Toner

Abstract

To provide a toner that has very good low temperature fixability and has good hot offset resistance and scratch resistance.SOLUTION: A toner has a toner particle containing a binder resin and inorganic fine particles. The binder resin contains a crystalline vinyl resin having a specific monomer unit having at least two long-chain alkyl groups. The content of the specific monomer unit is 5.0 mass% or more with respect to the mass of the crystalline vinyl resin. The inorganic fine particles each have an alkyl group on its surface. The content of the inorganic fine particles is 0.10-15.00 mass% with respect to the mass of the toner particle.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to toner used in electrophotography, electrostatic recording, electrostatic printing, and toner jet methods.

Background Art

[0002] In recent years, as full-color copiers using the electrophotographic method have become widespread, the demand for high-speed printing and energy conservation has been increasing further. In particular, under the "Sustainable Development Goals (SDGs)" adopted by the United Nations, efforts to suppress greenhouse gas emissions including CO2 are being made in countries around the world, and the demand for energy conservation is becoming even stronger. As a measure for energy conservation, in order to reduce the power consumption in the fixing process, a technique for fixing toner at a lower temperature is being studied.

[0003] It is known that by using a crystalline resin having sharp meltability as the main component of the binder resin of the toner, it has excellent low-temperature fixability compared to a toner whose main component is an amorphous resin. For example, in Patent Document 1, a toner that achieves both excellent low-temperature fixability and heat-resistant storage stability by having a crystalline resin as a matrix and an amorphous resin as a domain has been proposed. Also, in Patent Document 2, a toner using a crystalline vinyl resin has been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] Toners containing a crystalline vinyl resin such as behenyl acrylate as a main component of a binder resin have made it possible to fix the toner at a lower fixing temperature than before. However, the present inventors have recognized that toners containing a crystalline vinyl resin may be inferior to conventional toners in terms of rubbing resistance and hot offset resistance. The present disclosure is directed to a toner having extremely excellent low-temperature fixability and excellent hot offset resistance and rubbing resistance.

Means for Solving the Problems

[0006] The present disclosure is a toner having toner particles containing a binder resin and inorganic fine particles, The binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1), The content of the monomer unit represented by the following formula (1) is 5.0% by mass or more based on the mass of the crystalline vinyl resin, The inorganic fine particles have an alkyl group on the surface, The present disclosure relates to a toner in which the content of the inorganic fine particles is 0.10 to 15.00% by mass based on the mass of the toner particles.

Chemical formula

Advantages of the Invention

[0007] According to the present disclosure, it is possible to provide a toner having extremely excellent low-temperature fixability and excellent hot offset resistance and rubbing resistance.

Modes for Carrying Out the Invention

[0008] In the present disclosure, descriptions such as "XX or more and YY or less" and "XX to YY" representing numerical ranges mean numerical ranges including the lower limit and the upper limit which are endpoints, unless otherwise specified. When numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined. In the present disclosure, descriptions such as "at least one selected from the group consisting of XX, YY, and ZZ" mean any one of XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ.

[0009] The "monomer unit" refers to the reacted form of the monomer substance in the polymer. For example, in the main chain where vinyl monomers in the polymer are polymerized, one section of the carbon-carbon bond is taken as one unit. The vinyl monomer can be represented by the following formula (3).

Chemical formula

[0010] In formula (3), R A represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and R B represents an arbitrary substituent. The crystalline vinyl resin refers to a resin that shows a distinct endothermic peak in differential scanning calorimetry (DSC) measurement and is synthesized from any vinyl monomer.

[0011] The present disclosure relates to a toner having toner particles containing a binder resin and inorganic fine particles, wherein the binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1), the content of the monomer unit represented by the following formula (1) is 5.0% by mass or more based on the mass of the crystalline vinyl resin, the inorganic fine particles have an alkyl group on the surface, Regarding a toner in which the content of the inorganic fine particles is 0.10 to 15.00% by mass based on the mass of the toner particles. [Chemical formula] (In formula (1), at least two of R 1 ~R 4 are each independently -X-COOR 5 , and the rest are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a single bond or an alkylene group having 1 or 2 carbon atoms, and R 5 is an alkyl group having 16 to 30 carbon atoms.)

[0012] The present inventors considered the cause of the decrease in the hot offset resistance of the toner containing the above-described crystalline vinyl resin as follows. Crystalline vinyl resins including the resin using behenyl acrylate used in the toner often have a melting point lower than the fixing temperature of the toner and become low-viscosity by melting during fixing. However, toners using crystalline vinyl resins have low viscosity in the high-temperature region and are likely to have reduced hot offset resistance.

[0013] In order to suppress this phenomenon, it is conceivable to increase the resin viscosity in the high-temperature region. However, when the viscosity of the crystalline vinyl resin or the amorphous resin used in combination is increased, the low-temperature fixability decreases. Therefore, it is difficult to solve this problem by adjusting the viscosities of the crystalline vinyl resin and the amorphous resin. Thus, as a result of intensive studies by the present inventors, it has been found that by using inorganic fine particles surface-treated with an alkyl group and a crystalline vinyl resin having a monomer unit represented by formula (1), it is possible to improve the hot offset resistance while maintaining the low-temperature fixability, and furthermore, the abrasion resistance is also improved.

[0014] Regarding the reason, the inventors of the present invention consider as follows. In the toner layer during fixing and melting, the alkyl group of the crystalline vinyl resin and the alkyl group on the surface of the inorganic fine particles interact with each other, and the cohesive force of the toner layer during fixing and melting becomes stronger. In particular, like the monomer unit represented by the formula (1), when having at least two alkyl groups of R 5 the interaction works strongly. As a result, even if the toner layer melts and flows, the dispersion of the inorganic fine particles is maintained, and the cohesive force becomes stronger throughout the toner layer, so the hot offset resistance is improved. Furthermore, the interaction also occurs in the toner layer after fixing, and the abrasion resistance is also improved.

[0015] In the toner of the present disclosure, the binder resin contains a crystalline vinyl resin having a monomer unit represented by the formula (1), and the content of the monomer unit represented by the formula (1) is 5.0% by mass or more based on the mass of the crystalline vinyl resin. And among R 1 ~R 4 of the formula (1), at least two are each independently -X-COOR 5 and the rest are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X is a single bond or an alkylene group having 1 or 2 carbon atoms, and R 5 is an alkyl group having 16 to 30 carbon atoms.

[0016] The distance between the alkyl group side chains of the crystalline vinyl resin is shortened by the monomer unit represented by the formula (1), so that the crystal domains in the toner are likely to grow, and good low-temperature fixability is obtained by improving the sharp meltability. When R 5 exceeds 30, the low-temperature fixability is likely to decrease. Also, when R 5 is less than 16, the low-temperature fixability and storage stability are likely to decrease, and the effect of improving the hot offset resistance cannot be obtained.

[0017] To become a grown crystal domain, among R 1 ~R 4 of the formula (1), at least two are -COOR 5 (R 5is preferably an alkyl group having 16 to 30 carbon atoms). Also, In formula (1), R 1 and one of R 2 and one of R 3 and R 4 are each independently -COOR 5 (R 5 is preferably an alkyl group having 16 to 30 carbon atoms). R 5 is preferably an alkyl group having 18 to 28 carbon atoms, and more preferably an alkyl group having 18 to 24 carbon atoms. The alkyl group of R 5 is preferably linear. It is more preferable that R 5 is a linear alkyl group having 18 carbon atoms or a linear alkyl group having 22 carbon atoms.

[0018] Also, the crystalline vinyl resin contains 5.0% by mass or more of the monomer unit represented by formula (1) based on the mass of the crystalline vinyl resin. When the content of the monomer unit represented by formula (1) is 5.0% by mass or more, the low-temperature fixability is improved. Also, the effect of improving the above-described hot offset resistance can be obtained. Since the low-temperature fixability improves as the content of the monomer unit represented by formula (1) increases, the content of the monomer unit represented by formula (1) is preferably 30.0% by mass or more, and more preferably 50.0% by mass or more based on the mass of the crystalline vinyl resin. The content of the monomer unit represented by formula (1) based on the mass of the crystalline vinyl resin is preferably 5.0 to 85.0% by mass, more preferably 30.0 to 80.0% by mass, and even more preferably 45.0 to 75.0% by mass.

[0019] Similarly, from the viewpoint of low-temperature fixability, the content of the crystalline vinyl resin is preferably 30% or more, more preferably 50% or more, based on the mass of the binder resin. On the other hand, from the viewpoint of storage stability, the content of the crystalline vinyl resin is preferably 80% or less, based on the mass of the binder resin. The content of the crystalline vinyl resin based on the mass of the binder resin is preferably 30 to 80% by mass, more preferably 50 to 80% by mass, and even more preferably 50 to 70% by mass.

