External additive particles, method for producing external additive particles, and toner

Abstract

To provide an external additive particle with which it is possible to obtain a toner that can have good fluidity and the charge amount of which hardly changes depending on an environment even when successive image outputs are carried out.SOLUTION: Provided is an external additive particle that contains a polymer having a vinyl polymer part and a polysiloxane part, wherein the percentage of atomic number of silicon atoms is 4.0% to 25.0% with respect to the sum total of atomic number of carbon, oxygen and silicon atoms in the external additive particle, the polymer having the structure indicated by formula (1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to external additive particles, a method for producing external additive particles, and a toner. [Background technology]

[0002] In recent years, there has been a demand for even faster speeds and longer life for electrophotographic image forming devices. In response to these demands, toners with excellent fluidity and developability are being investigated, which have the stress resistance to withstand long periods of friction in the developing device and can obtain high image quality even in high-speed printing.

[0003] Patent Document 1 discloses that the fluidity and the like of a toner can be improved by incorporating a toner additive having an organic polymer skeleton and a polysiloxane skeleton into the toner. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 8-202071 Summary of the Invention [Problem to be solved by the invention]

[0005] One aspect of the present disclosure is to provide external additive particles that can produce toner that has excellent fluidity and whose charge amount is less likely to change depending on the environment, even when continuous image output is performed.

[0006] Another aspect of the present disclosure is directed to providing a toner to which the external additive particles according to the present disclosure are externally added.

[0007] Another aspect of the present disclosure is directed to providing a method for producing external additive particles according to the present disclosure. [Means for solving the problem]

[0008] According to one aspect of the present disclosure, there is provided an external additive particle comprising a polymer having a vinyl polymer portion and a polysiloxane portion, the ratio of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms in the external additive particles is 4.0% or more and 25.0% or less; The polymer has a structure represented by the following formula (1): The external additive particles are provided.

[0009] [ka]

[0010] (In formula (1), R' is a hydrogen atom or a methyl group; L2 is SiO 3 / 2 Units and SiO 2 / 2 It is a polysiloxane moiety containing units, SiO 2 / 2 At least one silicon atom constituting the unit has two alkyl groups having 1 to 10 carbon atoms bonded to the silicon atom, L1 is *―COOR 1 -**, *-CH2-**, or *-COOR 1 -SiR 2 2-O-** and R 1 is an alkylene group having 1 to 10 carbon atoms, and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, and * represents R ’ and ** is the bonding site with the carbon atom bonded to SiO included in L2. 3 / 2 (These are the bonding sites for the silicon atoms that make up the unit.)

[0011] According to another aspect of the present disclosure, there is provided a toner comprising toner particles and an external additive on the surfaces of the toner particles, A toner is provided in which the external additive is the external additive particles according to the present disclosure.

[0012] According to another aspect of the present disclosure, there is provided a method for producing external additive particles containing a polymer, the method comprising: The manufacturing method comprises: (i) a step of performing a radical polymerization reaction of a monomer raw material containing at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6), to obtain a polymer having a hydrolyzable group X;

[0013] [ka]

[0014] (In formulas (4) to (6), X 1 ~X 7 are each independently a hydrolyzable group X, and each R' is independently a hydrogen atom or a methyl group. 5 and R 6 are each independently an alkylene group having 1 to 10 carbon atoms, and R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms), (ii) adding a polysiloxane A having a hydrolyzable group Y; (Polysiloxane A: SiO 2 / 2 It is a polysiloxane containing SiO 2 / 2 At least the unit is SiO represented by the following formula (7): 2 / 2 SiO 2 represented by the following formula (8) 2 / 2 Polysiloxane having units

[0015] [ka]

[0016] (In formula (7), R 9 is an alkyl group having 1 to 10 carbon atoms, and R 10 is an alkylene group having 1 to 10 carbon atoms, and Y is a hydrolyzable group. 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms. (iii) performing a hydrolysis reaction and a polycondensation reaction between the hydrolyzable group X of the polymer and the hydrolyzable group Y of the polysiloxane A to obtain particles containing a polymer in which the polymer and the polysiloxane A are bonded by a siloxane bond; Including, Method for producing external additive particles. [Effects of the Invention]

[0017] According to one aspect of the present disclosure, it is possible to provide external additive particles that can produce a toner that has excellent fluidity and whose charge amount is less likely to change depending on the environment, even when continuous image output is performed.

[0018] According to another aspect of the present disclosure, a toner to which the external additive particles according to the present disclosure are externally added can be provided.

[0019] According to another aspect of the present disclosure, a method for producing external additive particles according to the present disclosure can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0020] Unless otherwise specified, the expressions "xx or more and xx or less" and "xx to xx" 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.

[0021] In this disclosure, SiO N / 2 This refers to a unit in which, of the four valences of a silicon atom, N are bonded to oxygen atoms, and each of the N oxygen atoms is bonded to Si. In other words, this refers to a unit in which each of the N oxygen atoms forms a siloxane bond (Si-O-Si).

[0022] <Background to the invention> The technology disclosed in Patent Document 1 certainly provides a toner additive that can impart excellent fluidity. The inventors speculate that this is because the polysiloxane skeleton increases the mechanical strength of the particles, and the organic polymer skeleton increases affinity with the binder resin of the toner, making it less likely to separate from the toner particles. After further investigation of the above additive, they found that controlling the proportion of silicon atoms in the external additive particles makes it easier to improve the fluidity of the toner.

[0023] On the other hand, when continuous image output is performed using a toner containing the above-mentioned external additive particles with a controlled silicon atom ratio, the difference in toner charge tends to be large between when used in a room temperature, low humidity environment and when used in a high temperature, high humidity environment. The inventors speculate that this is because the friction between the above-mentioned external additive particles having a polysiloxane moiety and the toner particles is easily affected by humidity, and as a result, the triboelectric charge of the toner tends to change. From the perspective of stably outputting high-quality images in various environments, it is preferable that the change in the toner charge depending on the environment is small. Therefore, it has been recognized that further improvement of the above-mentioned external additive particles is necessary.

[0024] Based on the above considerations, the present inventors have investigated external additive particles that can provide a toner having excellent fluidity and whose charge amount is less likely to change depending on the environment, and have found that incorporating a structure represented by the following formula (1) into a polymer contained in the external additive particles is effective in realizing a toner having the above properties.

