Image forming method, toner, and two-component developer

Abstract

To achieve both of the excellent durable stability and blade cleaning property when organic silicon polymer particles are used as an external additive for toner.SOLUTION: There is provided an image formation method including a charging step, a latent image formation step, a development step, a transfer step, a fixation step and a cleaning step. A fatty acid metal salt exists in a cleaning part where an image carrier is in contact with a cleaning blade, toner includes toner particles and an external additive, and the external additive includes organic silicon polymer particles and inorganic silica particles. When a transition amount from the toner of the organic silicon polymer particles is A mass% and a transition amount from the toner of the inorganic silica particles is B mass% with the toner before water washing treatment as a reference in a case where the water washing treatment is performed on the toner, A and B satisfy a specific relation.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to an external additive for a toner, a toner used in an electrophotographic system, an image forming method using a two-component developer containing the toner, the toner, and the two-component developer. [Background technology]

[0002] In recent years, as full-color electrophotographic copying machines have become widespread, there has been an increasing demand for toners used in electrophotography to meet the demands of high-speed printing and to have a longer life.

[0003] Conventionally, silica has been widely used as an external additive for toner. For example, in Patent Document 1, highly hydrophobic spherical sol-gel silica particles are added to toner base particles to improve the charging stability of the toner. However, when printing an image with low print density over a long period of time, or when printing an image in a high-temperature, high-humidity environment, the toner comes into contact with a lot of components such as the carrier and is subjected to stress. In such an environment, however, the silica particles become embedded in the surface of the toner particles, causing a significant change in the surface condition of the toner, leaving room for improvement in terms of the toner's adhesion, fluidity, and charging stability.

[0004] On the other hand, in Patent Documents 2 and 3, polyalkylsilsesquioxane microparticles are added to toner particles to improve the durability and stability of the toner. Polyalkylsilsesquioxane microparticles have a lower hardness than inorganic external additives such as silica, and have the property of reducing the difference in hardness between them and the toner particle surface, thereby preventing them from sinking into the toner particle surface during prolonged use. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2007-99582 [Patent Document 2] International Publication No. 2015 / 107961 [Patent Document 3] Japanese Patent Application Laid-Open No. 2018-4949 Summary of the Invention [Problem to be solved by the invention]

[0006] The toner to which the polyalkylsilsesquioxane fine particles are externally added can suppress particle embedding, and therefore can maintain good developability, transferability, and fluidity throughout long-term use. However, it has been found that the use of polyalkylsilsesquioxane fine particles poses a problem in blade cleaning of the photoreceptor surface. This is thought to be because the polyalkylsilsesquioxane fine particles are spherical and have too high rolling properties, preventing the formation of a blocking layer by the external additive at the cleaning blade nip. The problem to be solved by the present disclosure is to provide an image forming method that solves the above-mentioned problems, specifically, to provide an image forming method that has excellent blade cleaning properties and excellent durability and stability even when organosilicon polymer particles such as polyalkylsilsesquioxane fine particles are used as an external toner additive. [Means for solving the problem]

[0007] The present disclosure provides: a charging step of charging the image carrier; a latent image forming step of forming an electrostatic latent image on the image carrier charged in the charging step; a developing step of developing the electrostatic latent image formed on the image carrier using a toner or a two-component developer containing a toner to form a toner image on the image carrier; a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member; a fixing step of fixing the toner image transferred onto the transfer material; and a cleaning step of contacting a cleaning blade with the surface of the image bearing member after transfer to remove residual toner remaining on the surface of the image bearing member; An image forming method comprising: The cleaning portion where the image bearing member and the cleaning blade come into contact contains a fatty acid metal salt. exists, The toner comprises toner particles and an external additive, the external additive comprises organosilicon polymer particles and inorganic silica particles, When the toner is subjected to a water washing treatment, the toner before the water washing treatment is used as a reference. the amount of the organosilicon polymer particles transferred from the toner is A% by mass, When the amount of the inorganic silica particles transferred from the toner is B mass %, The A and the B satisfy the following formulas (1) and (2), Applicable External additives further contains fatty acid metal salt particles, The toner or the two-component developer containing the toner is developed on the image carrier, and the fatty acid metal salt Supplying particles, The image forming method is characterized in that, when the toner is subjected to a water washing treatment, the amount of the fatty acid metal salt particles that migrates from the toner is defined as C mass % based on the toner before the water washing treatment, and C is 0.01 to 1.00. 0.5≦A+B≦4.0 (1) 0.3≦B / A≦2.0 (2) [Effects of the Invention]

[0008] According to the present disclosure, it is possible to provide an electrophotographic method that can achieve both excellent durability and cleaning properties. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic cross-sectional view showing an image forming apparatus according to the present invention. [Figure 2] FIG. 2 is a diagram showing a step of supplying a fatty acid metal salt used in an example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] In the present disclosure, unless otherwise specified, the expressions "XX or more and YY or less" or "XX to YY" representing a numerical range mean a numerical range including the lower and upper limits, which are the endpoints. When a numerical range is described in stages, the upper and lower limits of each numerical range can be combined in any way.

[0011] According to the inventors' research, it has been found that the use of organosilicon polymer particles as an external toner additive can prevent the external additive from embedding in the toner particle surface, resulting in better durability and stability than the commonly used silica. Because silica is hard compared to toner particles, it acts like a hard object is being pressed against a soft object, making it easy for the external additive to embed in the toner particle surface. On the other hand, organosilicon polymer particles are softer than silica and have an appropriate hardness, making it possible to prevent the external additive from embedding in the toner particle surface.

[0012] Furthermore, after extensive research, it was found that the image forming method of the present disclosure can achieve excellent cleaning performance. It is believed that in order to stably prevent toner slippage during blade cleaning, it is necessary to form a blocking layer made of external additives near the cleaning blade nip. The blocking layer is a layer composed mainly of external additives that resides on the opposite side of the drum's traveling direction from the contact surface between the drum and cleaning blade. The presence of the blocking layer prevents toner from slipping through the cleaning blade. The properties of the external additive are important for stably forming this blocking layer. External additives with too high slipperiness move too quickly and are not suitable for forming a blocking layer. The property of the external additive required for forming a blocking layer is cohesiveness, which suppresses the movement of external additives when they gather together. The organosilicon polymer particles used in the present invention are fine particles with high slipperiness, making it difficult to form a blocking layer. Therefore, in the present disclosure, the organosilicon polymer particles are used in the vicinity of the cleaning blade nip. By mixing the particles with inorganic silica particles and fatty acid metal salt, blade cleaning performance is improved.The mechanism by which this effect is achieved is thought to be that when the scale-shaped fatty acid metal salt and two types of particles with different hardness (low-hardness organosilicon polymer particles and high-hardness inorganic silica particles) are mixed together and pressurized in the blade nip, the highly slippery organosilicon polymer particles are given the appropriate degree of cohesion.

[0013] A fatty acid metal salt is present in the cleaning portion where the image bearing member and the cleaning blade come into contact. Specifically, it is preferable to have a step of supplying a fatty acid metal salt to the cleaning portion after the transfer step. Alternatively, a method in which fatty acid metal salt particles are externally added to toner particles, developed on an image carrier, and then supplied to a cleaning blade may also be suitably used. That is, the external additive preferably further contains fatty acid metal salt particles.

[0014] When a toner is subjected to a water washing treatment, the amount of organosilicon polymer particles that migrate from the toner is A mass % and the amount of inorganic silica particles that migrate from the toner is B mass %, based on the toner before the water washing treatment. A and B satisfy the following formulas (1) and (2). 0.5≦A+B≦4.0 (1) 0.3≦B / A≦2.0 (2) Furthermore, A+B is preferably 0.6 or more and 2.4 or less. B / A is preferably 0.5 or more and 1.6 or less. As the values ​​of A and B increase, the amounts of organosilicon polymer particles and inorganic silica particles supplied to the cleaning blade increase. If A+B is less than 0.5, the amounts of organosilicon polymer particles and inorganic silica particles supplied to the cleaning blade become too small, making it difficult to form a stable blocking layer. Conversely, if A+B exceeds 4.0, the amounts of organosilicon polymer particles and inorganic silica particles supplied to the cleaning blade become too large, leading to component contamination. Furthermore, if B / A is less than 0.3, the proportion of organosilicon polymer particles among the particles supplied to the cleaning nip will be too high, making it impossible to form a blocking layer. On the other hand, if B / A exceeds 2.0, the proportion of organosilicon polymer particles present on the toner surface will be too low, impairing durability and stability. The migration amounts A and B can be controlled by changing the external addition strength and addition amount of organosilicon polymer particles and inorganic silica particles.

[0015] The number-average particle size of the primary particles of the organosilicon polymer particles is preferably 50 to 200 nm, more preferably 55 to 190 nm, and even more preferably 100 to 140 nm. The number-average particle size of the primary particles of the inorganic silica particles is preferably 50 to 200 nm, more preferably 80 to 120 nm. When the number-average particle size of the primary particles of the organosilicon polymer particles and inorganic silica particles is 50 nm or more, the proportion of organosilicon polymer particles and inorganic silica particles that slip through the cleaning blade can be reduced, making it easier to form a stable blocking layer. In particular, when the number-average particle size of the primary particles of the inorganic silica particles is 50 nm or more, the inorganic silica particles are less likely to be embedded in the toner particles, improving spacer function and durability. Furthermore, when the number average particle size of the primary particles of the organosilicon polymer particles and inorganic silica particles is 200 nm or less, it becomes easier to uniformly add the organosilicon polymer particles and inorganic silica particles to the toner surface, making it easier to achieve good durability and stability.