[0020] The toner particles contain a binder resin and inorganic fine particles. The inorganic fine particles have an alkyl group on the surface, and the content of the inorganic fine particles needs to be 0.10 to 15.00% by mass based on the mass of the toner particles. When the content of the inorganic fine particles is within the above range, the alkyl group of the crystalline vinyl resin and the alkyl group on the surface of the inorganic fine particles interact with each other, so that the cohesive force of the toner layer becomes stronger, and thus good hot offset resistance and abrasion resistance can be obtained.

[0021] The more the inorganic fine particles having an alkyl group on the surface, the greater the interaction. Therefore, from the viewpoints of abrasion resistance and hot offset resistance, the content of the inorganic fine particles needs to be 0.10% by mass or more, preferably 1.00% by mass or more. On the other hand, when the content of the inorganic fine particles is large, the low-temperature fixability decreases due to the filler effect. From the viewpoint of low-temperature fixability, the content of the inorganic fine particles needs to be 15.00% by mass or less, preferably 13.00% by mass or less. The content of the inorganic fine particles is preferably 1.00 to 13.00% by mass, more preferably 7.00 to 13.00% by mass, and even more preferably 9.00 to 13.00% by mass, based on the mass of the toner particles. The alkyl group in the inorganic fine particles is, for example, derived from a surface treatment agent. The inorganic fine particles can be surface-treated inorganic fine particles.

[0022] The inorganic fine particles are preferably incorporated into the toner particles. In the cross-sectional observation of the toner by a transmission electron microscope, it is preferable that the toner particles contain inorganic fine particles in a region 0.3 μm or more inside from the surface of the toner particles. Thereby, the viscosity inside the toner particles during fixing increases, and the cohesive force increases in the entire toner layer formed by fixing and melting, so that good hot offset resistance can be obtained.

[0023] In the present disclosure, the inside of the toner particles means a range not affected by the external additives present on the toner surface, and 80% or more of the inorganic fine particles are included in a region 0.3 μm or more inside from the surface of the toner particles. A specific measurement method will be described later. That is what it means. A specific measurement method will be described later.

[0024] Note that the toner has a general particle size as a toner. Specifically, the weight average particle size (D4) of the toner is preferably 3.0 to 10.0 μm, more preferably 4.0 to 8.0 μm. In the present disclosure, the region 0.3 μm or more inside from the surface of the toner particles in the toner having such a particle size is discussed.

[0025] Examples of methods for causing the inorganic fine particles to exist in a region 0.3 μm or more inside from the surface of the toner particles include the following methods. In a grinding method in which raw materials such as a binder resin and wax are melt-kneaded, the kneaded product is cooled, and then ground and classified, a method of previously mixing the inorganic fine particles with other raw materials in the raw material mixing step; A suspension granulation method in which a solution in which a binder resin, wax, and the inorganic fine particles are dissolved or dispersed in a solvent is introduced into an aqueous medium and suspension granulated, and the solvent is removed to obtain toner particles; A suspension polymerization method in which a monomer composition in which the inorganic fine particles, wax, etc. are uniformly dispersed or dissolved in a monomer is dispersed in a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer, and a polymerization reaction is carried out to produce toner particles; A method in which the inorganic fine particles are previously contained in a monomer composition in an emulsion polymerization method in which polymerization is directly carried out in the presence of a water-soluble polar polymerization initiator to generate toner particles; An emulsion aggregation method obtained through a step of aggregating at least polymer fine particles, wax, and the inorganic fine particles to form fine particle aggregates and a ripening step of causing fusion between the fine particles in the fine particle aggregates; There is a method of coating the surface of core fine particles containing the inorganic fine particles with a shell not containing the inorganic fine particles to form fine particles having a core-shell structure, etc.

[0026] The number average particle diameter of the primary particles of the inorganic fine particles is preferably 10 to 500 nm, and more preferably 100 to 300 nm. By satisfying the above number average particle diameter, the alkyl group present on the surface of the inorganic fine particles and the alkyl group in the crystalline vinyl resin can more easily interact with each other, and better abrasion resistance and hot offset resistance can be obtained.

[0027] Further, the content of the alkyl group on the surface of the inorganic fine particles is preferably 0.10 to 5.00% by mass, and more preferably 0.15 to 3.20% by mass based on the mass of the inorganic fine particles. By satisfying the above content, the alkyl group present on the surface of the inorganic fine particles and the alkyl group in the crystalline vinyl resin can more easily interact with each other, and better abrasion resistance and hot offset resistance can be obtained. Further, when the content of the alkyl group on the surface of the inorganic fine particles is 5.00% by mass or less based on the mass of the inorganic fine particles, the gloss is likely to be improved.

[0028] Further, the difference between the number of carbon atoms of the alkyl group on the surface of the inorganic fine particles and the R in the formula (1) 5 is preferably 5 or less. The difference is preferably from 0 to 5, more preferably from 1 to 4. By satisfying the difference in the number of carbon atoms, the alkyl group present on the surface of the inorganic fine particles and the alkyl group in the crystalline vinyl resin can more easily interact with each other, and better abrasion resistance and hot offset resistance can be obtained. In addition, when there are a plurality of types of alkyl groups having different numbers of carbon atoms on the surface of the inorganic fine particles, a weighted average value weighted by the molar amount (mol%) of the alkyl group is adopted. Further, when a plurality of types of alkyl groups having different numbers of carbon atoms are used for R in the formula (1), similarly, a weighted average value weighted by the molar amount (mol%) of the alkyl group is adopted. 5 Similarly, when a plurality of types of alkyl groups having different numbers of carbon atoms are used for R in the formula (1), a weighted average value weighted by the molar amount (mol%) of the alkyl group is adopted.

[0029] Further, the content (mass%) of the monomer unit represented by the formula (1) based on the mass of the toner particles is preferably 20 times or more the content (mass%) of the alkyl group on the surface of the inorganic fine particles based on the mass of the toner particles. The content (mass%) of the monomer unit represented by the formula (1) based on the mass of the toner particles is 20 to 8000 times the content (mass%) of the alkyl group on the surface of the inorganic fine particles based on the mass of the toner particles. is preferably, more preferably 20 to 1500 times, and even more preferably 80 to 150 times. By satisfying the relationship of the content, the alkyl group present on the surface of the inorganic fine particles and the alkyl group in the crystalline vinyl resin can more easily interact with each other, and better abrasion resistance and hot offset resistance can be obtained.

[0030] In the crystalline vinyl resin, the monomer unit represented by the formula (1) is, for example, a monomer unit derived from at least one polymerizable monomer selected from ester compounds obtained by reacting a carboxylic acid having at least two carboxyl groups bonded to a carbon-carbon double bond with an alcohol having at least two alkyl groups having 16 to 30 carbon atoms.

[0031] Examples of the ester compound obtained by reacting a carboxylic acid having at least two carboxyl groups bonded to a carbon-carbon double bond with an alcohol having at least two alkyl groups having 16 to 30 carbon atoms include diesters of fumaric acid and an alcohol having an alkyl group having 16 to 30 carbon atoms [distearyl fumarate, dinonadecyl fumarate, dieicosyl fumarate, diheneicosanyl fumarate, dibehenyl fumarate, dilignoceryl fumarate, dioctacosyl fumarate, dimyristyl fumarate, didotriacontyl fumarate, etc.], esters of fumaric acid and two kinds of alcohols having an alkyl group having 16 to 30 carbon atoms [behenyl stearyl fumarate, etc.], diesters of maleic acid and an alcohol having an alkyl group having 16 to 30 carbon atoms [distearyl maleate, dinonadecyl maleate, dieicosyl maleate, diheneicosanyl maleate, dibehenyl maleate, dilignoceryl maleate, dioctacosyl maleate, dimyristyl maleate, didotriacontyl maleate, etc.], esters of maleic acid and two kinds of alcohols having an alkyl group having 16 to 30 carbon atoms [behenyl stearyl maleate, etc.], diesters of methylene malonic acid and an alcohol having an alkyl group having 16 to 30 carbon atoms [distearyl methylene malonate, dinonadecyl methylene malonate, dieicosyl methylene malonate, diheneicosanyl methylene malonate, dibehenyl methylene malonate, dilignoceryl methylene malonate, dioctacosyl methylene malonate, dimyristyl methylene malonate, didotriacontyl methylene malonate, etc.], esters of methylene malonic acid and two kinds of alcohols having an alkyl group having 16 to 30 carbon atoms [behenyl stearyl methylene malonate, etc.], diesters of itaconic acid and an alcohol having an alkyl group having 16 to 30 carbon atoms [distearyl itaconate, dinonadecyl itaconate, dieicosyl itaconate, diheneicosanyl itaconate, dibehenyl itaconate, dilignoceryl itaconate, dioctacosyl itaconate, dimyristyl itaconate, didotriacontyl itaconate, etc.], and esters of itaconic acid and two kinds of alcohols having an alkyl group having 16 to 30 carbon atoms [behenyl stearyl itaconate, etc.]. Examples thereof also include ester compounds of ethenetricarboxylic acid and an alcohol having an alkyl group with 16 to 30 carbon atoms, and ester compounds of ethenetetracarboxylic acid and an alcohol having an alkyl group with 16 to 30 carbon atoms.