[0025] [ka]

[0026] (In formula (1), R' is a hydrogen atom or a methyl group; L2 is SiO 3 / 2 SiO units, and SiO2 units in which two alkyl groups with 1 to 10 carbon atoms are bonded to a silicon atom. 2 / 2is a polysiloxane moiety comprising units, L1 is *―COOR 1 -**, *-CH2-**, or *-COOR 1 -SiR 2 2-O-** and R 1 is an alkylene group having 1 to 10 carbon atoms, and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, and * represents R ’ and ** is the bonding site with the carbon atom bonded to SiO included in L2. 3 / 2 (This is the bonding site with the silicon atoms that make up the unit.) The present inventors speculate that the inclusion of a polymer having the above structure in the external additive particles makes the external additive particles less susceptible to the effects of humidity. This is because the SiO 2 / 2 This is thought to be because the inclusion of the external additive unit makes the polysiloxane moiety more likely to exhibit hydrophobic properties, and as a result, the present inventors speculate that the toner to which the external additive particles are externally added will have less change in charge amount depending on the environment (especially humidity).

[0027] Each of the constituent elements will be described in detail below.

[0028] <Polymer having a vinyl polymer moiety and a polysiloxane moiety> The polymer contained in the external additive particles has a vinyl polymer portion and a polysiloxane portion.

[0029] The vinyl polymer portion in the polymer is an organic polymer skeleton formed by polymerizing a vinyl-based polymerizable monomer. The inclusion of the vinyl polymer skeleton is thought to increase affinity with the resin constituting the toner particles, making it difficult for the external additive particles to separate from the toner particles.

[0030] Furthermore, the polymer contained in the external additive particles contains not only a vinyl polymer portion but also a siloxane portion, which makes the external additive particles containing the polymer according to the present disclosure likely to have sufficient mechanical strength and be resistant to plastic deformation, and therefore the toner to which the external additive particles are externally added can have excellent fluidity.

[0031] Particles having only a polysiloxane skeleton, such as silica particles, have high mechanical strength but low affinity with the resin that constitutes the toner particles, and may separate from the toner particles, which may reduce the fluidity of the toner.

[0032] Furthermore, particles having only an organic polymer skeleton, such as polymethyl methacrylate particles, have low mechanical strength, and therefore, when used as external additive particles, they are likely to undergo plastic deformation or breakage due to mechanical impact in a developing machine, etc. As a result, the toner may be more likely to adhere to various components, and the fluidity of the toner may be reduced.

[0033] <The ratio of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms> The proportion of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms in the external additive particles is 4.0% or more and 25.0% or less.

[0034] The present inventors believe that the above ratio is an index of how many siloxane moieties are present in the external additive particles.

[0035] When the above ratio is 4.0% or more, sufficient siloxane moieties are present in the external additive particles, which is thought to make the external additive particles less susceptible to plastic deformation, making it easier to obtain a toner with excellent fluidity. Furthermore, when the ratio is 25.0% or less, the amount of siloxane moieties in the external additive particles is less likely to become excessive, and a sufficient amount of vinyl polymer moieties is contained in the external additive particles, which is thought to make the external additive particles less likely to separate from the toner particles, making it easier to obtain a toner with excellent fluidity. Therefore, the ratio is 25.0% or less, preferably 20.0% or less, more preferably 15.0% or less, and even more preferably 10.0% or less. That is, the ratio is more preferably 4.0% or more and 10.0% or less.

[0036] The ratio of the number of atoms described above can be controlled by adjusting the type and amount of the monomer unit containing a silicon atom and the type and amount of the monomer unit not containing a silicon atom when producing the polymer contained in the external additive particles. It can also be controlled by the order of the radical polymerization reaction, hydrolysis reaction, and polycondensation reaction when producing the polymer contained in the external additive particles.

[0037] <Structure in polymer> The polymer according to the present disclosure has a structure represented by the following formula (1):

[0038] [ka]

[0039] (In formula (1), R' is a hydrogen atom or a methyl group; L2 is SiO 3 / 2 Units and SiO 2 / 2 It is a polysiloxane moiety containing units, SiO 2 / 2 At least one silicon atom constituting the unit has two alkyl groups having 1 to 10 carbon atoms bonded to the silicon atom, L1 is *―COOR 1 -**, *-CH2-**, or *-COOR1 -SiR 2 2-O-** and R 1 is an alkylene group having 1 to 10 carbon atoms, and R 2 are each independently an alkyl group having 1 to 10 carbon atoms, and * represents R ’ and ** is the bonding site with the carbon atom bonded to SiO included in L2. 3 / 2 (These are the bonding sites for the silicon atoms that make up the unit.)

[0040] As described above, the polysiloxane portion in the above structure is SiO , in which two alkyl groups having 1 to 10 carbon atoms are bonded to the silicon atom. 2 / 2 It is believed that the inclusion of the SiO 2 unit reduces the environmentally dependent change in charge amount of the toner to which the external additive particles according to the present disclosure are externally added. 3 / 2 The present inventors believe that because the polymer contains units and there are three-dimensionally bonded portions in the polysiloxane portion, the polymer is likely to have sufficient mechanical strength and become external additive particles that are resistant to plastic deformation.

[0041] SiO contained in the above L2 2 / 2 The unit is SiO, in which two alkyl groups with 1 to 5 carbon atoms are bonded to a silicon atom. 2 / 2 More preferably, it is a SiO unit in which two alkyl groups having 1 to 3 carbon atoms are bonded to a silicon atom. 2 / 2 It is more preferable that at least one of the two alkyl groups bonded to the silicon atom is a methyl group. 2 / 2 More preferably, it is a unit, and even more preferably, it is an SiO 2 unit in which two methyl groups are bonded to a silicon atom. 2 / 2 It is a unit.

[0042] Above R 1 is preferably an alkylene group having 1 to 5 carbon atoms. 2 are each independently preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. 1 -** is preferred.

[0043] In addition, SiO contained in L2 (polysiloxane portion) 3 / 2 At least one silicon atom constituting the unit preferably has a group represented by the following formula (2) bonded thereto. R 3 -SiO 2 / 2 -R 4 -※···(2) (In the above formula (2), R 3 is an alkyl group having 1 to 6 carbon atoms, and R 4 is an alkylene group having 1 to 10 carbon atoms, and * indicates the bonding site with the silicon atom.

[0044] The polysiloxane portion is SiO represented by formula (2) 3 / 2 The present inventors speculate that the inclusion of such a unit reduces the environmentally dependent change in the charge amount of the toner and increases the mechanical strength of the external additive particles.

[0045] Above R 3 More preferably, R is an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. 4 More preferably, it is an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms.

