toner

Abstract

To provide a toner that is excellent in low-temperature fixability, hot offset resistance, and image glossiness, and can maintain electrification start-up and transfer properties even after a long-term use.SOLUTION: A toner has a toner particle. The toner particle contains a toner core particle containing a binder resin. The binder resin contains a resin A. The resin A contains a monomer unit M1 having a specific structure and a monomer unit M2 containing an organic silicon polymer part in specific amounts. The organic silicon polymer part has a T3 unit structure and a T2 unit structure. In solid-state 29Si-NMR DD / MAS measurement of the resin A, the ratio of the peak area corresponding to silicon atoms taking the T3 unit structure and the ratio of the peak area corresponding to silicon atoms taking the T2 unit structure satisfy a specific relationship. The weight average molecular weight Mw of tetrahydrofuran insolubles in the resin A is within a specific range.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This disclosure relates to toner used in recording methods utilizing electrophotography, electrostatic recording, and toner jet recording. [Background technology]

[0002] In recent years, the printer market has seen a demand for smaller printer bodies, higher print quality, and an increase in the number of pages that can be printed per toner cartridge. To achieve miniaturization while maintaining the required print volume, it is necessary to reduce the space occupied by the printer and toner cartridge, as well as the number of parts. To reduce the space occupied by the toner cartridge, it is necessary to fill a larger amount of toner into a smaller space than before.

[0003] However, when a larger amount of toner is packed into a smaller space than before, the toner inside the cartridge is subjected to a greater load and is agitated more severely than before. Under such conditions, as the number of printed pages increases, external additives that have adhered to the toner surface may become embedded, or in severe cases, the toner itself may crack or deform. Therefore, toner requires a higher level of stress resistance than before.

[0004] Furthermore, reducing the number of parts can be achieved by improving the charging stability of the toner, thereby enabling the miniaturization and reduction of charging components. Against this backdrop, toners are required to have greater stress resistance and electrostatic stability than before, and one way to achieve this is to investigate the use of resins containing organosilicon polymers.

[0005] For example, Patent Document 1 proposes a toner that is highly resistant to stress such as in-machine agitation while maintaining excellent low-temperature fixation by forming a thin shell of organosilicon polymer on the toner surface. Patent Document 2 proposes a method to suppress toner degradation due to agitation and bleeding of materials inside the toner particles by providing an organosilicon polymer layer on the surface of the toner particles by having a vinyl resin having organosilicon polymer moieties on the surface of the toner particles. Patent Document 3 suppresses the release of organosilicon polymers from the surface of toner particles by using a resin having organosilicon polymer moieties, thereby suppressing changes in the toner over time. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 9-179341 [Patent Document 2] Japanese Patent Publication No. 2015-096948 [Patent Document 3] Japanese Patent Publication No. 2020-181187 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] However, when using organosilicon polymers, the thermoplasticity of organosilicon polymers is lower than that of general toner resins, which increases the toner fixing temperature. Also, the toner viscosity does not decrease easily during fixing. Therefore, in all of the methods described in Patent Documents 1 to 3, although the toner's resistance to stress is improved, the viscosity of the toner when melted becomes high. As a result, the gloss of the fixed image decreases, making it difficult to obtain high-quality prints. In addition, in some cases, it may impair the adhesion between the paper and the toner, or the release properties between the toner and the fuser, affecting the fixing performance. Thus, it is difficult to achieve both toner durability and image glossiness with conventional methods.

[0008] This disclosure provides a toner that exhibits excellent low-temperature fixability, hot offset resistance, and image gloss, and that can maintain charge rise and transferability even after long-term use. [Means for solving the problem]

[0009] A toner having toner particles, The toner particles contain toner core particles containing a binder resin, The binder resin contains resin A, The resin A is a styrene-acrylic copolymer, The resin A contains 65 to 85% by mass of monomer unit M1 represented by the following formula (1), The resin A contains 0.05 to 2.00% by mass of monomer units M2 containing an organosilicon polymer moiety represented by the following formula (2), The organosilicon polymer moiety has a T3 unit structure and a T2 unit structure, The solid resin A 29 In Si-NMR DD / MAS measurements, When A(%) is the ratio of the peak area corresponding to silicon atoms with a T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer moiety, and B(%) is the ratio of the peak area corresponding to silicon atoms with a T2 unit structure, A and B satisfy the following equations (3) and (4), 0.3 ≤ A / B ≤ 2.7 (3) 62 ≤ A + B ≤ 100 (4) A toner characterized in that the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of resin A, determined by gel permeation chromatography, is between 50,000 and 250,000. TIFF0007877103000001.tif40170TIFF0007877103000002.tif36170(In formula (2), L 2 This is a single bond, ―COO-(CH2) n - or -NH-(CH2) n - indicates (n is an integer from 1 to 10), R 2represents a hydrogen atom or a methyl group, and * represents a site that binds to the silicon atom of the organosilicon polymer moiety. L 2 is -COO-(CH2) n - in the case where the carbonyl is bonded to the carbon having R 2 and L 2 is -NH-(CH2) n - in the case where NH is bonded to the carbon having R 2 .)

Advantages of the Invention

[0010] According to the present disclosure, it is possible to provide a toner that is excellent in low-temperature fixing property, hot offset resistance, and image glossiness, and can maintain charge rise and transferability even after long-term use.

Modes for Carrying Out the Invention

[0011] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified. When the numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined. The "monomer unit" refers to the reacted form of the monomer substance in the polymer. For example, in the main chain where vinyl monomers in the polymer are polymerized, one section of the carbon-carbon bond is taken as one unit. The vinyl monomer can be represented by the following formula (C). TIFF0007877103000003.tif30170 <00​​​​​​​​​Organosilicon polymers are more brittle and have superior stress resistance compared to styrene-acrylic and polyester resins used in toner applications. On the other hand, organosilicon polymers have strong heat resistance and lower thermoplasticity compared to styrene-acrylic and polyester resins, making them difficult to fix on their own. Thus, hybridization of resins is a method that utilizes the properties of each material while maintaining their respective advantages. However, when organosilicon polymer moieties are introduced into styrene-acrylic resin or polyester resin, the durability of the toner improves compared to when styrene-acrylic resin or polyester resin is used alone, but the low-temperature fixing properties and image gloss decrease.

[0014] One reason for the decrease in low-temperature fixability and image gloss is the large molecular weight of the resin. However, it has been found that resins with organosilicon polymer moieties have inferior low-temperature fixability compared to resins without organosilicon polymer moieties, even if their molecular weight is similar.

[0015] The inventors of the present invention hypothesized that, because organosilicon polymers have many polar groups, crosslinking due to non-covalent bonding by these polar groups might occur when they are introduced into a resin, and conducted thorough research. As a result, they found that the above problem can be solved with the following configuration.

[0016] This disclosure is, A toner having toner particles, The toner particles contain toner core particles containing a binder resin, The binder resin contains resin A, The resin A is a styrene-acrylic copolymer, The resin A contains 65 to 85% by mass of monomer unit M1 represented by the following formula (1), The resin A contains 0.05 to 2.00% by mass of monomer units M2 containing an organosilicon polymer moiety represented by the following formula (2), The organosilicon polymer moiety has a T3 unit structure and a T2 unit structure, The solid resin A29 In Si-NMR DD / MAS measurements, When A(%) is the ratio of the peak area corresponding to silicon atoms with a T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer moiety, and B(%) is the ratio of the peak area corresponding to silicon atoms with a T2 unit structure, A and B satisfy the following equations (3) and (4), 0.3 ≤ A / B ≤ 2.7 (3) 62 ≤ A + B ≤ 100 (4) The present invention relates to a toner characterized in that the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of resin A, as determined by gel permeation chromatography, is between 50,000 and 250,000. TIFF0007877103000004.tif40170TIFF0007877103000005.tif36170(In formula (2), L 2 This is a single bond, ―COO-(CH2) n - or -NH-(CH2) n - indicates (n is an integer from 1 to 10), R 2 * indicates a hydrogen atom or a methyl group, and * indicates a site that bonds with a silicon atom in the organosilicon polymer. 2 ga-COO-(CH2) n - If the carbonyl is R 2 Bonded to a carbon having L 2 -NH-(CH2) n - If NH is R 2 (It bonds to a carbon atom that has a carbon atom.)

[0017] The toner contains toner particles, and the toner particles contain toner core particles containing a binder resin. The binder resin contains resin A. Resin A is a styrene-acrylic copolymer and has a monomer unit M1 represented by the following formula (1) and a monomer unit M2 containing an organosilicon polymer moiety, represented by the following formula (2). In other words, resin A is a styrene-acrylic resin containing an organosilicon polymer moiety. TIFF0007877103000006.tif40170

[0018] TIFF0007877103000007.tif36170(In formula (2), L 2 This is a single bond, ―COO-(CH2) n - or -NH-(CH2) n - indicates (where n is an integer from 1 to 10 (preferably 2 to 8, more preferably 2 to 5)), R 2 is hydrogen This indicates an atom or a methyl group, and * indicates a site that bonds with a silicon atom in the organosilicon polymer. 2 ga-COO-(CH2) n - If the carbonyl is R 2 Bonded to a carbon having L 2 -NH-(CH2) n - If NH is R 2 (It bonds to a carbon atom that has a carbon atom.)

[0019] When toner melts during fixing, hydrogen bonds are formed between the ester groups, hydroxyl groups, and carboxyl groups contained in the resin. As a result, the viscosity of the toner increases during melting, making it difficult to fix the molten toner smoothly onto the paper, and reducing the glossiness of the image.

[0020] As a result of their investigation, the inventors have found that by setting the content and structure of monomer units M1 and M2 in resin A within a specific range, it is possible to provide a toner that has excellent low-temperature fixing properties and high image gloss, which could not be achieved conventionally, while maximizing the durability advantages of resins containing organosilicon polymer moieties.

[0021] Resin A contains 65 to 85% by mass of monomer unit M1 represented by the above formula (1). Most styrene-acrylic resins used in toner applications are composed of styrene monomers and vinyl monomers having ester groups. When the content of monomer unit M1 in resin A is less than 65% by mass, the amount of vinyl monomer with ester groups increases relatively, resulting in an increase in proton acceptors in the binder resin. Furthermore, the hydroxyl group of monomer unit M2 in resin A, which will be explained in detail later, is a proton donor. Therefore, when the content of monomer unit M1 in resin A is less than 65% by mass, hydrogen bonding is more likely to occur in the binder resin, leading to a decrease in image gloss.

[0022] On the other hand, if the monomer unit M1 content in resin A is 85% by mass or more, the glass transition temperature of resin A increases, causing resin A itself to harden, resulting in a decrease in low-temperature fixability and image gloss.

[0023] The monomer unit M1 content in resin A is preferably 70% by mass or more, more preferably 73% by mass or more. Furthermore, it is preferably 83% by mass or less, and more preferably 80% by mass or less. For example, preferred ranges include 70-83% by mass and 73-80% by mass.