[0032] Also, from the viewpoint of the low-temperature fixability of the toner, it is preferably at least one selected from the group consisting of ester compounds of fumaric acid and an alcohol having an alkyl group with 16 to 30 carbon atoms, and ester compounds of maleic acid and an alcohol having an alkyl group with 16 to 30 carbon atoms. More preferably, it is at least one selected from ester compounds of fumaric acid and an alcohol having an alkyl group with 16 to 30 carbon atoms. The alkyl groups in these polymerizable monomers are preferably linear.

[0033] The polymerizable monomer capable of forming the monomer unit represented by formula (1) may be used alone or in combination of two or more. The crystalline vinyl resin may contain other monomer units other than the monomer unit represented by formula (1) to such an extent that the effects of the present disclosure are not impaired, if necessary. Examples of the polymerizable monomer forming other monomer units include monomers having a nitrile group; acrylonitrile, methacrylonitrile. (Meth)acrylic acid-2-hydroxyethyl, (meth)acrylic acid-2-hydroxypropyl, (meth)acrylic acid 2-hydroxyethylamide, (meth)acrylic acid 2-hydroxypropylamide, and the like.

[0034] Among them, it is preferable to use at least one polymerizable monomer selected from the group consisting of acrylonitrile, methacrylonitrile, acrylic acid, and methacrylic acid. In the case of this combination, a toner having excellent low-temperature fixability, hot offset resistance, and good rub resistance can be obtained. More preferably, it is preferable to use at least one polymerizable monomer selected from the group consisting of acrylonitrile and methacrylonitrile, and at least one polymerizable monomer selected from the group consisting of 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0035] The crystalline vinyl resin preferably contains a monomer unit represented by the following formula (N). The monomer unit represented by the following formula (N) corresponds to acrylonitrile and methacrylonitrile. Further, the crystalline vinyl resin preferably contains a monomer unit represented by the following formula (H). The monomer unit represented by the formula (H) corresponds to 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and the like. That is, the crystalline vinyl resin preferably contains at least one monomer unit selected from the group consisting of the monomer unit represented by the following formula (N) and the monomer unit represented by the following formula (H).

Chemical formula

[0036] In formula (N), R 6 is a hydrogen atom or a methyl group. In formula (H), R 7 is an alkylene group having 1 to 4 carbon atoms (preferably 2 or 3), and R 8 is a hydrogen atom or a methyl group. The content of the monomer unit represented by the formula (N) in the crystalline vinyl resin is preferably 1.0 to 45.0% by mass, more preferably 5.0 to 25.0% by mass. Further, the crystalline vinyl resin preferably contains the monomer unit represented by the formula (H) in an amount of 1.0 to 20.0% by mass, more preferably 3.0 to 10.0% by mass. Further, the total content of the monomer unit represented by the formula (N) and the monomer unit represented by the formula (H) in the crystalline vinyl resin is preferably 5.0 to 50.0% by mass, more preferably 10.0 to 20.0% by mass.

[0037] In addition, examples of the polymerizable monomer that forms other monomer units other than the monomer unit represented by the formula (1) include the following polymerizable monomers. Monomers having an amide group; for example, monomers obtained by reacting acrylamide, an amine having 1 to 30 carbon atoms, and a carboxylic acid having 2 to 30 carbon atoms having an ethylenically unsaturated bond (such as acrylic acid and methacrylic acid) by a known method Monomers having a urea group; for example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine, and isopropylamine), secondary amines (such as di-normal ethylamine, di-normal propylamine, di-normal butylamine, etc.), aniline, and cyclohexylamine, etc.] with an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond by a known method, etc. Monomers having a carboxy group; for example, methacrylic acid, acrylic acid, 2-carboxyethyl (meth)acrylate Vinyl esters; for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pivalate, and vinyl octylate Styrene and its derivatives; styrene, o-methylstyrene, etc. (Meth)acrylic acid ester; methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc. Unsaturated polyene; unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; butadiene, isoprene, etc. Aromatic divinyl compound; dialkylate compounds linked by an alkyl chain; dialkylate compounds linked by an alkyl chain containing an ether bond; dialkylate compounds linked by a chain containing an aromatic group and an ether bond; polyester type dialkylates; polyfunctional crosslinking agents.

[0038] Examples of the aromatic divinyl compound include divinylbenzene, divinylnaphthalene, etc. Examples of the dialkylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of the above compounds with methacrylate.

[0039] Among them, when using styrene and its derivatives such as styrene and o-methylstyrene, the hot offset resistance is good. More preferably, the crystalline vinyl resin contains a monomer unit corresponding to styrene. The crystalline vinyl resin preferably contains 5.0 to 75.0% by mass of the monomer unit corresponding to styrene, and more preferably 10.0 to 40.0% by mass.

[0040] Also, preferably, the crystalline vinyl resin contains a monomer unit corresponding to (meth)acrylic acid ester. The crystalline vinyl resin preferably contains 0.0 to 5.0% by mass of the monomer unit corresponding to (meth)acrylic acid ester, and more preferably 0.5 to 3.0% by mass.

[0041] The crystalline vinyl resin can be produced using the exemplified polymerizable monomer and a polymerization initiator. From the viewpoint of efficiency, the polymerization initiator may be used in an amount of 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.

[0042] Examples of the polymerization initiator include the following. 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4 -Dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, ketone peroxides such as cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioil peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate.

[0043] From the viewpoint of charge stability, the acid value of the crystalline vinyl resin is preferably 0 mgKOH / g to 100 mgKOH / g, more preferably 0 mgKOH / g to 50 mgKOH / g. Similarly, the hydroxyl value is preferably 0 mgKOH / g to 100 mgKOH / g, more preferably 0 mgKOH / g to 50 mgKOH / g.

[0044] The weight average molecular weight Mw of the crystalline vinyl resin is not particularly limited, but is preferably 10,000 to 100,000, more preferably 15,000 to 30,000.

[0045] The binder resin may contain an amorphous resin. Known amorphous resins can be used to the extent that the effects of the present disclosure are not impaired. From the viewpoint of low-temperature fixability, the binder resin preferably contains 30 to 80% by mass of the crystalline vinyl resin.

[0046] Examples of known amorphous resins include the following. Polyvinyl chloride, phenol resin, natural resin-modified phenol resin, natural resin-modified maleic acid resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone-indene resin, petroleum resin, vinyl resin.

[0047] Among these, the amorphous resin preferably contains at least one resin selected from the group consisting of a hybrid resin in which a vinyl resin and a polyester resin are combined, a polyester resin, and a vinyl resin. The amorphous resin more preferably contains an amorphous polyester resin. Using an amorphous polyester resin is preferable because it is easy to achieve both high levels of low-temperature fixability and hot offset resistance.

[0048] As the amorphous polyester resin, a polyester resin usually used in toner can be preferably used. Examples of the monomers used in the polyester resin include polyhydric alcohols (di- or trihydric or higher alcohols), polyvalent carboxylic acids (di- or trihydric or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters.

[0049] Examples of the polyhydric alcohol include the following. Examples of the dihydric alcohol include the following bisphenol derivatives. Polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene(6)-2,2-bis(4-hydroxyphenyl)propane, etc.

[0050] Examples of other polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene. These polyhydric alcohols can be used alone or in combination of two or more.

[0051] Examples of the polyvalent carboxylic acid include the following. Examples of the divalent carboxylic acid include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, anhydrides of these acids, and lower alkyl esters of these acids. Among these, maleic acid, fumaric acid, terephthalic acid, n-dodecenyl succinic acid, and adipic acid are preferably used.

[0052] As the divalent carboxylic acid, alkenyl succinic acids such as n-dodecenyl succinic acid, isododecenyl succinic acid, n-octenyl succinic acid, and isooctenyl succinic acid may be used. Since these alkenyl succinic acids have an alkenyl group, they easily interact with the long-chain alkyl unit of the crystalline vinyl resin. Since this interaction is smaller than the interaction between polar groups, the filler effect is likely to be exhibited by the interaction when the strain is small, but the filler effect is difficult to be exhibited when the strain is large. Thereby, the low-temperature fixability of the toner may be improved.

[0053] Examples of the trivalent or higher carboxylic acid, its acid anhydride, or its lower alkyl ester include the following. 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra( methylenecarboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimer acid, acid anhydrides of these acids, or lower alkyl esters of these acids.

[0054] Among these, derivatives such as 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its acid anhydride are preferably used because they are inexpensive and the reaction control is easy. These polycarboxylic acids can be used alone or in combination of two or more. Also, linear saturated fatty acids such as behenic acid may be used.