[0046] In addition, from the viewpoint of the change in the charge amount of the toner depending on the environment, SiO contained in L2 (polysiloxane part) 2 / 2 At least one silicon atom constituting the unit preferably has bonded thereto an alkyl group having 1 to 3 carbon atoms and a group represented by the following formula (3). (R 32 )(R 33 )(Si(R 34 )3)Si-R 31 -※※···(3) (In the above formula (3), R 32 , R 33 , and R 34 are each independently an alkyl group having 1 to 3 carbon atoms, and R 31 is an alkylene group having 1 to 3 carbon atoms, and ※※ is the bonding site to the silicon atom.

[0047] The method for obtaining the polymer according to the present disclosure includes a method of carrying out vinyl polymerization using a vinyl monomer containing a silicon atom bonded to a hydrolyzable group such as an alkoxy group, followed by hydrolysis of the hydrolyzable group and polycondensation reaction to form a siloxane bond.In addition, in this method, vinyl polymerization is first carried out to form a polymer chain, and then hydrolysis and polycondensation are carried out to form a siloxane bond in the polymer or between the polymers, thereby obtaining a polymer in which the vinyl polymer is crosslinked by a siloxane bond.That is, as one of the preferred aspects of the polymer according to the present disclosure, the polymer is preferably a polymer in which the vinyl polymer is crosslinked by a siloxane bond.It is believed that by including this polymer in the external additive particles, the mechanical strength of the external additive particles is easily increased and plastic deformation is less likely to occur.

[0048] In the above method, when the hydrolysis and polycondensation reactions are carried out, the polysiloxane moiety (L2) according to the present disclosure is introduced into the polymer by adding a polysiloxane described below.

[0049] Furthermore, since it is believed that the effects of the present disclosure can be more easily obtained, the polymer according to the present disclosure is preferably contained in an amount of 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more, relative to the mass of the external additive particles.

[0050] <D50 of external additive particles> In order to appropriately control the adhesive force of the external additive particles to the toner, when the 50% particle size of the external additive particles based on volume distribution is defined as D50, it is preferable that D50 is 50 nm or more and 200 nm or less.

[0051] <Method for producing external additive particles> When producing the external additive particles, it is preferable to carry out a radical polymerization reaction using a compound containing both a radical polymerizable group and a hydrolyzable group that forms a siloxane bond by hydrolysis and polycondensation in the molecule. Then, SiO 2 represented by the following formula (7) is added. 2 / 2SiO 2 represented by the following formula (8) 2 / 2 It is preferable to add a polysiloxane having a unit, and then carry out a hydrolysis reaction of the hydrolyzable group and a polycondensation reaction to obtain polycondensate particles. By carrying out the radical polymerization reaction first, the main skeleton of the polymer contained in the external additive particles becomes a vinyl polymer moiety, which is thought to increase affinity with the resin constituting the toner, and to increase the fluidity of the toner to which the external additive particles are externally added. In the present disclosure, at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6) is cited as a monomer containing both a radical polymerizable group and a hydrolyzable group in its molecule.

[0052] That is, one aspect of the present disclosure is a method for producing external additive particles containing a polymer, the method comprising: The manufacturing method comprises: (i) a step of performing a radical polymerization reaction of a monomer raw material containing at least one compound selected from the group consisting of a compound represented by the following formula (4), a compound represented by the following formula (5), and a compound represented by the following formula (6), to obtain a polymer having a hydrolyzable group X;

[0053] [ka]

[0054] (In formulas (4) to (6), X 1 ~X 7 are each independently a hydrolyzable group X, and each R' is independently a hydrogen atom or a methyl group. 5 and R 6 are each independently an alkylene group having 1 to 10 carbon atoms, and R 7 and R 8 are each independently an alkyl group having 1 to 10 carbon atoms), (ii) adding a polysiloxane A having a hydrolyzable group Y; (Polysiloxane A: SiO 2 / 2 It is a polysiloxane containing SiO 2 / 2At least the unit is SiO represented by the following formula (7): 2 / 2 SiO 2 represented by the following formula (8) 2 / 2 Polysiloxane having units

[0055] [ka]

[0056] (In formula (7), R 9 is an alkyl group having 1 to 10 carbon atoms, and R 10 is an alkylene group having 1 to 10 carbon atoms, and Y is a hydrolyzable group. 11 and R 12 are each independently an alkyl group having 1 to 10 carbon atoms. (iii) performing a hydrolysis reaction and a polycondensation reaction between the hydrolyzable group X of the polymer and the hydrolyzable group Y of the polysiloxane A to obtain particles containing a polymer in which the polymer and the polysiloxane A are bonded by a siloxane bond; Including, The method for producing external additive particles is preferred.

[0057] By carrying out a hydrolysis reaction and a polycondensation reaction between the hydrolyzable group X of the polymer obtained in step (i) and the hydrolyzable group Y of the polysiloxane A, a polymer in which the polymer and the polysiloxane A are bonded is obtained. As a result, the polymer preferably has the polysiloxane moiety represented by L2 above. In addition, the SiO contained in the polysiloxane A 2 / 2 At least one silicon atom constituting the unit preferably has bonded thereto an alkyl group having 1 to 3 carbon atoms and a group represented by the following formula (3). (R 32 )(R 33 )(Si(R 34 )3 O )Si-R 31 -※※···(3) (In the above formula (3), R 32 , R 33 , and R 34are each independently an alkyl group having 1 to 3 carbon atoms, and R 31 is an alkylene group having 1 to 3 carbon atoms, and ※※ is the bonding site to the silicon atom.

[0058] Furthermore, in this production method, hydrolysis and polycondensation are carried out after the molecular chain of the vinyl polymer is formed, so it is thought that the amount of siloxane bonds is unlikely to become excessive, making it easier to obtain external additive particles in which the proportion of silicon atoms in number is controlled.

[0059] In formulas (4) to (6), R 5 ~R 8 The number of carbon atoms in R in formula (7) is more preferably 1 to 5. 9 More preferably, R is an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group. 10 More preferably, it is an alkylene group having 1 to 5 carbon atoms, and even more preferably an alkylene group having 1 to 3 carbon atoms.

[0060] Furthermore, R in equation (8) 11 and R 12 is more preferably an alkyl group having 1 to 5 carbon atoms, even more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group.