[0016] The Young's modulus of the organosilicon polymer particles is preferably 1500 MPa to 30000 MPa, more preferably 4000 MPa to 8000 MPa, and even more preferably 5000 MPa to 7000 MPa. If the Young's modulus is above 30,000 MPa, the organosilicon polymer particles themselves are less likely to break when the toner is subjected to stress from components such as the carrier. Furthermore, if the Young's modulus is 30,000 MPa or less, stress is more easily alleviated when the toner is subjected to stress from components such as the carrier, preventing external additives from becoming embedded in the toner particle surface and achieving excellent durability and stability. The Young's modulus of the organosilicon polymer particles can be controlled by changing the structure of the functional groups bonded to the Si in the constituent compounds. Specifically, it can be controlled by changing the abundance ratio of the M unit structure (S1), D unit structure (S2), T unit structure (S3), and Q unit structure (S4) constituent compounds.

[0017] [ka]

[0018] Ra, Rb, Rc, Rd, Re, and Rf each independently represent a group having 1 to 6 carbon atoms (preferably represents an alkyl group of 1 to 3, more preferably 1 or 2, and even more preferably 1).

[0019] The Young's modulus of the inorganic silica particles is preferably 50,000 MPa or more and 90,000 MPa or less. When the Young's modulus of the inorganic silica particles is within this range, the inorganic silica particles have an appropriate hardness, which makes it easy to impart appropriate cohesiveness to the organosilicon polymer particles when the inorganic silica particles are pressed together with the fatty acid metal salt and the organosilicon polymer particles at the blade nip, facilitating the formation of a blocking layer.

[0020] The amount of organosilicon polymer particles added is preferably 0.2 parts by weight to 10.0 parts by weight, more preferably 0.5 parts by weight to 7.0 parts by weight, and even more preferably 1.0 parts by weight to 5.0 parts by weight, per 100 parts by weight of toner particles. By adjusting the amount to within the above range, excellent blade cleaning performance and durability can be obtained. By adjusting the amount to 0.2 parts by weight or more, the amount of organosilicon polymer particles necessary for forming the blocking layer can be reliably secured, improving cleaning performance. Furthermore, by adjusting the amount to 10.0 parts by weight or less, contamination of components by the organosilicon polymer particles can be suppressed, and good durability and stability can be obtained.

[0021] The amount of inorganic silica particles added is preferably 0.8 parts by mass or more and 3.7 parts by mass or less, and more preferably 1.5 parts by mass or more and 2.5 parts by mass or less, relative to 100 parts by mass of toner particles. When the amount of inorganic silica particles added is within the above range, it becomes easy to control A and B so as to satisfy 0.5≦A+B≦4.0 and 0.3≦A / B≦2.0.

[0022] The theoretical BET specific surface area of ​​the organosilicon polymer particles is X (m 2 / g), and the BET specific surface area of ​​the organosilicon polymer particles measured by the BET multipoint method is defined as Y(m 2 / g), it is preferable that X and Y satisfy the following formula (3). 2.0≦Y / X≦8.5 (3) Furthermore, it is more preferable that X and Y satisfy 2.8≦Y / X≦8.2, and it is even more preferable that they satisfy 4.2≦Y / X≦8.0. By setting Y / X in the above range, good cleaning properties can be obtained. A higher Y / X value means that the organosilicon polymer particles have microscopic irregularities on their surfaces (more pores). By maintaining this value at 2.0 or higher, excellent cleaning performance can be achieved. This is thought to be because the microscopic irregularities on the surface favor the cohesion of the fatty acid metal salt and inorganic silica particles, which is essential for the formation of a blocking layer. On the other hand, maintaining the ratio at 8.5 or lower prevents excessive pores from increasing moisture adsorption, improving charging stability.

[0023] The cleaning blade may be supported by either a swinging type, in which the blade is pressed against an image carrier such as a photoreceptor so that it swings around a swing fulcrum, or a fixed type, in which the blade does not swing. The swinging type is preferred to further prevent toner from passing through. The swinging type increases the ability to follow the surface of the photoreceptor, improving cleaning performance against toner passing through.

[0024] The contact pressure of the cleaning blade against the image carrier is preferably 20.0 N / m or more and 40.0 N / m or less, and more preferably 20.0 N / m or more and 30.0 N / m or less, as a linear pressure per unit length in the longitudinal direction at the contact point. By setting it to 20.0 N / m or more, a cleaning blade nip is stably formed, resulting in good cleaning performance. Furthermore, by setting it to 40.0 N / m or less, wear and scratches on the photoreceptor are suppressed, resulting in a highly durable cleaning system. The contact pressure can be measured by installing a load cell at the part where the cleaning blade is fixed.

[0025] <Organosilicon polymer particles> The method for producing organosilicon polymer particles is not particularly limited, but it is preferable to form organosilicon polymer particles through hydrolysis and condensation polymerization of silicon compounds (silane monomers) by the sol-gel method. Specifically, it is preferable to form organosilicon polymer particles by polymerizing a mixture of a bifunctional silane having two siloxane bonds, a trifunctional silane having three siloxane bonds, and a tetrafunctional silane having four siloxane bonds through hydrolysis and condensation polymerization. That is, the organosilicon polymer is preferably a condensation polymer of at least one silicon compound selected from the group consisting of bifunctional silane, trifunctional silane, and tetrafunctional silane, more preferably a condensation polymer of trifunctional silane, a condensation polymer of bifunctional silane and trifunctional silane, a condensation polymer of trifunctional silane and tetrafunctional silane, or a condensation polymer of tetrafunctional silane and bifunctional silane, and even more preferably a condensation polymer of tetrafunctional silane and bifunctional silane.

[0026] The present inventors have discovered that in the process for producing organosilicon polymer particles, excellent durability and blade cleaning properties can be achieved by adjusting the mixing ratio of the above monomers, the solvent temperature during the hydrolysis and condensation reactions, the type of catalyst, the stirring time, and the solution pH.

[0027] There are no particular limitations on the method for producing organosilicon polymer particles. For example, they can be obtained by adding a silane compound dropwise to water, hydrolyzing and condensing the particles in the presence of a catalyst, and then filtering and drying the resulting suspension. The particle size can be controlled by adjusting the type of catalyst, the compounding ratio, the reaction initiation temperature, and the dropwise addition time. Examples of acidic catalysts include hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while examples of basic catalysts include, but are not limited to, aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0028] The organosilicon polymer particles are preferably produced by the following method. Specifically, it preferably comprises a first step of obtaining a hydrolysate of an organosilicon compound, a second step of mixing the hydrolysate with an alkaline aqueous medium and subjecting the hydrolysate to a polycondensation reaction, and a third step of mixing the polycondensation reaction product with an aqueous solution to form particles. In some cases, a hydrophobizing agent may be further added to the spherical organosilicon polymer particle dispersion to obtain hydrophobized spherical organosilicon polymer particles.

[0029] In the first step, an organosilicon compound is contacted with a catalyst by stirring, mixing, or the like in an aqueous solution in which an acidic or alkaline substance serving as a catalyst is dissolved in water. Known catalysts can be suitably used. Specific examples of acidic catalysts include acetic acid, hydrochloric acid, hydrofluoric acid, sulfuric acid, and nitric acid, while basic catalysts include aqueous ammonia, sodium hydroxide, and potassium hydroxide.

[0030] The amount of catalyst used may be adjusted appropriately depending on the type of organosilicon compound and catalyst. Preferably, the amount of catalyst used is 1×10 -3 The amount is selected in the range of 1 part by mass to 1 part by mass. The amount of catalyst used is 1×10 -3 If the amount of catalyst used is 1 part by mass or more, the reaction will proceed sufficiently. On the other hand, if the amount of catalyst used is 1 part by mass or less, the concentration of impurities remaining in the fine particles will be low, making hydrolysis easier. The amount of water used is preferably 2 to 15 moles per mole of organosilicon compound. If the amount of water is 2 moles or more, the hydrolysis reaction will proceed sufficiently, and if the amount is 15 moles or less, productivity will improve.

[0031] The reaction temperature is not particularly limited, and may be carried out at room temperature or under heated conditions, but it is preferable to carry out the reaction at a temperature maintained at 10 to 60°C, as this allows the hydrolysate to be obtained in a short time and the partial condensation reaction of the produced hydrolysate to be suppressed. The reaction time is not particularly limited, and depends on the reactivity of the organosilicon compound used, the composition of the reaction solution prepared by mixing the organosilicon compound, acid, and water, and the temperature of the product. The selection may be made appropriately taking productivity into consideration.

[0032] In the second step of the method for producing organosilicon polymer particles, the raw material solution obtained in the first step is mixed with an alkaline aqueous medium to polycondense the particle precursor, thereby obtaining a polycondensation reaction solution. The alkaline aqueous medium is a liquid obtained by mixing an alkaline component, water, and, if necessary, an organic solvent.

[0033] The alkaline component used in the alkaline aqueous medium is one whose aqueous solution is basic and acts as a neutralizer for the catalyst used in step 1 and as a catalyst for the polycondensation reaction in step 2. Examples of such alkaline components include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; ammonia; and organic amines such as monomethylamine and dimethylamine.

[0034] The amount of the alkali component used is an amount that neutralizes the acid and effectively acts as a catalyst for the polycondensation reaction. For example, when ammonia is used as the alkali component, the amount is usually selected in the range of 0.01 mass % or more and 12.5 mass % or less per 100 parts by mass of the mixture of water and the organic solvent.

[0035] In the second step, in order to prepare an alkaline aqueous medium, an organic solvent may be used in addition to the alkaline component and water. The organic solvent is not particularly limited as long as it is compatible with water, but an organic solvent that dissolves 10 g or more of water per 100 g at room temperature and normal pressure is preferred.

[0036] Specific examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, glycerin, trimethylolpropane, and hexanetriol; ethers such as ethylene glycol monoethyl ether, acetone, diethyl ether, tetrahydrofuran, and diacetone alcohol; and amide compounds such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

[0037] Among the organic solvents listed above, alcohol solvents such as methanol, ethanol, 2-propanol, butanol, etc. are preferred. Furthermore, from the viewpoint of hydrolysis and dehydration condensation reactions, it is more preferred to select as the organic solvent the same alcohol as the alcohol produced by elimination.

