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] The present disclosure relates to toners for use 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 image quality for printed materials, and an increase in the number of pages that can be printed per toner cartridge. In order to meet the required printable number while still being compact, it is necessary to reduce the space required for printers and toner cartridges, as well as the number of parts. In order to reduce the space required for toner cartridges, it is necessary to pack more toner into a smaller space than before.

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

[0004] Furthermore, the reduction in the number of parts can be achieved by increasing the charging stability of the toner, thereby making the charging member more compact and reducing its size. In light of this background, toners are being required to have greater stress resistance and charge stability than ever before, and as one means to achieve this, the use of resins containing organosilicon polymers is being investigated.

[0005] For example, Patent Document 1 proposes a toner that has excellent low-temperature fixing properties and is resistant to stresses such as in-machine agitation by forming a thin layer of an organosilicon polymer shell on the toner surface. Patent Document 2 proposes a method of providing an organosilicon polymer layer on the toner surface by having a vinyl resin having an organosilicon polymer moiety on the surface layer of the toner particles, thereby suppressing toner deterioration due to agitation and bleeding of materials inside the toner particles. Patent Document 3 proposes using a resin having an organosilicon polymer moiety to suppress the release of the organosilicon polymer from the toner particle surface and suppress 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] JP 2015-096948 A [Patent Document 3] JP 2020-181187 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, when using an organosilicon polymer, the thermoplasticity of the organosilicon polymer is lower than that of a general toner resin, so the fixing temperature of the toner rises. In addition, the toner viscosity is less likely to decrease during fixing. Therefore, in any of the methods of Patent Documents 1 to 3, although the resistance of the toner to stress is improved, the viscosity of the toner when melted increases. As a result, the gloss of the fixed image decreases, making it difficult to obtain a high-quality print. In some cases, the adhesiveness between the paper and the toner and the releasability between the toner and the fixing device are hindered, affecting the fixing property. Thus, it is difficult to achieve both the durability of the toner and the gloss of the image with the conventional method.

[0008] The present disclosure provides a toner that is excellent in low-temperature fixing property, hot offset resistance, and image glossiness, and is capable of maintaining 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 mass % of a monomer unit M1 represented by the following formula (1), Resin A contains 0.05 to 2.00 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, Resin A solid 29 In Si-NMR DD / MAS measurement, When the ratio of the peak area corresponding to silicon atoms of the T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer segment is A (%) and the ratio of the peak area corresponding to silicon atoms of the T2 unit structure is B (%), The A and the B satisfy the following formulas (3) and (4), 0.3≦A / B≦2.7 (3) 62≦A+B≦100 (4) The toner is characterized in that the weight average molecular weight Mw of the tetrahydrofuran soluble portion of the resin A, as determined by gel permeation chromatography, is 50,000 to 250,000. TIFF2024011644000001.tif40170TIFF2024011644000002.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 2indicates a hydrogen atom or a methyl group, and * indicates the site of bonding with the silicon atom of the organosilicon polymer moiety. 2 -COO-(CH2) n -, carbonyl is R 2 Attached to the carbon bearing L 2 -NH-(CH2) n -, NH is R 2 ) Effect 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 is capable of maintaining charge rise and transferability even after long-term use. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] In the present disclosure, the description of a numerical range such as "XX or more and YY or less" or "XX to YY" means a numerical range including the lower and upper limits, which are the endpoints, unless otherwise specified. When a numerical range is described in stages, the upper and lower limits of each numerical range can be arbitrarily combined. "Monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, one section of carbon-carbon bond in the main chain of a polymer in which a vinyl monomer is polymerized is considered to be one unit. A vinyl monomer can be represented by the following formula (C). TIFF2024011644000003.tif30170

[0012] [In formula (C), R A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group); R B represents an optional substituent.]

[0013] Organosilicon polymers are more brittle and have better stress resistance than styrene-acrylic resins and polyester resins used in toner applications. On the other hand, organosilicon polymers have strong heat resistance and lower thermoplasticity than styrene-acrylic resins and polyester resins, making them difficult to fix by themselves. In this way, resin hybridization is one way to utilize the properties of each material while balancing them. However, when an organosilicon polymer moiety is introduced into a styrene-acrylic resin or a polyester resin, the toner durability is improved compared to when a styrene-acrylic resin or a polyester resin is used alone, but the low temperature fixability and image glossiness are reduced.

[0014] One of the causes of poor low-temperature fixing ability and poor image gloss is the large molecular weight of the resin. However, it has been found that resins that have an organosilicon polymer moiety have inferior low-temperature fixing ability compared to resins that do not have an organosilicon polymer moiety, even if the molecular weight is about the same.

[0015] The present inventors suspected that because organosilicon polymers have many polar groups, when they are introduced into a resin, crosslinking occurs through non-covalent bonds due to the polar groups, and conducted extensive research. As a result, they discovered that the above problems can be solved by the following configuration.

[0016] The present disclosure relates to 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 mass % of a monomer unit M1 represented by the following formula (1), Resin A contains 0.05 to 2.00 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, Resin A solid29 In Si-NMR DD / MAS measurement, When the ratio of the peak area corresponding to silicon atoms of the T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer segment is A (%) and the ratio of the peak area corresponding to silicon atoms of the T2 unit structure is B (%), The A and the B satisfy the following formulas (3) and (4), 0.3≦A / B≦2.7 (3) 62≦A+B≦100 (4) The toner is characterized in that the weight average molecular weight Mw of the tetrahydrofuran soluble portion of the resin A, as determined by gel permeation chromatography, is from 50,000 to 250,000. TIFF2024011644000004.tif40170TIFF2024011644000005.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 2 indicates a hydrogen atom or a methyl group, and * indicates the site of bonding with the silicon atom of the organosilicon polymer moiety. 2 -COO-(CH2) n -, carbonyl is R 2 Attached to the carbon bearing L 2 -NH-(CH2) n -, NH is R 2 )

[0017] The toner has 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. TIFF2024011644000006.tif40170

[0018] TIFF2024011644000007.tif36170(In formula (2), L 2 is a single bond, -COO-(CH2) n - or -NH-(CH2) n - (n is an integer of 1 to 10 (preferably 2 to 8, more preferably 2 to 5)), R 2 is hydrogen The symbol * indicates the bond site with the silicon atom of the organosilicon polymer moiety. 2 -COO-(CH2) n -, carbonyl is R 2 Attached to the carbon bearing L 2 -NH-(CH2) n -, NH is R 2 )

[0019] When the 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 when it melts, making it impossible to fix the molten toner smoothly onto the paper, and reducing the gloss of the image.

[0020] As a result of extensive investigations, the present inventors have found that by adjusting the contents and structures of monomer units M1 and M2 in resin A to fall within specific ranges, it is possible to provide a toner that has excellent low-temperature fixing properties and high image gloss, which were previously unattainable, while maximizing the durability advantages of resins that contain organosilicon polymer moieties.

[0021] Resin A contains 65 to 85% by mass of the monomer unit M1 represented by the above formula (1). Most of the styrene-acrylic resins used for toner applications are composed of styrene monomers and vinyl monomers having an ester group. When the content of the monomer unit M1 in the resin A is less than 65% by mass, the amount of the vinyl monomer having an ester group increases relatively, and therefore the proton acceptor increases in the binder resin. In addition, the hydroxyl group of the monomer unit M2 in the resin A, which will be described in detail later, is a proton donor. Therefore, when the content of the monomer unit M1 in the resin A is less than 65% by mass, hydrogen bonds are easily formed in the binder resin, and the image glossiness decreases.

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

[0023] The content of the monomer unit M1 in the resin A is preferably 70% by mass or more, and more preferably 73% by mass or more. Also, it is preferably 83% by mass or less, and more preferably 80% by mass or less. For example, it is preferably in the range of 70 to 83% by mass, or 73 to 80% by mass.

[0024] Resin A contains 0.05 to 2.00 mass % of monomer unit M2, which contains an organosilicon polymer moiety and is represented by formula (2) above. As described above, the organosilicon polymer moiety contained in the 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 the ester groups of other resin components. Therefore, when the content of the monomer unit M2 in resin A is less than 0.05% by mass, the amount of proton donor is reduced, making it difficult for hydrogen bonds to form in the binder resin. As a result, the viscosity of the toner decreases when it is melted by the heat of the fixing device, causing hot offset and a decrease in the gloss of the image due to the surface of the fixed image becoming rough.

[0025] On the other hand, when the content of the monomer unit M2 in the resin A exceeds 2.00% by mass, the proton donor is large, and hydrogen bonds are easily formed in the binder resin, so that the viscosity of the toner when melted increases, resulting in a large number of irregularities in the fixed image and a decrease in the image gloss.

[0026] The content of the monomer unit M2 in the 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. Also, it is preferably 1.80% by mass or less, and more preferably 1.50% by mass or less. For example, it is preferably in the range of 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, or 1.00 to 1.50% by mass.