[0061] The hydrolyzable group according to the present disclosure refers to a functional group that is converted to a hydroxy group when hydrolyzed while bonded to a silicon atom, or a hydroxy group. Examples include at least one selected from the group consisting of a hydroxy group, a fluoro group, a chloro group, a bromo group, an iodo group, an alkoxy group, and an acyloxy group. Preferred alkoxy groups include a methoxy group, an ethoxy group, and a propoxy group, and preferred acyloxy groups include an acetoxy group. Preferred hydrolyzable groups according to the present disclosure are a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, and an acetoxy group, and more preferred are a methoxy group and an ethoxy group. The radically polymerizable group according to the present disclosure refers to a substituent having a radically reactive double bond in its structure, such as a vinyl group, an acryloxyalkyl group, or a methacryloxyalkyl group.

[0062] From the viewpoint of toner fluidity, the content of at least one compound selected from the group consisting of compounds represented by formulas (4) to (6) is preferably 50 to 80% by mass, more preferably 60 to 75% by mass, based on the total mass of the monomer raw materials having a radical polymerizable group.

[0063] <Radical polymerization reaction (step (i))> The radical polymerization reaction method is preferably an emulsion polymerization method. The emulsion polymerization method is a polymerization method in which a medium such as water, a monomer that is poorly soluble in the medium, and an emulsifier (surfactant) or an ionic comonomer are mixed, and a polymerization initiator that is soluble in the medium is added thereto. The emulsion polymerization method is preferably a soap-free emulsion polymerization method in which polymerization is performed without using a surfactant. The present inventors believe that this is because the soap-free emulsion polymerization method prevents the surfactant from remaining on the surface of the external additive particles, making it easier to control the affinity between the toner particles and the external additive particles.

[0064] The radical polymerization initiator used in the radical polymerization is not particularly limited, but is preferably at least one compound selected from persulfates, azo compounds, and peroxides, and more preferably persulfates. The amount of the radical polymerization initiator is not particularly limited, but is preferably 0.1 to 10 mass% relative to the total mass of the monomer raw materials having a radical polymerizable group, and more preferably 0.3 to 5.0 mass%. When the amount of the radical polymerization initiator is within the above range, the radical polymerization can proceed sufficiently and the amount of heat generated in the reaction system is less likely to be excessive, which is preferable.

[0065] The temperature during radical polymerization can be appropriately selected depending on the type and amount of the radical polymerization initiator used, and is preferably in the range of 30 to 100°C, more preferably in the range of 50 to 80°C.

[0066] The radical polymerization step (step (i)) is preferably carried out under conditions of 6.0≦pH≦8.0, more preferably 6.5≦pH≦7.5. When the pH of the reaction system is within the above range, it is thought that hydrolysis of hydrolyzable groups and polycondensation reactions are less likely to occur during the progress of the radical polymerization reaction. For this reason, the radical polymerization reaction is preferably carried out in a buffer solution. There are no particular limitations on the buffer solution, and any buffer solution showing a pH near neutral, such as a phosphate buffer solution or an MES buffer solution, may be used.

[0067] Furthermore, in the case of radical polymerization, not only a monomer containing both a radically polymerizable group and a hydrolyzable group but also other monomers having a radically polymerizable group may be used.

[0068] Examples of other monomers include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, unsaturated carboxylic acid esters such as acrylic acid esters, methacrylic acid esters, crotonates, itaconic acid esters, maleates, and fumarates, acrylamides, methacrylamides, aromatic vinyl compounds such as styrene, α-styrene, and divinylbenzene, vinyl esters such as vinyl acetate, and vinyl halide compounds such as vinyl chloride. These monomers may be used alone or in combination. Monomers containing two or more radically polymerizable groups, such as divinylbenzene, trimethylolpropane trimethacrylate, and ethylene glycol dimethacrylate, may also be used.

[0069] <Hydrolysis reaction and polycondensation reaction (step (iii))> In the production method according to the present disclosure, after the above-mentioned radical polymerization reaction, the above-mentioned polysiloxane A is added, and a hydrolysis reaction and a polycondensation reaction are carried out.

[0070] The methods for the hydrolysis and polycondensation reactions are not particularly limited, but a preferred method is to add a catalyst such as an acid or a base to an emulsion containing particles obtained by radical polymerization, and then perform hydrolysis and polycondensation directly to obtain polymer particles. Alternatively, the particles obtained by radical polymerization may be isolated from the emulsion by filtration, centrifugation, vacuum concentration, or other procedures, and then a catalyst may be added to perform hydrolysis and polycondensation. Furthermore, step (iii) according to the present disclosure preferably includes a step of performing the reaction under conditions of 10.0≦pH≦12.0.

[0071] When carrying out hydrolysis or polycondensation after particle formation by radical polymerization reaction, a catalyst such as acetic acid, hydrochloric acid, ammonia, urea, alkanolamine, tetraalkylammonium hydroxide, alkali metal hydroxide, or alkaline earth metal hydroxide may be used.

[0072] Examples of more preferred catalysts from the viewpoint of further promoting polycondensation include organic titanium compounds such as titanium tetraisopropoxide, titanium tetrabutoxide, and diisopropoxy-bis(acetylacetonate) titanate; organic aluminum compounds such as aluminum triisopropoxide, aluminum tri-sec-butoxide, aluminum trisacetylacetonate, and aluminum isopropoxide-bisacetylacetonate; organic zirconium compounds such as zirconium tetrabutoxide and tetrakis(acetylacetonate)zirconium; organic tin compounds such as dibutyltin diacetate, dibutyltin diethylhexanoate, and dibutyltin dimaleate; and acidic phosphate esters. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of organic tin compounds and acidic phosphate esters is preferred.

[0073] The solvent used in producing the external additive particles may contain an organic solvent other than water and the catalyst. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, pentanol, ethylene glycol, propylene glycol, and 1,4-butanediol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate, (cyclo)paraffins such as isooctane and cyclohexane, ethers such as dioxane and diethyl ether, and aromatic hydrocarbons such as benzene and toluene. Two or more of these organic solvents may be mixed and used.

[0074] The hydrolysis reaction and polycondensation reaction can be carried out, for example, by adding an appropriate catalyst to the emulsion prepared by the radical polymerization reaction and stirring at a temperature in the range of 0 to 100°C, preferably 0 to 70°C, for 3 to 24 hours.

[0075] <Post-processing> The particles obtained by carrying out the radical polymerization and hydrolysis-polycondensation as described above are isolated from the slurry by a method such as filtration, centrifugation, vacuum concentration, spray drying, or flash vacuum drying, and then preferably dried at 30 to 100° C., more preferably at 30 to 80° C., and even more preferably at 50 to 70° C. By carrying out such a drying treatment, external additive particles having appropriate charging properties and appropriate mechanical strength are easily obtained.