[0055] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the aforementioned polyhydric alcohol and polycarboxylic acid are charged simultaneously, and polymerized through an esterification reaction or transesterification reaction and a condensation reaction to produce a polyester resin. Also, the polymerization temperature is not particularly limited, but a range of 180°C or higher and 290°C or lower is preferable. When polymerizing the polyester resin, for example, polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used. The polyester resin used for the amorphous resin is preferably one obtained by polycondensation using at least one of a titanium-based catalyst and a tin-based catalyst.

[0056] Examples of the amorphous vinyl resin used as the amorphous resin include polymers of polymerizable monomers containing an ethylenically unsaturated bond. The ethylenically unsaturated bond refers to a carbon-carbon double bond capable of radical polymerization, and examples thereof include a vinyl group, a propenyl group, an acryloyl group, and a methacryloyl group.

[0057] Examples of the polymerizable monomers include the following. Styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene; Acrylic acid esters such as acrylic acid and acrylic acid esters, such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; Methacrylic acid esters such as methacrylic acid and methacrylic acid esters, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; Also, acrylonitrile, methacrylonitrile, acrylamide, etc.

[0058] Furthermore, polymerizable monomers having a hydroxy group, such as acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene, 4-(1-hydroxy-1-methylhexyl)styrene. These can be used alone or in combination of multiple kinds.

[0059] Among them, styrene, acrylic acid ester, methacrylic acid ester, acrylonitrile, etc. are preferable. Also, n-octyl acrylate, dodecyl acrylate, acrylic acid-2 Monomers that are condensates of acrylic acid or methacrylic acid and alcohols having 6 to 22 carbon atoms, such as 2-ethylhexyl acrylate, stearyl acrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, and stearyl methacrylate, may be used. These monomers easily interact with the long-chain alkyl units of the crystalline vinyl resin. Since this interaction is smaller than the interaction between polar groups, the filler effect is likely to be exhibited by the interaction when the strain is small, but it is difficult to exhibit the filler effect when the strain is large. As a result, the low-temperature fixability of the toner may be improved.

[0060] In addition to the above, various polymerizable monomers capable of vinyl polymerization may be used in combination with the amorphous vinyl resin as needed. Examples of the polymerizable monomer include the following. Unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, and N-vinyl pyrrolidone; vinyl naphthalenes; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, and mesaconic acid; unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, and alkenyl succinic anhydride; half esters of unsaturated dibasic acids such as methyl maleate half ester, ethyl maleate half ester, butyl maleate half ester, methyl citraconate half ester, ethyl citraconate half ester, butyl citraconate half ester, methyl itaconate half ester, methyl alkenyl succinate half ester, methyl fumarate half ester, and methyl mesaconate half ester; esters of unsaturated dibasic acids such as dimethyl maleate and dimethyl fumarate; acid anhydrides of α,β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; anhydrides of the α,β-unsaturated acids and lower fatty acids; polymerizable monomers having a carboxy group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, their acid anhydrides, and their monoesters.

[0061] Also, the amorphous vinyl resin may be a polymer crosslinked with a crosslinkable polymerizable monomer as exemplified below, if necessary. Examples of the crosslinkable polymerizable monomer include the following. Aromatic divinyl compounds; diacrylate compounds linked by an alkyl chain; diacrylate compounds linked by an alkyl chain containing an ether bond; diacrylate compounds linked by a chain containing an aromatic group and an ether bond; polyester type diacrylates; polyfunctional crosslinking agents. Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.

[0062] Examples of the diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3 - butylene glycol diacrylate, 1,4 - butanediol diacrylate, 1,5 - pentanediol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of the above compounds with methacrylate.

[0063] The amorphous vinyl resin is styrene, o - methylstyrene, m - methylstyrene, p - methylstyrene, p - phenylstyrene, p - ethylstyrene, 2,4 - dimethylstyrene, p - n - butylstyrene, p - tert - butylstyrene, p - n - hexylstyrene, It is preferable that it is a polymer of a polymerizable monomer containing at least one selected from the group consisting of p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene, and 4-(1-hydroxy-1-methylhexyl)styrene.

[0064] Further, the amorphous vinyl resin may be a copolymer of monomers including at least one polymerizable monomer selected from the group, and at least one crosslinkable polymerizable monomer selected from the group consisting of divinylbenzene, divinylnaphthalene, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and neopentyl glycol dimethacrylate. The content of the crosslinkable polymer in the monomer may be about 0.5% by mass to 5.0% by mass.

[0065] The amorphous vinyl resin may be a resin produced using a polymerization initiator. From the viewpoint of efficiency, the polymerization initiator may be used in an amount of 0.05 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Examples of the polymerization initiator include the following.

[0066] 2,2'-Azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(1-cyclohexanecarbonitrile), 2-carbamoylazoisobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, ketone peroxides such as cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α,α'-bis(tert-butylperoxyisopropyl)benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioil peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl)peroxycarbonate, acetylcyclohexylsulfonyl peroxy D, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-amyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, di-tert-butyl peroxyazelate.

[0067] As the vinyl resin and polyester resin used to form a hybrid resin in which a vinyl resin and a polyester resin are bonded, those similar to the vinyl resin and polyester resin used as the amorphous resin described above can be used.

[0068] As a method for producing a hybrid resin in which a vinyl resin and a polyester resin are bonded, for example, a method of polymerization using a compound (hereinafter referred to as "both-reactive compound") that can react with any of the monomers that generate both resins can be mentioned.

[0069] Examples of the both-reactive compound include compounds such as fumaric acid, acrylic acid, methacrylic acid, citraconic acid, maleic acid, and dimethyl fumarate in the monomers of the condensation polymerization resin and the addition polymerization resin. Among these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.

[0070] When a hybrid resin in which a vinyl resin and a polyester resin are bonded is used, the content ratio of the vinyl resin in the hybrid resin is preferably 10% by mass or more, 20% by mass or more, 40% by mass or more, 60% by mass or more, 80% by mass or more, and preferably 100% by mass or less, 90% by mass or less.

[0071] The inorganic fine particles have an alkyl group on the surface. For example, the inorganic fine particles are surface-treated with a compound having an alkyl group. That is, it is preferable that the inorganic fine particles are surface-treated inorganic fine particles with a compound having an alkyl group. Since the inorganic fine particles have an alkyl group on the surface, they can interact with the alkyl group of the crystalline vinyl resin, and good abrasion resistance and hot offset resistance can be obtained.

[0072] Examples of the compound having an alkyl group include fatty acids or their metal salts, silicone oils, cyclic siloxanes, silane coupling agents, titanium coupling agents, aliphatic alcohols, etc. Among them, the compound having an alkyl group preferably contains at least one selected from the group consisting of fatty acids and their metal salts, silicone oils, cyclic siloxanes, and silane coupling agents, because the effects of good abrasion resistance and hot offset resistance can be more easily obtained.

[0073] Examples of the fatty acid and its metal salt include lauric acid, stearic acid, behenic acid, lithium laurate, lithium stearate, sodium stearate, zinc laurate, zinc stearate, calcium stearate, aluminum stearate, etc.

[0074] Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, alkyl-modified silicone oil, etc. As the method for treating with silicone oil, known techniques can be used. For example, the inorganic fine particles and the silicone oil are mixed using a mixer; the silicone oil is sprayed into the inorganic fine particles using a sprayer; or the silicone oil is dissolved in a solvent and then the inorganic fine particles are mixed. The treatment method is not limited to this.

[0075] Examples of cyclic siloxanes include cyclic siloxanes such as octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), dodecamethylcyclohexasiloxane (D6) (for example, those having 3 to 8 dimethylsiloxane units).

[0076] Examples of silane coupling agents include hexamethyldisilazane, trimethylsilane, trimethylethoxysilane, isobutyltrimethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethylethoxysilane, dimethyldimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, cetyltrimethoxysilane.

[0077] Examples of aliphatic alcohols include ethanol, n-propanol, 2-propanol, n-butanol, t-butanol, n-octanol, stearyl alcohol, 1-tetracosanol, etc. Examples of the method for treating aliphatic alcohols include, for example, heating to a temperature above the boiling point and vaporizing, and then treating with inorganic fine particles in a vaporized state.

[0078] Inorganic fine particles include fine particles of oxides composed of silica, alumina, titania, magnesium oxide, zirconium oxide, chromium oxide, cerium oxide, tin oxide, zinc oxide, etc., as well as amorphous carbon (such as carbon black), nitrides (such as silicon nitride), carbides (such as silicon carbide), and inorganic fine particles composed of metal salts (such as strontium titanate, calcium sulfate, barium sulfate, calcium carbonate).