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

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

[0029] By having the T unit in the organosilicon polymer moiety, the proton donation by the hydroxyl group of the organosilicon polymer moiety can be controlled within a specific range, and the viscosity of the toner when melted can be controlled within an appropriate range. Furthermore, the T units are classified into structures such as T1 unit structures having two reactive groups such as hydroxyl groups, T2 unit structures having one reactive group such as hydroxyl groups, and T3 unit structures having no reactive groups such as hydroxyl groups. When the organosilicon polymer portion has T3 unit structures and T2 unit structures, and the ratio A of silicon atoms that take up the T3 unit structures and the ratio B of silicon atoms that take up the T2 unit structures satisfy the above formulas (3) and (4), the image can have excellent gloss and low-temperature fixability, and image fog can be suppressed.

[0030] The above A and B satisfying formulas (3) and (4) indicates that the organosilicon polymer segment contains many T2 and T3 unit structures and few T1 unit structures. The T1 unit structure is highly reactive and, due to heat during fixing, the organosilicon polymer undergoes a coupling reaction with itself, causing an increase in viscosity. Therefore, if there are many T1 unit structures in the organosilicon polymer portion, the image glossiness decreases.

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

[0032] When the value of A / B satisfies the formula (3), the toner has good charge build-up and excellent durability. An A / B ratio of less than 0.3 indicates that there are many T2 unit structures in the organosilicon polymer moiety, and therefore, as mentioned above, the number of conductive sites derived from water molecules increases, reducing the charge of the toner and causing image fog. On the other hand, an A / B ratio of more than 2.7 indicates that there are few T2 unit structures in the organosilicon polymer portion, which means that the charge build-up effect is not obtained and image fog due to charge build-up is likely to occur.

[0033] The value of A / B is preferably 0.5 or more, more preferably 1.0 or more, and even more preferably 1.5 or more. Also, it is preferably 2.5 or less, more preferably 2.3 or less, and even more preferably 2.0 or less. For example, it is preferably in the range of 0.5 to 2.5, 1.0 to 2.3, or 1.5 to 2.0.

[0034] When the value of A+B satisfies formula (4), the organosilicon polymer portion contains T3 unit structures and T2 unit structures. Since the coordinate structure is sufficiently present, the toner is less likely to thicken, and the image glossiness is improved. The value of A+B is preferably 65 or more, more preferably 70 or more, and even more preferably 75 or more. Also, it is preferably 95 or less, more preferably 90 or less, and even more preferably 85 or less. For example, preferred ranges include 65 to 95, 70 to 90, and 75 to 85.

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

[0036] The weight average molecular weight Mw of the tetrahydrofuran (THF) soluble portion of Resin A is 50,000 to 250,000 as determined by gel permeation chromatography. 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 a decrease in 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 be embedded when the toner is used for a long period of time. As a result, the charge amount of the toner decreases, and image fogging tends to occur.

[0037] The weight average molecular weight Mw of the tetrahydrofuran soluble matter of the resin A is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 or more. Also, it is preferably 240,000 or less, more preferably 230,000 or less, and even more preferably 220,000 or less. For example, it is preferably in the range of 60,000 to 240,000, 70,000 to 230,000, or 80,000 to 220,000.

[0038] It is preferable that Resin A does not contain THF insoluble matter. When Resin A contains THF insoluble matter, the organosilicon polymer moiety derived from the monomer unit M2 is insoluble in THF, and the hydroxyl groups in Resin A are far from each other, so that three-dimensional network-like hydrogen bonds are formed starting from Resin A. This network structure increases the toner viscosity when melted, and reduces the image gloss when fixed.

[0039] The present disclosure will be described in detail below in light of a more preferred scope thereof. <Regarding the resin that constitutes the toner core particles> Resin A is a styrene-acrylic resin, and may contain, as a constituent material other than the monomer unit M1 and the monomer unit M2, a polymer made of a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer.

[0040] Examples of the monofunctional polymerizable monomer 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 vinyl ketones, vinyl isopropyl ketone, and vinyl ketones.

[0041] Examples of the polyfunctional polymerizable monomer include the following. Multifunctional 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] Examples of materials constituting the monomer unit M2 include polymerizable monomers having an organosilicon polymer moiety and a vinyl-based polymerization moiety, and combinations of such polymerizable monomers with various bifunctional and trifunctional organosilicon compounds. Examples of polymerizable monomers having an organosilicon polymer moiety and a vinyl-based polymerization moiety include the following.

[0043] Trifunctional vinyl silanes such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyldiethoxymethoxysilane, vinylethoxydimethoxysilane, vinyltriisocyanatesilane, vinyltrichlorosilane, vinylmethoxydichlorosilane, vinylethoxydichlorosilane, vinyldimethoxychlorosilane, vinylmethoxyethoxychlorosilane, vinyldiethoxychlorosilane, vinyltriacetoxysilane, vinyldiacetoxymethoxysilane, vinyldiacetoxyethoxysilane, vinylacetoxydimethoxysilane, vinylacetoxymethoxyethoxysilane, vinylacetoxydiethoxysilane, vinyltrihydroxysilane, vinylmethoxydihydroxysilane, vinylethoxydihydroxysilane, vinyldimethoxyhydroxysilane, vinylethoxymethoxyhydroxysilane, and 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 moiety to which the monomer unit M2 is bonded is preferably a polymer of an organosilicon compound having a structure represented by the following formula (5). R-Si-R a Type 3(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. When the organosilicon polymer moiety is a siloxane-polymerizable vinyl polymer, it may be combined with, for example, the following organosilicon compounds, including the compound of formula (5) above. Trifunctional methylsilanes such as methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, methylacetoxymethoxyethoxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, and 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 may contain an amino group, i.e., resin A may be a resin formed by amidating a carboxy group in a polyester resin with an amino group in an aminosilane. The aminosilane is not particularly limited, but examples thereof 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-aminopropyl silicone.

[0046] Resin A preferably contains 3 to 10% by mass of monomer unit M3 represented by the following formula (8). When the content of monomer unit M3 in resin A is within the above range, sharp melting properties can be achieved in the fixing temperature range of the binder resin. As a result, low-temperature fixing properties and image glossiness are further improved, and the occurrence of hot offset can be suppressed. TIFF2024011644000008.tif34170

[0047] (In formula (8), L 1 -COO-(CH2) n -, where n is an integer of 11 to 31 (preferably 11 to 22, more preferably 11 to 13), and L 1 The carbonyl of R is attached to a carbon atom in the main chain. 1 represents a hydrogen atom or a methyl group. The content of the monomer unit M3 in the resin A is more preferably from 4 to 9 mass %, and further preferably from 5 to 8 mass %. More preferably, the monofunctional polymerizable monomer corresponding to the 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. When the content of resin A is 50% by mass or more, low-temperature fixability and image glossiness can be improved. 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 it is preferably 90% by mass or less, and more preferably 85% by mass or less.

[0049] The binder resin may contain a known resin other than the resin A. The known resins include, in particular, There are no limitations to the type of resin, but examples include styrene-acrylic resin, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, mixed resins or composite resins thereof. Styrene-acrylic resin and polyester resin are preferred in that they are inexpensive, easily available, and have excellent low-temperature fixing properties. Furthermore, it is more preferred to include styrene-acrylic resin in that they have excellent development durability. Examples of the constituent material of the styrene-acrylic resin used as the binder resin include polymers composed of monofunctional polymerizable monomers or polyfunctional polymerizable monomers given as examples of the constituent materials other than the monomer unit M1 and the monomer unit M2 of the resin A, and 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. From the viewpoint of improving low-temperature fixability, the weight average molecular weight Mw of the tetrahydrofuran soluble portion of resin B measured 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 further preferably 3000 to 6000.

[0051] When the weight average molecular weight Mw of the tetrahydrofuran soluble portion of resin B is within the above range, resin B has a lower viscosity than the binder resin, and therefore acts as an adhesive with paper, improving low temperature fixability.

[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 mass %, more preferably 95 to 100 mass %. When the content of monomer unit M1 in resin B is within the above range, hydrogen bonds are unlikely to be formed with other resins such as resin A, and low-temperature fixability can be improved.

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

[0054] <Existence of organosilicon polymer in toner core particles> The toner particles contain an organosilicon polymer on the surface of the toner core particle. As described above, the toner core particles contain resin A, and resin A has monomer unit M2 containing an organosilicon polymer moiety. From the viewpoint of charge rise, it is preferable that the organosilicon polymer moiety contained in monomer unit M2 is 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 the toner core particle is defined as P(Si) and the sum of the peak intensities of all ions in the toner core particle is defined as P(T), it is preferable that the following formula (6) is satisfied. 0.004≦P(Si) / P(T)≦0.040 (6)

[0055] When P(Si) / P(T) is within the above range, the organosilicon polymer is present in a large amount on the surface of the toner core particles, and the toner charge build-up is improved due to the conductive effect, and image fogging is suppressed. In addition, the presence of the organosilicon polymer on the surface of the toner core particles makes the fixing surface flat. This results in improved image gloss.