[0076] From the viewpoint of toner chargeability, it is preferable to treat the surface of the external additive particles obtained by the above production method with a surface treatment agent in order to treat the hydroxyl groups remaining on the surface of the external additive particles and to adjust the amount of negative charge. Examples of the surface treatment agent include silicon compounds such as organoalkoxysilane and hexamethyldisilazane, titanium compounds such as tetrabutyl titanate, and hydrolyzates and condensates thereof.

[0077] The method for the surface treatment is not particularly limited, as long as it can coat the surfaces of the external additive particles with the surface treatment agent. For example, the surface treatment can be carried out by placing the external additive particles in a suitable container, then adding the surface treatment agent, and mixing and contacting them with stirring at room temperature (25°C ± 5°C) to about 100°C for 3 to 24 hours. In this case, the surface treatment can be more uniformly carried out by dissolving the surface treatment agent in a solvent such as methanol and gradually adding this dropwise while mixing and contacting. The amount of surface treatment agent present on the surface of the external additive can be adjusted by appropriately selecting the type of surface treatment agent, the surface treatment time, the particle size of the external additive, and the like. If necessary, the surface-treated object can be washed with, for example, alcohol to obtain an external additive from which unnecessary substances have been removed.

[0078] <Toner> Furthermore, the external additive particles according to the present disclosure are preferably contained on the surface of toner particles. That is, one aspect of the present disclosure is a toner containing toner particles and an external additive on the surface of the toner particles, wherein the external additive is the external additive particle according to the present disclosure.

[0079] The toner particles preferably contain a binder resin, such as a polyester resin, a vinyl resin, an epoxy resin, or a polyurethane resin.

[0080] The binder resin preferably has a glass transition point (Tg) of 45 to 70°C from the viewpoint of storage stability.

[0081] <Method of manufacturing toner particles> The method for producing the toner particles according to the present disclosure is not particularly limited, and for example, a pulverization method or a polymerization method such as an emulsion polymerization method, a suspension polymerization method, or a solution suspension method can be used.

[0082] The pulverization method will now be described. In the pulverization method, first, the binder resin, colorant, wax, charge control agent, etc. that constitute the toner particles are thoroughly mixed using a mixer such as a Henschel mixer or a ball mill. Next, the resulting mixture is melted and kneaded using a thermal kneader such as a twin-screw kneading extruder, a heated roll, a kneader, or an extruder, and then cooled and solidified, followed by pulverization and classification. This yields toner particles.

[0083] Examples of kneaders include the following: KRC kneader (manufactured by Kurimoto Iron Works); Buss-Co kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by The Japan Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Kneadex (manufactured by Mitsui Mining Co., Ltd.); MS-type pressure kneader, kneader-ruder (manufactured by Nippon Spindle Co., Ltd.); and Banbury mixer (manufactured by Kobe Steel, Ltd.).

[0084] Examples of pulverizers include the following: Counter Jet Mill, Micron Jet, Innomizer (manufactured by Hosokawa Micron Corporation); IDS-type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Mfg. Co., Ltd.); Cross Jet Mill (manufactured by Kurimoto Iron Works Co., Ltd.); Urmax (manufactured by Nisso Engineering Co., Ltd.); SK Jet-O-Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Industrial Co., Ltd.); and Super Rotor (manufactured by Nisshin Engineering Co., Ltd.).

[0085] Examples of classifiers include the following: Cruseal, Micron Classifier, and Spedic Classifier (manufactured by Seishin Enterprise Co., Ltd.); Turbo Classifier (manufactured by Nisshin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), and TSP Separator (manufactured by Hosokawa Micron Corporation); Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), and Dispersion Separator (manufactured by Nippon Pneumatic Industry Co., Ltd.); and YM Microcut (manufactured by Yaskawa Corporation).

[0086] The suspension polymerization method will be described. In the suspension polymerization method, first, a polymerizable monomer capable of producing a binder resin and various additives, if necessary, are mixed, and the materials are dissolved or dispersed using a disperser to prepare a polymerizable monomer composition. Examples of the various additives include colorants, waxes, charge control agents, polymerization initiators, and chain transfer agents. Examples of dispersers include homogenizers, ball mills, colloid mills, and ultrasonic dispersers. Next, the polymerizable monomer composition is added to an aqueous medium containing poorly water-soluble inorganic fine particles, and droplets of the polymerizable monomer composition are prepared using a high-speed disperser such as a high-speed stirrer or ultrasonic disperser (granulation step). The polymerizable monomer in the droplets is then polymerized to obtain toner particles (polymerization step). The polymerization initiator may be mixed during the preparation of the polymerizable monomer composition, or may be mixed into the polymerizable monomer composition immediately before forming droplets in the aqueous medium. Furthermore, the toner particles may be added in a state of being dissolved in a polymerizable monomer or another solvent, as required, during or after the granulation of the droplets, i.e., immediately before the start of the polymerization reaction. After the polymerizable monomer is polymerized to obtain a binder resin, the resulting mixture may be subjected to a solvent removal treatment as required to obtain a dispersion of toner particles.

[0087] <Method of adding external additives to toner particles> The toner according to the present disclosure can be obtained by mixing toner particles and external additives using a mixer such as a Henschel mixer.

[0088] Examples of mixers include the following: Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); Super mixer (manufactured by Kawata Corporation); Ribocone (manufactured by Okawara Manufacturing Co., Ltd.); Nauta mixer, Turbulizer, Cyclomix (manufactured by Hosokawa Micron Corporation); Spiral pin mixer (manufactured by Pacific Machinery Works Co., Ltd.); and Lödige mixer (manufactured by Matsubo Corporation).

[0089] The toner particles preferably contain, on their surfaces, the above-described external additive particles as well as other external additives, such as those listed below.

[0090] Fluorine-based resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; fine powder silica such as wet-process silica and dry-process silica, fine powder titanium oxide, fine powder alumina, treated silica obtained by surface-treating these with a silane compound, a titanium coupling agent, or silicone oil; oxides such as zinc oxide and tin oxide; double oxides such as strontium titanate, barium titanate, calcium titanate, strontium zirconate, and calcium zirconate; carbonate compounds such as calcium carbonate and magnesium carbonate, etc.

[0091] <Various additives for toner> If necessary, the toner may contain one or more additives selected from colorants, waxes, magnetic materials, charge control agents, etc. Various additives used in the toner will be specifically described below.