[0079] In particular, it is preferable that the inorganic fine particles contain at least one selected from the group consisting of calcium carbonate, silica, titanium oxide, alumina, metal titanate, magnesium silicate, and barium sulfate. It is more preferable that the inorganic fine particles contain calcium carbonate. The inorganic fine particles are treated with a hydrophobizing agent such as fatty acids, silane compounds, polydimethylsiloxane, cyclic siloxanes, bis(trimethylsilyl)amine, silicone oil, or a mixture thereof. like that. is preferable.

[0080] When the number average diameter of the primary particles of the inorganic fine particles having an alkyl group on the surface is 10 nm to 500 nm, it is preferable because better hot offset resistance and abrasion resistance are likely to be exhibited. Further, as long as the effects of the present disclosure are not impaired, inorganic fine particles other than the above may be contained regardless of the presence or absence of surface treatment. Further, among the inorganic fine particles having an alkyl group on the surface, the above-described R 5 When the difference in the number of carbon atoms from is 5 or less, the interaction with the alkyl group of the monomer unit of the formula (1) is further improved, and the hot offset resistance and the abrasion resistance are further improved, which is preferable. Further, as the inorganic fine particles having an alkyl group on the surface in the toner particles, one kind may be used alone or two or more kinds may be contained.

[0081] The toner particles may contain a colorant as necessary, separately from the inorganic fine particles. Examples of the colorant include the following. Examples of the black colorant include carbon black; those toned to black using a yellow colorant, a magenta colorant, and a cyan colorant. For the colorant, a pigment may be used alone, but it is preferable to use a dye and a pigment in combination to improve the vividness from the viewpoint of the image quality of the full-color image.

[0082] Examples of the pigment for magenta toner include the following. C.I. 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; C.I. Pigment Violet 19; C.I. Vat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0083] Examples of dyes for magenta toner include the following. C.I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. Disperse Red 9; C.I. Solvent Violet 8, 13, 14, 21, 27; oil-soluble dyes such as C.I. Disperse Violet 1, C.I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; basic dyes such as C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0084] Examples of pigments for cyan toner include the following. C.I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. Vat Blue 6; C.I. Acid Blue 45, copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton. As a dye for cyan toner, there is C.I. Solvent Blue 70.

[0085] Examples of pigments for yellow toner include the following. C.I. 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; C.I. Vat Yellow 1, 3, 20. As a dye for yellow toner, there is C.I. Solvent Yellow 162.

[0086] The content of the colorant is preferably 0.1 part by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0087] The toner particles may contain wax. Examples of the wax include the following. Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; those obtained by partially or completely deoxidizing fatty acid esters such as deacidified carnauba wax.

[0088] Furthermore, the following are included. 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 and 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; saturated ones such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide Fatty acid bisamides; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, N,N'-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide, N,N'-distearyl isophthalic acid amide; fatty acid metal salts (commonly referred to as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate; waxes grafted with vinyl monomers such as styrene and acrylic acid onto aliphatic hydrocarbon waxes; partial esterified products of fatty acids and polyhydric alcohols such as monoglyceryl behenate; methyl ester compounds having a hydroxy group obtained by hydrogenating vegetable oils and fats.

[0089] The wax content is preferably 2.0 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0090] The toner particles may contain a charge control agent as needed. As the charge control agent, known ones can be used, and in particular, metal compounds of aromatic carboxylic acids that are colorless, have a fast charging speed of the toner, and can stably maintain a certain charge amount are preferred.

[0091] Examples of the negative charge control agent include metal compounds of salicylic acid, metal compounds of naphthoic acid, metal compounds of dicarboxylic acid, polymer compounds having a sulfonic acid or carboxylic acid in the side chain, polymer compounds having a sulfonate or sulfonic acid esterified product in the side chain, polymer compounds having a carboxylate or carboxylic acid esterified product in the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0092] The charge control agent may be added internally or externally to the toner particles. The content of the charge control agent is preferably 0.2 parts by mass to 10.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0093] The toner may contain toner particles and external additives. As the external additives, inorganic fine particles such as silica, titanium oxide, aluminum oxide, and metal titanate salts are preferable. The inorganic fine particles are preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil, or a mixture thereof.

[0094] As the external additive for improving fluidity, inorganic fine particles having a specific surface area of 50 m 2 / g or more and 400 m 2 / g or less are preferable, and for stabilizing durability, inorganic fine particles having a specific surface area of 10 m 2 / g or more and 50 m 2 / g or less are preferably used. In order to achieve both improved fluidity and stabilized durability, inorganic fine particles having a specific surface area within the above range may be used in combination. The mixing of the toner particles and the external additive can be carried out using a known mixer such as a Henschel mixer. The content of the external additive is preferably 0.1 part by mass to 10.0 parts by mass, more preferably 0.5 part by mass to 5.0 parts by mass, based on 100 parts by mass of the toner particles.

[0095] The toner can be used as a one-component developer, but it is preferably used as a two-component developer by mixing with a magnetic carrier in terms of obtaining a stable image over a long period. That is, a two-component developer containing the toner and the magnetic carrier, and the toner is preferably the above-described toner.

[0096] Examples of the magnetic carrier include iron powder or iron powder with an oxidized surface; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earths, alloy particles thereof, or oxide particles thereof; magnetic materials such as ferrite; and magnetic material-dispersed resin carriers (so-called resin carriers) containing the magnetic material and a binder resin for holding the magnetic material in a dispersed state; and the like, which are generally known. When the toner is mixed with a magnetic carrier and used as a two-component developer, the content ratio of the toner in the two-component developer is preferably 2% by mass to 15% by mass, more preferably 4% by mass to 13% by mass.

[0097] The method for manufacturing toner particles is not particularly limited, and conventionally known manufacturing methods such as suspension polymerization method, emulsion aggregation method, melt kneading method, and dissolution suspension method can be adopted. Hereinafter, the melt kneading method will be described as an example, but it is not limited thereto.

[0098] First, in the raw material mixing step, as materials constituting the toner particles, a binder resin containing a crystalline vinyl resin and, if necessary, an amorphous resin, and inorganic fine particles, and if necessary, other components such as wax, colorant, charge control agent, etc. are weighed and blended in predetermined amounts and mixed. Examples of the mixing device include double cone mixer, V-type mixer, drum type mixer, super mixer, Henschel mixer, Nauta mixer, and Mechano Hybrid (manufactured by Nippon Coke & Engineering Co., Ltd.).

[0099] Next, the mixed materials are melt kneaded to disperse inorganic fine particles and other components in the binder resin containing the crystalline vinyl resin. In the melt kneading step, a batch type kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. Due to the advantage of continuous production, single screw or twin screw extruders are the mainstream. For example, KTK type twin screw extruder (manufactured by Kobe Steel, Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikegai Iron Works), twin screw extruder (manufactured by K.C.K. Co., Ltd.), co-kneader (manufactured by Buss Co., Ltd.), and Neodeck (manufactured by Nippon Coke & Engineering Co., Ltd.) can be mentioned. Further, the resin composition obtained by melt kneading may be rolled with a two-roll or the like and cooled with water or the like in the cooling step.

[0100] Then, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarsely pulverizing with a pulverizer such as a crusher, hammer mill, or feather mill, it may be further finely pulverized with a fine pulverizer such as a Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Industry), or an air jet type fine pulverizer.

[0101] Thereafter, if necessary, classification may be performed using a classifier or a sieve such as an elbow jet of the inertial classification method (manufactured by Nippon Steel Mining Co., Ltd.), a turbo plex of the centrifugal classification method (manufactured by Hosokawa Micron Corporation), a TSP separator (manufactured by Hosokawa Micron Corporation), or a faculty (manufactured by Hosokawa Micron Corporation) to obtain toner particles.

[0102] Before manufacturing the toner, a binder resin may be obtained by crosslinking an amorphous resin with a polymerization initiator while kneading a mixture of a crystalline vinyl resin and an uncrosslinked amorphous resin. Alternatively, a crystalline vinyl resin and an uncrosslinked amorphous resin may be dissolved in a solvent, and a polymerization initiator may be added while stirring in a coexisting system to perform a crosslinking reaction to obtain a binder resin. By this method, it is easy to finely disperse the amorphous resin in the crystalline vinyl resin. It is preferable to obtain a binder resin by crosslinking an amorphous resin with a polymerization initiator while kneading a mixture of a crystalline vinyl resin and an uncrosslinked amorphous resin. That is, the amorphous resin is preferably crosslinked. From the viewpoint of forming the above crosslinking, when the amorphous resin contains a polyester resin, the polyester resin preferably has a structure corresponding to the above-described bifunctional reactive compound such as fumaric acid.

[0103] The measurement methods for various physical properties of the toner and raw materials will be described below. <Method for Identifying Monomer Units Constituting Binder Resin and Measuring Content Ratio of Monomer Units> Identification of monomer units constituting the crystalline vinyl resin and the amorphous resin and measurement of the content ratio of the monomer units are performed under the following conditions by 1 1H-NMR. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400 MHz Pulse condition: 5.0 μs Frequency range: 10500 Hz Number of integrations: 64 times Measuring temperature: 30 °C Sample: 50 mg of the measurement sample is placed in a sample tube with an inner diameter of 5 mm, and deuterated chloroform (CDCl3) is added as a solvent, and this is dissolved in a constant temperature bath at 40 °C for preparation.