[0056] The value of P(Si) / P(T) is preferably 0.008 or more, more preferably 0.010 or more. Also, it is preferably 0.030 or less, more preferably 0.020 or less. For example, it is preferably in the range of 0.008 to 0.030, or 0.010 to 0.020. The value of P(Si) / P(T) can be increased by making the organosilicon polymer moiety present in a large amount on the surface of the toner core particle. Specifically, this can be controlled by adjusting the method of adding a resin containing an organosilicon polymer moiety or the method of adding and reacting a monomer having an organosilicon polymer moiety in the polymerization step during toner production described below.

[0057] The toner particles preferably have convex portions on the surface of the toner core particles, and the convex portions are preferably formed of an organosilicon polymer. The organosilicon polymer has a structure represented by the following formula (7), and when the toner particle surface is observed with a scanning probe microscope, R is the number average diameter of the maximum diameter of the convex portions, and H is the number average height of the convex portions, and R is 80 to 250 nm, and H is 25 to 100 nm. When the above is satisfied, transferability can be improved. R-SiO 3 / 2 (7) (In formula (4), R represents an alkyl group, an alkenyl group, an acyl group, an aryl group, or a methacryloxyalkyl group.)

[0058] When the number-average diameter R is 80 nm or more, the contact area between the surface of the toner core particle and the protrusions does not become too small, and the force received from the members during fixing is easily transmitted from the protrusions to the surface of the toner core particle, thereby promoting deformation at the initial stage of fixing. Furthermore, when the number-average diameter R is 250 nm or less, the area of ​​the toner core particle surface covered by each protrusion can be prevented from becoming too large, which is advantageous in terms of low-temperature fixability.

[0059] The number-average diameter R is more preferably 90 nm or more, and even more preferably 100 nm or more. Also, it is more preferably 200 nm or less, and even more preferably 150 nm or less. For example, it is preferably in the range of 90 to 200 nm, or 100 to 150 nm. The number-average diameter R can be increased by gradually increasing the pH conditions for the condensation reaction of the organosilicon polymer when forming the organosilicon polymer protrusions on the surface, while the number-average diameter R can be decreased by increasing the pH during the condensation reaction of the organosilicon polymer or decreasing the concentration of the organosilicon polymer.

[0060] When the average height H is 25 nm or more, the area of ​​the contact surface between the toner and the fixing roller does not become too large, so that the force acting on the toner can be concentrated on the contact surface, and deformation at the initial stage of fixing can be promoted. Furthermore, when the average height H is 100 nm or less, the distance from the contact surface of the convex portion with the member to the surface of the toner core particle can be prevented from becoming too large, which is advantageous in terms of fixability.

[0061] The average height H is more preferably 30 nm or more, and even more preferably 40 nm or more. Also, it is more preferably 80 nm or less, and even more preferably 60 nm or less. For example, it is preferably in the range of 30 to 80 nm, or 40 to 60 nm. The average height H can be increased by increasing the concentration of the organosilicon polymer when the organosilicon polymer protrusions are formed on the surface, while the average height H can be decreased by decreasing the concentration of the organosilicon polymer when the organosilicon polymer protrusions are formed on the surface.

[0062] The organosilicon compound for obtaining the organosilicon polymer can be any conventionally known organosilicon compound without any particular limitation, and is preferably 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 independently represents a halogen atom or an alkoxy group, and R represents an alkyl group, an alkenyl group, an aryl group, an acyl group, or a methacryloxyalkyl group.

[0063] Specific 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; vinyltrimethoxysilane Silane, trifunctional vinyl silane compounds such as vinyl triethoxy silane; trifunctional allyl silane compounds such as allyl trimethoxy silane, allyl triethoxy silane, allyl diethoxy methoxy silane, allyl ethoxy dimethoxy silane; trifunctional gamma-methacryloxypropyl silane compounds such as gamma-methacryloxypropyl trimethoxy silane, gamma-methacryloxypropyl triethoxy silane, gamma-methacryloxypropyl diethoxy methoxy silane, gamma-methacryloxypropyl ethoxy dimethoxy silane; and the like trifunctional silane compounds.

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

[0065] Examples of color pigments for yellow 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 the black colorant, carbon black, aniline black, acetylene black, titanium black, and those toned to black using the above-mentioned yellow, magenta and cyan colorants can be used.

[0066] These colorants can be used alone or in mixture, or in the form of a solid solution. The colorant is selected in terms of hue angle, chroma, brightness, light resistance, OHP transparency, and dispersibility in toner particles. These colorants are preferably used in an amount of 1 to 20 parts by mass per 100 parts by mass of the binder resin or the polymerizable monomer that forms the binder resin.

[0067] Furthermore, a magnetic material can be used as the black colorant. Examples of the magnetic material include magnetite, hematite, and ferrite. When using a magnetic material as the black colorant, it is preferable to use a magnetic material whose surface has been hydrophobized. Examples of the hydrophobizing agent used in this case include a silane coupling agent and a titanium coupling agent.

[0068] The magnetic material preferably has a number-average particle size of 2 μm or less, 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 the polymerizable monomer that forms the binder resin.

[0069] The toner core particles may contain a release agent. As the release agent, any known release agent can be used without any particular limitation. Specific examples thereof include the following. 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, sazol wax, and montan acid ester wax; and partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax, partial esters of 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 content of the release agent is preferably 2.5 to 40.0 parts by mass, more preferably 3.0 to 15.0 parts by mass, based on 100 parts by mass of the binder resin. These release agents may be used alone or in combination of two or more kinds, and it is preferable to use a combination of a hydrocarbon wax and an ester wax from the viewpoint of fixability. When two or more kinds of release agents are used in combination, it is preferable that the total content of the release agents is within the above range.

[0071] The toner core particles preferably contain a plasticizer, which 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 requirements, it is possible to efficiently plasticize the resin constituted mainly of the monomer unit M1, and to improve the low-temperature fixability.

[0072] Examples of the plasticizer containing an ester compound of a diol having 2 to 6 carbon atoms and an aliphatic monocarboxylic acid having 14 to 22 carbon atoms include ethylene glycol distearate, ethylene glycol dibehenate, ethylene glycol dimyritate, ethylene glycol dilactate, 1,4-butanediol distearate, hexanediol dimyritate ... All dibehenate, hexanediol stearate, etc. can be used. The content of the plasticizer is preferably 5 to 25 parts by mass, and more preferably 10 to 15 parts by mass, based on 100 parts by mass of the binder resin or the polymerizable monomer.

[0073] A charge control agent may be used in the toner. The charge control agent can keep the chargeability of the toner stable. As the charge control agent, various charge control agents that have been conventionally used in toner applications can be used. The charge control agent is added in an amount of 0.01 to 10.00 parts by mass with respect to 100 parts by mass of the binder resin or polymerizable monomer.

[0074] In order 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 any known fluidity improver can be used. Specific examples include the following. 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 which have been hydrophobized; silica fine powders such as wet-process silica and dry-process silica, or surface-treated silica fine powders obtained by subjecting such silica fine powders to surface treatment with a treating agent such as a silane coupling agent, a titanium coupling agent or silicone oil.

[0075] The fluidity improver is preferably added in an amount of 0.01 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 fixability. In addition, the above-mentioned fluidity improver preferably has a number average particle diameter (D1) of 4 to 120 nm for primary particles.

[0076] The toner can be used as a one-component or two-component developer in any development method. When used as a two-component developer, the average particle size of the carrier is preferably 10 to 100 μm, more preferably 20 to 50 μm. When the carrier and the toner 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 diameter 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 diameter is within the above range, good fluidity is obtained, and the latent image can be developed faithfully.

[0078] The following describes the method for producing the toner, but the method is not limited to these. There are no particular limitations on the method for incorporating resin A containing an organosilicon polymer moiety into the toner core particles, and any known method can be used. For example, in the kneading and pulverizing method, there is a method in which resin A containing an organosilicon polymer moiety is kneaded together with the toner constituent materials, or a method in which resin A containing an organosilicon polymer moiety is adhered to the surface of toner base particles and then heat-treated to fix the resin A to obtain toner core particles. In addition, examples of wet manufacturing methods include a method in which resin A containing an organosilicon polymer moiety is dissolved together with the toner constituent materials to form particles, a method in which resin A containing an organosilicon polymer moiety is added after the formation of toner base particles and then heat-treated to fix the particles to obtain toner core particles, and a method in which a reactive organosilicon compound is added together with a polymerization initiator during particle formation, and incorporated into the toner base particles to obtain toner core particles.