[0024] Resin A contains 0.05 to 2.00% by mass of monomer units M2 containing organosilicon polymer moieties, represented by the above formula (2). As mentioned above, the organosilicon polymer portion contained in monomer unit M2 has a hydroxyl group, which is a proton donor, and therefore forms hydrogen bonds with the ester groups in resin A and other resin components. For this reason, if the content of monomer unit M2 in resin A is less than 0.05% by mass, the number of proton donors decreases, and hydrogen bonds are less likely to form in the binder resin. As a result, the viscosity of the toner decreases when it melts due to the heat of the fuser, leading to hot offset and a decrease in image gloss due to roughness of the fixed image surface.

[0025] On the other hand, if the monomer unit M2 content in resin A exceeds 2.00% by mass, there are many proton donors, and hydrogen bonds are more likely to form in the binder resin, resulting in a higher viscosity when the toner melts. As a result, many irregularities occur in the fixed image, and the image glossiness decreases.

[0026] The monomer unit M2 content in resin A is preferably 0.10% by mass or more, more preferably 0.50% by mass or more, and even more preferably 1.00% by mass or more. Furthermore, it is preferably 1.80% by mass or less, and more preferably 1.50% by mass or less. For example, preferred ranges include 0.10 to 1.80% by mass, 0.50 to 1.80% by mass, 1.00 to 1.80% by mass, 0.50 to 1.50% by mass, and 1.00 to 1.50% by mass.

[0027] The organosilicon polymer moiety contained in monomer unit M2 in resin A has a T3 unit structure and a T2 unit structure. 29 In Si-NMR DD / MAS measurements, when A (%) is the ratio of the peak area corresponding to silicon atoms with a T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer moiety, and B (%) is the ratio of the peak area corresponding to silicon atoms with a T2 unit structure, then A and B satisfy the following equations (3) and (4). 0.3 ≤ A / B ≤ 2.7 (3) 62 ≤ A + B ≤ 100 (4)

[0028] Polymers of organosilicon compounds have a skeletal structure composed of four basic units: M units, D units, T units, and Q units, because silicon has four bonding sites. The M units, D units, T units, and Q units are structures formed by the bonding of monofunctional, difunctional, trifunctional, and tetrafunctional organosilicon compounds, respectively.

[0029] The presence of T units in the organosilicon polymer moiety allows for the proton donation by the hydroxyl groups of the organosilicon polymer moiety to be limited to a specific range, thereby enabling the viscosity of the toner during melting to be controlled within an appropriate range. Furthermore, T units are classified into structures such as the T1 unit structure, which has two reactive groups such as hydroxyl groups; the T2 unit structure, which has one reactive group such as a hydroxyl group; and the T3 unit structure, which does not have any reactive groups such as hydroxyl groups. When the organosilicon polymer moiety has both T3 and T2 unit structures, and the proportion of silicon atoms A that takes on the T3 unit structure and the proportion of silicon atoms B that take on the T2 unit structure satisfy the above formulas (3) and (4), then excellent image gloss and low-temperature fixation are achieved, and image fogging can be suppressed.

[0030] The fact that A and B satisfy equations (3) and (4) above indicates that there are many T2 and T3 unit structures and few T1 unit structures in the organosilicon polymer moiety. The T1 unit structure is highly reactive, and the heat generated during fixing causes coupling reactions between organosilicon polymers, leading to increased viscosity. Therefore, if there are many T1 unit structures in the organosilicon polymer region, the image glossiness decreases.

[0031] On the other hand, the T2 unit structure has low reactive activity and does not thicken easily even when heated during fixing, but the hydroxyl groups in the T2 unit structure readily form conductive sites derived from water molecules by hydrogen bonding with water molecules in the atmosphere. As a result, if there are many T2 unit structures in the organosilicon polymer, the charge of the toner decreases, causing image fogging.

[0032] When the A / B value satisfies equation (3), the toner has good charge build-up and excellent durability. An A / B ratio of less than 0.3 indicates a high concentration of T2 unit structures within the organosilicon polymer. Therefore, as mentioned above, an increase in conductive sites derived from water molecules reduces the toner's charge, resulting in image fogging. On the other hand, an A / B ratio exceeding 2.7 indicates a low number of T2 unit structures in the organosilicon polymer moiety. Therefore, the charge rise effect is not obtained, and image fogging due to charge buildup is more likely to occur.

[0033] The A / B value is preferably 0.5 or higher, more preferably 1.0 or higher, and even more preferably 1.5 or higher. Furthermore, it is preferably 2.5 or lower, more preferably 2.3 or lower, and even more preferably 2.0 or lower. For example, preferred ranges include 0.5 to 2.5, 1.0 to 2.3, and 1.5 to 2.0.

[0034] If the value of A+B satisfies equation (4), then the organosilicon polymer contains a T3 unit structure and a T2 unit structure. Because a sufficient layer structure is present, the toner is less likely to thicken, improving image glossiness. The value of A+B is preferably 65 or higher, more preferably 70 or higher, and even more preferably 75 or higher. It is also preferably 95 or lower, more preferably 90 or lower, and even more preferably 85 or lower. For example, preferred ranges include 65-95, 70-90, and 75-85.

[0035] A / B is organosilicon polymer The reaction ratio can be controlled by the type of silane coupling agent used to form the site, as well as by manufacturing conditions such as temperature and pH during the condensation reaction. Specifically, the A / B ratio can be increased by using a basic catalyst, while the A / B ratio can be decreased by using an acid catalyst. Also, A+B is organosilicon polymer The amount and method of adding silanol to form the site can be controlled by adjusting the reaction temperature. Specifically, increasing the amount of silanol added or optimizing the method of addition can increase A+B. Conversely, decreasing the amount of silanol added can decrease A+B.

[0036] The weight-average molecular weight Mw of the tetrahydrofuran (THF)-soluble component of resin A, determined by gel permeation chromatography, is between 50,000 and 250,000. When the molecular weight of resin A exceeds 250,000, the viscosity becomes high regardless of the presence or absence of non-covalent bonds, resulting in decreased low-temperature fixability and image gloss. On the other hand, when the weight-average molecular weight Mw of resin A is less than 50,000, the hardness of resin A itself is low, and external additives tend to become embedded when the toner is used for a long period of time. As a result, the charge of the toner decreases, and image fogging is more likely to occur.

[0037] The weight-average molecular weight Mw of the tetrahydrofuran-soluble component of resin A is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 or more. It is also preferably 240,000 or less, more preferably 230,000 or less, and even more preferably 220,000 or less. For example, preferred ranges include 60,000 to 240,000, 70,000 to 230,000, and 80,000 to 220,000.

[0038] It is preferable that resin A does not contain THF-insoluble matter. If resin A contains THF-insoluble matter, the organosilicon polymer portion derived from monomer unit M2 is insoluble in THF, and the distance between hydroxyl groups in resin A is large, so a three-dimensional network of hydrogen bonds is formed starting from resin A. This network structure increases the toner viscosity during melting and reduces the image gloss during fixing.

[0039] The following provides a more detailed explanation, taking into account the more preferred scope of this disclosure. <Regarding the resin component of toner core particles> Resin A is a styrene-acrylic resin, and may contain polymers made of monofunctional polymerizable monomers or polyfunctional polymerizable monomers as constituent materials other than monomer units M1 and M2.

[0040] Examples of monofunctional polymerizable monomers include the following: Styrene derivatives such as α-methylstyrene and β-methylstyrene; alkyl acrylic polymerizable monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, n-propyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, stearyl acrylate, and behenyl acrylate; methacrylic polymerizable monomers such as methyl methacrylate, n-propyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-nonyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl Monofunctional polymerizable monomers used in general toner applications, such as lucetone and vinyl isopropyl ketone.

[0041] Examples of polyfunctional polymerizable monomers include the following: Polyfunctional polymerizable monomers used in general toner applications, such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, 1,6-hexanediol diacrylate, and neopentyl glycol diacrylate.

[0042] Materials that constitute the monomer unit M2 include polymerizable monomers having an organosilicon polymer moiety and a vinyl polymer moiety, and combinations of the polymerizable monomer with various difunctional and trifunctional organosilicon compounds. Examples of polymerizable monomers having organosilicon polymerized moieties and vinyl polymerized moieties include the following:

[0043] Trifunctional vinylsilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltriisocyanatesilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, vinyldiethoxyhydroxysilane. Trifunctional allylsilanes such as allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, allyltriacetoxysilane, and allyltrihydroxysilane. Trifunctional methacryloalkylsilanes such as 3-methacryloxypropyltrimethoxysilane and 3-methacryloxypropyltriethoxysilane. Trifunctional acryloxyalkylsilanes such as 3-acryloxypropyltrimethoxysilane and 3-acryloxypropyltriethoxysilane.

[0044] The organosilicon polymer site to which the monomer unit M2 is bonded is preferably a polymer of an organosilicon compound having the structure represented by the following formula (5). R-Si-R a 3 formula(5) (In formula (5), R a Each of these independently represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms, while R represents an alkyl group having 1 to 6 carbon atoms. When the organosilicon polymer moiety is a vinyl polymer that can be polymerized with siloxane, combinations with the compound of formula (5) above, as well as, for example, the following organosilicon compounds, are possible. Trifunctional methylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane. Trifunctional silanes such as ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, and hexyltrihydroxysilane. Trifunctional phenylsilanes such as phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0045] The organosilicon polymer moiety described above may have an amino group. That is, resin A may be a resin in which the carboxyl group in the polyester resin and the amino group in the aminosilane are amidated. Examples of aminosilanes are not limited to those mentioned above, but include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-6-(aminohexyl)3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, and 3-aminopropylsilicone.

[0046] Resin A preferably contains 3 to 10% by mass of monomer unit M3 represented by the following formula (8). By having a monomer unit M3 content within the above range in resin A, sharp melt properties can be achieved in the fixing temperature range of the binder resin. As a result, low-temperature fixing properties and image gloss are further improved, and the occurrence of hot offset can be suppressed. TIFF0007877103000008.tif34170

[0047] (In formula (8), L 1 ha-COO-(CH2) n - indicates (where n is an integer between 11 and 31 (preferably 11 to 22, more preferably 11 to 13)), L 1 The carbonyl group is bonded to the carbon atom in the main chain. 1 (This represents a hydrogen atom or a methyl group.) The content of monomer unit M3 in resin A is more preferably 4 to 9% by mass, and even more preferably 5 to 8% by mass. More preferably, the monofunctional polymerizable monomer corresponding to monomer unit M3 is lauryl acrylate or behenyl acrylate.

[0048] The content of resin A in the toner is preferably 50% by mass or more. A resin A content of 50% by mass or more improves low-temperature fixation and image gloss. The content of resin A is more preferably 55% by mass or more, and even more preferably 60% by mass or more. There is no particular upper limit, but 90% by mass or less and 85% by mass or less are preferred.

[0049] The binder resin may contain resin A or other known resins. There are no restrictions, but examples include styrene-acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, and mixtures or composite resins thereof. Styrene-acrylic resin and polyester resin are preferred because they are inexpensive, readily available, and have excellent low-temperature fixation properties. Furthermore, it is even more preferable to include styrene-acrylic resin because it has excellent developability. Examples of constituent materials for the styrene-acrylic resin used as a binder include polymers consisting of monofunctional polymerizable monomers or polyfunctional polymerizable monomers listed in the examples of constituent materials other than monomer units M1 and M2 of resin A, or copolymers obtained by combining two or more of these.