[0104] As the measurement sample, each resin such as the crystalline vinyl resin fractionated by the method described below can be used. Hereinafter, an example using a crystalline vinyl resin will be described. The obtained 1 From the 1H-NMR chart, among the peaks attributed to the components of the monomer unit represented by formula (1) contained in the crystalline vinyl resin, a peak independent of the peaks attributed to the components of other monomer units is selected, and the integral value S1 of this peak is calculated. Similarly, for the other monomer units contained in the crystalline vinyl resin, the integral value S2 is calculated in the same manner.

[0105] For example, when the monomer unit constituting the crystalline vinyl resin is the monomer unit represented by formula (1) and one other monomer unit, the content ratio of the monomer unit represented by formula (1) is obtained as follows using the above integral values S1 and S2. Note that n1 and n2 are the number of hydrogens in the component to which the peak focused on each site is attributed. Content ratio (mol%) of the monomer unit represented by formula (1) = {(S1 / n1) / ((S1 / n1)+(S2 / n2))}×100 Content ratio (mol%) of the other monomer unit = {(S2 / n2) / ((S1 / n1)+(S2 / n2))}×100 Even when there are two or more other monomer units, the content ratio of the monomer unit can be calculated in the same manner (using S3···S x , n3···n x ). The content ratio of each monomer unit in the amorphous resin can be calculated in the same manner. In addition, when a polymerizable monomer that does not contain a hydrogen atom in a component other than the vinyl group is used, 13The measured nuclear nucleus using 13C-NMR 13 is 13C, and the measurement is performed in single pulse mode, 1 and is calculated in the same manner as 1H-NMR. Based on the molecular weight of the monomer unit, it can be converted from mol% to mass%. Also, for the carbon number of an alkyl group such as R 5 in formula (1), 1 it can be calculated from the integration ratio of proton peaks in the 1H-NMR chart.

[0106] <Method for measuring weight average molecular weight (Mw) of resin etc. using gel permeation chromatography (GPC)> The weight average molecular weight (Mw) of the tetrahydrofuran (THF) soluble component of resin etc. is measured as follows using gel permeation chromatography (GPC). First, dissolve the resin etc. in tetrahydrofuran (THF) over 24 hours at room temperature. Then, filter the resulting solution through a solvent-resistant membrane filter "Micron Disc" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in THF is about 0.8 mass%. Using this sample solution, measure under the following conditions. Apparatus: HLC8220 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: 7 columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Oven temperature: 40.0 °C Sample injection volume: 0.10 mL

[0107] In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (trade names: "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0108] <Method for Measuring the Weight Average Particle Size (D4) of Toner (Particles)> The weight average particle size (D4) of toner (particles) is measured and calculated with a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube and the dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) attached for setting measurement conditions and analyzing measurement data at an effective measurement channel number of 25,000 channels. The electrolytic aqueous solution used for measurement is a solution prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass. For example, "ISOTON II" (manufactured by Beckman Coulter, Inc.) can be used. Before performing measurement and analysis, the settings of the dedicated software are made as follows.

[0109] On the "Change Screen for Standard Measurement Method (SOM)" of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1 time, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter, Inc.). By pressing the measurement button for threshold / noise level, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement. On the "Conversion Setting Screen from Pulse to Particle Size" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less. The specific measurement method is as follows.

[0110] (1) Pour approximately 200 mL of the electrolytic aqueous solution into a 250 mL round-bottom glass beaker dedicated to the Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 revolutions per second. Then, use the "aperture tube flash" function of the dedicated software to remove dirt and bubbles in the aperture tube. (2) Pour approximately 30 mL of the electrolytic aqueous solution into a 100 mL flat-bottom glass beaker, and add approximately 0.3 mL of a dilution obtained by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with ion-exchanged water as a dispersant. (3) Place a predetermined amount of ion-exchanged water in the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikka Kikai Bios Co., Ltd.) with an electrical output of 120 W, which incorporates two oscillators with an oscillation frequency of 50 kHz and a 180-degree phase shift, and add approximately 2 mL of Contaminon N to this water tank. (4) Set the beaker in (2) above in the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height position of the beaker so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker in (4) above with ultrasonic waves, add approximately 10 mg of toner (particles) little by little to the electrolytic aqueous solution and disperse it. Then, continue the ultrasonic dispersion treatment for another 60 seconds. Note that during ultrasonic dispersion, appropriately adjust the water temperature in the water tank to be 10°C or higher and 40°C or lower. (6) Drop the electrolytic aqueous solution in (5) above in which the toner (particles) is dispersed into the round-bottom beaker in (1) above installed in the sample stand using a pipette, and adjust so that the measured concentration is approximately 5%. Then, perform the measurement until the measured number of particles reaches 50,000. (7) Analyze the measurement data using the dedicated software attached to the device to calculate the weight average particle size (D4). Note that when set to graph / volume% in the dedicated software, the "average diameter" on the "analysis / volume statistical value (arithmetic mean)" screen is the weight average particle size (D4).

[0111] <Measurement Method for Melting Point of Crystalline Vinyl Resin; Peak Top Tm> The melting point of the crystalline vinyl resin is measured under the following conditions using a DSC Q1000 (manufactured by TA Instruments). Temperature rising rate: 10 °C / min Measurement start temperature: 20 °C Measurement end temperature: 180 °C For the temperature correction of the device detection part, the melting points of indium and zinc are used, and for the heat quantity correction, the heat of fusion of indium is used. Specifically, 5 mg of the sample is precisely weighed, placed in an aluminum pan, and differential scanning calorimetry is performed. As a reference, an empty silver pan is used. The peak temperature of the maximum endothermic peak in the first heating process is defined as the melting point of the crystalline vinyl resin; peak top Tm. Note that the maximum endothermic peak refers to the peak with the maximum endothermic quantity when there are multiple peaks.

[0112] <Cross-sectional Observation of Toner> First, a thin slice serving as a reference sample for the abundance is prepared. After sufficiently dispersing the crystalline resin in the visible light curable resin (Aronix LCR series D800), short-wavelength light is irradiated to cure it. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a 250-nm thin slice sample. Similarly, a thin slice sample is also prepared for the amorphous resin. In addition, the crystalline resin and the amorphous resin are mixed at 0 / 100, 30 / 70, 70 / 30, and 0 / 100 on a mass basis, and a kneaded product obtained by melt kneading is prepared. For these as well, a thin slice sample is prepared by dispersing them in the visible light curable resin, curing them, and then cutting them out. Next, the cut samples are observed for the cross-sections of these reference samples using a transmission electron microscope (JEOL JEM-2800 electron microscope manufactured by JEOL Ltd.) (TEM-EDX), and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen. The mapping conditions are as follows. Accelerating voltage: 200 kV Electron beam irradiation size: 1.5 nm Lifetime limit: 600 sec Dead time: 20 - 30 Mapping resolution: 256 × 256

[0113] Based on the (average in an area of 10 nm square) spectral intensity of each element, (intensity of oxygen element / intensity of carbon element) and (intensity of nitrogen element / intensity of carbon element) are calculated, and a calibration curve is created for the mass ratio of crystalline resin and amorphous resin. When the monomer unit of the crystalline resin contains a nitrogen atom, future quantification will be performed using the calibration curve of (intensity of nitrogen element / intensity of carbon element). Next, the toner sample is analyzed. After sufficiently dispersing the toner in a visible light curable resin (Aronix LCR series D800), short wavelength light is irradiated to cure it. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a 250 nm thin flake sample. Next, observation is performed on the cut-out sample using a transmission electron microscope (JEOL JEM -2800) (TEM-EDX). A cross-sectional image of the toner particles is obtained, and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, nitrogen, silicon, calcium, titanium, strontium, and copper.

[0114] <Method for measuring the primary particle diameter of inorganic fine particles in toner particles> After identifying the particles from the elemental mapping obtained by the cross-sectional observation of the toner described above from the elements constituting the inorganic fine particles, the area occupied by the inorganic fine particles in the toner cross-section is calculated by binarization processing. The toner particles for determining the number average diameter of the primary particles of the inorganic fine particles are selected such that the equivalent circle diameter obtained from the cross-sectional area in the micrograph is within the range of ±10% of the weight average particle diameter (D4) obtained by the method described above using a Coulter counter. The number average diameter of the primary particles of the inorganic fine particles is calculated from the equivalent circle diameter of the region occupied by the inorganic fine particles In addition, in order to exclude the influence of the external additive, the inorganic fine particles existing inside the contour of the toner particles were measured. Also, 100 primary particles were randomly selected and measured. For the binarization process and the calculation of the area ratio, Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) is used.