[0079] Among these, the suspension polymerization method is preferred from the viewpoint of facilitating orientation of the resin A containing the organosilicon polymer moiety on the surface of the toner core particle. A method for producing toner particles using the suspension polymerization method will be described below. First, a polymerizable monomer capable of producing a binder resin and various other materials as required are mixed and dissolved or dispersed using a disperser to prepare a polymerizable monomer composition (dissolving step). The various materials include a colorant, a release agent, a plasticizer, a charge control agent, a polymerization initiator, a chain transfer agent, and the like. The dispersing machine may be a homogenizer, a ball mill, a colloid mill, or an ultrasonic dispersing machine.

[0080] Next, the polymerizable monomer composition is introduced into an aqueous medium containing a dispersion aid, and droplets of the polymerizable monomer composition are prepared using a high-speed dispersing machine such as a high-speed stirrer or an ultrasonic dispersing machine (granulation process). Thereafter, the polymerizable monomer in the droplets is polymerized to obtain toner core particles (polymerization step).

[0081] The polymerization initiator may be mixed when the polymerizable monomer composition is prepared, or may be mixed into the polymerizable monomer composition immediately before forming droplets in the aqueous medium. Alternatively, the compound may be added in a state dissolved in the polymerizable monomer or in another solvent, as required, during or after the granulation of the droplets, that is, immediately before the start of the polymerization reaction. After the polymerizable monomer is polymerized to obtain a binder resin, a solvent removal treatment is performed as necessary to obtain a toner. A dispersion of the core particles may be obtained.

[0082] The resin containing the organosilicon polymer moiety may be added during (i) the dissolution step, or (ii) after completion of the polymerization step, a particle dispersion of the resin containing the organosilicon polymer moiety may be added and thermally fixed. Alternatively, the organosilicon compound may be incorporated into the binder resin by adding a vinyl monomer containing the organosilicon polymer moiety and a polymerization initiator during the polymerization step (iii). From the viewpoint of arranging the organosilicon compound moiety near the surface, the method (ii) or (iii) is preferred.

[0083] When the binder resin is obtained by the emulsion aggregation method or the suspension polymerization method, the polymerizable monomer may be any conventionally known monomer without any particular limitation. Specific examples of the polymerizable monomer include the vinyl monomers exemplified for the binder resin.

[0084] There are no particular limitations on the method for providing the organosilicon polymer moiety on the surface of the toner core particle, and any known method can be used. For example, a method of adding a monomer containing an organosilicon polymer during the polymerization process of the toner core particles described above to obtain toner core particles containing a resin having an organosilicon polymer moiety can be mentioned. Also included is a method of polymerizing a monomer containing an organosilicon polymer in an aqueous medium in which the toner core particles are dispersed, and a method of polymerizing a monomer containing an organosilicon polymer in advance and adding the obtained polymer during the production process of the toner core particles to obtain toner core particles containing a resin having an organosilicon polymer moiety can be mentioned.

[0085] There are no particular limitations on the monomer, so long as it contains an organosilicon polymer, and any known monomer can be used. Specific examples include the following: Trifunctional silane compounds having a methacryloxyalkyl group as a substituent, such as γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxyoctyltrimethoxysilane, γ-methacryloxypropyldiethoxymethoxysilane, and γ-methacryloxypropylethoxydimethoxysilane; trifunctional silane compounds having an acryloxyalkyl group as a substituent, such as γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-acryloxyoctyltrimethoxysilane, γ-acryloxypropyldiethoxymethoxysilane, and γ-acryloxypropylethoxydimethoxysilane;

[0086] The dispersion aid used in the granulation step may be a known dispersion stabilizer, surfactant, etc. Specifically, the following may be mentioned as the dispersion stabilizer. Inorganic dispersion stabilizers such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, aluminum phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina; and organic dispersion stabilizers such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, and starch.

[0087] The surfactants include the following: Anionic surfactants such as alkyl sulfate salts, 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] Among these, it is preferable to use an inorganic dispersion stabilizer, and a dispersion stabilizer containing a phosphate such as tricalcium phosphate, hydroxyapatite, magnesium phosphate, zinc phosphate, or aluminum phosphate is preferable. It is more preferable to include a stabilizer.

[0089] As the polymerization initiator, any known polymerization initiator can be used without any particular limitation. Specific examples thereof include the following. 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, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1-hydroperoxide, pertriphenylacetic acid-tert-hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl permethoxyacetate, per-N-(3-tolyl)-tert-butyl palmitate-tert-butylbenzoyl peroxide Peroxide-based polymerization initiators represented by t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy pivalate, t-butyl peroxy isobutyrate, t-butyl peroxy neodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, etc.; azo- or diazo-based polymerization initiators represented by 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc.; and the like.

[0090] The toner of the present disclosure can be used in conventionally known image forming apparatuses without any particular restrictions, for example, image forming apparatuses using a one-component contact development system, a two-component development system, or a one-component jumping development system.

[0091] The methods for measuring various physical properties will be described below. <Separation of Resin A and Resin B from Toner> The various physical properties can also be measured using resin A and other materials such as resins separated from the toner by the following method. Weigh out 10.0 g of toner particles, place them in a cylindrical filter paper (Toyo Roshi No. 84) and place them in a Soxhlet extractor. Extract for 20 hours using 200 mL of THF as the solvent, and the solid obtained by removing the solvent from the extract is the THF-soluble portion of the toner. The THF-soluble portion contains resin A and resin B. This is done multiple times to obtain the required amount of THF-soluble portion.

[0092] For the solvent gradient elution method, a gradient preparative HPLC (Shimadzu LC-20AP high pressure gradient preparative system, Waters SunFire preparative column 50mmφ250mm) is used. The column temperature is 30°C, the flow rate is 50mL / min, and the mobile phase uses acetonitrile as a poor solvent and THF as a good solvent. 0.02g of the THF soluble fraction obtained by extraction is dissolved in 1.5mL of THF to prepare the sample for separation. The mobile phase starts with a composition of 100% acetonitrile, and 5 minutes after the sample injection, the ratio 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. Which fraction components are resin A and which are resin B will be described later. 1 It can be distinguished by H-NMR measurement.

[0093] <Method for identifying monomer units contained in Resin A and Resin B and measuring the content ratio of each monomer unit> To identify the various monomer units in Resin A and Resin B, 1 H-NMR spectroscopy is used. The content ratio of each monomer unit in the resin is measured by 1 H-NMR The test is carried out under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times: 64 Measurement temperature: 30℃ Sample: 50 mg of resin A or resin B is placed in a sample tube with an inner diameter of 5 mm as a measurement sample, deuterated chloroform (CDCl3) is added as a solvent, and this is dissolved in a constant temperature bath at 40°C to prepare the sample.

[0094] The following explanation will be given using Resin A as an example. Obtained 1 From the H-NMR chart, a peak that is independent of the peaks that are assigned to the components of the monomer unit M1 and the components of other monomer units is selected, and the integral value i1 of this peak is calculated. Similarly, from the peaks attributable to the components of the monomer unit M2, a peak independent of the peaks attributable to the components of the monomer units derived from other monomers is selected, and the integral value i2 of this peak is calculated. Similarly, from the peaks attributable to the monomer unit M3 constituent element, a peak independent of the peaks attributable to the constituent elements of the monomer units derived from other monomers is selected, and the integral value i3 of this peak is calculated. The integral value I1 of the peak attributable to the methylene group of the polymer main chain of the resin containing the monomer unit M1 is calculated. Similarly, the integral value I2 of the peak assigned to the methylene group of the polymer main chain of the resin containing the monomer unit M2 is calculated. Similarly, the integral value I3 of the peak assigned to the methylene group of the polymer main chain of the resin containing the monomer unit M3 is calculated.

[0095] The content of the monomer unit M1 is determined using the integral values ​​i1, i2, i3 and I1, I2, I3 as follows: where n1, n2, n3, N1, N2, and N3 are the numbers of hydrogen atoms in the constituent elements to which the peak of interest for each site belongs. 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. Content of monomer unit M1 (mol%) ={(i1 / n1) / (I1 / N1)}×100 Similarly, the content ratio of the monomer unit M2 and the monomer unit M3 is determined as follows. Content of monomer unit M2 (mol%) ={(i2 / n2) / (I2 / N2)}×100 Content of monomer unit M3 (mol%) ={(i3 / n3) / (I3 / N3)}×100 Resin B can also be analyzed using a similar procedure.