[0092] <Magnetic material> The toner may contain magnetic particles and be used as a magnetic toner. In this case, the magnetic particles may also serve as a colorant.

[0093] Examples of magnetic particles contained in the magnetic toner include the following.

[0094] Iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, or alloys and mixtures thereof of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, bismuth, calcium, manganese, titanium, tungsten, and vanadium.

[0095] The magnetic particles preferably have an average particle size of 2 μm or less, more preferably 0.05 μm or more and 0.5 μm or less, and the content of the magnetic particles is preferably 20 parts by mass or more and 200 parts by mass or less, more preferably 40 parts by mass or more and 150 parts by mass or less, per 100 parts by mass of the binder resin.

[0096] <Coloring agent> Examples of colorants include the following:

[0097] As a black colorant, for example, carbon black, grafted carbon, or the yellow / magenta / cyan colorants shown below are used to tone the color to black.

[0098] Yellow colorants include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.

[0099] Examples of magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds, etc. Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, etc.

[0100] The colorants may be used alone or in combination, or in the form of a solid solution. The colorants are selected in consideration of hue angle, chroma, brightness, weather resistance, transparency for overhead projectors, and dispersibility in the toner.

[0101] The content of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

[0102] <Wax> Examples of waxes include the following:

[0103] Low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymers, aliphatic hydrocarbon waxes such as polyolefin wax, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, block copolymers of aliphatic hydrocarbon waxes, and oxides thereof.

[0104] Ester waxes whose main component is fatty acid ester, such as carnauba wax; partially or completely deoxidized fatty acid esters, such as deoxidized carnauba wax.

[0105] <Charge control agent> The charge control agent is not particularly limited, but is preferably an organic metal complex or a chelate compound, such as a monoazo metal complex, an acetylacetone metal complex, or a metal complex or metal salt of an aromatic hydroxycarboxylic acid or an aromatic dicarboxylic acid.

[0106] Specific examples that can be used include Spilon Black TRH, T-77, and T-95 (Hodogaya Chemical Co., Ltd.), and BONTRON (registered trademark) S-34, S-44, S-54, E-84, E-88, and E-89 (Orient Chemical Co., Ltd.). Charge control resins can also be used in combination with the above-mentioned charge control agents.

[0107] <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 may also be mixed with a magnetic carrier and used as a two-component developer.

[0108] As the magnetic carrier, for example, iron with an oxidized surface, iron with an unoxidized surface, nickel, cobalt, manganese, chromium, rare earth metals, and alloys or oxides thereof are preferably used.

[0109] Furthermore, it is preferable that the surface of the magnetic carrier contains or is coated with a styrene-based resin, an acrylic-based resin, a silicone-based resin, a fluorine-based resin, or a polyester.

[0110] <Various measurement methods, etc.> Various measurement methods will be described below.

[0111] <Method for measuring the ratio of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms present in external additive particles, and the abundance ratio of carbon atoms to silicon atoms> Carbon and oxygen atoms The concentrations (atomic %) of carbon atoms and oxygen atoms present in the external additive particles are calculated using elemental analysis by combustion. The device for elemental analysis is shown below. Equipment used: PerkinElmer 2400II fully automatic elemental analyzer Silicon atoms The concentration (atomic %) of silicon atoms present in the external additive particles is measured by elemental analysis using inductively coupled plasma atomic emission spectrometry (ICP-AES) with alkali fusion. The ICP-AES device is shown below. Equipment used: Shimadzu ICPS-8100 The obtained composition ratio is converted into mole percent, and the converted value is used to calculate the ratio of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms in the external additive particles.

[0112] <Measuring method for the 50% particle size (D50) of a particle sample based on its volume distribution> The 50% particle size (D50) of the volume distribution standard of the fine particle sample is measured using a dynamic light scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso). Specifically, the range is set to 0.001 μm to 10 μm, and the measurement is performed according to the following procedure.

[0113] To prevent the sample from agglomerating, a dispersion of the sample is placed in an aqueous solution containing Family Fresh (Kao Corporation) and stirred. After stirring, the sample is poured into the above-mentioned device and measured twice to obtain the average value.

[0114] The measurement conditions are as follows: measurement time is 30 seconds, the refractive index of the sample particles is 1.49, the dispersion medium is water, and the refractive index of the dispersion medium is 1.33.

[0115] The volume particle size distribution of the measurement sample is measured, and the particle size at which the cumulative volume from the small particle diameter side in the cumulative volume distribution is 50% is defined as the 50% particle size (D50) of the volume distribution standard for each microparticle. [Example]

[0116] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to these examples. Unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0117] Example 1 <External Additive 1 Manufacturing Example> The following materials were placed in a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a stirrer. Phosphate buffer solution (pH = 7.0, prepared using sodium dihydrogen phosphate dihydrate (Kishida Chemical Co., Ltd.) and disodium hydrogen phosphate dodecahydrate (Kishida Chemical Co., Ltd.)) 200 parts Sodium p-styrenesulfonate (Kishida Chemical Co., Ltd.) 0.13 parts Monomer having a radical polymerizable group and a hydrolyzable group: 11.0 parts of 3-(trimethoxysilyl)propyl methacrylate (Tokyo Chemical Industry Co., Ltd.) Non-hydrolyzable monomer: styrene (Tokyo Chemical Industry Co., Ltd.) 4.7 parts Next, the mixture was heated to 65-70°C while passing nitrogen gas through it. After stirring for 30 minutes, 0.51 parts of potassium peroxodisulfate (Kishida Chemical Co., Ltd.) was added as an initiator, and the mixture was stirred for 6 hours to carry out vinyl polymerization, yielding a particle emulsion. To the resulting particle emulsion, 28% by mass ammonia water (Kishida Chemical Co., Ltd.) was added as an ammonia treatment to adjust the pH of the emulsion to 11.0, and then 0.19 parts of KF-9908 (Shin-Etsu Chemical Co., Ltd.) was added as polysiloxane (B). The mixture was then stirred at 50°C for 24 hours to hydrolyze and polycondense the hydrolyzable groups contained in the particles and polysiloxane B. Ultrafiltration was then performed to remove excess solute, and concentration / filtration was repeated a total of five times. The mixture was then spray-dried to obtain external additive 1, which had a 50% particle size (hereinafter referred to as D50) based on volume distribution of 130 nm. The physical properties of external additive 1 are shown in Table 2.