[0050] The toner core particles preferably contain resin B in addition to the binder resin and resin A mentioned above. From the viewpoint of improving low-temperature fixation, the weight-average molecular weight Mw of the tetrahydrofuran-soluble portion of resin B, determined by gel permeation chromatography, is preferably 2000 to 7000. The weight-average molecular weight Mw of the tetrahydrofuran-insoluble portion of resin B is more preferably 2500 to 6500, and even more preferably 3000 to 6000.

[0051] If the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of resin B is within the above range, resin B has a lower viscosity than the binder resin, and therefore resin B acts as an adhesive to the paper, improving low-temperature fixation.

[0052] Resin B is preferably a styrene-acrylic resin containing monomer unit M1. The content of monomer unit M1 in resin B is preferably 85 to 100% by mass, and more preferably 95 to 100% by mass. When the content of monomer unit M1 in resin B is within the above range, hydrogen bonds are less likely to form with other resins such as resin A, and low-temperature fixation properties can be improved.

[0053] The monomer unit M1 contained in resin B is preferably composed of a single unit, but from the viewpoint of adjusting the glass transition temperature of resin B, it may also be a copolymer of monomer unit M1 and one or more other monomer units. The polymerizable monomer used for copolymerization can be appropriately set depending on the toner particles to be produced, but for example, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. As monofunctional polymerizable monomers and polyfunctional polymerizable monomers, the monofunctional polymerizable monomers and polyfunctional polymerizable monomers exemplified with respect to resin A can be used. For example, n-butyl acrylate is preferred.

[0054] <Regarding the state of existence of organosilicon polymers in toner core particles> The toner particles contain organosilicon polymers on the surface of the toner core particles. As mentioned above, the toner core particles contain resin A, and resin A has monomer units M2 containing organosilicon polymer moieties. From the viewpoint of charge buildup, it is preferable that the organosilicon polymer moieties contained in monomer units M2 be present on the surface of the toner core particles. Specifically, when the peak intensity of Si obtained by time-of-flight secondary ion mass spectrometry (TOF-SIMS) of toner core particles is denoted as P(Si), and the sum of the peak intensities of all ions in the toner core particles is denoted as P(T), it is preferable that the following equation (6) is satisfied. 0.004≦P(Si) / P(T)≦0.040 (6)

[0055] When P(Si) / P(T) is within the above range, a large amount of organosilicon polymer is present on the surface of the toner core particles, which improves the charging rise of the toner due to its conductive effect and suppresses image fogging. In addition, the presence of organosilicon polymer on the surface of the toner core particles makes the fixing surface flat. This improves image glossiness.

[0056] The value of P(Si) / P(T) is preferably 0.008 or higher, and more preferably 0.010 or higher. It is also preferably 0.030 or lower, and more preferably 0.020 or lower. For example, the ranges of 0.008 to 0.030 and 0.010 to 0.020 are preferred. The P(Si) / P(T) value can be increased by ensuring that a large number of organosilicon polymer moieties are present on the surface of the toner core particles. Specifically, this can be controlled by adjusting the method of adding a resin containing organosilicon polymer moieties or by adjusting the method of adding and reacting monomers having organosilicon polymer moieties during the polymerization process in toner manufacturing, as described later.

[0057] Toner particles preferably have protrusions on the surface of the toner core particles, and the protrusions are preferably formed by an organosilicon polymer. The organosilicon polymer has a structure represented by the following formula (7), and when the surface of the toner particles is observed with a scanning probe microscope, R is the number-average diameter of the maximum diameter of the protrusions, and H is the number-average height of the protrusions, where R is 80 to 250 nm and H is 25 to 100 nm. When the above conditions are met, transferability can be improved. R-SiO 3 / 2 (7) (formula( 7 (In this case, R represents an alkyl group, alkenyl group, acyl group, aryl group, or methacryloxyalkyl group.)

[0058] When the average particle diameter R is 80 nm or greater, the contact area between the toner core particle surface and the protrusions does not become too small, making it easier for the force received from the material during fixing to be transmitted from the protrusions to the toner core particle surface, thereby promoting deformation in the initial stages of fixing. Furthermore, when the average particle diameter R is 250 nm or less, it is possible to suppress the excessively large area covered by each protrusion on the toner core particle surface, which provides a significant advantage in low-temperature fixation.

[0059] The number-average diameter R is more preferably 90 nm or greater, and even more preferably 100 nm or greater. It is also more preferably 200 nm or less, and even more preferably 150 nm or less. For example, preferred ranges include 90 to 200 nm and 100 to 150 nm. The number-average diameter R can be increased by gradually raising the pH conditions of the organosilicon polymer condensation reaction when forming protrusions on the surface. On the other hand, the number-average diameter R can be decreased by increasing the pH during the organosilicon polymer condensation reaction or by decreasing the concentration of the organosilicon polymer.

[0060] When the average height H is 25 nm or more, the contact surface area between the toner and the fuser roller does not become too large, allowing the force applied to the toner to be concentrated on the contact surface, and promoting deformation during the initial fixing phase. Furthermore, when the average height H is 100 nm or less, it is possible to suppress the distance from the contact surface with the convex member to the surface of the toner core particles from becoming too large, which is advantageous for adhesion.

[0061] The average height H is more preferably 30 nm or greater, and even more preferably 40 nm or greater. It is also more preferably 80 nm or less, and even more preferably 60 nm or less. For example, preferred ranges include 30 to 80 nm and 40 to 60 nm. The average height H can be increased by increasing the concentration of the organosilicon polymer when forming the protrusions on the surface. Conversely, the average height H can be decreased by decreasing the concentration of the organosilicon polymer when forming the protrusions on the surface.

[0062] There are no particular restrictions on the organosilicon compounds used to obtain organosilicon polymers; conventionally known organosilicon compounds can be used. In particular, it is preferable to use at least one organosilicon compound selected from the group consisting of organosilicon compounds represented by the following formula (9). R-Si-R a Type 3(9) (In formula (9), R a Each of these independently represents a halogen atom or an alkoxy group, and R represents an alkyl group, alkenyl group, aryl group, acyl group, or methacryloxyalkyl group.

[0063] Examples of such silane compounds include the following: Trifunctional methylsilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, and methylethoxydimethoxysilane; trifunctional silane compounds such as ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane; trifunctional phenylsilane compounds such as phenyltrimethoxysilane and phenyltriethoxysilane; vinyltrimethoxy Trifunctional vinylsilane compounds such as silanes and vinyltriethoxysilanes; trifunctional allylsilane compounds such as allyltrimethoxysilane, allyltriethoxysilane, allyldiethoxymethoxysilane, and allylethoxydimethoxysilane; trifunctional γ-methacryloxypropylsilane compounds such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, and γ-methacryloxypropylethoxydimethoxysilane; and other trifunctional silane compounds.

[0064] Toner core particles may contain colorants. Examples of colorants include magenta colorants, cyan colorants, yellow colorants, and black colorants. Examples of magenta coloring pigments include CI Pigment Red 3, 5, 17, 22, 23, 38, 41, 112, 122, 123, 146, 149, 150, 178, 179, 190, 202, and CI Pigment Violet 19, 23. Examples of cyan coloring pigments include CI Pigment Blue 15, 15:1, 15:3, or copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted onto the phthalocyanine skeleton.

[0065] Examples of yellow coloring pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 17, 55, 74, 83, 93, 94, 95, 97, 98, 109, 110, 154, 155, 166, 180, and 185. As black colorants, carbon black, aniline black, acetylene black, titanium black, and those colored black using the yellow, magenta, and cyan colorants mentioned above can be used.

[0066] These colorants can be used individually, in combination, or even in solid solution form. The colorants are selected based on their hue angle, saturation, brightness, lightfastness, OHP transparency, and dispersibility in toner particles. It is preferable to use 1 to 20 parts by mass of these colorants per 100 parts by mass of the binder resin or polymerizable monomer that forms the binder resin.

[0067] Furthermore, magnetic materials can also be used as black colorants. Examples of magnetic materials include magnetite, hematite, and ferrite. When using magnetic materials as black colorants, it is preferable to use magnetic materials whose surfaces have been hydrophobicized. Examples of hydrophobic treatment agents that can be used in this case include silane coupling agents and titanium coupling agents.

[0068] The magnetic material preferably has a number-average particle size of 2 μm or less, and more preferably 0.1 to 0.5 μm. These magnetic materials are preferably used in an amount of 40 to 150 parts by mass per 100 parts by mass of the binder resin or polymerizable monomer that forms the binder resin.

[0069] The toner core particles may contain a release agent. Any known release agent can be used without any particular restrictions. Specifically, the following are examples: Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax; block copolymers of aliphatic hydrocarbon waxes; ester waxes mainly composed of fatty acid esters such as carnauba wax, sazole wax, and montanic acid ester wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax, and partially esterified fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and methyl ester compounds having hydroxyl groups obtained by hydrogenating vegetable oils and fats.

[0070] The release agent content is preferably 2.5 to 40.0 parts by mass, and more preferably 3.0 to 15.0 parts by mass, per 100 parts by mass of the binder resin. These release agents may be used individually or in combination of two or more types, and preferably a combination of hydrocarbon wax and ester wax is preferred from the viewpoint of adhesion. When two or more release agents are used in combination, it is preferable that the total content of the release agents is within the above range.

[0071] Toner core particles preferably contain a plasticizer. The plasticizer preferably contains an ester compound of a diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms. By using a plasticizer that satisfies the above conditions, resins composed primarily of monomer units M1 can be efficiently plasticized, thereby improving low-temperature fixation.

[0072] Plasticizers containing ester compounds of diols with 2 to 6 carbon atoms and aliphatic monocarboxylic acids with 14 to 22 carbon atoms include ethylene glycol distearate, ethylene glycol dibehenate, and ethylene glycol dimiryl SteEthylene glycol dilactate, 1,4-butanediol distearate, hexanediol dimyris Te , hexane All-dibehenate, hexanediol stearate, etc., can be used. The plasticizer content is preferably 5 to 25 parts by mass, more preferably 10 to 15 parts by mass, per 100 parts by mass of the binder resin or polymerizable monomer.

[0073] A charge control agent may be used in the toner. The charge control agent helps maintain the toner's charge stability. Various charge control agents that have been conventionally used in toner applications can be used as the charge control agent. The amount of charge control agent added is 0.01 to 10.00 parts by mass per 100 parts by mass of the binder resin or polymerizable monomer.

[0074] To improve the fluidity of the toner particles, a fluidity improver may be added to the toner particles. The fluidity improver is not particularly limited, and known ones can be used. Specifically, the following are examples: Fluorine-based resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate, and lead stearate; metal oxides such as titanium oxide powder, aluminum oxide powder, and zinc oxide powder, or powders of the above metal oxides that have been hydrophobized; silica fine powders such as wet-process silica and dry-process silica, or surface-treated silica fine powders obtained by surface-treating these silica fine powders with treatment agents such as silane coupling agents, titanium coupling agents, and silicone oils.