[0096] <Calculation of Tetrahydrofuran Insoluble Content of Resin and Toner> 10 g of resin or toner is weighed out and placed in a cylindrical filter paper (Toyo Roshi No. 84), and subjected to Soxhlet extraction with 200 ml of tetrahydrofuran (THF) for 20 hours. The cylindrical filter paper is then removed and vacuum dried at 40°C for 20 hours, the mass of the residue is measured, and the amount of tetrahydrofuran (THF) insoluble matter of the toner is calculated using the following formula. Amount of THF insoluble matter = (mass of residue / mass of toner before Soxhlet extraction) x 100 (mass%)

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

[0098] In calculating the molecular weight of a sample, a molecular weight calibration curve prepared using standard polystyrene resins (e.g., trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0099] <Method of measuring weight average particle diameter (D4) and number average particle diameter (D1) of toner> The measurement device used is a precision particle size distribution measurement device using the pore electrical resistance method, "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.), equipped with a 100 μm aperture tube. The measurement conditions are set and the measurement data is analyzed using the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.). The measurement is performed with an effective measurement channel count of 25,000. The electrolyte solution used for the measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter). Before carrying out the measurements and analyses, the dedicated software was set up as follows.

[0100] In the "Change standard measurement method (SOMME)" screen of the dedicated software, set the total count number in the 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" (Beckman Coulter). Press the "Threshold / Noise level measurement button" to automatically set the threshold and noise level. In addition, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement." In the "Pulse to particle size conversion setting" screen of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm to 60 μm. The specific measurement method is as follows.

[0101] (1) Pour about 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made exclusively for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture flush" function of the dedicated software to remove dirt and air bubbles from inside the aperture tube. (2) About 30 ml of the electrolyte solution is placed in a 100 ml flat-bottom glass beaker. Add to the beaker a 10% by weight aqueous solution of "Contaminon N" (a pH 7 neutral detergent for cleaning precision measuring instruments, made of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) as a dispersant. Add 0.3 ml of a solution prepared by diluting 100% ethanol (manufactured by Epson) three times with ion-exchanged water. (3) Prepare an ultrasonic disperser "Ultrasonic Dispension System Tetra150" (manufactured by Nikkaki Bios Co., Ltd.) that has two built-in oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees, and has an electrical output of 120 W. Place 3.3 L of ion-exchanged water in the ultrasonic disperser's water tank, and add 2 mL of Contaminon N to this water tank. (4) The beaker (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolyte solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, 10 mg of toner is added little by little to the electrolyte solution and dispersed. Then, ultrasonic dispersion treatment is continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to 10 to 40°C. (6) Using a pipette, add the electrolyte solution (5) in which the toner is dispersed to the round-bottom beaker (1) placed in the sample stand, and adjust the measurement concentration to 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software that comes with the device, and the weight average particle size (D4) and number average particle size (D1) are calculated. Note that when the dedicated software is set to graph / volume %, the "average diameter" on the "analysis / volume statistics (arithmetic mean)" screen is the weight average particle size (D4), 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 structures of the organosilicon polymer forming the organosilicon polymer sites or protrusions in resin A and measurement of the proportion of each unit structure> NMR is used to identify the unit structures of the organosilicon polymer moiety in resin A or the organosilicon polymer that forms the convex portions on the toner particle surface and to measure the proportion of each unit structure. The convex portions of the resin A separated by the above method or the organosilicon polymer separated from the toner are used as samples. The means for separating the convex portions is as follows. 1 g of toner is placed in a vial, dissolved in 31 g of chloroform, and dispersed in an ultrasonic homogenizer for 30 minutes to produce a dispersion liquid. Ultrasonic processing device: Ultrasonic homogenizer VP-050 (manufactured by Taitec Co., Ltd.) Microchip: Step type microchip, tip diameter φ2mm Tip position of the microchip: Center of the glass vial, 5 mm above the bottom of the vial Ultrasonic conditions: 30% intensity, 30 minutes During this process, ultrasonic waves are applied while the vial is cooled with ice water so as not to increase the temperature of the dispersion liquid.

[0103] The dispersion liquid was transferred to a glass tube (50 mL) for a swing rotor, and centrifuged at 58.33 S in a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.). -1Centrifugation is performed under the conditions of 100° C., 30 minutes, and 100° C. When measuring toner, materials other than the convex parts on the toner particle surface can be removed by collecting the upper layer of the glass tube after centrifugation. A chloroform solution containing the organosilicon polymer is collected and the chloroform is removed by vacuum drying (40°C / 24 hours) to obtain a sample of the organosilicon polymer that forms the convex parts on the toner particle surface. When measuring Resin A, the upper layer of the glass tube after centrifugation is collected to obtain a sample.

[0104] Using the above samples, the ratio of the abundance of each unit structure in the resin containing the organosilicon polymer, the proportion of silicon atoms having T2 unit structures and the proportion of silicon atoms having T3 unit structures relative to the total amount of silicon atoms in the organosilicon polymer were measured using solid 29 Measured and calculated by Si-NMR. The hydrocarbon group represented by R in the organosilicon polymer is 13 Confirm by C-NMR.

[0105] << 13 C-NMR (solid) measurement conditions≫ Equipment: JEOL RESONANCE JNM-ECX500II Sample tube: 3.2mmφ Sample: Resin A or a sample of the organosilicon polymer that forms the convex portion 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: 2s Number of times accumulated: 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 11 ), hexyl group (Si-CH13 The hydrocarbon group represented by R above is confirmed based on the presence or absence of signals due to a phenyl group (Si-C6H5) or the like.

[0106] The structure of the bond to the Si in the organosilicon compound is 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 of each unit structure in the organosilicon polymer. By identifying the positions of each peak using a standard sample, the structure that bonds to Si can be identified. In addition, the abundance ratio of each unit structure can be calculated from the obtained peak area.

[0107] solid 29 Specifically, the Si-NMR measurement conditions 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: Powdered material filled into test tube Sample rotation speed: 10kHz Relaxation delay: 180s Scan:2000 After the measurement, 29 From the Si-NMR spectrum, a plurality of silane components having different substituents and bonding groups of the organosilicon polymer in the resin or toner particles are separated into peaks of the following X1 structure, X2 structure, X3 structure, and X4 structure by curve fitting, and further the peaks derived from each structure such as the T2 unit structure, T3 unit structure, etc. are separated. Curve fitting is performed using EXcalibur for Windows (registered trademark) version 4.2 (EX series), software for JNM-EX400 manufactured by JEOL Ltd. Click "1D Pro" from the menu icon to load the measurement data. Next, select "Curve fitting function" from "Command" on the menu bar to perform curve fitting. Curve fitting is performed for each component so that the difference (composite peak difference) between the composite peak obtained by combining the peaks obtained by curve fitting and the peak of the measurement result is minimized. The structure represented by X3 below is the T3 unit structure in the present 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) TIFF2024011644000009.tif169170

[0108] In the formulae (A1), (A2), and (A3), Ri, Rj, Rk, Rg, Rh, and Rm each represent an organic group such as a hydrocarbon group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, an acetoxy group, or an alkoxy group bonded to a silicon atom. After peak separation, the sum of all integral values ​​of D units, T units, and Q units present in the chemical shift range of -140 to 100 ppm is calculated, and this is taken as the total peak area corresponding to the silicon atoms in the organosilicon polymer moiety. If you need to check the structure in more detail, 13 C-NMR and 29 Along with the Si-NMR measurement results 1 The identification may be performed by the results of H-NMR measurement.

[0109] <Time-of-Flight Secondary Ion Mass Spectroscopy (TOF-SIMS) Analysis Method> The equipment and measurement conditions used are shown below. Measurement device: nanoTOF II (product name, manufactured by ULVAC-PHI, Inc.) Primary ion species: Bi 3++ Acceleration voltage: 30kV Primary ion current: 0.05pA Repetition rate: 8.2kHz Raster mode: Unbunch Raster size: 100μm×100μm Measurement mode: Positive Neutralization gun: Used Measurement time: 600 seconds Sample preparation: Toner core particles fixed on an indium sheet Sample pretreatment: None When performing an analysis based on toner particles, the toner particles are laid out on cellophane tape (registered trademark, Nichiban Co., Ltd.), and then further cellophane tape is attached on top of that. The cellophane tape is then peeled off, and the cellophane tape with the remaining toner particles is fixed to an indium sheet for measurement. Measurement is performed with a scanning electron microscope (SEM) without deposition, and it is confirmed that toner core particles without protrusions on the surface have been obtained. Using ULVAC-PHI's standard software (TOF-DR), evaluation is performed based on the mass numbers of Si ions and fragment ions originating from the resin or organosilicon compound in the toner core particles. The peak intensity (P(Si)) attributable to silicon with mass number 28 (m / z28) and the sum of the peak intensities of all ions with mass numbers from 1 to 1850 (P(T)) are determined.