[0038] In the third step, the polycondensation reaction product obtained in the second step is mixed with an aqueous solution to form particles. Water (tap water, pure water, etc.) is preferably used as the aqueous solution, but components compatible with water, such as salts, acids, alkalis, organic solvents, surfactants, and water-soluble polymers, may also be added to the water. The temperatures of the polycondensation reaction liquid and the aqueous solution when mixed are not particularly limited, and are preferably selected in the range of 5 to 70°C, taking into consideration the composition, productivity, etc.

[0039] The organosilicon polymer particles can be recovered by any known method without any particular restrictions. For example, floating powder can be scooped out or filtration can be used, but filtration is preferred due to its simple operation. There are no particular restrictions on the filtration method, and known equipment such as vacuum filtration, centrifugal filtration, and pressure filtration can be selected. The filter paper, filters, filter cloth, etc. used in filtration are not particularly limited as long as they are industrially available, and can be selected appropriately depending on the equipment used.

[0040] The organosilicon polymer particles may be surface treated with a known means such as a silane coupling agent or silicone oil to adjust the degree of hydrophobicity.

[0041] The monomer to be used can be appropriately selected depending on its compatibility with the solvent and catalyst, its hydrolysis property, etc., but tetraethoxysilane is preferred as the tetrafunctional silane. The trifunctional silane is preferably trimethoxymethylsilane. The bifunctional silane is preferably dimethyldimethoxysilane.

[0042] The organosilicon polymer particles are preferably particles of a condensation polymer of at least one organosilicon compound selected from the group consisting of organosilicon compounds having a structure represented by the following formula (A):

[0043] [ka]

[0044] In formula (A), R 12 , R 13 , R 14 and R 15 R each independently represents an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2), a phenyl group, or a reactive group (for example, a halogen atom, a hydroxy group, an acetoxy group, or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms)). 12 , R 13 , R 14 and R 15 At least one of the groups is the reactive group. R 12 , R 13 , R 14 and R 15 are preferably each independently an alkyl group having 1 to 6 carbon atoms (preferably 1 to 3, more preferably 1 or 2) or an alkoxy group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms).

[0045] To obtain organosilicon polymer particles, an organosilicon compound having four reactive groups in one molecule (tetrafunctional silane) of formula (A), R 12 is an alkyl group or a phenyl group, and three reactive groups (R 13 , R 14 , R 15 ), an organosilicon compound (trifunctional silane) having R in formula (A) 12 , R 13 is an alkyl group or a phenyl group, and two reactive groups (R 14 , R 15 ), an organosilicon compound (bifunctional silane) having R in formula (A) 12 , R13 , R 14 is an alkyl group or a phenyl group, and one reactive group (R 15 ) can be used.

[0046] These reactive groups undergo hydrolysis, addition polymerization, and condensation polymerization to form crosslinked structures, resulting in organosilicon polymer particles. 13 , R 14 and R 15 The hydrolysis, addition polymerization, and condensation polymerization can be controlled by the reaction temperature, reaction time, reaction solvent, and pH.

[0047] Examples of tetrafunctional silanes include tetramethoxysilane, tetraethoxysilane, and tetraisocyanate silane.

[0048] Trifunctional silanes include methyltrimethoxysilane, methyltriethoxysilane, methyldiethoxymethoxysilane, methylethoxydimethoxysilane, methyltrichlorosilane, methylmethoxydichlorosilane, methylethoxydichlorosilane, methyldimethoxychlorosilane, methylmethoxyethoxychlorosilane, methyldiethoxychlorosilane, methyltriacetoxysilane, methyldiacetoxymethoxysilane, methyldiacetoxyethoxysilane, methylacetoxydimethoxysilane, and methylacetoxymethoxyethoxysilane. Examples thereof include hydroxysilane, methylacetoxydiethoxysilane, methyltrihydroxysilane, methylmethoxydihydroxysilane, methylethoxydihydroxysilane, methyldimethoxyhydroxysilane, methylethoxymethoxyhydroxysilane, methyldiethoxyhydroxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltriacetoxysilane, ethyltrihydroxysilane, propyltrimethoxysilane, propyltriethoxysilane, propyltrichlorosilane, propyltriacetoxysilane, propyltrihydroxysilane, butyltrimethoxysilane, butyltriethoxysilane, butyltrichlorosilane, butyltriacetoxysilane, butyltrihydroxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, hexyltrichlorosilane, hexyltriacetoxysilane, hexyltrihydroxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, phenyltriacetoxysilane, and phenyltrihydroxysilane.

[0049] Examples of bifunctional silanes include di-tert-butyldichlorosilane, di-tert-butyldimethoxysilane, di-tert-butyldiethoxysilane, dibutyldichlorosilane, dibutyldimethoxysilane, dibutyldiethoxysilane, dichlorodecylmethylsilane, dimethoxydecylmethylsilane, diethoxydecylmethylsilane, dichlorodimethylsilane, dimethoxydimethylsilane, diethoxydimethylsilane, and diethyldimethoxysilane. Examples include orchids.

[0050] In the first step of obtaining a hydrolyzate of an organosilicon compound, it is preferable to add 50.0 to 60.0 g of a silane compound to 43.0 g of water. When two types of silane compounds are added, the mass ratio of the two types of silane compounds to be added is preferably 0.8 to 4.0:1.

[0051] <Inorganic silica particles> As inorganic silica particles, particles that are made of silicon dioxide can be mentioned, for example, wet silica such as precipitation method, sol-gel method, or dry silica such as deflagration method, fumed method, but dry silica is more preferred because of easy shape control.In addition, the inorganic silica particles of the present disclosure also include the particles that are made by hydrophobic treatment of this silica with the hydrophobic treatment agent described below.

[0052] Dry silica is made from silicon halide compounds and the like as raw materials. Silicon tetrachloride is used as the silicon halide compound, but silanes such as methyltrichlorosilane and trichlorosilane can also be used alone or in a mixture of silicon tetrachloride and silanes as raw materials.

[0053] After vaporizing the raw material, the target silica is obtained by a so-called flame hydrolysis reaction, which involves reacting the raw material with water generated as an intermediate in an oxyhydrogen flame. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the reaction formula is as follows. SiCl4+2H2+O2→SiO2+4HCl

[0054] An example of the production of dry silica will be described below. Oxygen gas is supplied to the burner, the ignition burner is ignited, and then hydrogen gas is supplied to the burner to form a flame, into which the raw material silicon tetrachloride is added and gasified. Next, a flame hydrolysis reaction is carried out, and the resulting silica powder is collected. The average particle size and shape can be adjusted as desired by appropriately changing the flow rate of silicon tetrachloride, the flow rate of oxygen gas supplied, the flow rate of hydrogen gas supplied, and the residence time of silica in the flame.

[0055] The inorganic fine particles are preferably subjected to hydrophobic treatment. Examples of the hydrophobic treatment agent include silane. Although a compound, silicone oil or a mixture thereof can be used, those that have been hydrophobized with only a silane compound are more preferred from the viewpoint of obtaining excellent dispersibility of inorganic fine particles.

[0056] <Binder resin> The binder resin used for the toner particles is not particularly limited, and the following polymers can be used. Examples of suitable styrene copolymers include homopolymers of styrene and its substituted derivatives, such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene-acrylic acid ester copolymers, styrene-methacrylic acid ester copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; and polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral resins, terpene resins, coumarone-indene resins, and petroleum-based resins. Among these, polyester resins are preferred in terms of durability and charging stability.

[0057] <Coloring agent> The toner particles may contain a colorant. Examples of the colorant include the following:

[0058] Examples of black colorants include carbon black, and those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. As the colorant, a pigment may be used alone, but it is more preferable to use a dye and a pigment in combination to improve the clarity from the viewpoint of the image quality of a full-color image.

[0059] Examples of pigments for magenta toner include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0060] Dyes for magenta toner include solvent dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1; and basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0061] Examples of pigments for cyan toner include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, and 17; CI Vat Blue 6; CI Acid Blue 45; and copper phthalocyanine derivatives with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton. Phthalocyanine pigment. An example of a dye for cyan toner is CI Solvent Blue 70.

[0062] Yellow toner pigments include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Vat Yellow 1, 3, 20. An example of a yellow toner dye is CI Solvent Yellow 162.

[0063] The content of the colorant is preferably 0.1 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0064] <Wax> The toner particles may contain wax. Examples of wax include the following. Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or their block copolymers; waxes whose main component is fatty acid esters such as carnauba wax; partially or completely deoxidized fatty acid esters such as deoxidized carnauba wax.

[0065] Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexyl alcohol. Examples of suitable binder resins include saturated fatty acid bisamides such as m-xylene bisstearamide; unsaturated fatty acid amides such as ethylene bisoleamide, hexamethylene bisoleamide, N,N'-dioleyl adipamide, and N,N'-dioleyl sebacate; aromatic bisamides such as m-xylene bisstearamide and N,N'-distearyl isophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes obtained by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; and hydroxyl-containing methyl ester compounds obtained by hydrogenating vegetable oils. The wax content is preferably 2.0 to 30.0 parts by mass per 100 parts by mass of the binder resin.

[0066] <Charge control agent> The toner particles may contain a charge control agent as needed. Known charge control agents can be used, but particularly preferred are metal compounds of aromatic carboxylic acids, which are colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

[0067] Examples of negative charge control agents include metal salicylate compounds, metal naphthoate compounds, metal dicarboxylate compounds, polymeric compounds having sulfonic acid or carboxylic acid on the side chain, polymeric compounds having sulfonate salts or sulfonate esters on the side chain, polymeric compounds having carboxylate salts or carboxylate esters on the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0068] Positive charge control agents include quaternary ammonium salts, polymeric compounds having the quaternary ammonium salts in their side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The amount of charge control agent added is preferably 0.2 to 10 parts by mass per 100 parts by mass of the binder resin.