[0075] It is preferable to add the fluidity improver in an amount of 0.01 parts by mass to 5.00 parts by mass per 100 parts by mass of toner particles. If the amount added is within the above range, a sufficient fluidity improvement effect can be obtained while suppressing a decrease in fixation performance. Furthermore, it is preferable that the number average particle size (D1) of the primary particles of the above fluidity improver is 4 to 120 nm.

[0076] The toner can be used in either a one-component or two-component developer system. When used as a two-component developer, the average particle size of the carriers used is preferably 10 to 100 μm, more preferably 20 to 50 μm. Furthermore, when these carriers and toners are mixed to prepare a two-component developer, the toner concentration in the developer is preferably about 2 to 15% by mass.

[0077] The weight-average particle size of the toner is not particularly limited, but is preferably 4.0 to 11.0 μm, and more preferably 5.0 to 10.0 μm. When the weight-average particle size is within the above range, good fluidity is obtained, and the latent image can be developed faithfully.

[0078] The following describes toner manufacturing methods, but these are not the only manufacturing methods available. There are no particular restrictions on the method for incorporating resin A, which contains organosilicon polymer moieties, into toner core particles; known methods can be used. For example, in the kneading and grinding method, there are methods such as kneading resin A containing organosilicon polymer parts together with the toner constituent materials, or attaching resin A containing organosilicon polymer parts to the surface of toner mother particles and then fixing it with heat treatment to obtain toner core particles. Furthermore, in wet manufacturing methods, examples include a method in which resin A containing organosilicon polymer moieties is dissolved together with toner constituent materials to form particles, a method in which resin A containing organosilicon polymer moieties is added after the formation of toner mother particles and fixed by heat treatment to obtain toner core particles, and a method in which a reactive organosilicon compound is added together with a polymerization initiator during particle size determination to incorporate it into the toner mother particles and obtain toner core particles.

[0079] Among these methods, suspension polymerization is preferred because it facilitates the orientation of resin A, which contains organosilicon polymer moieties, onto the surface of toner core particles. The following describes a method for producing toner particles using this suspension polymerization method. First, polymerizable monomers capable of forming a binder resin, along with various materials as needed, are mixed and dissolved or dispersed using a disperser to prepare a polymerizable monomer composition (dissolution step). Examples of various materials include colorants, release agents, plasticizers, charge control agents, polymerization initiators, and chain transfer agents. Examples of dispersers include homogenizers, ball mills, colloid mills, or ultrasonic dispersers.

[0080] Next, the polymerizable monomer composition is added to an aqueous medium containing a dispersion aid, 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 step). Subsequently, the polymerizable monomers in the droplet are polymerized to obtain toner core particles (polymerization step).

[0081] The polymerization initiator may be mixed when preparing the polymerizable monomer composition, or it may be mixed into the polymerizable monomer composition immediately before forming droplets in an aqueous medium. Furthermore, polymerizable monomers or other solvents can be added as needed during or after droplet granulation, i.e., immediately before the polymerization reaction begins. After polymerizing polymerizable monomers to obtain a binder resin, a solvent removal treatment is performed as needed, and then toner It is best to obtain a dispersion of core particles.

[0082] The resin containing the organosilicon polymer moiety may (i) be added to the dissolution step, or (ii) a particle dispersion of the resin containing the organosilicon polymer moiety may be added after the completion of the polymerization step and then heat-set. Furthermore, (iii) the organosilicon polymer moiety may be incorporated into the binder resin by adding a vinyl monomer containing the organosilicon polymer moiety and a polymerization initiator during the polymerization process. polymer From the viewpoint of positioning the part near the surface, method (ii) or (iii) is preferred.

[0083] When obtaining a binder resin by methods such as emulsification and agglutination or suspension polymerization, conventionally known monomers can be used as polymerizable monomers without any particular restrictions. Specifically, vinyl monomers as exemplified for binder resins are examples.

[0084] There are no particular restrictions on the method for providing organosilicon polymer moieties on the surface of toner core particles; known methods can be used. For example, during the polymerization process of the toner core particles mentioned above, an organosilicon polymer part One method involves adding a monomer containing the organosilicon polymer to obtain toner core particles containing a resin having an organosilicon polymer moiety. Another method involves adding a monomer containing the organosilicon polymer in an aqueous medium in which the toner core particles are dispersed. part Methods for polymerizing monomers containing organosilicon polymers part One method involves polymerizing a monomer containing the above, and then adding the resulting polymer during the manufacturing process of toner core particles to obtain toner core particles containing a resin having an organosilicon polymer moiety.

[0085] Monomers are organosilicon polymers part There are no particular restrictions as long as it contains the specified substance; publicly known substances can be used. Specifically, the following are examples: γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxyoctyltrimethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, γ-methacryloxypropylethoxydimethoxysilane Trifunctional silane compounds having methacryloxyalkyl groups as substituents such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-acryloxypropyldiethoxymethoxysilane, γ-acryloxypropylethoxydimethoxysilane, etc., which have acryloxyalkyl groups as substituents.

[0086] As the dispersion aid used in the granulation process described above, known dispersion stabilizers and surfactants can be used. Specifically, the following can be used as dispersion stabilizers. 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, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salts of carboxymethylcellulose, and starch.

[0087] The following are examples of surfactants: Anionic surfactants such as alkyl sulfate esters, alkylbenzene sulfonates, 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.

[0088] In particular, it is preferable to include an inorganic dispersion stabilizer, and the dispersion contains phosphates such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, and aluminum phosphate. It is more preferable to include a stabilizer.

[0089] Any known polymerization initiator can be used without any particular restrictions. Specifically, the following are examples: Hydrogen peroxide, acetyl peroxide, cumyl peroxide, tert-butyl peroxide, propionyl peroxide, benzoyl peroxide, chlorobenzoyl peroxide, dichlorobenzoyl peroxide, bromomethylbenzoyl peroxide, lauroyl peroxide, ammonium persulfate, sodium persulfate, potassium persulfate, diisopropyl peroxycarbonate, tetraline hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetate-tert-hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, perN-(3-toluyl)palmitate-tert-butylbenzoyl peroxide Peroxide-based polymerization initiators such as t-butyl peroxy 2-ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide; azo-based or diazo-based polymerization initiators such as 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitride), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and azobisisobutyronitrile; etc.

[0090] The toner of this disclosure can be used in conventionally known image forming apparatuses without any particular limitations. Examples include image forming apparatuses using a one-component contact developing method, a two-component developing method, and a one-component jumping developing method.

[0091] The following describes methods for measuring various physical properties. <Separation of resins A and B from toner> Resin A and resin separated from the toner using the following method B It is also possible to measure various physical properties using materials such as those mentioned above. 10.0 g of toner particles are weighed and placed in cylindrical filter paper (Toyo Filter Paper Co., Ltd. No. 84) and subjected to a Soxhlet extractor. Extraction is carried out for 20 hours using 200 mL of THF as the solvent, and the solid obtained by desolventing the extract is the THF-soluble component of the toner. The THF-soluble component contains resin A and resin B. This process is repeated multiple times to obtain the required amount of THF-soluble component.

[0092] For the solvent gradient elution method, a gradient preparative HPLC (Shimadzu LC-20AP high-pressure gradient preparative system, Waters SunFire preparative column 50 mm diameter 250 mm) is used. The column temperature is 30°C, the flow rate is 50 mL / min, and acetonitrile is used as the poor solvent and THF as the good solvent for the mobile phase. 0.02 g of THF-soluble fraction obtained by extraction is dissolved in 1.5 mL of THF to be used as the sample for separation. The mobile phase is started with a composition of 100% acetonitrile, and 5 minutes after sample injection, the proportion of THF is increased by 4% per minute until the mobile phase composition becomes 100% THF over 25 minutes. The components can be separated by drying the obtained fraction. The specific fractional components that make up resin A and resin B will be described later. 1 This can be determined by H-NMR measurement.

[0093] <Identification of monomer units contained in resins A and B, and method for measuring the content ratio of each monomer unit> For the identification of various monomer units in resin A and resin B: 1 H-NMR spectroscopy is used. Furthermore, the content ratio of each monomer unit in the resin is measured as follows: 1 By H-NMR The following conditions will be met. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: 30℃ Sample: Place 50 mg of resin A or resin B as the measurement sample into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as the solvent, and dissolve in a constant temperature bath at 40°C to prepare the sample.

[0094] The following explanation will use resin A as an example. obtained 1 From the 1H-NMR chart, select a peak from among those attributed to the components of monomer unit M1 that is independent of the peaks attributed to the components of other monomer units, and calculate the integral value i1 of this peak. Similarly, from among the peaks attributed to the constituent elements of monomer unit M2, a peak independent of the peaks attributed to the constituent elements of monomer units derived from other monomers is selected, and the integral value i2 of this peak is calculated. Similarly, from among the peaks attributed to the monomer unit M3 component, a peak independent of the peaks attributed to monomer unit components derived from other monomers is selected, and the integral value i3 of this peak is calculated. The integral value I1 of the peaks attributed to the methylene group in the polymer main chain of the resin containing monomer unit M1 is calculated. Similarly, calculate the integral value I2 of the peak attributed to the methylene group in the polymer main chain of the resin containing monomer unit M2. Similarly, calculate the integral value I3 of the peak attributed to the methylene group in the polymer main chain of the resin containing monomer unit M3.

[0095] The content of monomer unit M1 is determined using the above integral values ​​i1, i2, i3 and I1, I2, I3 as follows. Note that n1, n2, n3, N1, N2, and N3 are the number of hydrogen atoms in the constituent element to which the peak of interest belongs for each part. n1 corresponds to i1, n2 corresponds to i2, n3 corresponds to i3, N1 corresponds to I1, N2 corresponds to I2, and N3 corresponds to I3. Percentage of monomer unit M1 (mol%) ={(i1 / n1) / (I1 / N1)}×100 Similarly, the content ratios of monomer unit M2 and monomer unit M3 are determined as follows. Percentage of monomer unit M2 content (mol%) ={(i2 / n2) / (I2 / N2)}×100 Percentage of monomer unit M3 content (mol%) ={(i3 / n3) / (I3 / N3)}×100 Resin B can be analyzed using the same procedure.

[0096] <Calculation of tetrahydrofuran-insoluble content in resins and toners> 10g of resin or toner is accurately weighed and placed in cylindrical filter paper (Toyo Filter Paper Co., Ltd. No. 84), and Soxhlet extraction is performed with 200ml of tetrahydrofuran (THF) for 20 hours. After that, the cylindrical filter paper is removed and vacuum-dried at 40°C for 20 hours, and the residue mass is measured. The amount of tetrahydrofuran (THF)-insoluble toner is then calculated using the following formula. THF insoluble content = (residue mass / toner mass before Soxhlet extraction) × 100 (mass %)

[0097] <Measurement of the weight-average molecular weight (Mw) of tetrahydrofuran-soluble components in resins and toners> The weight-average molecular weight Mw of the THF-soluble components of resins and toners is measured by gel permeation chromatography (GPC) as follows. The 200 mL THF solution used in the above insoluble component measurement was filtered through a solvent-resistant membrane filter, "Myshori Disc" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain the sample solution. The sample solution was prepared so that the concentration of THF-soluble components was 0.8% by mass. The measurement was performed under the following conditions. Equipment: HLC8120 GPC (Detector: RI) (Manufactured by Tosoh Corporation) Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0ml / min Oven temperature: 40.0℃ Sample injection volume: 0.10 ml

[0098] For calculating the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Co., Ltd.) is used.