[0110] <Method for measuring the content of Resin A in toner> The structure of resin A in the toner was identified and the composition was analyzed using a nuclear magnetic resonance spectrometer ( 1 H-NMR, 13 The measurement can be performed using C-NMR. The equipment used is described below. The sample used is resin A separated from the toner by the above method. Nuclear magnetic resonance ( 1 H-NMR, 13 C-NMR) Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of times accumulated: 64 The content of resin A in the toner can be calculated by determining the molar composition ratio from the signal integral ratio (area ratio) in the above NMR measurement. 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 is calculated from the weight composition ratio.

[0111] <Method of measuring the average height H and average diameter R of protrusions on the surface of a toner particle> The protrusions on the surfaces of the toner particles are observed by the following method. Using a scanning probe microscope (SPM) manufactured by Hitachi High-Tech Corporation, "AFM5500M," force curves are measured and derived for the protrusions made of organosilicon polymer on the surface of the toner particles, and for the surface layer of the toner core particles. The cantilever (hereinafter also referred to as the probe) used is "SI-DF3P2" sold by Hitachi High-Tech Fielding Corporation. The SPM used for the measurement is calibrated in advance for positional accuracy in the XYZ directions, and the tip curvature radius of the probe of the cantilever used for the measurement is measured in advance. The radius of curvature of the tip of the probe is measured using a probe evaluation sample "TGT1-NT-MDT" sold by Hitachi High-Tech Fielding Co., Ltd. The value of the tip radius of curvature is selected so that the surface layer of the toner core particle can be measured without contacting the protrusion. In this disclosure, a radius of curvature of 7 nm is used. Measurements are performed in dynamic force mode. To measure toner particles, first, conductive double-sided tape is attached to the sample stage of the scanning probe microscope, and toner particles are sprayed onto it. Excess toner particles are then removed from the sample stage by air blowing, creating a measurement sample. The shape of this sample is measured using a scanning probe microscope (AFM5500M). The protrusions and the surfaces of the toner core particles are identified and observed within an area of ​​1 μm×1 μm on the surface of the toner particles. The concave portions during shape measurement correspond to the surfaces of the toner core particles, and the convex portions correspond to the convex portions of the toner particles. As the toner particles, 50 toner particles having a particle diameter equal to the weight average particle diameter (D4) of the toner particles are selected and used as the measurement target. After the shape measurement, the obtained 1 μm×1 μm measurement data is subjected to tilt correction, and then the maximum surface height Sp and the width from the maximum peak to the minimum valley of the surface Sz / Smax are calculated. The tilt correction of the measurement data is performed using the AFM5000II, which is the analysis software provided with the AFM5500M, by performing surface correction on the measurement data in the order of linear surface correction, quadratic surface correction, and cubic surface correction. In the present disclosure, tilt correction is performed on the measurement data by performing analysis processing in the above analysis software in the order of linear tilt correction (linear surface correction), quadratic tilt correction (quadratic surface correction), and cubic tilt correction (cubic surface correction). Sp means the maximum height from the outermost surface of a toner particle to the apex of a protrusion in a range of 1 μm×1 μm, and Sz / Smax means the maximum diameter of the protrusion. Sp can be calculated by referring to the Sp value displayed when starting the surface roughness analysis in the analysis tab of the above analysis software for data that has been subjected to tilt correction. When the obtained Sp is set as the height h1 (nm) of the protrusion, the maximum heights h1 to h50 of the apex of the protrusion of 50 toner particles are obtained by the above method, and the number average value of h1 to h50 is set as the average height H (nm) of the protrusion. In addition, Sz / Smax can be calculated by referring to the Sz / Smax value displayed when starting the surface roughness analysis in the analysis tab of the above analysis software for the data that has been subjected to the tilt correction. When the obtained Sz / Smax is set as the maximum diameter r1 (nm) of the protrusions, the maximum diameters r1 to r50 of the protrusions of 50 toner particles are obtained by the above method, and the number average value of r1 to r50 is set as the average diameter R (nm) of the protrusions.

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

[0113] The toner of the present disclosure will be specifically described below with reference to production examples and examples. However, these do not limit the present disclosure in any way. In the production examples and examples, "parts" and "%" are all based on mass unless otherwise specified.

[0114] <Production Example of Water Dispersion of Resin A-1> 200 parts of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, and refluxed under a nitrogen stream. Styrene monomer 72.0 parts Butyl acrylate 25.0 parts Lauryl acrylate 3.0 parts 0.08 parts 3-(trimethoxysilyl)propyl methacrylate The mixture was added dropwise to the reaction vessel with stirring and maintained for 10 hours. After that, the solvent was removed by distillation, and the mixture was dried at 40°C under reduced pressure to obtain a vinyl resin. A reaction vessel equipped with a condenser, a thermometer, and a nitrogen inlet tube was charged with 200.0 parts of methyl ethyl ketone, 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 aqueous potassium hydroxide solution was gradually added and the mixture was stirred for 1 minute, after which 500.0 parts of ion-exchanged water was gradually added dropwise to emulsify the mixture. The obtained emulsion was distilled under reduced pressure to remove the solvent, and ion-exchanged water was added to adjust the resin concentration to 20%, to obtain an aqueous dispersion of resin particles A-1.

[0115] <Production Examples of Water Dispersions of Resins A-2 to A-13> Aqueous dispersions of Resins A-2 to A-13 were obtained in the same manner as in 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] <Production Example of Resin A-14> (Main resin manufacturing process) The following materials were charged into an autoclave equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and a reaction was carried out under a nitrogen atmosphere at normal pressure and 200°C for 5 hours. Bisphenol A-propylene oxide 2.0 mole adduct 71.2 parts Terephthalic acid 28.0 parts Tetrabutoxytitanate 0.2 parts The following materials were then added and reacted at 220°C for 3 hours. Trimellitic acid 0.8 parts Tetrabutoxytitanate 0.3 parts The reaction was further carried out for 2 hours under a reduced pressure of 10 to 20 mmHg. The obtained resin was dissolved in chloroform, and the solution was dropped into ethanol for reprecipitation and filtration to obtain the main polyester resin.

[0117] (Amidation process) 100.0 parts of the above polyester resin was dissolved in 400.0 parts of N,N-dimethylacetamide, and the following materials were added thereto, and the mixture was stirred at room temperature for 5 hours to cause a reaction. ·3-Aminopropyltrimethoxysilane 2.00 parts ·Triethylamine 3.7 parts Condensing agent (DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride) 3.7 parts After the reaction was completed, the reaction mixture was dropped into methanol, reprecipitated, and filtered to produce Resin A-14, in which the carboxyl group in the polyester and the amino group in the aminosilane were amidated. The physical properties of the resulting resin A-14 are shown in Table 2.

[0118] [Table 1] [Table 2]

[0119] In Table 2, the weight average molecular weight Mw indicates the weight average molecular weight Mw of the tetrahydrofuran soluble portion of each resin.

[0120] <Production Example of Resin B-1> 200 parts of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, and refluxed under a nitrogen stream. Styrene monomer 98.0 parts Butyl acrylate 2.0 parts The mixture was mixed and dropped into the reaction vessel while stirring, and the mixture was maintained for 10 hours. After that, the solvent was removed by distillation, and the mixture was dried at 40° C. under reduced pressure to obtain a resin B-1 having a weight average molecular weight of 3,000.

[0121] <Production Examples of Resins B-2 to B-4> Resins B-2 to B-4 were obtained in the same manner as in 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 indicates the weight average molecular weight Mw of the tetrahydrofuran soluble portion of each resin.

[0123] <Production Example of Polyester Resin A> The following materials were charged into an autoclave equipped with a pressure reducing device, a water separating device, a nitrogen gas introducing device, a temperature measuring device, and a stirrer, and a reaction was carried out under a nitrogen atmosphere at normal pressure and 200°C for 5 hours. Bisphenol A-propylene oxide 2.0 mole adduct 71.2 parts Terephthalic acid 28.0 parts Tetrabutoxytitanate 0.2 parts The following materials were then added and reacted at 220°C for 3 hours. Trimellitic acid 0.8 parts Tetrabutoxytitanate 0.3 parts The reaction was further carried out for 2 hours under a reduced pressure of 10 to 20 mmHg. The obtained resin was dissolved in chloroform, and the solution was dropped into ethanol for reprecipitation and filtration to obtain a polyester resin having a weight average molecular weight of 15,000 and containing no THF insoluble matter.

[0124] <Toner manufacturing example> <Toner 1 Manufacturing Example> [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 and Engineering Co., Ltd.) and further dispersed using zirconia particles with a diameter of 1.7 mm at 220 rpm for 5.0 hours. The zirconia particles were then removed to prepare colorant dispersion 1 in which the pigment was dispersed.

[0125] Next, the following materials were added to Colorant Dispersion 1: Styrene 47.0 parts n-Butyl acrylate 24.7 parts Lauryl acrylate 3.0 parts Hexanediol diacrylate 0.1 parts 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, in the dissolving / dispersing step, the above materials were kept at 65° C. and uniformly dissolved and dispersed at 500 rpm using a TK homomixer to prepare a polymerizable monomer composition 1.

