B: Image density 1.45 or more and less than 1.50 C: Image density 1.40 or more and less than 1.45 D: Image density less than 1.40

[0153] <Charge rise after exposure to high temperatures> After evaluating the transferability, an image with a printing rate of 1% was printed on 1,000 sheets. Then, the sheet was left standing in a HH environment for another 48 hours. After that, 10 sheets of density check images (solid images) were printed in succession to check the image density. A: Image density of 1.30 or higher was obtained from the first sheet. B: Image density of 1.30 or more was obtained on the second or third sheet. C: Image density of 1.30 or more was obtained on the 4th to 10th sheets. D: The image density was less than 1.30 even on the 10th sheet.

[0154] <Durability> After leaving the printer at high temperature, the charge buildup was evaluated, and then 14,000 images with a printing rate of 1% were printed. Then, a density check image (solid image) was printed, and the image density was confirmed. A: Image density 1.40 or higher B: Image density 1.35 or more and less than 1.40 C: Image density 1.30 or more and less than 1.35 D: Image density less than 1.30

[0155] <Fixation> The image forming apparatus and toner cartridge were left standing in a low-temperature, low-humidity environment (15°C / 10% RH: hereinafter referred to as LL environment) for 48 hours. Subsequently, a density check image (solid image) was printed while changing the fixing temperature, and the fixing temperature was confirmed. The lowest temperature at which cold offset did not occur was taken as the fixing temperature, and the evaluation was based on the following criteria. A: Fixing temperature below 170°C B: Fixing temperature 170℃ or higher and lower than 180℃ C: Fixing temperature 180℃ or higher but lower than 190℃ D: Fixing temperature 190°C or higher

[0156] <Electrostatic adhesion> The image forming apparatus and toner cartridge were left standing in a low temperature and low humidity environment (15°C / 10% RH: hereinafter referred to as LL environment) for 48 hours, followed by printing 10 solid images in succession and checking for image sticking. A: No sticking is observed B: Slight sticking is observed C: Sticking is observed. D: It sticks and is difficult to remove.

[0157] [Table 7]

[0158] The present disclosure relates to the following configuration and method: (Configuration 1) A toner having toner particles containing resin A and resin B, the resin A is a vinyl resin having at least one sulfonic acid group selected from the group consisting of a sulfonic acid group, a sulfonate salt group, and a sulfonate ester group, Resin B is a polyester resin, In a depth direction analysis of the toner particles by time-of-flight secondary ion mass spectrometry, The depth at which the abundance ratio of the resin A is maximum within a depth of 10 nm from the surface of the toner particle is defined as DA (nm), The abundance ratio of the resin A at the depth DA calculated from the spectrum at the depth DA is CA S (%), and the abundance ratio of resin B at depth DA is CB S (%)year, The abundance ratio of the resin A at a depth of 75 nm calculated from the spectrum at a depth of 75 nm is CA 75 (%), and the abundance ratio of resin B at a depth of 75 nm is CB 75 When set to (%), CA S is 40.0 to 85.0, CA S / CA 75 is 1.5 to 5.0, CB S / CB 75 is 1.5 to 5.0, CA S / CB S is 1.0 to 6.0, (CA S / CB S ) / (CA 75 / CB 75 ) is between 0.5 and 3.0 A toner characterized by: (Configuration 2) The CA S / CA 75 2. The toner according to configuration 1, wherein the σ is 2.0 to 5.0. (Configuration 3) 3. The toner according to claim 1, wherein the toner particles contain inorganic fine particles. (Configuration 4) 4. The toner according to configuration 3, wherein the inorganic fine particles are surface-treated with a treating agent having an alkyl group having 4 to 20 carbon atoms. (Configuration 5) 5. The toner according to claim 3, wherein the inorganic fine particles are magnetic. (Configuration 6) the toner particles contain an ester wax, In a depth direction analysis of the toner particles by time-of-flight secondary ion mass spectrometry, the abundance ratio CW of the ester wax at the depth DA is S (%) is 10 or less, The toner according to any one of configurations 1 to 5, wherein the ester wax is at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the formula (5), and a compound represented by the formula (6): [ka] (In formula (4), formula (5) and formula (6), R 31 and R 41 each independently represents an alkylene group having 2 to 8 carbon atoms, and R 32 , R 33 , R 42 , R 43 , R 51 and R 52 each independently represents a linear alkyl group having 14 to 24 carbon atoms. (Configuration 7) the toner particles contain a resin C, 7. The toner according to any one of configurations 1 to 6, wherein the resin C is a vinyl resin having no sulfonic acid group. (Configuration 8) 8. The toner according to configuration 7, wherein the resin C has a monomer unit represented by the following formula (1): [ka] (In formula (1), R 1represents a hydrogen atom or a methyl group, and R 2 represents a linear alkyl group having 10 to 14 carbon atoms. (Configuration 9) 9. The toner according to any one of configurations 1 to 8, wherein the ester group concentration of the resin B is 2.0 to 10.0 mmol / g. (Configuration 10) 10. The toner according to any one of configurations 1 to 9, wherein the concentration of the sulfonic acid group in the resin A is 0.05 to 0.50 mmol / g. (Configuration 11) The resin A is an amorphous resin, 11. The toner according to any one of configurations 1 to 10, wherein the resin B is an amorphous resin. (Method 12) A toner manufacturing method for manufacturing the toner according to any one of Configurations 1 to 11, A method for producing a toner, comprising a heat treatment step of treating a toner particle precursor containing the resin A and the resin B in an aqueous medium at a temperature of 95 to 120°C and a pH of 7.5 to 10.0 for 10 minutes or more. (Method 13) The method for producing a toner according to Method 12, wherein the toner particle precursor contains inorganic fine particles. (Method 14) 14. The toner manufacturing method according to Method 13, wherein the inorganic fine particles are surface-treated with a treating agent having an alkyl group having 4 to 20 carbon atoms. (Method 15) 15. The toner manufacturing method according to Method 13 or 14, wherein the inorganic fine particles are magnetic.