[0099] <Method for measuring the weight-average particle size (D4) and number-average particle size (D1) of toner> The measurement device used is the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the included dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter). The measurement is performed using 25,000 effective measurement channels. The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to a concentration of approximately 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter) can be used. Before performing the measurements and analysis, the dedicated software was configured as follows.

[0100] In 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 Particle 10.0 μm" (manufactured by Beckman Coulter). Press the "Measure Threshold / Noise Level Button" to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement". In the dedicated software's "Pulse to Particle Size Conversion Settings" screen, set the bin spacing to logarithmic particle size, the particle size bins to 256 particle size bins, and the particle size range from 2 μm to 60 μm. The specific measurement method is as follows:

[0101] (1) Pour approximately 200 ml of the electrolytic solution into a 250 ml round-bottom glass beaker specifically designed for the Multisizer 3, set it on the sample stand, and stir the mixture with the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Place approximately 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker. Add "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant. Add 0.3 ml of a diluted solution prepared by diluting the product (manufactured by [company name]) three times by mass with deionized water. (3) Prepare an ultrasonic dispersant "Ultrasonic Dispension System Tetra150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120W, which incorporates two oscillators with an oscillation frequency of 50kHz, with their phases shifted by 180 degrees. Add 3.3 liters of deionized water to the water tank of the ultrasonic dispersant, and add 2 ml of Contaminon N to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic aqueous solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add 10 mg of toner to the electrolytic aqueous solution in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to 10-40°C as appropriate. (6) Using a pipette, the electrolyte aqueous solution from (5) containing dispersed toner is dropped into the round-bottom beaker from (1) placed in the sample stand, and the concentration is adjusted to 5%. The measurement is then continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight-average particle size (D4) and the number-average particle size (D1). 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), and when the dedicated software is set to graph / number%, the "average diameter" on the "Analysis / number statistics (arithmetic mean)" screen is the number-average particle size (D1).

[0102] <Identification of the unit structure of organosilicon polymers forming organosilicon polymer moieties or protrusions in resin A, and measurement of the proportion of each unit structure> NMR is used to identify the unit structure of the organosilicon polymer that forms protrusions on the surface of resin A or the toner particles, and to measure the proportion of each unit structure. The protrusions of the organosilicon polymer separated from resin A or toner using the method described above are used as a sample. The means for separating the protrusions are as follows. Dissolve 1 g of toner in 31 g of chloroform in a vial and disperse. Prepare the dispersion by treating it with an ultrasonic homogenizer for 30 minutes. Ultrasonic processing equipment: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.) Microchip: Stepped microchip, tip diameter φ2mm Microchip tip position: Center of the glass vial, 5mm above the bottom of the vial. Ultrasound conditions: Intensity 30%, 30 minutes At this time, the vial is cooled with ice water while applying ultrasound to prevent the dispersion from rising in temperature.

[0103] The dispersion was transferred to a 50 mL glass tube for a swing rotor and then centrifuged in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) until it reached 58.33 S. -1Then, centrifuge is performed under conditions of 30 minutes. When measuring toner, materials other than the protrusions on the surface of the toner particles can be removed by taking a sample of the upper layer of the glass tube after centrifugation. A chloroform solution containing an organosilicon polymer is taken, and the chloroform is removed by vacuum drying (40°C / 24 hours) to obtain a sample of the organosilicon polymer that forms the protrusions on the surface of the toner particles. When measuring resin A, the upper layer of the glass tube after centrifugation is collected to obtain the sample.

[0104] Using the above sample, the relative abundance of each unit structure in the resin containing the organosilicon polymer, and the proportion of silicon atoms taking the T2 unit structure and the proportion of silicon atoms taking the T3 unit structure relative to the total amount of silicon atoms in the organosilicon polymer, were determined in the solid. 29 Measurement and calculation are performed using Si-NMR. In the organosilicon polymer, the hydrocarbon group represented by R is, 13 Confirmation is performed by 13C-NMR.

[0105] ≪ 13 Measurement conditions for C-NMR (solid state) Equipment: JEOLRESONANCE JNM-ECX500II Sample tube: 3.2mmφ Sample: Resin A or a sample of organosilicon polymer forming a protrusion. Measurement temperature: room temperature Pulse mode: CP / MAS Measurement nuclear frequency: 123.25MHz ( 13 C) Reference substance: Adamantane (external standard: 29.5ppm) Sample rotation speed: 20kHz Contact time: 2ms Delay time: 2 seconds Total number of times: 1024 Under the above conditions, the methyl group (Si-CH3), ethyl group (Si-C2H5), propyl group (Si-C3H7), butyl group (Si-C4H9), and pentyl group (Si-C5H) bonded to the silicon atom are as follows: 11 ), hexyl group (Si-C6H13 The presence or absence of a signal caused by a phenyl group (Si-C6H5), etc., is used to identify the hydrocarbon group represented by R.

[0106] The structure that bonds to Si in organosilicon compounds is solid 29 Identified by Si-NMR. Solid 29 In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional group bonded to the Si in each unit structure of the organosilicon polymer. By identifying the position of each peak using a standard sample, the structure bonded to Si can be identified. Furthermore, the abundance ratio of each unit structure can be calculated from the obtained peak area.

[0107] solid 29 The specific measurement conditions for Si-NMR are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DD / MAS method 29 Si 45° Sample tube: Zirconia 3.2mmφ Sample: Filled in a test tube in powder form. Sample rotation speed: 10kHz Relaxation delay: 180s Scan: 2000 After measurement, solid 29 From the Si-NMR spectrum, multiple silane components with different substituents and bonding groups in the organosilicon polymer in the resin or toner particles are separated into peaks corresponding to the following X1, X2, X3, and X4 structures by curve fitting, and further peaks originating from each structure such as the T2 unit structure and T3 unit structure are separated. Curve fitting is performed using EXcalibur for Windows® version 4.2 (EX series), software for the JNM-EX400 manufactured by JEOL Ltd. The measurement data is loaded by clicking "1D Pro" from the menu icon. Next, "Curve fitting function" is selected from "Command" in the menu bar to perform curve fitting. Curve fitting is performed for each component so that the difference between the composite peak (the summation of each peak obtained by curve fitting) and the peak in the measurement result (composite peak difference) is minimized. The structure shown as X3 below is the T3 unit structure in this disclosure. X1 structure: (Ri)(Rj)(Rk)SiO 1 / 2 (A1) X2 structure: (Rg)(Rh)Si(O 1 / 2 )2(A2) X3 structure: RmSi(O 1 / 2 )3(A3) X4 structure: Si(O 1 / 2 )4(A4) TIFF0007877103000009.tif169170

[0108] In formulas (A1), (A2), and (A3), Ri, Rj, Rk, Rg, Rh, and Rm represent organic groups such as hydrocarbon groups having 1 to 6 carbon atoms, halogen atoms, hydroxyl groups, acetoxy groups, or alkoxy groups bonded to silicon. After peak separation, the sum of all integral values ​​in D, T, and Q units for which the chemical shift is in the range of -140 to 100 ppm is calculated and taken as the sum of the peak areas corresponding to silicon atoms in the organosilicon polymer moiety. If you need to examine the structure in more detail, please refer to the above. 13 C-NMR and 29 Along with the Si-NMR measurement results 1 Identification may also be performed based on the results of 1H-NMR measurements.

[0109] <Analytical method using time-of-flight secondary ion mass spectrometry (TOF-SIMS)> The equipment used and measurement conditions are as follows. • Measurement device: nanoTOF II (product name, manufactured by ULVAC-PHI, Inc.) • Primary ion species: Bi 3++ • Acceleration voltage: 30kV • Primary ion current: 0.05 pA • Repetition frequency: 8.2kHz • Raster Mode: Unbunch • Raster size: 100μm x 100μm • Measurement mode: Positive • Neutralizing electron gun: Used • Measurement time: 600 seconds • Sample preparation: Toner core particles are fixed onto an indium sheet. • Sample pretreatment: None When analyzing toner particles, the toner particles are spread on top of cellophane tape (registered trademark, Nichiban Co., Ltd.), and then adhered with more cellophane tape. The adhered cellophane tape is peeled off, and the cellophane tape with the remaining toner particles is fixed to an indium sheet for measurement. A scanning electron microscope (SEM) is used to measure the un-deposited toner core particles and confirm that toner core particles without surface protrusions have been obtained. The evaluation is performed using ULVAC-PHI standard software (TOF-DR) based on the mass number of Si ions and fragment ions originating from the resin or organosilicon compound in the toner core particles. Determine the peak intensity (P(Si)) derived from silicon with mass number 28 (m / z28) and the sum of the peak intensities (P(T)) of all ions with mass numbers from 1 to 1850.

[0110] <Method for measuring the content of resin A in toner> The structure and compositional analysis of resin A in the toner were performed using a nuclear magnetic resonance (NMU) spectrometer. 1 H-NMR, 13 This can be performed using 1C-NMR. The apparatus used is described below. The sample used is resin A, which is separated from the toner using the method described above. Nuclear magnetic resonance apparatus ( 1 H-NMR, 13 (C-NMR) Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 The content of resin A in the toner can be calculated by determining the molar composition ratio from the signal integration ratio (area ratio) obtained in the NMR measurement described above. The weight composition ratio is calculated by multiplying the molar composition ratio by the molecular weight of each compound, and the content of resin A in the toner can then be determined from this.