[0126] (Preparation of aqueous medium 1) 11.2 parts of sodium phosphate (12-hydrate) was added to a reaction vessel containing 390.0 parts of ion-exchanged water, and the mixture was kept at 65°C for 1.0 hours while purging with nitrogen. The mixture was stirred at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). While maintaining the stirring, an aqueous calcium chloride solution in which 7.4 parts of calcium chloride (2-hydrate) was dissolved in 10.0 parts of ion-exchanged 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 the aqueous medium 1 at 70° C. and the rotation speed of the stirring device at 12,500 rpm, the polymerizable monomer composition was charged into the aqueous medium 1, and 7.0 parts of t-butyl peroxypivalate as a polymerization initiator was added. Granulation was continued for 10 minutes while maintaining the stirring device at 12,500 rpm.

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

[0129] [Polymerization step II] After the polymerization step I was completed, 0.08 parts of 3-methacryloxypropyltrimethoxysilane and 0.12 parts of methyltrimethoxysilane were added and stirred for 5 minutes while the temperature was raised to 85°C. Then, 1.0 parts of a 0.1% by mass aqueous potassium persulfate solution was added, and the polymerization reaction was carried out for 1 hour. After 1 hour, a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 9.0. The temperature was then raised to 98°C and heated for 3.0 hours to remove residual monomers, and then the temperature was lowered to 55°C.

[0130] [Surface treatment process II] Ion-exchanged water heated to 55°C was added to the obtained slurry to adjust the slurry concentration to 30.0%. Then, 4.0 parts of methyltrimethoxysilane was added to the slurry with the adjusted concentration, and 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 9.5. After the pH adjustment, the mixture was kept at 55°C for 5.0 hours while continuing to stir. The temperature was then lowered to 25°C.

[0131] [Cleaning 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, and then washed with ion-exchanged water, filtered and dried 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] <Production Examples of Toners 2-6, 15, 24, 31-33> In the manufacturing example of Toner 1, the constituent materials of the toner were changed to those shown in Table 4, and Except for changing the conditions for the preparation as shown in Table 5, the same procedure as in the preparation example of toner 1 was carried out to obtain toners 2 to 6, 15, 24, and 31 to 33. The physical properties of the obtained toners 2 to 6, 15, 24, and 31 to 33 are shown in Tables 6-1 and 6-2.

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

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

[0135] [Surface treatment process I] While stirring the slurry obtained in the polymerization step III, an aqueous sodium carbonate solution was added to adjust the pH to 8.5. The aqueous dispersion of resin A-1 was added thereto so that the solid content was 5.0 parts, and the mixture was stirred for 15 minutes. Next, the temperature of the dispersion of the toner core particles to which the resin particles were attached was heated and maintained at 80°C, and stirring was continued for 1 hour. Then, the mixture was cooled to 55°C.

[0136] [Surface treatment process II] Ion exchange water heated to 55°C was added to the slurry obtained in the surface treatment step I to adjust the slurry concentration to 30.0%. Then, 4.0 parts by mass of methyltrimethoxysilane was added to the slurry with the adjusted concentration, and a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 9.5. After the pH adjustment, the mixture was kept at 55°C for 5.0 hours while continuing to stir. The temperature was then lowered to 25°C.

[0137] [Cleaning 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, and then washed with ion-exchanged water, filtered and dried 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> Toners 8 to 10, 12 to 14, 18 to 23, 26, 28 and 29 were obtained in the same manner as in 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 process were changed to those 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 preparation step, granulation step, polymerization step I and polymerization step III] The toner composition preparation step, granulation step, and polymerization step I were carried out in the same manner as in the production example of toner 1, except that the toner constituent materials shown in Table 3 were used. In addition, the polymerization step III was carried out in the same manner as in the production example of toner 7.

[0140] [Cleaning process] The slurry obtained in the 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, and then filtered and dried while being washed with ion-exchanged water, toner particles 11 were obtained.

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

[0142] <Production Examples of Toners 16, 17, 27 and 30> In the same manner as in the production example of toner 1, except that the toner constituent materials shown in Table 4 were used, the toner composition preparation step, granulation step, and polymerization step I were performed, and the polymerization step III was performed in the same manner as in the production example of toner 7. Thereafter, the surface treatment step II and the washing step were performed in the same manner as in the production example of toner 1, toners 16, 17, 27, and 30 were obtained. The constituent materials and process conditions of the obtained toners 16, 17, 27 and 30 are shown in Tables 4 and 5, and the physical properties are shown in Tables 6-1 and 6-2.

[0143] <Toner 25 Manufacturing Example> In the production example of toner 1, the toner composition preparation step, granulation step, and polymerization step I were performed in the same manner as in the production example of toner 1, except that the toner constituent materials shown in Table 4 were used, and the polymerization step III was performed in the same manner as in the production example of toner 7. Thereafter, the washing step and external addition step were performed in the same manner as in the production example of toner 11, toner 25 was obtained. 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 production 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, as in Toner 1. The abbreviations in Table 4 stand for the following: Plasticizer 1: Ethylene glycol distearate Plasticizer 2: Hexanediol dimyristallate Plasticizer 3: Hexanediol dibehenate

[0146] [Table 5]

[0147] The abbreviations in Table 5 stand for the following: 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 portion of each toner.

[0150] [Table 6-2]

[0151] The toner was evaluated according to the evaluation methods described below. <Retention evaluation> Fixation evaluation was performed using a color laser printer [Canon LBP9600C] that had its fixing unit removed and was modified so that unfixed images could be output. Fixation tests of unfixed images were performed using a fixing tester that had been modified so that the fixing temperature and process speed could be adjusted. The evaluation was performed by filling 300 g of Toner 1 into a black cartridge from which the toner had been removed.

[0152] [Evaluation of low-temperature fixability] The modified LBP9600C machine was used, and the recording medium was color laser copier paper (Canon Marketing Japan, GF-C081, 80 g / m 2 The unfixed image was output using a toner cartridge with a toner load of 0.40 mg / cm2. 2 An unfixed image measuring 2.0 cm in length and 15.0 cm in width was formed 1.0 cm from the upper end in the paper feed direction. Under normal temperature and humidity conditions (23°C, 60% RH), the process speed was set to 300 mm / s, the fixing linear pressure was set to 27.4 kgf, and the initial temperature was 120°C, and the set temperature was increased in increments of 5°C, while the unfixed image was fixed at each temperature. The low temperature fixing property of the above image was evaluated by evaluating the low temperature side fixing start point. The evaluation of the low temperature side fixing start point was performed using the value of the image density reduction rate as an evaluation index. The image density was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). First, the image density of the center of the fixed image was measured, and then the image density was measured at 4.9 kPa (50 g / cm 2The surface of the image was rubbed five times with Silbon paper (Dasper K-3) at a speed of 0.2 m / sec under a load of 100 g / cm2, and the image density was measured again. The reduction rate (%) of the image density before and after rubbing was calculated and used as the image density reduction rate. The side fixing start point is the lowest temperature at which the image density reduction rate becomes 10.0% or less. The low temperature fixability was evaluated according to the following criteria. (Evaluation Criteria) A: The low temperature side fixing start point is 140℃ or less B: Low temperature side fixing start point is 145℃ or more and 155℃ or less C: The low temperature side fixing start point is 160℃ or more and 170℃ or less D: The low temperature side fixing start point is 175°C or higher

[0153] [Evaluation of hot offset resistance] The modified LBP9600C machine was used, and the recording medium was color laser copier paper (Canon Marketing Japan, GF-C081, 80 g / m 2 The unfixed image was output using a toner cartridge with a toner load of 0.20 mg / cm2. 2 An unfixed image measuring 2.0 cm in length and 15.0 cm in width was formed 1.0 cm from the upper end in the paper feed direction. Under normal temperature and humidity conditions (23°C, 60% RH), the process speed was set to 330 mm / s, the fixing linear pressure was set to 27.4 kgf, and the unfixed image was fixed at each temperature while the set temperature was increased in increments of 10°C from an initial temperature of 190°C. The fixing temperature at the point when hot offset occurred at the trailing edge of the evaluation paper in the paper feed direction as it passed through the fixing unit was confirmed, and evaluation was performed based on the following evaluation criteria. (Evaluation Criteria) A: Hot offset occurs at temperatures of 220°C or higher. B: Hot offset occurs at a temperature of 200°C or higher and less than 220°C. C: Hot offset occurs at a temperature of less than 200°C

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

[0155] <Development evaluation> The development evaluation was performed by modifying an HP Color Laser jet Enterprise M653dn and setting the process speed to 340 mm / s. The toner in the cartridge was removed, the inside was cleaned with an air blower, and then 250 g of toner was filled and the evaluation was performed.