[0069] <Inorganic fine powder> In addition to the external additives described above, other inorganic fine powders can also be used in combination with the toner as needed. The inorganic fine powders may be internally added to the toner particles or may be mixed with the toner particles as an external additive. When used as an external additive, inorganic fine powders such as silica are preferred. The inorganic fine powders are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0070] As an external additive, 2 / g or more 400m 2 / g or less is preferred. By using inorganic fine particles with a specific surface area within the above range in combination, it is possible to fine-tune the fluidity and chargeability of the toner. Even when inorganic fine particles are used in combination, the effects of the organosilicon polymer particles and inorganic silica particles or fatty acid metal salts of the present disclosure are still exhibited. The inorganic fine powder is preferably used in an amount of 0.1 parts by mass or more and 10.0 parts by mass or less per 100 parts by mass of toner particles.

[0071] <Fatty acid metal salts> The preferred fatty acid metal salts are salts of metals selected from zinc, calcium, magnesium, aluminum, and lithium. Fatty acid zinc or fatty acid calcium is particularly preferred, and the effects of the present disclosure are more pronounced when these are used.

[0072] Furthermore, the fatty acid of the fatty acid metal salt is preferably a higher fatty acid having 12 to 22 carbon atoms. Using a fatty acid having 12 or more carbon atoms makes it easier to suppress the generation of free fatty acids. The amount of free fatty acids is preferably 0.20% by mass or less. If the fatty acid has 22 or less carbon atoms, the melting point of the fatty acid metal salt does not become too high, making it easier to achieve good fixability. As the fatty acid, stearyl acid is particularly preferred.

[0073] Examples of fatty acid metal salts include metal stearates such as zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, and lithium stearate, and zinc laurate.

[0074] In order to form a blocking layer in the vicinity of the cleaning blade nip, it is important that a fatty acid metal salt is present in the cleaning portion where the image carrier and the cleaning blade contact each other. In order to have a fatty acid metal salt present in the cleaning portion where the image carrier and the cleaning blade contact each other, the external additive preferably contains fatty acid metal salt particles.

[0075] That is, the present disclosure: A toner having toner particles containing a binder resin and a colorant, and an external additive, the external additive comprises organosilicon polymer particles, inorganic silica particles, and fatty acid metal salt particles; When the toner is subjected to a water washing treatment, the toner before the water washing treatment is used as a reference. the amount of the organosilicon polymer particles transferred from the toner is A% by mass, When the amount of the inorganic silica particles transferred from the toner is B mass %, The toner is characterized in that A and B satisfy the following formulae (1) and (2). 0.5≦A+B≦4.0 (1) 0.3≦B / A≦2.0 (2)

[0076] When fatty acid metal salt particles are externally added to toner particles, when the toner is subjected to a water washing treatment, the amount of the fatty acid metal salt particles that migrates from the toner is expressed as C mass % based on the toner before the water washing treatment. C is preferably 0.01 to 1.00, more preferably 0.05 to 0.50. When C is 0.01 or more, a sufficient amount of fatty acid metal salt particles is supplied to the cleaning blade, making it easy to form a blocking layer. On the other hand, when C is 1.00 or less, component contamination due to the fatty acid metal salt particles supplied to the cleaning blade is unlikely to occur.

[0077] When fatty acid metal salt particles are externally added to toner particles, the amount added is preferably 0.01 to 1.00 parts by mass per 100 parts by mass of toner particles. When the amount added is within the above range, it becomes easy to control C to 0.01 to 1.00.

[0078] The number-average particle size of the primary particles of the fatty acid metal salt particles is preferably 200 nm or more and 3000 nm or less. If it is 200 nm or more, the fatty acid metal salt particles are prevented from strongly adhering to the toner surface during external addition, and the fatty acid metal salt particles are more likely to transfer to the cleaning blade. Conversely, if it is 3000 nm or less, the fatty acid metal salt particles are sufficiently dispersed in the cleaning blade nip portion, improving cleaning performance.

[0079] <Developer> The toner can be used as a one-component developer, but in order to further improve dot reproducibility and to provide stable images over a long period of time, it can also be mixed with a magnetic carrier and used as a two-component developer. That is, it is preferable that the toner is the above-mentioned toner, which is a two-component developer containing a toner and a magnetic carrier.

[0080] Examples of magnetic carriers that can be used include commonly known ones such as iron oxide, unoxidized iron powder; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, alloy particles thereof, and oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing a magnetic material and a binder resin that holds the magnetic material in a dispersed state. The mixing ratio of the magnetic carrier and the toner is preferably such that the toner concentration in the two-component developer is 2% by mass or more and 15% by mass or less, more preferably 4% by mass or more and 13% by mass or less.

[0081] <Method of manufacturing toner particles> The method for producing the toner particles is not particularly limited, and known production methods such as suspension polymerization, emulsion aggregation, melt-kneading, and dissolution suspension methods can be used.

[0082] The resulting toner particles can be mixed with the external additives, and optionally other external additives, to obtain a toner. The toner particles and external additives can be mixed using a mixer such as a double cone mixer, a V-type mixer, a drum mixer, a super mixer, a Henschel mixer, a Nauta mixer, a Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or a Nobilta (manufactured by Hosokawa Micron Corporation).

[0083] <Image forming process> An example of an image forming apparatus according to the present invention is shown in FIG. 1. The figure is a vertical cross-sectional view showing the schematic configuration of a digital copying machine. The copying machine shown in the figure uses a drum-type electronic copying machine as an image carrier. The device is equipped with a photosensitive member 101. This photosensitive member 101 is driven to rotate in the direction of the arrow by a driving means (not shown). Around the photosensitive member 101, in approximately the same order along the direction of rotation, are arranged a charging roller 102 as a charging means, an exposure means 103, a developing unit 104, a transfer charger 105, and a cleaning device 107. Furthermore, a fixing unit 106 is arranged downstream (on the left side in the drawing) of the transfer charger 105 in the transport direction (direction of the arrow) of a transfer material 108.

[0084] The surface of the photoreceptor 101 is charged by a charging roller 102 (charging process). Next, a laser beam emitted from an exposure means 103 removes the charge from the laser beam irradiated portion, forming an electrostatic latent image (latent image forming process). The electrostatic latent image on the photoreceptor 101 is developed by a developer 104 using charged toner or a two-component developer containing toner (developing process). The developed toner image on the photoreceptor 101 is transferred by a transfer charger 105 to a transfer material 108 being transported in the direction of the arrow (transfer process). After the toner image transfer, the transfer material 108 is transported to a fixing device 106, where it is heated and pressed to fix the toner image to the surface (fixing process). Residual toner remaining on the photoreceptor after transfer is collected by a cleaning device 107 (cleaning process).

[0085] <Cleaning process> A brush roller, an elastic roller, or an elastic blade is generally used to clean the toner on the electrophotographic image carrier. In the cleaning process, a cleaning blade is preferably brought into contact with the surface of the image carrier after transfer to remove the residual toner remaining on the surface of the image carrier. The most commonly used method is to bring the elastic blade into contact with the counter-direction of movement of the photoreceptor, as this allows for a simple configuration. The elastic material used for the elastic blade is not particularly limited, and any known elastic material used for cleaning blades can be used. For example, a rubber blade can be used.

[0086] The image forming apparatus is not particularly limited in other configuration as long as it employs a blade as a cleaning member, and examples thereof include known image forming apparatuses that include an image carrier and a developing unit that forms a toner image on the surface of the image carrier.

[0087] <Step of supplying fatty acid metal salt> The fatty acid metal salt is present in the cleaning section where the image carrier and the cleaning blade contact each other. That is, it is preferable to include a step of supplying the fatty acid metal salt to the cleaning section after the transfer step. This step makes it possible to stably supply the fatty acid metal salt to the cleaning blade. As a supplying means, a method of supplying the fatty acid metal salt to the surface of the image carrier while scraping it off with a brush roller can be mentioned. Alternatively, a method of externally adding fatty acid metal salt particles to toner particles, developing the toner on an image carrier, and supplying the toner to a cleaning blade may also be suitably used. That is, it is preferable that the external additive further contains fatty acid metal salt particles, and that the toner or a two-component developer containing the toner is developed on an image carrier to supply the fatty acid metal salt particles to a cleaning section.

[0088] Generally, to obtain solidified fatty acid metal salts, they are heated to melt them, poured into a mold, and cooled to solidify, resulting in a molded body. Furthermore, mixing other particles into the molding process can prevent the fatty acid metal salts from clumping together and sticking together, allowing the fatty acid metal salt particles to be supplied to the image carrier surface in a more loosened state. However, if other particles are mixed in, the amount of mixing should be 30% by volume or less, as this reduces the strength of the molded body.

[0089] An example of the supply configuration when scraping off solidified fatty acid metal salt will be explained using the cleaning device 107 in Figure 1. 1071 is a cleaning blade, and a fur brush roller 1072 that assists cleaning is provided upstream of the position where it contacts the image carrier. A molded body 1073 containing fatty acid metal salt is placed on the left side of the fur brush roller 1072 so as to come into contact with the cleaning blade. Furthermore, a fatty acid metal salt pushing member 1074 is provided which pushes the fatty acid metal salt molding toward the fur brush roller by the rotation of the gear. The amount scraped off by the fur brush roller 1072 can be controlled by the fatty acid metal salt pushing member 1074, and a desired amount of fatty acid metal salt particles is supplied to the image carrier surface 101.