[0111] <Method for measuring the average height H and average diameter R of protrusions on the surface of toner particles> Observe the protrusions on the surface of the toner particles using the following method. Using the Hitachi High-Tech AFM5500M scanning probe microscope (SPM), force curves are measured and derived for the protrusions formed by organosilicon polymers on the surface of toner particles and the surface layer of toner core particles. The cantilever (hereinafter also referred to as the probe) used is the SI-DF3P2 sold by Hitachi High-Tech Fielding Co., Ltd. The SPM used for measurement is calibrated in the XYZ directions in advance, and the radius of curvature of the probe tip is measured in advance. The radius of curvature of the probe tip is measured using a probe evaluation sample such as "TGT1-NT-MDT" sold by Hitachi High-Tech Fielding Co., Ltd. The value of the tip radius of curvature is selected to allow measurement of the toner core particle surface without contact with the convex portion. In this disclosure, a value of 7 nm is used. Measurements are performed in dynamic force mode. For toner particle measurement, conductive double-sided tape is first attached to the sample stage of the scanning probe microscope, and toner particles are sprayed onto it. Then, excess toner particles are removed from the sample stage by air blowing to prepare the measurement sample. The shape of this sample is then measured using a scanning probe microscope (AFM5500M). Next, the protrusions and the surface of the toner core particles are identified and observed within a 1 μm × 1 μm area on the surface of the toner particles. The concave areas during shape measurement correspond to the surface of the toner core particles, and the convex areas correspond to the convex parts of the toner particles. For the toner particles, 50 toner particles with a particle size equal to the weight-average particle size (D4) of the toner particles are selected and used for measurement. After shape measurement, the tilt correction of the obtained 1 μm × 1 μm measurement data is performed, and then the maximum surface height Sp and the width Sz / Smax from the maximum peak to the minimum valley of the surface are calculated. The tilt correction of the measurement data is performed using AFM5000II, the analysis software included with AFM5500M, and the correction is performed by applying surface correction to the measurement data in the order of first-order surface correction, second-order surface correction, and third-order surface correction. In this disclosure, the tilt correction is performed on the measurement data by performing analysis processing in the order of first-order tilt correction (first-order surface correction), second-order tilt correction (second-order surface correction), and third-order tilt correction (third-order surface correction) using the above analysis software. Sp represents the maximum height from the outermost surface of a toner particle to the apex of a protrusion within a 1 μm × 1 μm area, and Sz / Smax represents the maximum diameter of the protrusion. Sp can be calculated by referring to the Sp value displayed when the surface roughness analysis is launched in the analysis tab of the analysis software for the data after tilt correction. When the obtained Sp is taken as the height of the protrusion h1 (nm), the maximum heights of the protrusion apex h1 to h50 for 50 toner particles are determined using the above method, and the average value of h1 to h50 is taken as the average height of the protrusion H (nm). Furthermore, Sz / Smax can be calculated by referring to the Sz / Smax value displayed when the surface roughness analysis is launched in the analysis tab of the analysis software, using the data after tilt correction. When the obtained Sz / Smax is taken as the maximum diameter r1 (nm) of the protrusions, the maximum diameters r1 to r50 of the protrusions of 50 toner particles are determined using the above method, and the average number of r1 to r50 is taken as the average diameter R (nm) of the protrusions.

[0112] <Method for identifying plasticizers in toner particles> The structure and compositional analysis of plasticizers in toner particles are performed using a nuclear magnetic resonance (NMU) spectrometer. 1 H-NMR, 13 This can be performed using 1C-NMR. The apparatus used is described below. The sample may also be toner particles obtained from toner. Nuclear magnetic resonance apparatus ( 1 H-NMR, 13 (C-NMR) Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 [Examples]

[0113] The toner of this disclosure will be described in detail below with reference to manufacturing examples and embodiments. However, these are not intended to limit the scope of this disclosure. Unless otherwise specified, all "parts" and "%" in the manufacturing examples and embodiments refer to mass.

[0114] <Example of manufacturing aqueous dispersion of resin A-1> Two hundred parts of xylene were charged into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube, and refluxed under a nitrogen stream. As monomers, • Styrene monomer 72.0 parts Butyl acrylate 25.0 parts • Lauryl acrylate 3.0 parts • 3-(trimethoxysilyl)propyl methacrylate 0.08 parts The mixture was added dropwise to the reaction vessel while stirring, and held for 10 hours. Subsequently, the solvent was removed by distillation, and the mixture was dried under reduced pressure at 40°C to obtain a vinyl resin. In a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube, 200.0 parts of methyl ethyl ketone were charged, and 99.88 parts of the vinyl resin obtained above and 0.12 parts of methyltrimethoxysilane were added and dissolved. Next, 40.0 parts of a 1.0 mol / L potassium hydroxide aqueous solution were added in stages, and after stirring for 1 minute, 500.0 parts of deionized water were added dropwise in stages to emulsify the mixture. The resulting emulsion is subjected to vacuum distillation to remove the solvent, and then ion-exchanged water is added to adjust the resin concentration to 20%. Fat A A water dispersion of -1 was obtained.

[0115] <Examples of manufacturing aqueous dispersions of resins A-2 to A-13> Aqueous dispersions of resins A-2 to A-13 were obtained in the same manner as the production example of the aqueous dispersion of resin A-1, except that the types and amounts of various monomers used in the aqueous dispersion of resin A-1 were changed as shown in Table 1.

[0116] <Manufacturing example of resin A-14> (Main resin manufacturing process) The following materials were placed in an autoclave equipped with a vacuum device, water separator, nitrogen gas introduction device, temperature measuring device, and stirring device, and the reaction was carried out for 5 hours at atmospheric pressure and 200°C under a nitrogen atmosphere. • Bisphenol A-propylene oxide 2.0 molar adduct 71.2 parts Terephthalic acid 28.0 parts • Tetrabutoxytitanate 0.2 parts After that, the following materials were added and the mixture was reacted at 220°C for 3 hours. • Trimellitic acid 0.8 parts • Tetrabutoxytitanate 0.3 parts The reaction was further carried out under reduced pressure of 10-20 mmHg for 2 hours. The resulting resin was dissolved in chloroform, and this solution was added dropwise to ethanol, reprecipitated, and filtered to obtain the main polyester resin.

[0117] (Amidation process) 400.0 parts of N,N-dimethylacetamide was dissolved in 100.0 parts of the above polyester resin, and the following materials were added and the mixture was stirred at room temperature for 5 hours to allow the reaction to proceed. • 3-aminopropyltrimethoxysilane 2.00 parts • Triethylamine 3.7 parts • Condensing agent (DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazine-2-yl)-4-methylmorpholinium chloride) 3.7 parts After the reaction was complete, the mixture was added dropwise to methanol, reprecipitated, and filtered to produce resin A-14, in which the carboxyl groups in the polyester and the amino groups in the aminosilane were amidated. The physical properties of the obtained resin A-14 are shown in Table 2.

[0118] [Table 1] [Table 2]

[0119] In Table 2, the weight-average molecular weight Mw represents the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of each resin.

[0120] <Example of manufacturing resin B-1> Two hundred parts of xylene were charged into a reaction vessel equipped with a stirrer, condenser, thermometer, and nitrogen inlet tube, and refluxed under a nitrogen stream. As monomers, • Styrene monomer 98.0 parts Butyl acrylate 2.0 parts The mixture was added dropwise to the reaction vessel while stirring and held for 10 hours. After that, the solvent was removed by distillation, and the mixture was dried under reduced pressure at 40°C to obtain resin B-1 with a weight-average molecular weight of 3000.

[0121] <Manufacturing examples of resins B-2 to B-4> Resins B-2 to B-4 were obtained in the same manner as the production example of resin B-1, except that the monomer composition of resin B-1 was changed to the monomer composition shown in Table 3. [Table 3]

[0122] In Table 3, the weight-average molecular weight Mw represents the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of each resin.

[0123] <Example of Polyester Resin A Production> The following materials were placed in an autoclave equipped with a vacuum device, water separator, nitrogen gas introduction device, temperature measuring device, and stirring device, and the reaction was carried out for 5 hours at atmospheric pressure and 200°C under a nitrogen atmosphere. • Bisphenol A-propylene oxide 2.0 molar adduct 71.2 parts Terephthalic acid 28.0 parts • Tetrabutoxytitanate 0.2 parts After that, the following materials were added and the mixture was reacted at 220°C for 3 hours. • Trimellitic acid 0.8 parts • Tetrabutoxytitanate 0.3 parts The reaction was further carried out under reduced pressure of 10-20 mmHg for 2 hours. The resulting resin was dissolved in chloroform, and this solution was added dropwise to ethanol, reprecipitation occurred, and the mixture was filtered to obtain a polyester resin with a weight-average molecular weight of 15,000 and no THF-insoluble components.

[0124] <Examples of toner manufacturing> <Example of Toner 1 manufacturing> [Toner composition preparation process] (Preparation of polymerizable monomer composition 1) • Styrene 25.0 parts • Carbon Black 5.0 parts The above materials were placed in an attritor (manufactured by Nippon Coke Industries Co., Ltd.), and then dispersed using 1.7 mm diameter zirconia particles at 220 rpm for 5.0 hours. After the zirconia particles were removed, a colorant dispersion 1 containing dispersed pigment was prepared.

[0125] Next, the following materials were added to the colorant dispersion 1. • Styrene 47.0 parts n-butyl acrylate 24.7 parts • Lauryl acrylate 3.0 parts • Hexanediol diacrylate 0.1 part • Polyester resin A 2.0 parts ·Resin B-1 10.0 parts • Release agent (hydrocarbon wax, melting point: 79°C) 5.0 parts • Plasticizer (ethylene glycol distearate) 10.0 parts Next, as a dissolution and dispersion step, the above materials were kept warm at 65°C and uniformly dissolved and dispersed at 500 rpm using a TK homomixer to prepare polymerizable monomer composition 1.

[0126] (Adjustment of water-based medium 1) 390.0 parts of deionized water were placed in a reaction vessel, 11.2 parts of sodium phosphate (dodecahydrate) were added, and the mixture was kept warm at 65°C for 1.0 hour while purging with nitrogen. The mixture was stirred at 12,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). While maintaining stirring, a calcium chloride aqueous solution, prepared by dissolving 7.4 parts of calcium chloride (dihydrate) in 10.0 parts of deionized water, was added to the reaction vessel all at once 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 6.0, and aqueous medium 1 was prepared.

[0127] [Granulation process] While maintaining the temperature of aqueous medium 1 at 70°C and the rotation speed of the stirring device at 12500 rpm, a polymerizable monomer composition was added to aqueous medium 1, and 7.0 parts of t-butyl peroxypivalate, a polymerization initiator, were added. Granulation was then carried out for 10 minutes while maintaining the stirring speed at 12500 rpm.

[0128] [Polymerization step I] The high-speed stirring device was replaced with a stirrer equipped with propeller blades, and polymerization was carried out for 5.0 hours while stirring at 200 rpm and maintaining a temperature of 70°C.

[0129] [Polymerization step II] After polymerization step I was completed, the mixture was heated to 85°C and maintained thereafter. 0.08 parts of 3-methacryloxypropyltrimethoxysilane and 0.12 parts of methyltrimethoxysilane were added and the mixture was stirred for 5 minutes. Then, 1.0 part of a 0.1% by mass aqueous solution of potassium persulfate was added, and the polymerization reaction was carried out for 1 hour. After 1 hour, a 1 mol / L aqueous solution of sodium hydroxide was added to adjust the pH to 9.0. Furthermore, the residual monomer was removed by raising the temperature to 98°C and heating for 3.0 hours, after which the temperature was lowered to 55°C.

[0130] [Surface Treatment Process II] The obtained slurry was adjusted to a slurry concentration of 30.0% by adding deionized water heated to 55°C. Then, 4.0 parts of methyltrimethoxysilane were added to the adjusted slurry, and a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 9.5. After pH adjustment, the mixture was maintained at 55°C for 5.0 hours while stirring was continued. Subsequently, the temperature was lowered to 25°C.

[0131] [Washing process] The slurry obtained by the above method was adjusted to pH 1.5 with 1 mol / L hydrochloric acid and stirred for 1.0 hour. Then, it was filtered and dried while washing with deionized water to obtain Toner 1. The constituent materials and process conditions of Toner 1 are shown in Tables 4 and 5, and the physical properties are shown in Tables 6-1, 6-2, and 7.

[0132] <Manufacturing examples for toners 2-6, 15, 24, and 31-33> In the manufacturing example of toner 1, the constituent materials of the toner were changed to those shown in Table 4, and each process was performed as follows: Toners 2-6, 15, 24, and 31-33 were obtained in the same manner as in the manufacturing example of toner 1, except that the conditions for production were changed as shown in Table 5. The physical properties of the obtained toners 2-6, 15, 24, and 31-33 are shown in Tables 6-1 and 6-2.