[0118] <Production Example of Toner Particle 1> The following materials were premixed in a Henschel mixer, and then melt-kneaded using a twin-screw extruder (product name: PCM-30, manufactured by Ikegai Iron Works Co., Ltd.) with the temperature set so that the melt temperature at the discharge outlet would be 150°C, to obtain a kneaded material. Amorphous polyester (propylene oxide adduct of bisphenol A / terephthalic acid = 50 / 50, number average molecular weight: 3000, acid value: 12) 100 parts Magnetic iron oxide particles 75 parts Fischer-Tropsch wax (Sasol C105, melting point: 105°C) 2 parts Charge control agent (Hodogaya Chemical Co., Ltd., T-77) 2 parts The resulting kneaded product was cooled, coarsely pulverized with a hammer mill, and then finely pulverized with a pulverizer (product name: Turbo Mill T250, manufactured by Turbo Kogyo Co., Ltd.) to obtain a finely pulverized powder. The finely pulverized powder obtained was classified with a multi-division classifier utilizing the Coanda effect to obtain toner particles 1 having a weight average particle size of 7.2 μm.

[0119] <Toner 1 manufacturing example> The external additive was added to the toner particles 1 in a dry manner. 100.0 parts of the toner particles 1, 1.3 parts of the external additive 1, and 1.5 parts of fumed silica (BET specific surface area: 200 m) were added to a Henschel mixer. 2 / g) was added and externally mixed in. Thereafter, the mixture was sieved through a mesh with an opening of 150 μm, and toner 1 in which external additive 1 was externally added to toner particles 1 was obtained.

[0120] <Evaluation> Toner 1 was used to carry out the following evaluations.

[0121] <Evaluation of toner fluidity> The fluidity of the toner was measured by the following method.

[0122] First, using a powder tester (PT-X, manufactured by Hosokawa Micron Corporation), 3 g of toner 1 was sieved through sieves (plain woven wire mesh, JIS Z8801-1 standard) with mesh sizes of 150 μm, 100 μm, and 45 μm for 10 seconds while vibrating the sieves at a vibration intensity of 4.0. The fluidity of the toner was evaluated using the fluidity index (%) given by the following formula, where A is the amount of toner remaining on the 150 μm mesh sieve, B is the amount of toner remaining on the 100 μm mesh sieve, and C is the amount of toner remaining on the 45 μm mesh sieve. The evaluation results are shown in Table 3. A fluidity index of 30% or less was determined to be an indication that the effects of the present disclosure were achieved.

[0123] Fluidity index (%) = [(A + 0.6 × B + 0.2 × C) / measured sample mass] × 100 <Evaluation of changes in toner charge amount due to environmental changes (before durability testing)> First, two samples were prepared by placing 0.5 g of Toner 1 and 9.5 g of Carrier N-01 (manufactured by the Imaging Society of Japan) in a 50 mL polyethylene container. One sample was then placed in a room temperature, low humidity environment (20°C, 10% RH, hereafter referred to as the NL environment), and the other sample was placed in a high temperature, high humidity environment (30°C, 80% RH, hereafter referred to as the HH environment) overnight. Each sample was then shaken for 5 minutes at a rate of 200 shakes per minute, and the toner charge was measured using a TB-200 blow-off powder charge analyzer (manufactured by Toshiba Chemical Co.). The blow-off time was 2 minutes. The charge of the toner placed in the HH environment was then subtracted from the charge of the toner placed in the NL environment to determine the environmental difference in toner charge (μC / g).

[0124] <Evaluation of changes in toner charge amount due to environmental changes (after durability test)> An HP LaserJet Enterprise M609dn (manufactured by HP) was used as the image forming apparatus, and Toner 1 was placed in a cartridge, and 5,000 images were output under the following conditions. ·Paper: GFC-081 (81.0g / m 2 )(Canon Marketing Japan Inc.) Toner coverage on paper: 0.35mg / cm 2 Process speed: 377 mm / sec The residual toner in the cartridge was then removed, and the same evaluation as in the evaluation of the environmental stability of toner charge was performed using the residual toner. The measured value of the toner charge amount obtained in this evaluation was used as the toner charge amount after the durability test, and the environmental difference in toner charge amount (μC / g) was calculated in the same manner as in the evaluation of the environmental stability of toner charge.

[0125] After the durability test, it was determined that the effect of the present disclosure was obtained when the environmental difference in toner charge amount was 30 μC / g or less.

[0126] The environmental difference in the toner charge amount obtained in the above two evaluations was substituted into the following formula to calculate the amount of variation.

[0127] Fluctuation amount (μC / g) = (environmental difference in toner charge amount after durability test (μC / g)) - (environmental difference in toner charge amount before durability test (μC / g)) <Evaluation of external additive particle crushing and detachment from toner particles> Evaluation of crushing of external additive particles and detachment from toner particles was carried out after the durability test. After outputting 5,000 images, the toner 1 remaining in the cartridge was removed, and the surface of the removed toner 1 was observed using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation), and an SEM image was obtained. In the obtained image, if crushed deposits were observed on the surface of the toner, it was judged as crushing, and if recesses from which external additive particles had detached were observed on the surface of the toner, it was judged as detachment.

[0128] <Example 2~ 9、 11 and Comparative Examples 1 to 3> The same procedure as in Example 1 was carried out except that the materials used were changed as shown in Table 1, and external additives 2 to 9、11~ After obtaining 14, the same evaluation was carried out. 9、11~ The physical properties of Example 14 are shown in Table 2. The evaluation results are shown in Table 3. Comparative Example 1 is a comparative example in which the structure shown in (1) above is not contained in the polymer having a vinyl polymer moiety. This is because the polysiloxane (B) added in Comparative Example 1 does not have a reactive site capable of bonding with the polymer.

[0129] <Comparative Example 4> The same procedure as in Example 1 was carried out to obtain External Additive 15, except that External Additive 1 was changed to the following External Additive 15. Then, a toner was produced in the same manner as in Example 1, and evaluated. The evaluation results are shown in Table 3.