[0090] The methods for measuring physical properties according to the present disclosure will be described below. <Separation of external additives and toner particles from toner> Physical properties can also be measured using external additives separated from toner using the following method. 200 g of sucrose (Kishida Chemical) is added to 100 mL of ion-exchanged water and dissolved in a hot water bath to prepare a sucrose concentrate. 31 g of the sucrose concentrate and 6 mL of Contaminon N (a 10% by weight aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and any clumps of toner are broken up using a spatula or similar tool.

[0091] The centrifuge tube is shaken for 20 minutes in a shaker (Iwaki Sangyo KM Shaker (model: V.SX)) at 350 strokes per minute. After shaking, the solution is transferred to a glass tube (50 mL) for a swing-out rotor and centrifuged at 3500 rpm for 30 minutes. After centrifugation, the toner particles are present in the top layer in the glass tube, and the external additives are present in the lower aqueous solution. The lower aqueous solution is sampled and centrifuged to separate the sucrose and the external additives, and the external additives are collected. If necessary, centrifugation is repeated to thoroughly separate the external additives, after which the dispersion is dried and the external additives are collected. When a plurality of external additives are added, the external additives can be selected by using a centrifugal separation method or the like.

[0092] <Method for Identifying Organosilicon Polymer Particles> The organosilicon polymer particles contained in the toner can be identified by a combination of shape observation using an SEM and elemental analysis using EDS.

[0093] Using a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.), the toner is observed at a maximum magnification of 50,000 times. The focus is adjusted to the surface of the toner particles, and the external additives are observed. EDS analysis is performed on each particle of the external additive, and based on the presence or absence of a Si element peak, it is determined whether the analyzed particle is an organosilicon polymer particle.

[0094] When a toner contains both organosilicon polymer particles and inorganic silica particles, the organosilicon polymer particles are identified by comparing the ratio of the elemental contents of Si and O (atomic %) (Si / O ratio) with that of a standard.

[0095] EDS analysis is performed on the respective samples of organosilicon polymer particles and inorganic silica particles under the same conditions to obtain the elemental contents (atomic %) of Si and O.

[0096] The Si / O ratio of the organosilicon polymer particles is designated as A, and the Si / O ratio of the inorganic silica particles is designated as B. Measurement conditions are selected such that A is significantly greater than B. Specifically, the standard is measured 10 times under the same conditions, and the arithmetic mean values ​​for A and B are obtained. The measurement conditions are selected so that the obtained mean value A / B>1.1.

[0097] If the Si / O ratio of the particle being judged is on the A side of [(A+B) / 2], the particle is judged to be an organosilicon polymer particle.

[0098] Tospearl 120A (Momentive Performance Materials Japan, LLC) was used as a sample of organosilicon polymer particles, and HDK V15 (Asahi Kasei) was used as a sample of silica particles.

[0099] <Method for measuring the number average particle size of primary particles of organosilicon polymer particles, inorganic silica particles, and fatty acid metal salt particles> This is performed using a scanning electron microscope "S-4800" (product name: manufactured by Hitachi, Ltd.) in combination with elemental analysis using energy dispersive X-ray analysis (EDS).

[0100] In a field of view magnified up to 50,000 times, the fine particles are randomly photographed using the elemental analysis method using EDS described above. From the captured image, 100 organosilicon polymer particles, inorganic silica particles, and fatty acid metal salt particles are randomly selected, the major axis of the primary particles of the target particles is measured, and the arithmetic average value is taken as the number-average particle size. The observation magnification is adjusted appropriately depending on the size of the particles of interest.

[0101] <Method for quantifying organosilicon polymer particles and inorganic silica particles contained in toner> 1 g of toner is placed in a vial and dissolved in 31 g of chloroform, and dispersed in an ultrasonic homogenizer for 30 minutes to produce a dispersion. Then, using a centrifuge, the organosilicon polymer particles and inorganic silica particles are separated based on the difference in specific gravity to obtain samples, and the contents of the organosilicon polymer particles and inorganic silica particles are determined.

[0102] First, the pressed toner is measured using fluorescent X-rays, and the silicon content in the toner is determined by performing analytical processing such as the calibration curve method or FP method.

[0103] Next, the respective constituent compounds forming the organosilicon polymer particles and inorganic silica particles were subjected to solid 29 The structure is identified using Si-NMR and pyrolysis GC / MS, and the silicon content in the organosilicon polymer particles and inorganic silica particles is determined. The silicon content in the toner determined by fluorescent X-rays and the solid 29 The contents of organosilicon polymer particles and inorganic silica particles in the toner are calculated from the relationship between the silicon content in the organosilicon polymer particles and inorganic silica particles determined by Si-NMR and pyrolysis GC / MS.

[0104] <Method for measuring the amount of organosilicon polymer particles, inorganic silica particles, and fatty acid metal salt particles transferred from toner when the toner is washed with water> (Water washing process) Weigh out 20 g of a 30% by weight aqueous solution of "Contaminon N" (a neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, with a pH of 7) into a 50 mL vial and mix it with 1 g of toner. The mixture is placed in a KM Shaker (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., and shaken for 120 seconds at a speed of 50. Depending on the adhesion state of the organosilicon polymer particles, inorganic silica particles, or fatty acid metal salt particles (when fatty acid metal salt particles are used as an external additive), the organosilicon polymer particles, inorganic silica particles, or fatty acid metal salt particles may migrate from the toner particle surface to the dispersion liquid.

[0105] Then, the mixture was centrifuged using a centrifuge (H-9R; manufactured by Kokusan Co., Ltd.) (16.67 S -1 for 5 minutes) to separate the toner from the organosilicon polymer particles, inorganic silica particles, or fatty acid metal salt particles that have migrated to the supernatant liquid. The precipitated toner is dried by vacuum drying (40°C / 24 hours) and then washed with water to obtain the toner.

[0106] Next, a Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation) is used to photograph the toner that has not been subjected to the above-mentioned washing process (toner before washing) and the toner obtained through the above-mentioned washing process (toner after washing).

[0107] The captured toner surface image is then analyzed using the image analysis software Image-Pro Plus Analysis was performed using ver. 5.0 (Nippon Roper Co., Ltd.) and the coverage rate was calculated. The imaging conditions for the S-4800 are as follows:

[0108] (1) Sample preparation Apply a thin layer of conductive paste to a sample stage (aluminum sample stage 15 mm x 6 mm), then spray toner onto it. Then, use air to remove excess toner from the sample stage and allow it to dry thoroughly. Place the sample stage in the sample holder and adjust the sample stage height to 36 mm using the sample height gauge. (2) S-4800 observation condition setting When measuring the coverage, elemental analysis by the energy dispersive X-ray analysis (EDS) described above is first performed to distinguish between organosilicon polymer particles, silica particles, and fatty acid metal salt particles on the surface of the toner particles before measurement. Pour liquid nitrogen into the anti-contamination trap attached to the S-4800 housing until it overflows and leave it for 30 minutes. Start the S-4800's "PC-SEM" and perform flushing (cleaning the FE chip, which is the electron source). Click the accelerating voltage display area on the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2 and execute it. Confirm that the emission current due to flushing is 20-40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position. Click the accelerating voltage display to open the HV setting dialog, and set the accelerating voltage to [1.1 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Upper (U)] and [+BSE] for the SE detector, and select [LA100] in the selection box to the right of [+BSE] to set the mode for observation using backscattered electron images. Also in the [Basic] tab of the operation panel, set the probe current in the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [4.5 mm]. Press the [ON] button in the accelerating voltage display on the control panel to apply the accelerating voltage. (3) Calculation of the number average particle size (D1) of the toner Drag within the magnification display area on the control panel to set the magnification to 5000 (5k). Rotate the focus knob [COARSE] on the operation panel to achieve a certain degree of focus, then adjust the aperture alignment. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture], and rotate the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the image movement or adjust it so that it moves as little as possible. Close the aperture dialog, and use autofocus to adjust the focus. Repeat this operation twice more to adjust the focus. Thereafter, the particle diameters of 300 toner particles are measured to determine the number average particle diameter (D1). The particle diameter of each particle is the maximum diameter observed when the toner particles are observed. (4) Focus adjustment For the particles with a number average particle diameter (D1) of ±0.1 μm obtained in (3), align the midpoint of the maximum diameter with the center of the measurement screen, and drag within the magnification display section of the control panel to set the magnification to 10,000 (10k) times. Rotate the focus knob [COARSE] on the operation panel until the image is in focus. Adjust the aperture alignment using the [Align] button. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circle. Next, select [Aperture] and rotate the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the image movement or minimize its movement. Close the aperture dialog and use autofocus to adjust the focus. Then, set the magnification to 50,000 (50k)x and adjust the focus using the focus knob and STIGMA / ALIGNMENT knob as described above, then use autofocus to adjust the focus again. Repeat this process to adjust the focus. Here, a large tilt angle of the observation surface tends to reduce the accuracy of the coverage measurement, so when adjusting the focus, select a surface that is in focus across the entire observation surface at the same time, ensuring that the surface is as evenly tilted as possible for analysis. (5) Save image Adjust the brightness in ABC mode, take a photo at a size of 640 x 480 pixels, and save it. Use this image file for the following analysis. Take one photo for each toner, and obtain images for 25 toner particles. (6) Image analysis The image obtained using the above method is binarized using the following analysis software to calculate the coverage. At this time, the above screen is divided into 12 squares and each is analyzed. The analysis conditions for the image analysis software Image-Pro Plus ver. 5.0 are as follows:

[0109] (Analysis conditions for software Image-ProPlus5.1J) From the "Measure" menu on the toolbar, select "Count / Size" and then "Options" to set the binarization conditions. Select 8 connectivity in the object extraction options and set smoothing to 0. In addition, do not select pre-sort, fill holes, or encompass lines, and set "Exclude boundaries" to "None." From the "Measure" menu on the toolbar, select "Measurement Items" and enter 2 to 107 in the area selection range. The coverage rate is calculated by enclosing a square area. The area (C) of the area should be 24,000 to 26,000 pixels. Automatic binarization is performed using "Processing" - Binarization, and the total area (D) of areas without organosilicon polymer particles, silica particles, or fatty acid metal salt particles is calculated.