[0133] <Example of Toner 7 manufacturing> [Toner composition preparation process, granulation process, and polymerization process I] In the example of manufacturing toner 1, the toner composition preparation step, granulation step, and polymerization step I were carried out in the same manner as described in Table 4, except that the toner constituent materials were used.

[0134] [Polymerization step III] After polymerization step I was completed, the temperature was raised to 98°C and heated for 4.0 hours to remove residual monomers. The temperature was then lowered to 25°C.

[0135] [Surface treatment process I] While stirring the slurry obtained in polymerization step III, an aqueous sodium carbonate solution was added to adjust the pH to 8.5. An aqueous dispersion of resin A-1 was added thereto such that the added amount of the solid content became 5.0 parts, and stirring was carried out for 15 minutes. Subsequently, the temperature of the dispersion of toner core particles to which resin particles adhered was maintained by heating at 80°C, and stirring was continued for 1 hour. Thereafter, it was cooled to 55°C.

[0136] [Surface treatment step II] Ion-exchanged water heated to 55°C was added to the slurry obtained in surface treatment step I to adjust the slurry concentration to 30.0%. Thereafter, 4.0 parts by mass of methyltrimethoxysilane was added to the slurry with adjusted concentration, and further an aqueous sodium hydroxide solution of 1 mol / L was added to adjust the pH to 9.5. After adjusting the pH, 55°C was maintained for 5.0 hours while maintaining stirring. Subsequently, the temperature was decreased to 25°C.

[0137] [Washing step] The slurry obtained by the above method was adjusted to pH 1.5 with 1 mol / L hydrochloric acid, stirred for 1.0 hour, and then filtered and dried while washing with ion-exchanged water to obtain toner 7. The constituent materials and process conditions of toner 7 are shown in Tables 4 and 5, and the physical properties are shown in Tables 6-1 and 6-2.

[0138] [Production examples of toners 8 to 10, 12 to 14, 18 to 23, 26, 28, and 29][[ID=ID=19]] In the production example of toner 7, toners 8 to 10, 12 to 14, 18 to 23, 26, 28, and 29 were obtained in the same manner as the production example of toner 7, except that the constituent materials of the toner were changed to those shown in Table 3 and the conditions in each step were changed as shown in Table 5. The physical properties of the obtained toners 8 to 10, 12 to 14, 18 to 23, 26, 28, and 29 are shown in Tables 6-1 and 6-2.

[0139] [Production example of toner 11] [Toner composition adjustment step, granulation step, polymerization step I, and polymerization step III] In the manufacturing example of Toner 1, the toner composition preparation process, granulation process, and polymerization process I were carried out in the same manner as in the manufacturing example of Toner 7, except that the toner constituent materials were as listed in Table 3. Polymerization process III was also carried out in the same manner as in the manufacturing example of Toner 7.

[0140] [Washing process] The slurry obtained in polymerization step III was cooled to 55°C, stirred for 5 hours, and then cooled to 25°C. The cooled slurry was adjusted to pH 1.5 with 1 mol / L hydrochloric acid and stirred for 1.0 hour. After washing with deionized water, it was filtered and dried to obtain toner particles 11.

[0141] [External addition process] To 100 parts of the obtained toner particles 11, 4.0 parts of sol-gel silica fine particles with a number-average particle size of 40 nm, surface-treated with 25% by mass of hexamethyldisilazane, were added and mixed in a Henschel mixer (FM-10 model, manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) to obtain toner 11. The temperature of the Henschel mixer was adjusted so that the temperature of the mixture reached 30°C. The physical properties of the obtained toner 11 are shown in Tables 6-1 and 6-2.

[0142] <Manufacturing examples of toners 16, 17, 27, and 30> In the manufacturing example of toner 1, the toner composition preparation step, granulation step, and polymerization step I were carried out in the same manner as in the manufacturing example of toner 7, except that the toner constituent materials were as listed in Table 4. Polymerization step III was then carried out in the same manner as in the manufacturing example of toner 7. Subsequently, surface treatment step II and cleaning step were carried out in the same manner as in the manufacturing example of toner 1 to obtain toners 16, 17, 27, and 30. The constituent materials and process conditions for the obtained toners 16, 17, 27, and 30 are shown in Tables 4 and 5, and their physical properties are shown in Tables 6-1 and 6-2.

[0143] <Manufacturing example of toner 25> In the manufacturing example of toner 1, the toner composition preparation step, granulation step, and polymerization step I were carried out in the same manner as in the manufacturing example of toner 7, except that the toner constituent materials were as listed in Table 4. Polymerization step III was then carried out in the same manner as in the manufacturing example of toner 7. Subsequently, the washing step and external additive step were carried out in the same manner as in the manufacturing example of toner 11 to obtain toner 25. The constituent materials and process conditions of the obtained toner 25 are shown in Tables 4 and 5, and the physical properties are shown in Tables 6-1 and 6-2.

[0144] [Table 4]

[0145] In addition to the materials shown in Table 4 above, in the manufacturing of each toner, 5.0 parts of carbon black, 5.0 parts of hydrocarbon wax, and 0.1 parts of hexanediol diacrylate were added in the toner composition preparation step, similar to Toner 1. The abbreviations in Table 4 have the following meanings: Plasticizer 1: Ethylene glycol distearate Plasticizer 2: Hexanediol dimyris Te te Plasticizer 3: Hexanediol dibehenate

[0146] [Table 5]

[0147] The abbreviations in Table 5 have the following meanings: S1:3-Methacryloxypropyltrimethoxysilane S2: Methyltrimethoxysilane S3: 40nm sol-gel silica

[0148] [Table 6-1]

[0149] In Table 6-1, the weight-average molecular weight Mw indicates the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of each toner.

[0150]

Table 6-2

[0151] The evaluation of the toner was carried out according to the evaluation method described below. <Fixing Evaluation> The fixing evaluation was carried out using a modified color laser printer [Canon LBP9600C] with the fixing unit removed so that an unfixed image could be output. A fixing test of the unfixed image was carried out using a fixing tester modified so that the fixing temperature and process speed could be adjusted. The evaluation was carried out by filling 300 g of Toner 1 into the black cartridge from which the toner had been removed.

[0152] [Evaluation of Low-Temperature Fixing Property] Using the above-mentioned modified LBP9600C, as the recording medium, color laser copier paper (manufactured by Canon Marketing Japan Inc., GF-C081, 80 g / m 2 ) was used to output an unfixed image. The unfixed image was formed in a portion 1.0 cm from the upper end in the paper passing direction as an unfixed image having a length of 2.0 cm and a width of 15.0 cm so that the toner loading amount would be 0.40 mg / cm 2 . Under normal temperature and humidity environment (23°C, 60% RH), the process speed was set to 300 mm / s and the fixing line pressure was set to 27.4 kgf. With the initial temperature set to 120°C, the set temperature was sequentially increased by 5°C, and the fixing of the above unfixed image was carried out at each temperature. Regarding the above image, the evaluation of the low-temperature fixing property was carried out by evaluating the low-temperature fixing start point. The evaluation of the low-temperature fixing start point was based on the value of the image density reduction rate as an evaluation index. The image density was measured using an X-Rite color reflection densitometer (Series 500: manufactured by X-Rite). First, the image density at the center of the fixed image was measured, and then, with respect to the portion where the image density was measured, 4.9 kPa (50 g / cm 2The image surface was rubbed five times at a speed of 0.2 m / s with Silbon paper (Dasper K-3) under a load of ) and the image density was measured again. The percentage decrease in image density before and after rubbing was then calculated and used as the image density decrease rate value. Low temperature The starting point for lateral fixation is the lowest temperature at which the image density reduction rate falls below 10.0%. Low-temperature fixation was evaluated according to the following criteria. (Evaluation Criteria) A: The fixing start point on the low-temperature side is 140°C or lower. B: The fixing start point on the low-temperature side is between 145°C and 155°C. C: The fixing start point on the low-temperature side is between 160°C and 170°C. D: Low-temperature fixing start point is 175°C or higher

[0153] [Evaluation of resistance to hot offset] Using the modified LBP9600C mentioned above, the recording medium used was color lasercopier paper (Canon Marketing Japan, GF-C081, 80g / m²). 2 The unfixed image was output using ). The unfixed image had a toner load of 0.20 mg / cm². 2 To achieve this, an unfixed image measuring 2.0 cm vertically and 15.0 cm horizontally was formed 1.0 cm from the top edge in the direction of paper feeding. Under normal temperature and humidity conditions (23°C, 60%RH), the process speed was set to 330 mm / s and the fixing pressure to 27.4 kgf. The initial temperature was 190°C, and the temperature was gradually increased by 10°C at each temperature while fixing the unfixed image described above. The fixing temperature at which a hot offset occurred at the trailing edge of the evaluation paper in the paper feeding direction as it passed through the fuser was checked, and the results were evaluated based on the following evaluation criteria. (Evaluation Criteria) A: Hot offset occurs at temperatures above 220°C. B: Hot offset occurs at temperatures between 200°C and 220°C. C: Hot offset occurs at temperatures below 200°C

[0154] [Evaluation of image glossiness] In the low-temperature fixing evaluation, the evaluation was performed using images fixed at 180°C. Image glossiness was measured using a GLOSS SENSER PG-3D (NIPPON DENSHOKU IND. CO.,LTD) at a 75° angle. The evaluation criteria for image glossiness are as follows: (Evaluation Criteria) A: Gloss is 50 or more B: Gross score between 40 and 50 C: Gross is between 30 and 40 D: Gross is less than 30

[0155] <Development Evaluation> The development evaluation was performed using a modified HP Color LaserJet Enterprise M653dn with a process speed of 340 mm / s. The toner was removed from the cartridge, the inside was cleaned with compressed air, and then 250 g of toner was refilled for evaluation.