[0156] [Image overlap] To evaluate image fogging, a 5cm x 5cm post-it note was attached to the center of a plain paper (HP Brochure Paper 200g, Glossy, HP, 200g / m 2 ) was used. To evaluate image fogging, the images were printed on color laser copier paper (Canon Marketing Japan, 80 g / m2) in a low-temperature, low-humidity environment (temperature 15°C, humidity 10% RH). 2 ) was used to print 100 sheets of images with a horizontal line coverage rate of 1%. Then, using plain paper with a Post-it note attached, which was prepared for the evaluation of image fog described above, 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 a Post-it note attached was prepared in addition to the plain paper with a Post-it note attached used above, and one all-white image was printed out in gloss paper mode. The reflectance (%) of the non-image area and the area hidden by the post-it on the paper for evaluating image fog output by the above method 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 obtained from the reflectance (%) of the area hidden by the post-it was taken as the initial image fog value. In addition, the same evaluation was performed on color laser copier paper (Canon, 80 g / m 2 ) was used to print 10,000 sheets of an image with a horizontal line coverage of 1%, and the image fog after durability testing was evaluated. Image fog was evaluated according to the following evaluation criteria. The smaller the value, the more image fog is suppressed. (Evaluation Criteria) A: Less than 0.5% B: 0.5% or more but less than 1.5% C: 1.5% or more and less than 3.0% D: 3.0% or more

[0157] [Component contamination evaluation] It is known that if the charging member is contaminated, charging unevenness occurs on the photoreceptor, which causes uneven density in a halftone image. Therefore, the contamination of the member was evaluated by evaluating the halftone tone stability. The evaluation was performed as follows. A new conductive member was newly installed in the drum unit, and an image was output. The evaluation paper was color laser copier paper (Canon Marketing Japan, 80 g / m 2 ) was used to output 499 images with halftones printed all over the surface. After that, the image density of the edge (30 mm from each of the left and right edges) and center of the 500th evaluation sheet was measured, and the density difference between the edge and center was evaluated. The image density was measured with an X-Rite color reflection densitometer (X-rite 500 Series, manufactured by X-rite). A rating of C or higher was judged to be good. (Evaluation Criteria) A: The concentration difference after durability evaluation is less than 0.04 B: The concentration difference after durability evaluation is 0.04 or more and less than 0.08 C: The difference in density after durability evaluation is 0.08 or more and less than 0.12 D: The concentration difference after durability evaluation is 0.12 or more

[0158] <Transfer evaluation> [Transferability] Evaluation was performed using a commercially available color laser printer Satera LBP7700C (manufactured by Canon). The toner in the cartridge was removed, the inside was cleaned with an air blower, and then Toner 1 (200 g) was filled in. 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 10.0 RH%). A horizontal line pattern with a printing rate of 1% was printed on 10 sheets to evaluate the initial transferability. The toner amount on the photoconductor was 0.50 mg / cm 2 A solid image was output under the conditions adjusted so that the toner remaining on the photoreceptor during the formation of the solid image was taped and peeled off with Mylar tape. The peeled off tape was then applied to an evaluation paper (Canon Marketing Japan, GF-C081, 80 g / cm 2 The reflectance difference was calculated by subtracting the reflectance T0 of the tape alone pasted on the paper from the reflectance T1 of the tape pasted on the paper. A horizontal line pattern with a printing rate of 1% was printed on 15,000 sheets to carry out a durability test, and the transferability after durability test was evaluated in the same manner. The reflectance was measured using a REFLECTMETER MODEL TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) The transferability was evaluated according to the following criteria. (Evaluation Criteria) A: Reflectance difference is 3.0% or less B: Reflectance difference is more than 3.0% and 6.0% or less C: Reflectance difference is more than 6.0% and less than 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 toner evaluation results 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 configurations. (Configuration 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 mass % of a monomer unit M1 represented by the following formula (1), Resin A contains 0.05 to 2.00 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, Resin A solid 29 In Si-NMR DD / MAS measurement, When the ratio of the peak area corresponding to silicon atoms of the T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer segment is A (%) and the ratio of the peak area corresponding to silicon atoms of the T2 unit structure is B (%), The A and the B satisfy the following formulas (3) and (4), 0.3≦A / B≦2.7 (3) 62≦A+B≦100 (4) The toner is characterized in that the weight average molecular weight Mw of the tetrahydrofuran soluble portion of the resin A, as determined by gel permeation chromatography, is 50,000 to 250,000. TIFF2024011644000018.tif40170TIFF2024011644000019.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 2indicates a hydrogen atom or a methyl group, and * indicates the site of bonding with the silicon atom of the organosilicon polymer moiety. 2 -COO-(CH2) n -, carbonyl is R 2 Attached to the carbon bearing L 2 -NH-(CH2) n -, NH is R 2 ) (Configuration 2) 2. The toner according to claim 1, wherein the organosilicon polymer portion is a polymer of an organosilicon compound having a structure represented by the following formula (5): R-Si-R a Type 3(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 particle is P(Si) and the total peak intensity of all ions in the toner core particle is P(T), The toner according to configuration 1 or 2, wherein P(Si) and 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 protrusions formed 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, The number average diameter of the maximum diameter of the protrusions is R, When the number average height of the convex portion is H, The R is 80 to 250 nm, 5. The toner according to any one of configurations 1 to 4, wherein H is 25 to 100 nm. R-SiO3 / 2 (7) (Configuration 6) The resin A contains 3 to 10 mass % of a monomer unit M3 represented by the following formula (8): The toner according to any one of Configurations 1 to 5. TIFF2024011644000020.tif34170 (in formula (8), L 1 -COO-(CH2) n - (n is an integer between 11 and 31), L 1 The carbonyl of R is attached to a carbon atom in the main chain. 1 represents a hydrogen atom or a methyl group.) (Structure 7) the toner particles contain a plasticizer, The toner according to any one of configurations 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. (Configuration 8) The toner particles contain a resin B, The toner according to any one of configurations 1 to 7, wherein the weight average molecular weight Mw of the tetrahydrofuran soluble portion of the resin B, as determined by gel permeation chromatography, is 2,000 to 7,000. (Configuration 9) 9. The toner according to Configuration 8, wherein the resin B contains the monomer unit M1 in an amount of 85 to 100% by mass. (Configuration 10) The toner according to any one of configurations 1 to 9, wherein the toner has a tetrahydrofuran insoluble content of 0 to 10% by mass. (Configuration 11) L in the monomer unit M3 1 7. The toner according to configuration 6, wherein n is an integer of 11 to 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 a monomer unit M1 represented by the following formula (1), Resin A contains 0.05 to 2.00 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, Resin A solid ２９ In the Si-NMR DD / MAS measurement, When the ratio of the peak area corresponding to silicon atoms of the T3 unit structure to the total peak area corresponding to silicon atoms in the organosilicon polymer segment is defined as A (%), and the ratio of the peak area corresponding to silicon atoms of the T2 unit structure is defined as B (%), The A and the B satisfy the following formulas (3) and (4), 0.3≦A / B≦2.7 (3) 62≦A+B≦100 (4) The toner is characterized in that the weight average molecular weight Mw of the tetrahydrofuran soluble portion of the resin A, as determined by gel permeation chromatography, is from 50,000 to 250,000. (In formula (2), L ２ is a single bond, -COO-(CH ２ ) ｎ - or -NH-(CH ２ ) ｎ - (n is an integer from 1 to 10), R ２ indicates a hydrogen atom or a methyl group, and * indicates the site of bonding with the silicon atom of the organosilicon polymer moiety. ２ -COO-(CH ２ ) ｎ -, the carbonyl is R ２ is bonded to a carbon having L ２ -NH-(CH ２ ) ｎ -, NH is R ２ )

2. 2. The toner according to claim 1, wherein the organosilicon polymer portion 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.

3. When the peak intensity of Si obtained by time-of-flight secondary ion mass spectrometry of the toner core particle is P(Si) and the sum of the peak intensities of all ions in the toner core particle is 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 , wherein the content of the resin A in the toner is 50% by mass or more.

5. the toner particles have protrusions formed 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, The number average diameter of the maximum diameter of the protrusions is R, When the number average height of the convex portions is H, R is 80 to 250 nm, 3. The toner according to claim 1, wherein H is from 25 to 100 nm. R-SiO ３／２ (7)

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

7. the toner particles contain a plasticizer, 3. The toner according to claim 1, 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 a resin B, 3. The toner according to claim 1, wherein the weight average molecular weight Mw of the tetrahydrofuran soluble portion of said resin B is from 2,000 to 7,000 as determined by gel permeation chromatography.

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

10. 3. The toner according to claim 1, wherein the toner has a tetrahydrofuran insoluble content of 0 to 10% by mass.

11. L in the monomer unit M3 １ 7. The toner according to claim 6, wherein n is an integer from 11 to 13.

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