[0110] The coverage rate can be calculated using the following formula from the area C of the square region and the total area D of the region free of organosilicon polymer particles, inorganic silica particles, or fatty acid metal salt particles. Coverage rate (%)=100-(D / C×100) The arithmetic mean value of all the data obtained is taken as the coverage rate.

[0111] Then, the coverage rate of the toner before washing and the toner after washing are calculated, and the "adhesion rate" is calculated as [coverage rate of toner after washing] / [coverage rate of toner before washing]×100. The "transfer amount" in the present disclosure is calculated by (1 - "adhesion rate") x (content of external additive). The content of the external additive is the mass % added at the time of external addition, and when calculating from the toner, the external additive is separated from the toner by the above-mentioned method and the content of the external additive is calculated.

[0112] <Method for measuring weight average particle size (D4) of toner particles> The weight-average particle size (D4) of the toner particles is measured with an effective number of 25,000 measurement channels using a precision particle size distribution measuring device equipped with a 100 μm aperture tube and using the narrow-pore electrical resistance method, the Coulter Counter Multisizer 3 (registered trademark, manufactured by Beckman Coulter, Inc.), and the accompanying dedicated software for setting measurement conditions and analyzing measurement data, the Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.), and the measurement data is analyzed and calculated. The aqueous 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, such as "ISOTON II" (manufactured by Beckman Coulter). Before carrying out the measurements and analysis, the dedicated software is set up as follows.

[0113] In the "Change Standard Measurement Method (SOM)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman Coulter). Press the threshold / noise level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement." In the dedicated software's "Pulse to particle size conversion setting screen," 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 or more and 60 μm or less. The specific measurement method is as follows:

[0114] (1) Pour approximately 200 ml of the electrolyte solution into a 250 ml round-bottom glass beaker made specifically for the Multisizer 3, set it on the sample stand, and stir the stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flush" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Approximately 30 ml of the above-mentioned aqueous electrolyte solution is placed in a 100 ml flat-bottom glass beaker, and approximately 0.3 ml of a dilution obtained by diluting "Contaminon N" (a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments, pH 7, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by weight with ion-exchanged water is added as a dispersant. (3) A predetermined amount of ion-exchanged water is placed in the water tank of an ultrasonic disperser, "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.), which has two built-in oscillators with an oscillation frequency of 50 kHz and a phase difference of 180 degrees and an electrical output of 120 W, and approximately 2 ml of the Contaminon N is added to this water tank. (4) Set the beaker (2) in the beaker fixing hole of the ultrasonic disperser, operate the ultrasonic disperser, and adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution in the beaker is maximized. (5) While the electrolyte solution in the beaker in (4) is irradiated with ultrasonic waves, approximately 10 mg of toner is added little by little to the electrolyte solution and dispersed. The ultrasonic dispersion process is then continued for another 60 seconds. During the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be between 10°C and 40°C. (6) Using a pipette, the electrolytic solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the measurement concentration is adjusted to approximately 5%. Then, measurements are continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is 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).

[0115] <Measurement of BET specific surface area of ​​organosilicon polymer particles> The BET specific surface area Y can be determined by a low-temperature gas adsorption method using a dynamic constant pressure method in accordance with the BET method (specifically, the BET multipoint method). Nitrogen gas is adsorbed onto the surface of a sample using a specific surface area measuring device (trade name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation), and the BET specific surface area Y (m 2 / g) can be calculated. In addition, the theoretical BET specific surface area X (m 2 / g) is calculated by the following formula, assuming that the particles are spherical. Theoretical BET specific surface area X= (4×π×number average particle size A 2 ) / (4 / 3×π×number average particle size A 3 / density)×1000 Density (cm) required for calculation 3 The value of true density measured using a dry density meter Accupyc 1330 (manufactured by Shimadzu Corporation) is used as the value of the density (density).

[0116] <Method for measuring Young's modulus of organosilicon polymer particles and inorganic silica particles> The Young's modulus of organosilicon polymer particles and inorganic silica particles is determined by microcompression testing using a Hysitron PI 85L Pico Indenter (manufactured by BRUKER). The Young's modulus (MPa) is calculated from the slope of the profile (load-displacement curve) of the displacement (nm) and test force (μN) obtained in the measurement. Equipment and fixtures Base system: Hysitron PI-85L Measuring indenter: 1 μm flat-end indenter SEM used: Thermo Fisher Versa 3D SEM conditions: -10°tilt, 13pA at 10keV Measurement conditions Measurement mode: Displacement control Maximum displacement: 30nm Displacement speed: 1 nm / sec Hold time: 2 seconds Unloading speed: 5nm / sec

[0117] ·Analysis method Hertz analysis is applied to the curve obtained when compressed from 0 nm to 10 nm in the load-displacement curve, and the Young's modulus of the particle is calculated.

[0118] Sample preparation Particles attached to a silicon wafer.

[0119] <Solid 29 Method for identifying constituent compounds of organosilicon polymer particles and measuring their abundance using Si-NMR solid 29 In Si-NMR, peaks are detected in different shift regions depending on the structure of the functional groups bonded to Si in the constituent compounds of the organosilicon polymer particles. By identifying the position of each peak using a standard sample, the structure bonded to Si can be identified. Furthermore, the abundance ratio of each constituent compound can be calculated from the obtained peak area. The ratio of the peak area of ​​Q unit structure, T unit structure, and D unit structure to the total peak area can be calculated.

[0120] solid29 The specific conditions for Si-NMR measurement are as follows: Equipment: JNM-ECX5002 (JEOL RESONANCE) Temperature: room temperature Measurement method: DDMAS method 29 Si 45° Sample tube: zirconia 3.2 mm diameter Sample: Filled in powder form into a test tube Sample rotation speed: 10kHz Relaxation delay: 180s Scan:2000

[0121] After the measurement, the peaks of the multiple silane components of the sample having different substituents and bonding groups are separated into the following M unit structure, D unit structure, T unit structure, and Q unit structure by curve fitting, and the peak area of ​​each is calculated. M unit structure: (Ra)(Rb)(Rc)SiO 1 / 2 (S1) D unit structure: (Rd)(Re)Si(O 1 / 2 )2(S2) T unit structure: RfSi(O 1 / 2 )3(S3) Q unit structure: Si(O 1 / 2 )4(S4) Let (S1+S2+S3+S4)=SA.

[0122] In the formulas (S1), (S2), and (S3), Ra, Rb, Rc, Rd, Re, and Rf represent silicon-bonded organic groups such as hydrocarbon groups having 1 to 6 carbon atoms (e.g., alkyl groups), and halogen atoms. 29 Along with the Si-NMR measurement results 13 C-NMR and 1 The results of H-NMR may also be used for identification. S2 / SA, S3 / SA, and S4 / SA are calculated from SA, S2, S3, and S4 thus determined. [Example]

[0123] The present disclosure will be specifically explained with reference to the following examples. However, these examples are not intended to limit the present disclosure in any way. Unless otherwise specified, "parts" and "%" in the following formulations are all based on mass.

[0124] <Production Example of Organosilicon Polymer Particles 1> 1. Hydrolysis process 43.0 g of RO water and 0.008 g of acetic acid as a catalyst were placed in a 200 ml beaker and stirred at 45° C. 54.0 g of trimethoxymethylsilane was added thereto and stirred for 1.5 hours to obtain a raw material solution.

[0125] 2. Polycondensation process 70.0 g of RO water, 340.0 g of methanol, and 2.0 g of 25% aqueous ammonia were placed in a 1000 ml beaker and stirred at 30°C to prepare an alkaline aqueous medium. The raw material solution obtained in step 1, Hydrolysis, was added dropwise to this alkaline aqueous medium over 1 minute. The mixture after the dropwise addition of this raw material solution was stirred for 1.5 hours while maintaining the temperature at 30°C to allow the polycondensation reaction to proceed, yielding a polycondensation reaction liquid.

[0126] 3.Particleization process 700g of RO water was placed in a 2000ml beaker, and the polycondensation reaction liquid obtained in 2. Polycondensation Step was added dropwise over 10 minutes while stirring at 25°C. The mixture was heated to 40°C and stirred for 1.0 hour while maintaining the temperature at 40°C, yielding a dispersion containing silicon polymer particles having siloxane bonds.

[0127] 4. Hydrophobization process 23 g of hexamethyldisilazane (a hydrophobizing agent) was added to the dispersion containing the siloxane-bonded silicon polymer particles obtained in the particle formation step 3, and the mixture was stirred at 60°C for 2.5 hours. After allowing to stand for 5 minutes, the powder that settled to the bottom of the solution was collected by suction filtration and dried under reduced pressure at 120°C for 24 hours to obtain organosilicon polymer particles 1. The number-average primary particle size of the resulting organosilicon polymer particles 1 measured by SEM was 120 nm. The physical properties of organosilicon polymer particles 1 are shown in Table 1.

[0128] <Production Example of Organosilicon Polymer Particles 2> Organosilicon polymer particles 2 were obtained in the same manner as in the preparation example for organosilicon polymer particles 1, except that in the condensation polymerization step, the stirring temperature of the mixture after dropwise addition of the raw material solution was changed to 35°C. The physical properties of the obtained organosilicon polymer particles 2 are shown in Table 1.

[0129] <Production Example of Organosilicon Polymer Particles 3> Organosilicon polymer particles 3 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the condensation polymerization step, the stirring temperature of the mixture after dropwise addition of the raw material solution was changed to 25°C. The physical properties of the obtained organosilicon polymer particles 3 are shown in Table 1.