Claims

1. A toner having toner particles containing resin A and resin B, the resin A is a vinyl resin having at least one sulfonic acid group selected from the group consisting of a sulfonic acid group, a sulfonate salt group, and a sulfonate ester group, Resin B is a polyester resin, In a depth direction analysis of the toner particles by time-of-flight secondary ion mass spectrometry, The depth at which the abundance ratio of the resin A is maximum within a depth of 10 nm from the surface of the toner particle is defined as DA (nm), The abundance ratio of the resin A at the depth DA calculated from the spectrum at the depth DA is CA Ｓ (%), and the proportion of resin B at depth DA is CB Ｓ (%)year, The abundance ratio of the resin A at a depth of 75 nm calculated from the spectrum at a depth of 75 nm is CA ７５ (%), and the abundance ratio of the resin B at a depth of 75 nm is CB ７５ When set to (%), CA Ｓ is 40.0 to 85.0, CA Ｓ / CA ７５ is 1.5 to 5.0, CB Ｓ / CB ７５ is 1.5 to 5.0, CA Ｓ / CB Ｓ is 1.0 to 6.0, (CA Ｓ / CB Ｓ ) / (CA ７５ / CB ７５ ) is 0.5 to 3.0; A toner characterized by:

2. The CA Ｓ / CA ７５ 2. The toner according to claim 1, wherein the ρ is 2.0 to 5.

0.

3. The toner according to claim 1 or 2, wherein the toner particles contain inorganic fine particles.

4. 4. The toner according to claim 3, wherein the inorganic fine particles are surface-treated with a treating agent having an alkyl group having 4 to 20 carbon atoms.

5. The toner according to claim 3 , wherein the inorganic fine particles are magnetic.

6. the toner particles contain an ester wax, In a depth direction analysis of the toner particles by time-of-flight secondary ion mass spectrometry, the abundance ratio CW of the ester wax at the depth DA is Ｓ (%) is 10 or less, The ester wax is at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6): The toner according to claim 1 or 2. (In formula (4), formula (5) and formula (6), R ３１ and R ４１ each independently represents an alkylene group having 2 to 8 carbon atoms; R ３２ , R ３３ , R ４２ , R ４３ , R ５１ and R ５２ each independently represents a linear alkyl group having 14 to 24 carbon atoms.

7. the toner particles contain a resin C, The resin C is a vinyl resin having no sulfonic acid group. The toner according to claim 1 or 2.

8. The toner according to claim 7 , wherein the resin C has a monomer unit represented by the following formula (1): (In formula (1), R １ represents a hydrogen atom or a methyl group, and R ２ represents a linear alkyl group having 10 to 14 carbon atoms.

9. 3. The toner according to claim 1, wherein the resin B has an ester group concentration of 2.0 to 10.0 mmol / g.

10. 3. The toner according to claim 1, wherein the sulfonic acid group concentration of the resin A is 0.05 to 0.50 mmol / g.

11. The resin A is an amorphous resin, The resin B is an amorphous resin. The toner according to claim 1 or 2.

12. A method for producing the toner according to claim 1 or 2, comprising the steps of: a heat treatment step of treating a toner particle precursor containing the resin A and the resin B in an aqueous medium at a temperature of 95 to 120°C and a pH of 7.5 to 10.0 for 10 minutes or more; A method for producing a toner comprising the steps of:

13. The method for producing a toner according to claim 12 , wherein the toner particle precursor contains inorganic fine particles.

14. 14. The method for producing a toner according to claim 13, wherein the inorganic fine particles are surface-treated with a treating agent having an alkyl group having 4 to 20 carbon atoms.

15. The method for producing a toner according to claim 13, wherein the inorganic fine particles are magnetic.

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