[0156] [Image overlap] To evaluate image vignetting, a 5cm x 5cm Post-it note is attached to the center of a piece of plain paper (HP Brochure Paper 200g, Glossy, HP Corporation, 200g / m² 2 ) was used. To evaluate image haze, the following conditions were met: under low temperature and low humidity conditions (temperature 15°C, humidity 10%RH), using color laser copier paper (manufactured by Canon Marketing Japan, 80g / m²). 2 Using the above method, 100 images with a 1% print density were printed with horizontal lines. Then, using plain paper with Post-it notes attached (prepared for the evaluation of image fill), one all-white image was printed in gloss paper mode. After that, the power to the main unit was turned off and the developing machine was left for 48 hours. After leaving it for 48 hours, a new sheet of plain paper with Post-it notes attached was prepared, separate from the plain paper with Post-it notes attached used above, and a completely white image was printed on it in gloss paper mode. The reflectance (%) of the non-image area and the area covered by the Post-it note on the paper output using the above method for evaluating image haze was measured using a "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.). The value obtained by subtracting the reflectance (%) of the non-image area from the reflectance (%) of the area covered by the Post-it note was taken as the initial image haze value. Furthermore, a similar evaluation was conducted using color laser copier paper (Canon, 80g / m²). 2 After printing 10,000 images with a 1% print density using horizontal lines, the image fade after durability was evaluated. Image vignetting was evaluated according to the following criteria. A lower numerical value indicates better suppression of image vignetting. (Evaluation Criteria) A: Less than 0.5% B: 0.5% or more and less than 1.5% C: 1.5% or more and less than 3.0% D: 3.0% or more

[0157] [Material contamination assessment] It is known that if a charged component is contaminated, uneven charging occurs on the photoreceptor, resulting in uneven density in the halftone image. Therefore, component contamination was evaluated by assessing the halftone gradation stability. The evaluation was performed as follows. A new conductive component was installed in the drum unit, and image output was performed. The evaluation paper used was color laser copier paper (manufactured by Canon Marketing Japan, 80 g / m²). 2 Using [a specific method / tool], 499 images with halftones printed across the entire surface were output. Then, the image density of the edges (30 mm from each of the left and right edges) and the center of the 500th evaluation sheet was measured, and the difference in density between the edges and the center was evaluated. Image density was measured using an X-Rite color reflectance densitometer (X-rite 500 Series, manufactured by X-rite). A rating of C or higher was considered good. (Evaluation Criteria) A: Concentration difference after durability evaluation is less than 0.04 B: Concentration difference after durability evaluation is 0.04 or more and less than 0.08. C: Concentration difference after durability evaluation is 0.08 or more and less than 0.12. D: Concentration difference of 0.12 or more after durability evaluation

[0158] <Transcription evaluation> [Transferability] The evaluation was conducted using a commercially available color laser printer, the Satera LBP7700C (manufactured by Canon). The toner was removed from the cartridge, the inside was cleaned with compressed air, and then toner 1 (200g) was refilled. The above cartridge was installed in the printer, and the following evaluation was performed in a low-temperature, low-humidity environment (temperature 15.0°C, humidity 10.0RH%). Ten horizontal line patterns with a print density of 1% were printed, and the initial transfer performance was evaluated. The amount of toner on the photoreceptor was 0.50 mg / cm². 2 A solid color image was printed under conditions adjusted to achieve the desired result, and the residual toner on the photoreceptor during image formation was taped off using Mylar tape. The removed tape was then placed on evaluation paper (Canon Marketing Japan, GF-C081, 80g / cm²). 2 The reflectance difference was calculated by subtracting the reflectance T0 of the paper with only tape applied from the reflectance T1 of the material applied on top. Furthermore, a durability test was conducted by printing 15,000 sheets of a horizontal line pattern with a print density of 1%, and the transferability after durability was evaluated using the same method. The reflectance was measured using a REFLECTMETER MODEL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.). Transferability was evaluated according to the following criteria. (Evaluation Criteria) A: Reflectance difference is 3.0% or less B: Reflectance difference is greater than 3.0% and less than or equal to 6.0% C: Reflectance difference is greater than 6.0% and less than or equal to 10.0% D: Reflectance difference exceeds 10.0%

[0159] In Examples 1 to 25, the above evaluations were performed using toners 1 to 24 and 33. In Comparative Examples 1 to 9, the above evaluations were performed using toners 25 to 32. The evaluation results for the toners are shown in Table 7. As shown in Table 7, the toner of Example 1 obtained good results in all evaluations.

Table 7

[0160] The present disclosure relates to the following configuration. (Configuration 1) A toner having toner particles, where the toner particles contain toner core particles containing a binder resin, the binder resin contains resin A, the resin A is a styrene-acrylic copolymer, the resin A contains 65 to 85% by mass of a monomer unit M1 represented by the following formula (1), the resin A contains 0.05 to 2.00% by mass of a monomer unit M2 containing an organosilicon polymer moiety represented by the following formula (2), the organosilicon polymer moiety has a T3 unit structure and a T2 unit structure, the solid of the resin A 29 in the DD / MAS measurement of Si-NMR, when the ratio of the peak area corresponding to the silicon atom in the organosilicon polymer moiety to the total peak area corresponding to the silicon atoms is A (%) for the peak area corresponding to the silicon atom having a T3 unit structure and B (%) for the peak area corresponding to the silicon atom having a T2 unit structure, the A and the B satisfy the following formulas (3) and (4), 0.3 ≦ A / B ≦ 2.7 (3) 62 ≦ A + B ≦ 100 (4) A toner characterized in that the weight average molecular weight Mw of the tetrahydrofuran-soluble component of the resin A by gel permeation chromatography is 50,000 to 250,000. TIFF0007877103000018.tif40170TIFF0007877l03000019.tif36170(In formula (2), L 2 is a single bond, -COO-(CH2) n - or -NH-(CH2) n - (n is an integer from 1 to 10), R <{ 2represents a hydrogen atom or a methyl group, and * represents a site bonded to the silicon atom of the organosilicon polymer moiety. L 2 is -COO-(CH2) n - in the case where the carbonyl is bonded to the carbon having R 2 and L 2 is -NH-(CH2) n - in the case where NH is bonded to the carbon having R 2 .) (Configuration 2) The toner according to Configuration 1, wherein the organosilicon polymer moiety is a polymer of an organosilicon compound having a structure represented by the following formula (5). R-Si-R a 3 Formula (5) (In Formula (5), R a each independently represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R represents an alkyl group having 1 to 6 carbon atoms.) (Configuration 3) When the peak intensity of Si obtained by time-of-flight secondary ion mass spectrometry of the toner core particles is P(Si) and the total peak intensity of all ions in the toner core particles is P(T), the toner according to Configuration 1 or 2, wherein the P(Si) and the P(T) satisfy the following formula (6). 0.004 ≦ P(Si) / P(T) ≦ 0.040 (6) (Configuration 4) The toner according to any one of Configurations 1 to 3, wherein the content of the resin A in the toner is 50% by mass or more. [ (Configuration 5) [ The toner particles have convex portions made of an organosilicon polymer on the surface of the toner core particles, [ the organosilicon polymer has a structure represented by the following formula (7), [ in the observation of the toner particle surface by a scanning probe microscope, [ when the number average diameter of the maximum diameter of the convex portions is R [ and the number average height of the convex portions is H, [ the R is 80 to 250 nm, [ the H is 25 to 10 nm, and the toner according to any one of Configurations 1 to 4. [ R-SiO3 / 2 (7) (Composition 6) The aforementioned resin A contains 3 to 10% by mass of monomer unit M3 represented by the following formula (8). or the toner described in one of configurations 1 to 5. TIFF0007877103000020.tif34170(In formula (8), L 1 Ha-COO-(CH2) n - indicates (where n is an integer from 11 to 31), L 1 The carbonyl group is bonded to the carbon atom in the main chain. 1 represents a hydrogen atom or a methyl group. (Composition 7) The toner particles contain a plasticizer, The toner according to any one of the compositions 1 to 6, wherein the plasticizer contains an ester compound of a diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms. (Composition 8) The toner particles contain resin B, The toner according to any one of configurations 1 to 7, wherein the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of resin B, determined by gel permeation chromatography, is 2000 to 7000. (Composition 9) The toner according to configuration 8, wherein the resin B contains 85 to 100% by mass of the monomer unit M1. (Composition 10) The toner according to any one of configurations 1 to 9, wherein the toner contains 0 to 10% by mass of tetrahydrofuran-insoluble matter. (Composition 11) In the monomer unit M3, L 1 The toner described in configuration 6, where n is an integer between 11 and 13.

Claims

1. A toner having toner particles, The toner particles contain toner core particles containing a binder resin, The binder resin contains resin A, The resin A is a styrene-acrylic copolymer, The resin A contains 65 to 85% by mass of monomer unit M1 represented by the following formula (1), The resin A contains 0.05 to 2.00% by mass of monomer units M2 containing an organosilicon polymer moiety represented by the following formula (2), The organosilicon polymer moiety has a T3 unit structure and a T2 unit structure, The solid of resin A ２９ In Si-NMR DD / MAS measurements, When A (%) is the ratio of the peak area corresponding to silicon atoms with a T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer moiety, and B (%) is the ratio of the peak area corresponding to silicon atoms with a T2 unit structure, A and B satisfy the following equations (3) and (4), 0.3 ≤ A / B ≤ 2.7 (3) 62 ≤ A + B ≤ 100 (4) A toner characterized in that the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of resin A, determined by gel permeation chromatography, is between 50,000 and 250,000. (In formula (2), L ２ represents a single bond, -COO-(CH ２ ) ｎ -, or -NH-(CH ２ ) ｎ - (n is an integer from 1 to 10), R ２ represents a hydrogen atom or a methyl group, and * represents the site that binds to the silicon atom of the organosilicon polymer moiety. When L ２ is -COO-(CH ２ ) ｎ -, the carbonyl binds to the carbon having R ２ ; when L ２ is -NH-(CH ２ ) ｎ -, NH binds to the carbon having R ２ .)

2. The toner according to claim 1, wherein the organosilicon polymer moiety is a polymer of an organosilicon compound having a structure represented by the following formula (5). R—Si—R ａ ３ Formula (5) (In formula (5), R ａ Each of these independently represents a halogen atom or an alkoxy group having 1 to 3 carbon atoms, and R represents an alkyl group having 1 to 6 carbon atoms.

3. When the peak intensity of Si obtained by time-of-flight secondary ion mass spectrometry of the toner core particles is denoted as P(Si), and the sum of the peak intensities of all ions in the toner core particles is denoted as P(T), The toner according to claim 1 or 2, wherein P(Si) and P(T) satisfy the following formula (6). 0.004≦P(Si) / P(T)≦0.040 (6)

4. The toner according to claim 1 or 2, wherein the content of resin A in the toner is 50% by mass or more.

5. The toner particles have protrusions made of an organosilicon polymer on the surface of the toner core particles, The organosilicon polymer has a structure represented by the following formula (7), In observing the surface of toner particles using a scanning probe microscope, Let R be the average diameter of the maximum diameter of the protrusions. When the average height of the protrusions is H, The R is 80 to 250 nm. The toner according to claim 1 or 2, wherein H is 25 to 100 nm. R-SiO ３／２ (7)

6. The toner according to claim 1 or 2, wherein the resin A contains 3 to 10% by mass of monomer unit M3 represented by the following formula (8). (In formula (8), L １ Ha-COO-(CH ２ ) ｎ It indicates - (where n is an integer from 11 to 31), L １ The carbonyl group is bonded to the carbon atom of the main chain. １ (This represents a hydrogen atom or a methyl group.)

7. The toner particles contain a plasticizer, The toner according to claim 1 or 2, wherein the plasticizer contains an ester compound of a diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms.

8. The toner particles contain resin B, The toner according to claim 1 or 2, wherein the weight-average molecular weight Mw of the tetrahydrofuran-soluble component of resin B, determined by gel permeation chromatography, is 2000 to 7000.

9. The toner according to claim 8, wherein the resin B contains 85 to 100% by mass of the monomer unit M1.

10. The toner according to claim 1 or 2, wherein the toner contains 0 to 10% by mass of tetrahydrofuran-insoluble matter.

11. L in the monomer unit M3 １ The toner according to claim 6, wherein n is an integer between 11 and 13.

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