[0115] <Method for confirming whether all inorganic fine particles are included in the region 0.3 μm or more inside from the toner particle surface> Observation of the cross-section of the toner particles was performed from an observation sample prepared in the same manner as the procedure in the method for measuring the number average diameter of the primary particles of the above-mentioned inorganic fine particles, and a magnified photograph was taken at a magnification of 10,000 to 20,000 times according to the particle size of the toner particles. In this magnified photograph, the area occupied by the inorganic fine particles was converted into binary image data using the image analysis software Image-ProPlus5.1J (manufactured by Media Cybernetics) from the luminance difference. Since the measurement target is the toner particles, the inside of the contour of the toner particles was measured. In the converted image, the position 0.3 μm from the surface of the toner particle (that is, the contour of the cross-section of the toner particle) was specified. Then, the area occupied by the inorganic fine particles 0.3 μm or more inside from the surface of the toner particle was calculated respectively. From these areas, using the density of the binder resin, inorganic fine particles, pigment, and the number average diameter of the inorganic fine particles, the content A (mass%) of the inorganic fine particles 0.3 μm or more inside from the surface of the toner particle and the content B (mass%) of the inorganic fine particles existing from the surface of the toner particle to a depth of 0.3 μm were calculated. In addition, the inorganic fine particles existing across the boundary 0.3 μm inside from the surface of the toner particle were divided by the area at the boundary and calculated, and counted as their respective areas. Those in which the relationship of these contents is in the range of A / (A + B)×100 ≧ 80 were defined as "containing inorganic fine particles in the region 0.3 μm or more inside from the surface of the toner particle". The calculation of A / (A + B)×100 was taken as the value calculated from the observation of 100 cross-sections of the toner particles.

[0116] <Method for separating toner particles from toner> When analyzing toner particles, if the surface of the toner particles is treated with an external additive or the like, the external additive is separated by the following method to obtain toner particles. Add 160 g of sucrose (manufactured by Koido Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve it while stirring with hot water to prepare a thick sucrose solution. Put 31 g of the above thick sucrose solution and 6 mL of Contaminon N (a 10% by mass aqueous solution of a neutral detergent for precision measuring instruments with a pH of 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) into a centrifuge tube to prepare a dispersion. Add 1.0 g of toner to this dispersion and loosen the toner clumps with a spatula or the like. Shake the centrifuge tube with a shaker (sold by AS ONE Corporation) at 350 spm (strokes per min) for 20 min. After shaking, transfer the solution to a glass tube (50 mL) for a swinging rotor and centrifuge it (H-9R Manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 min. By this operation, the toner particles and the detached external additive are separated. Visually confirm that the toner particles and the aqueous solution are sufficiently separated, and collect the separated toner particles in the uppermost layer with a spatula or the like. After filtering the collected toner with a vacuum filter, dry it with a dryer for 1 hour or more to obtain toner particles. Repeat this operation multiple times to ensure the required amount.

[0117] <Method for Separating Each Material from Toner Particles> Each material can be separated from the toner particles by utilizing the difference in solubility of each material contained in the toner particles in a solvent. First separation: Dissolve the toner in methyl ethyl ketone (MEK) at 23 °C to separate the soluble component (amorphous resin) and the insoluble component (crystalline vinyl resin, wax, colorant, inorganic fine particles, etc.). Second separation: Dissolve the insoluble component (crystalline vinyl resin, wax, colorant, inorganic fine particles, etc.) obtained in the first separation in MEK at 100 °C to separate the soluble component (crystalline vinyl resin, wax) and the insoluble component (colorant, inorganic fine particles, etc.). Third Separation: Dissolve the soluble components (crystalline vinyl resin, wax) obtained in the second separation in chloroform at 23°C to separate the soluble components (crystalline vinyl resin) from the insoluble components (wax). Fourth Separation: Disperse the insoluble components obtained in the second separation in tetrahydrofuran, and by changing the centrifugal force in the centrifugation method, separate the inorganic fine particles (e.g., calcium carbonate) and the colorant from the difference in specific gravity.

[0118] (When further containing a third resin in addition to the crystalline vinyl resin and the amorphous resin) First Separation: Dissolve the toner particles in methyl ethyl ketone (MEK) at 23°C to separate the soluble components (amorphous resin, third resin) from the insoluble components (crystalline vinyl resin, wax, colorant, inorganic fine particles, etc.). Second Separation: Dissolve the soluble components (amorphous resin, third resin) obtained in the first separation in toluene at 23°C to separate the soluble components (third resin) from the insoluble components (amorphous resin). Third Separation: Dissolve the insoluble components (crystalline vinyl resin, wax, colorant, inorganic fine particles, etc.) obtained in the first separation in MEK at 100°C to separate the soluble components (crystalline vinyl resin, wax) from the insoluble components (colorant, inorganic fine particles, etc.). Fourth Separation: Dissolve the soluble components (crystalline vinyl resin, wax) obtained in the third separation in chloroform at 23°C to separate the soluble components (crystalline vinyl resin) from the insoluble components (wax). Fifth Separation: Disperse the insoluble components obtained in the third separation in tetrahydrofuran, and by changing the centrifugal force in the centrifugation method, separate the inorganic fine particles and the colorant from the difference in specific gravity.

[0119] <Measurement of the content of inorganic fine particles based on the mass of toner particles> In the separation method of each material from the above-mentioned toner particles, the content of inorganic fine particles based on the mass of toner particles was measured by dividing the mass of the inorganic fine particles obtained in the fourth separation or the fifth separation by the mass of the toner particles.

[0120] <Measurement of the content of crystalline vinyl resin in toner particles> In the method for separating each material from toner particles, the content of the crystalline vinyl resin in the toner particles was measured by dividing the mass of the crystalline vinyl resin obtained by the third separation or the fourth separation by the mass of the toner particles.

[0121] <Structural Analysis of Surface Treatment Agent for Inorganic Fine Particles> The structure was analyzed as follows using a pyrolysis gas chromatography-mass spectrometer (GC-MS). 300 μg of calcium carbonate separated from toner particles by the above method was embedded in the following pyrophoil F590 and introduced into a pyrolysis furnace, heated at 590°C for 5 seconds in an inert (helium) atmosphere, and the decomposed gas generated was introduced into the injection port of the gas chromatograph, and the following oven pro file was carried out. The column outlet was connected to an MS analyzer by a transfer line, and a total ion chromatogram (TIC) was obtained by plotting the ion current on the vertical axis and the retention time on the horizontal axis. Next, in the obtained chromatogram, for all the detected peaks, the mass spectrum was extracted using the attached software, and the compounds were assigned based on the NIST-2017 database.

[0122] <Measurement of Amount of Surface Treatment Agent for Inorganic Fine Particles> The amount of the surface treatment agent of the inorganic fine particles separated from the toner particles by the above method was measured using a thermogravimetric-differential thermal analyzer (manufactured by Rigaku, differential thermal balance TG-DTA, ThermoPlus TG8120). The temperature was raised from 25°C to 400°C at a rate of 10°C / min, and the measured weight change was converted to the mass% of the alkyl group that reacted by combustion using the molecular formula determined by the structural analysis of the surface treatment agent, and the content of the alkyl group on the surface of the inorganic fine particles was calculated.

Example

[0123] The present disclosure will be specifically described by the following examples. However, these do not limit the present disclosure in any way. "Parts" in the following formulations are all based on mass unless otherwise specified.

[0124] <Production Example of Monomer 1 Capable of Forming Monomer Unit Represented by Formula (1)> Into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube, the following materials were charged under a nitrogen atmosphere. · 883 parts of behenyl alcohol (66 mol% based on the total number of moles of alcohol and carboxylic acid) 164 parts of fumaric acid (34 mol% based on the total number of moles of alcohol and carboxylic acid) · 2.5 parts of dibutyltin oxide · 1.0 part of 2,6 - di - tert - butyl - p - cresol Next, after replacing the inside of the flask with nitrogen gas, the temperature was gradually raised with stirring and stirred at 120 °C for homogenization. Then, the temperature was raised to 165 °C, and esterification under reduced pressure was carried out while removing the distillate water at 21 kPa for 3 hours. After that, esterification under reduced pressure was carried out by removing the distillate water at 21 kPa for 3 hours to obtain monomer 1.

[0125] <Production Examples of Monomers 2 - 10> In the production example of monomer 1, the reaction was carried out in the same manner except that the raw material mixture was changed as shown in Table 1 to obtain monomers 2 - 10.