[0130] [External additive 15 manufacturing example] The following materials were placed in a glass reactor equipped with a thermometer, a reflux condenser, a nitrogen gas inlet tube, and a stirrer. 200 parts deionized water Ionic monomer: sodium p-styrenesulfonate 0.13 parts Non-hydrolyzable monomer: 6.3 parts of butyl methacrylate (Tokyo Chemical Industry Co., Ltd.), and 4.7 parts of styrene Next, the mixture was heated to 65-70°C while passing nitrogen gas through it. After stirring for 30 minutes, 0.51 parts of potassium peroxodisulfate was added as an initiator, and stirring was continued for 6 hours to obtain a particle emulsion. 28% by mass aqueous ammonia (Kishida Chemical Co., Ltd.) was then added to adjust the pH of the emulsion to 11.0, and 0.19 parts of KF-9908 (Shin-Etsu Chemical Co., Ltd.) was added as polysiloxane (B). The mixture was then stirred at 50°C for 24 hours to hydrolyze the hydrolyzable groups contained in polysiloxane B and polycondense the mixture. Ultrafiltration was then performed to remove excess solute, and concentration / filtration was repeated a total of five times. The mixture was then spray-dried to obtain external additive 15. The physical properties of external additive 15 are shown in Table 2.

[0131] [Table 1]

[0132] The abbreviations in Table 1 are as follows: MA-TMSP: 3-(trimethoxysilyl)propyl methacrylate MA-TESP: 3-(triethoxysilyl)propyl methacrylate AA-TMSP: 3-(trimethoxysilyl)propyl acrylate MA-CDMSP: 3-(chlorodimethylsilyl)propyl methacrylate MAB: butyl methacrylate St: styrene NaPSS: sodium p-styrenesulfonate KPS: potassium peroxodisulfate KF-9908 (trade name): Triethoxysilylethyl polydimethylsiloxyethyl dimethicone (manufactured by Shin-Etsu Chemical Co., Ltd.) KF-9909 (trade name): Triethoxysilylethyl polydimethylsiloxyethylhexyl dimethicone (Shin-Etsu Chemical Co., Ltd.) KF-96-50cs (product name): Dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.) KF-9908 and KF-9909 used in the examples are SiO 2 represented by the following formula (10): 2 / 2 Unit: SiO represented by the following formula (11) 2 / 2 unit, and SiO represented by the following formula (12) 2 / 2 KF-9909 is a polysiloxane having an SiO 2 unit represented by the following formula (13): 2 / 2 It is a polysiloxane having units.

[0133] [ka]

[0134] [Table 2]

[0135] The values ​​in Table 2 were measured using the measurement method described above. In addition, Si / C+O+Si in Table 2 is the ratio of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms in the external additive particles.

[0136] [Table 3]

Claims

1. An external additive particle comprising a polymer having a vinyl polymer portion and a polysiloxane portion, the ratio of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms in the external additive particles is 4.0% or more and 25.0% or less; The polymer has a structure represented by the following formula (1): The external additive particles are characterized by: 【Chemical 1】 (In formula (1), R' is a hydrogen atom or a methyl group; L2 is SiO ３／２ Units and SiO ２／２ is a polysiloxane moiety containing units, SiO ２／２ At least one silicon atom constituting the unit has two alkyl groups having 1 to 10 carbon atoms bonded to the silicon atom, and at least one silicon atom constituting the SiO 3 / 2 unit has a group represented by the following formula (2): R 3 -SiO 2 / 2 -R 4 -*...(2) (In the above formula (2), R 3 is an alkyl group having 1 to 6 carbon atoms, R 4 is an alkylene group having 1 to 10 carbon atoms, and * indicates the bonding site with the silicon atom.) A group represented by L1 is *-COOR １ -** or *-COOR １ -SiR ２ ２ -O-**, and R １ is an alkylene group having 1 to 10 carbon atoms, and R ２ are each independently an alkyl group having 1 to 10 carbon atoms, and * is R ’ is the bonding site with the carbon atom bonded to SiO contained in L2. ３／２ It is the bonding site with the silicon atom that makes up the unit.)

2. the ratio of the number of silicon atoms to the total number of carbon atoms, oxygen atoms, and silicon atoms in the external additive particles is 4.0% or more and 10.0% or less; The external additive particles according to claim 1 .

3. When the 50% particle diameter of the external additive particles based on the volume distribution is defined as D50, 3. The external additive particles according to claim 1, wherein the D50 is 50 nm or more and 200 nm or less.

4. The SiO ２／２ The external additive particle according to any one of claims 1 to 3, wherein an alkyl group having 1 to 3 carbon atoms and a group represented by the following formula (3) are bonded to at least one silicon atom constituting the unit: (R) ３２ )(R ３３ )(Si(R ３４ ) ３ O)Si-R ３１ -※※・・・(3) (In the above formula (3), R ３２ , R ３３ , and R ３４ are each independently an alkyl group having 1 to 3 carbon atoms, and R ３１ is an alkylene group having 1 to 3 carbon atoms, and * is the bonding site with the silicon atom.)

5. 5. The external additive particle according to claim 1, wherein the polymer is a polymer in which a vinyl polymer is crosslinked by a siloxane bond.

6. A toner containing toner particles and an external additive on the surface of the toner particles, A toner, wherein the external additive is the external additive particles according to any one of claims 1 to 5.

7. A method for producing external additive particles containing a polymer, comprising: The manufacturing method comprises: (i) performing a radical polymerization reaction of a monomer raw material containing at least one compound selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (6) to obtain a polymer having a hydrolyzable group X; 【Chemistry 2】 (In formulas (4) and (6), X １ ~X3, X ７ are each independently a hydrolyzable group X, and each R' is independently a hydrogen atom or a methyl group. ５ and R ６ are each independently an alkylene group having 1 to 10 carbon atoms, and R ７ and R ８ are each independently an alkyl group having 1 to 10 carbon atoms. (ii) adding a polysiloxane A having a hydrolyzable group Y, (Polysiloxane A: SiO ２／２ It is a polysiloxane containing SiO units, ２／２ At least the unit is SiO represented by the following formula (7): ２／２ units and SiO represented by the following formula (8): ２／２ Polysiloxane having units 【Chemistry 3】 (In formula (7), R ９ is an alkyl group having 1 to 10 carbon atoms, and R １０ is an alkylene group having 1 to 10 carbon atoms, and Y is a hydrolyzable group. １１ and R １２ are each independently an alkyl group having 1 to 10 carbon atoms. (iii) performing a hydrolysis reaction and a polycondensation reaction between the hydrolyzable group X of the polymer and the hydrolyzable group Y of the polysiloxane A to obtain particles containing a polymer in which the polymer and the polysiloxane A are bonded by a siloxane bond; Including, Method for producing external additive particles.

8. The method for producing external additive particles according to claim 7, wherein the hydrolyzable group X and the hydrolyzable group Y are each independently at least one selected from the group consisting of a hydroxy group, a methoxy group, an ethoxy group, a propoxy group, and an acetoxy group.

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