[0130] <Production Example of Organosilicon Polymer Particles 4> Organosilicon polymer particles 4 were obtained in the same manner as in the preparation example for organosilicon polymer particles 1, except that in the condensation polymerization step, the stirring temperature of the mixed solution after dropwise addition of the raw material solution was changed to 35°C, and in the particulation step, the stirring temperature was changed to 45°C. The physical properties of the resulting organosilicon polymer particles 4 are shown in Table 1.

[0131] <Production Example of Organosilicon Polymer Particles 5> Organosilicon polymer particles 5 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that in the condensation polymerization step, the stirring temperature of the mixed solution after dropwise addition of the raw material solution was changed to 25°C, and in the particulation step, the stirring temperature was changed to 30°C. The physical properties of the resulting organosilicon polymer particles 5 are shown in Table 1.

[0132] <Production Example of Organosilicon Polymer Particles 6> Organosilicon polymer particles 6 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the silane compounds added in the hydrolysis step were changed to 42.0 g of trimethoxymethylsilane and 12.0 g of dimethyldimethoxysilane. The physical properties of the resulting organosilicon polymer particles 6 are shown in Table 1.

[0133] <Production Example of Organosilicon Polymer Particles 7> Organosilicon polymer particles 7 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the silane compounds added in the hydrolysis step were changed to 31.5 g of trimethoxymethylsilane and 22.5 g of tetraethoxysilane. The physical properties of the resulting organosilicon polymer particles 7 are shown in Table 1.

[0134] <Production Example of Organosilicon Polymer Particles 8> Organosilicon polymer particles 8 were obtained in the same manner as in the preparation example for organosilicon polymer particles 1, except that the amount of 25% aqueous ammonia added in the condensation polymerization step was changed to 1.4 g. The physical properties of the resulting organosilicon polymer particles 8 are shown in Table 1.

[0135] <Production Example of Organosilicon Polymer Particles 9> Organosilicon polymer particles 9 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the amount of 25% aqueous ammonia added in the condensation polymerization step was changed to 3.0 g. The physical properties of the resulting organosilicon polymer particles 9 are shown in Table 1.

[0136] <Production Example of Organosilicon Polymer Particles 10> Organosilicon polymer particles 10 were obtained in the same manner as in the preparation of organosilicon polymer particles 1, except that the silane compounds added in the hydrolysis step were changed to 27.0 g of tetraethoxysilane and 27.0 g of dimethyldimethoxysilane. The physical properties of the resulting organosilicon polymer particles 10 are shown in Table 1.

[0137] [Table 1]

[0138] <Production Example of Inorganic Silica Particles 1> Oxygen gas was supplied to the burner, and the ignition burner was ignited. Hydrogen gas was then supplied to the burner to form a flame, and the raw material silicon tetrachloride was added to the flame and gasified to obtain silica microparticles. The obtained silica microparticles were transferred to an electric furnace, spread in a thin layer, and then heat-treated at 900°C for sintering. Subsequently, the surface was treated with hexamethyldisilazane as a hydrophobic treatment to obtain inorganic silica particles 1. The number-average particle diameter of inorganic silica particles 1 was 100 nm. The Young's modulus of inorganic silica particles 1 was 70,000 MPa. <Production examples of inorganic silica particles 2 and 3> The amount of silicon tetrachloride added, the amount of oxygen gas supplied, the amount of hydrogen gas supplied, the concentration of silica fine particles, the residence time, the sintering temperature and time, and the type of surface treatment agent were adjusted to obtain inorganic silica particles 2 and 3. The number-average particle size of inorganic silica particles 2 was 50 nm, and the number-average particle size of inorganic silica particles 3 was 200 nm. The Young's modulus of inorganic silica particles 2 was 70,000 MPa, and the Young's modulus of inorganic silica particles 3 was 70,000 MPa.

[0139] <Production Example of Polyester Resin A1> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 76.9 parts (0.167 moles) Terephthalic acid (TPA) 25.0 parts (0.145 moles) Adipic acid 8.0 parts (0.054 moles) Titanium tetrabutoxide 0.5 parts The above materials were placed in a 4-liter, four-necked glass flask, fitted with a thermometer, stirring rod, condenser, and nitrogen inlet tube, and placed in a mantle heater. The atmosphere in the flask was then replaced with nitrogen gas, and the temperature was gradually raised with stirring until the mixture was allowed to react for 4 hours at 200°C. Subsequently, 1.2 parts (0.006 mol) of trimellitic anhydride (TMA) was added, and the mixture was allowed to react for 1 hour at 180°C, yielding polyester resin A1. The softening point of this polyester resin A1 was 90°C.

[0140] <Production Example of Polyester Resin A2> Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane 71.3 parts (0.155 moles) Terephthalic acid 24.1 parts (0.145 moles) Titanium tetrabutoxide 0.6 parts The above materials were placed in a 4-liter, four-necked glass flask, and a thermometer, stirring rod, condenser, and nitrogen inlet tube were attached. The flask was then placed in a mantle heater. After the atmosphere inside the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was allowed to react for 2 hours at 200°C. Thereafter, 5.8 parts (0.030 mol %) of trimellitic anhydride was added, and the mixture was allowed to react at 180°C for 10 hours to obtain polyester resin A2. The softening point of this polyester resin A2 was 130°C.

[0141] <Production Example of Toner Particle 1> Polyester resin A1 70.0 parts by weight Polyester resin A2 30.0 parts by weight Fischer-Tropsch wax (peak temperature of the maximum endothermic peak: 78°C) 5.0 parts by weight CI pigment blue 15:3 5.0 parts by weight 3,5-di-t-butylsalicylic acid aluminum compound 0.1 parts by weight

[0142] The raw materials shown in the above recipe were mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s -1 After mixing for 5 minutes, the mixture was kneaded in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 125°C and a rotation speed of 300 rpm. The resulting kneaded mixture was cooled and coarsely pulverized using a hammer mill to obtain a coarsely pulverized product with a diameter of 1 mm or less. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation). Further, classification was carried out using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles 1. The operating conditions for the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) during classification were a classification rotor rotation speed of 50.0 s -1 The resulting toner particles 1 had a weight average particle size (D4) of 6.2 μm.

[0143] <Toner 1 manufacturing example> Toner particles 1 100 parts by mass Organosilicon polymer particles 1 1.4 parts by weight Inorganic silica particles 1 2.0 parts by mass The above materials were mixed in a Henschel mixer FM-10C (Mitsui Miike Chemical Engineering Co., Ltd.) at a rotation speed of 65 s -1 The mixture was mixed for a rotation time of 10 minutes to obtain Toner 1. The amount of migration of Toner 1 is shown in Table 2.

[0144] <Production examples of toners 2-18, 22-27> Toners 2 to 18 and 22 to 27 were obtained in the same manner as in the production example of Toner 1, except that the external toner additive particles, addition amounts, and external addition conditions were changed to those shown in Table 2. The migration amounts of each toner are shown in Table 2.

[0145] <Production example of zinc stearate particles> A receiver equipped with a stirrer was prepared, and the stirrer was rotated at 350 rpm. 500 parts of a 0.5% by mass aqueous solution of sodium stearate was added to the receiver, and the liquid temperature was adjusted to 85°C. Next, 525 parts of a 0.2% by mass aqueous solution of zinc sulfate was added dropwise to the receiver over 15 minutes. After the entire amount was added, the mixture was aged for 10 minutes at the reaction temperature to terminate the reaction. Next, the fatty acid metal salt slurry thus obtained was filtered and washed. The washed fatty acid metal salt cake obtained was roughly crushed and then dried at 105°C using a continuous flash air dryer. Thereafter, it was dried in a nano grinding mill [NJ-300] (manufactured by Sunrex Co., Ltd.) with an air volume of 6.0 m 3 The mixture was pulverized at a processing speed of 80 kg / h at a flow rate of 1000 kJ / min, and then reslurried and subjected to a wet centrifugal classifier to remove fine and coarse particles. The mixture was then dried at 80°C using a continuous flash air dryer to obtain zinc stearate particles. The number-average particle size of the primary particles of the obtained zinc stearate particles was 500 nm.

[0146] <Production example of toners 19 to 21> In the manufacturing example of Toner 1, the types and amounts of external additives added were changed to those shown in Table 2. In the external addition step, organosilicon polymer particles and inorganic silica particles were added and the rotation speed was 65 s -1 ,times After mixing for 8 minutes, zinc stearate particles were added and the mixture was mixed at a rotation speed of 65 seconds. -1 The mixture was mixed for a rotation time of 2 minutes. Otherwise, toners 19 to 21 were produced in the same manner as toner 1. The migration amount of each toner is shown in Table 2.

[0147] [Table 2]

[0148] <Carrier 1 manufacturing example> Number average particle size 0.30 μm (1000 / 4π (kA / m) magnetic field magnetization strength 65 Am 2 / kg) of magnetite Number average particle size 0.50 μm (1000 / 4π (kA / m) magnetic field magnetization strength 65 Am 2 / kg) of magnetite To each of the above materials, 4.0 parts by mass of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was mixed and stirred at high speed in a container at 100° C. or higher to treat each of the fine particles.

[0149] Phenol: 10% Formaldehyde solution (40% formaldehyde, 10% methanol, 50% water): 6% Magnetite treated with the above silane compound: 58% Magnetite treated with the above silane compound: 26% The above materials, 5 parts of a 28% aqueous ammonia solution, and 20 parts of water were placed in a flask, and the mixture was heated to 85°C over 30 minutes and maintained at that temperature while stirring and mixing. A polymerization reaction was carried out for 3 hours, and the resulting phenolic resin was hardened. The hardened phenolic resin was then cooled to 30°C, and more water was added. The supernatant was then removed, and the precipitate was washed with water and air-dried. This was then dried at 60°C under reduced pressure (5 mmHg or less), yielding a spherical magnetic material-dispersed carrier 1. The 50% particle size (D50) on a volume basis was 34.2 μm.

[0150] <Manufacturing example of two-component developer 1> Toner 1 was added in an amount of 8.0 parts by mass to 92.0 parts by mass of Carrier 1, and the mixture was mixed in a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[0151] <Production examples of two-component developers 2 to 27> Two-component developers 2 to 27 were obtained by carrying out production in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 3.

[0152] [Table 3]

[0153] Example 1 The two-component developer 1 was evaluated as follows. A modified Canon imageRUNNER ADVANCE C5560 digital commercial printing printer was used as the image forming device, and two-component developer 1 was placed in the cyan position developer unit to evaluate cleaning performance. As shown in Figure 2, a fur brush roller 3 is installed on a metal plate 4 attached upstream of cleaning blade 1. The fur brush roller 3 abuts against solidified zinc stearate rods 2, and as it rotates, it scrapes off the zinc stearate and supplies it to the photosensitive drum surface. Toner and other materials removed by cleaning blade 1 are collected on toner collection sheet 5 and then collected in waste toner collection container 6.

[0154] Here, the discharge current amount in the primary charging process was 100 μA (the definition of discharge current is described in JP 2009-128842 A). The photosensitive drum used had a taper wear amount of 0.5 mg (the method for measuring taper wear amount is described in JP 2009-128842 A), and the photosensitive drum surface had Rz = 1.0 μm and Sm = 50 μm. The surface roughness of the photosensitive drum was measured as follows using a contact-type surface roughness measuring instrument (product name: Surfcorder SE3500, manufactured by Kosaka Laboratory Co., Ltd.).

[0155] The detector was a diamond stylus with an R of 2 μm and a force of 0.7 mN, the filter was 2CR, the cutoff value was 0.8 mm, the measurement length was 2.5 mm, and the feed rate was 0.1 mm, and the data for the 10-point average roughness Rz defined in JIS standard B0601 was processed. The average spacing Sm of the surface irregularities was measured under the same conditions and is the arithmetic mean value obtained from the following formula:

[0156]

number

[0157] Examples of surface roughening means for controlling the surface shape of the photosensitive drum include, but are not limited to, abrasive sheets and abrasive grinding.

[0158] The cleaning performance was evaluated under the following conditions. <Cleaning evaluation conditions> Test environment: Temperature 23°C, relative humidity 5% Discharge current during primary charging process: 120 μA Cleaning blade setting angle: 20° Cleaning blade support method: Oscillating type Cleaning blade contact pressure against photosensitive drum: 25.0 N / m Solid amount on photosensitive drum: 0.3 to 0.4 mg / cm 2 Under the above conditions, 1000 sheets of a horizontal band A4 chart with a print rate of 10% were printed, and then untransferred toner equivalent to 10 A3 solid sheets was supplied to the cleaning blade at a process speed of 260 mm / sec, and then taped, and the amount of toner that had slipped through the cleaning blade was measured. The amount of toner that had slipped through was estimated from the reflection density using X Rite by taping the photoreceptor.

[0159] The evaluation criteria are as follows: The evaluation results are shown in Table 4. A: Less than 0.010 (very good) B: 0.010 or more and less than 0.015 (good) C: 0.015 or more and less than 0.020 (a level that is not problematic in this disclosure) D: 0.020 or more (unacceptable in this disclosure)

[0160] <Transferability evaluation conditions> The "durability stability" of the present disclosure was verified by evaluating transferability under severe conditions in which the toner was subjected to durability degradation, that is, conditions that tend to cause external additives to be embedded in the toner particles. The durability conditions are as follows: Paper: CS-680(68.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner amount on photoconductor: 0.35 mg / cm 2 (FFh image, solid image) Test environment: Temperature 30°C, relative humidity 80% As a durability image output test, 10,000 sheets of A4 paper were output using a band chart with an image ratio of 0.1% and FFh output.

[0161] The transferability was evaluated using low-smoothness paper with a Beck smoothness of 15 to 20 degrees (Hammer Mill Great White, LTR size, basis weight 75 g / m 2 The image for evaluation was taken from the center of the A4 paper, 10 cm in diameter. 2 The image is placed, and the toner amount on the photoconductor is 0.35 mg / cm 2 (FFh image), and the image density after output was measured.

[0162] The transferability was evaluated based on the difference in image density between before and after the durability image output test. The image density was measured using a spectrodensitometer (X-Rite 504 Spectrodensitometer). The evaluation criteria were as follows. The evaluation results are shown in Table 4. A: Density difference is less than 0.10 B: Density difference is 0.10 or more and less than 0.15 C: Density difference is 0.15 or more and less than 0.25 D: Density difference is 0.25 or more Rank C or higher is considered to be a level at which the effects of the present disclosure are being obtained.

[0163] <Examples 2 to 18 and Comparative Examples 4 to 9> The developers used in each example are shown in Table 4. Other evaluation conditions were the same as in Example 1. The evaluation results are shown in Table 4. In Comparative Example 9, image defects occurred due to contamination of the components, making it impossible to properly evaluate the cleaning and transfer properties.

[0164] Example 19 The contact pressure of the cleaning blade against the photosensitive drum was set to 20.0 N / m. The other conditions were the same as in Example 1. The evaluation results are shown in Table 4.

[0165] Example 20 The contact pressure of the cleaning blade against the photosensitive drum was set to 40.0 N / m. The other conditions were the same as in Example 1. The evaluation results are shown in Table 4.

[0166] <Examples 21 to 23 and Comparative Examples 1 to 3> The fur brush roller 3 and zinc stearate rod 2 shown in Figure 1 were removed. The developer used is as shown in Table 4. Other conditions are shown in Table 4 together with the evaluation results.

[0167] [Table 4]

[0168] As a result of the evaluation, the toner of the present disclosure achieved excellent cleaning properties as shown in Table 4. [Explanation of symbols]

[0169] 101 Photoreceptor 102 charging roller 103 Exposure means 104 Developer 105 Transfer charger 106 Fixing device 107 Cleaning device 108 Transfer material 1071 Cleaning Blade 1072 Fatty acid metal salt - rectangular parallelepiped shaped abrasive particles coated brush roller 1073 Fatty acid metal salt - rectangular parallelepiped abrasive particle compact 1074 Fatty acid metal salt - rectangular parallelepiped abrasive particle compact indenter 1 cleaning blade 2 Fatty acid metal salt rod 3 Fur brush roller 4. Sheet Metal 5 Toner collection sheet 6 Waste toner collection container

Claims

1. a charging step of charging the image carrier; a latent image forming step of forming an electrostatic latent image on the image carrier charged in the charging step; a developing step of developing the electrostatic latent image formed on the image carrier using a toner or a two-component developer containing a toner to form a toner image on the image carrier; a transfer step of transferring the toner image to a transfer material with or without an intermediate transfer member; a fixing step of fixing the toner image transferred onto the transfer material; and a cleaning step of contacting a cleaning blade with the surface of the image bearing member after transfer to remove residual toner remaining on the surface of the image bearing member; An image forming method comprising: a fatty acid metal salt is present in a cleaning portion where the image bearing member and the cleaning blade contact each other; The toner comprises toner particles and an external additive, the external additive comprises organosilicon polymer particles and inorganic silica particles, When the toner is subjected to a water washing treatment, the toner before the water washing treatment is used as a reference. the amount of the organosilicon polymer particles transferred from the toner is A% by mass, When the amount of the inorganic silica particles transferred from the toner is B mass %, The A and the B satisfy the following formulas (1) and (2), The external additive further contains fatty acid metal salt particles, developing the toner or a two-component developer containing the toner on the image carrier, thereby supplying the fatty acid metal salt particles to the cleaning section; an amount of the fatty acid metal salt particles transferred from the toner when the toner is subjected to a water-washing treatment, the amount being C% by mass, based on the amount of the toner before the water-washing treatment; and 0.5≦A+B≦4.0 (1) 0.3≦B / A≦2.0 (2)

2. the number average particle size of the primary particles of the organosilicon polymer particles is 50 nm or more and 200 nm or less; 2. The image forming method according to claim 1, wherein the number average particle size of the primary particles of the inorganic silica particles is 50 nm or more and 200 nm or less.

3. 3. The image forming method according to claim 1, wherein the organosilicon polymer particles have a Young's modulus of 1,500 MPa or more and 30,000 MPa or less.

4. The theoretical BET specific surface area of ​​the organosilicon polymer particles is defined as X (m ２ / g), and the BET specific surface area of ​​the organosilicon polymer particles measured by the BET multipoint method is defined as Y(m ２ 4. The image forming method according to claim 1, wherein X and Y satisfy the following formula (3) when X=1 / (1 / 2) ... 2.0≦Y / X≦8.5 (3)

5. 5. The image forming method according to claim 1, wherein the contact pressure of the cleaning blade against the image bearing member is 20.0 N / m or more and 40.0 N / m or less as a linear pressure per unit length in the longitudinal direction at the contact point.

6. 6. The image forming method according to claim 1, further comprising a step of supplying a fatty acid metal salt to the cleaning section after the transferring step.

7. A toner having toner particles containing a binder resin and a colorant, and an external additive, the external additive comprises organosilicon polymer particles, inorganic silica particles, and fatty acid metal salt particles; When the toner is subjected to a water washing treatment, the toner before the water washing treatment is used as a reference. the amount of the organosilicon polymer particles transferred from the toner is A% by mass, When the amount of the inorganic silica particles transferred from the toner is B mass %, A toner in which A and B satisfy the following formulas (1) and (2), The toner is characterized in that, when the toner is subjected to a water washing treatment, the amount of the fatty acid metal salt particles that migrates from the toner is defined as C mass % based on the toner before the water washing treatment, and C is 0.01 to 1.

00. 0.5≦A+B≦4.0 (1) 0.3≦B / A≦2.0 (2)

8. A two-component developer containing a toner and a magnetic carrier, wherein the toner is the toner according to claim 7.

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