[0126]

Table 1

[0127] <Production Example of Crystalline Vinyl Resin 1> · Solvent: Toluene: 100.0 parts · Monomer composition: 100.0 parts (The monomer composition is a mixture of the following monomer 1, acrylonitrile, methyl acrylate, and styrene in the ratios shown below) 〔Monomer 1: 60.0 parts〕 〔Acrylonitrile: 20.0 parts〕 〔Methyl acrylate: 1.0 part〕 〔Styrene: 19.0 parts〕 · Polymerization initiator 0.5 part [t-Butyl peroxypivalate (manufactured by NOF Corporation: PERBUTYL PV)] The above materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. While stirring the inside of the reaction vessel at 200 rpm, the mixture was heated to 70 °C and subjected to a polymerization reaction for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the temperature of the above solution was lowered to 25 °C, the solution was charged into 1000.0 parts of methanol while stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered off, washed with methanol, and then vacuum-dried at 40 °C for 24 hours to obtain Crystalline Vinyl Resin 1. The physical properties are shown in Table 3.

[0128] <Production Examples of Crystalline Vinyl Resins 2 to 15> In the production example of Crystalline Vinyl Resin 1, the reaction was carried out in the same manner except that each monomer and the number of parts by mass were changed as shown in Table 2 to obtain Crystalline Vinyl Resins 2 to 15. The physical properties are shown in Table 3.

[0129] When the monomer using fumaric acid as the carboxylic acid in Table 1 was used, in formula (1), R 1 and R 2 either one of and R 3 and R 4 either one of is a crystalline vinyl resin containing a monomer unit of -COOR 5 . When the monomer using methylene malonic acid was selected, R 1 and R 2 and (or R 3 and R 4 and) are a vinyl resin containing a monomer unit of -COOR 5 . When the monomer using itaconic acid was selected, R 1 and R 2 (or R 3 and R 4 ) either one of is -X-COOR 5 (X is a methylene group having 1 carbon atom), and the other is a vinyl resin containing a monomer unit of -COOR 5 . When acrylic acid was selected, R1 , R 2 , R 3 , R 4 At least one of them is -COOR 5 A crystalline vinyl resin containing a monomer unit that becomes

[0130]

Table 2

[0131]

Table 3

[0132] <Production Example of Amorphous Resin 1> The following materials were charged into a reaction vessel equipped with a reflux condenser, a stirrer, a thermometer, and a nitrogen inlet tube under a nitrogen atmosphere. · Terephthalic acid: 633 parts · Behenic acid: 31 parts · 1,2 - Propanediol: 173 parts (24.8 mol% based on the total number of moles of polyvalent carboxylic acids) · Neopentyl glycol: 251 parts (26.3 mol% based on the total number of moles of polyvalent carboxylic acids) · Titanium diisopropoxybis(triethanolamineate): 2.0 parts After replacing the inside of the flask with nitrogen gas, it was homogenized by stirring for 30 minutes. Then the temperature was gradually raised, and vacuum esterification was carried out at 227 °C and 0.45 MPa for 5 hours, and then vacuum esterification was carried out at 4 kPa or less to recover 161 parts of 1,2 - propanediol. It was cooled to 180 °C, 2 parts of 2,6 - di - tert - butyl - 4 - methylphenol were added, and it was homogenized for 30 minutes. Then 68 parts of fumaric acid were added, and normal pressure esterification was carried out at 180 °C for 2 hours, and then vacuum esterification was carried out at 4 kPa or less for 15 hours, and it was taken out from the reaction vessel to obtain a polyester resin (amorphous resin 1).

[0133] <Production Example of Amorphous Resin 2> An autoclave was charged with 50.0 parts of xylene and purged with nitrogen, and then the temperature was raised to 185° C. in a sealed state with stirring. A mixture of 37.0 parts of styrene, 20.0 parts of n-butyl acrylate, 3.0 parts of methyl methacrylate, 18.0 parts of methyl acrylate, and 25.0 parts of acrylonitrile, as well as 1.0 part of di-tert-butyl peroxide and 40.0 parts of xylene, was continuously added dropwise to the autoclave for 3 hours while controlling the temperature inside the autoclave to 190° C. The mixture was further kept at the same temperature for 1 hour to complete the polymerization, and the solvent was removed to obtain amorphous resin 2.

[0134] <Production Example of Toner Particle 1> In a reactor equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 1:40 parts of amorphous resin and 1:40 parts of crystalline resin were mixed. The components were mixed in an amount of 60 parts and homogenized at 170°C. Then, 2 parts of di-t-butyl peroxide were added and crosslinking reaction was carried out at 170°C for 1 hour. After that, the pressure was reduced at 1.0 kPa for 2 hours at 170°C to remove decomposition products derived from the initiator. The obtained product was coarsely pulverized to 1 mm or less using a hammer mill to obtain binder resin 1. To 74.00 parts of this binder resin, cyan pigment (Pigment Blue 15:3) 6.00 parts of the mixture, 10.00 parts of inorganic fine particles 1, and 10.00 parts of hydrocarbon wax were added, and the mixture was mixed in a Henschel mixer (FM-75, manufactured by Nippon Coke and Engineering Co., Ltd.) at a rotation speed of 20 s. -1 The mixture was mixed in a twin-screw kneader (PCM-30, manufactured by Ikegai Corporation) set at a temperature of 120°C, with a screw rotation speed of 250 rpm and a discharge temperature of 110°C. The kneaded product obtained was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product obtained was finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.). It was further classified using Faculty F-300 (manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles 1 having a weight average particle size of 6.1 μm. The operating conditions were a classifying rotor rotation speed of 130 s -1 , Distributed rotor speed 120s -1 It was decided.

[0135] <Production Examples of Toner Particles 2 to 47> In the production example of toner particle 1, production was carried out in the same manner except that the types and amounts of the crystalline vinyl resin, amorphous resin, and inorganic fine particles used were changed to those shown in Tables 4, 5, and 6, and toner particles 2 to 34 and 36 to 47 were obtained. Note that for toner particle 35, in the mixing before kneading, inorganic fine particle 11 was not mixed, and after classification, inorganic fine particle 11 was mixed using a Henschel mixer FM-10C type (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 70 s -1 , and a rotation time of 30 min to obtain toner particle 35.

[0136]

Table 4

[0137]

Table 5

[0138]

Table 6

[0139] <Production Example of Toner 1> · 100 parts of toner particle 1 · 1 part of inorganic fine particle 14 The above materials were mixed using a Henschel mixer FM-10C type (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 50 s -1 , and a rotation time of 10 min to obtain toner 1. The physical properties are shown in Table 7.

[0140] <Production Examples of Toners 2 to 48> In the production example of toner 1, production was carried out in the same manner except that the toner particles were changed to those described in Table 6, and toners 2 to 47 were obtained. For toner 48, in the production of toner 1, inorganic fine particle 15 was used instead of inorganic fine particle 14. The physical properties of the obtained toners 2 to 48 are shown in Table 7.

[0141]

Table 7

[0142] <Production Example of Magnetic Carrier 1> · Number average particle size 0.30 μm, magnetization strength 65 A·m / kg under a magnetic field of 1000 / 4π (kA / m) of magnetite 1 2 / kg of magnetite 1 · Number average particle size 0.50 μm, magnetization strength 65 A·m / kg under a magnetic field of 1000 / 4π (kA / m) of magnetite 2 2 / kg of magnetite 2 To 100 parts of each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and high-speed mixing and stirring were carried out at 100 °C or higher in a container to treat each of the fine particles. · Phenol: 10 mass % · Formaldehyde solution: 6 mass % (formaldehyde 40 mass %, methanol 10 mass %, water 50 mass %) · Magnetite 1 treated with the above silane compound: 58 mass % · Magnetite treated with the above silane compound: 2.26% by mass 100 parts of the above material, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water were placed in a flask, heated to 85°C in 30 minutes while stirring and mixing, held for 3 hours to cause a polymerization reaction, and the resulting phenolic resin was cured. Thereafter, the cured phenolic resin was cooled to 30°C, water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60°C to obtain a magnetic carrier dispersion type spherical magnetic carrier 1. The volume-based 50% particle size (D50) of the magnetic carrier 1 was 34.2 μm.

[0143] <Production Example of Binary Developer 1> To 92.0 parts of the magnetic carrier 1, 8.0 parts of toner 1 was added and mixed using a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a binary developer 1.

[0144] <Production Examples of Binary Developers 2 to 48> In the production example of the binary developer 1, production was carried out in the same manner except that the toner was changed as shown in Table 8 to obtain binary developers 2 to 48.

[0145]

Table 8

[0146] <Example 1> Evaluation was carried out using the above binary developer 1. As an image forming apparatus, a modified machine of the Canon digital commercial printer imageRUNNER ADVANCE C7770 was used, and the binary developer 1 was placed in the cyan developer. As the modification points of the apparatus, the fixing temperature, the process speed, and the DC voltage V of the developer carrier The DC, the charging voltage VD of the electrostatic latent image carrier, and the laser power were changed so that they could be freely set. For the image output evaluation, an FFh image (solid image) with a desired image ratio was output, and the VDC, VD, and laser power were adjusted so that the toner loading amount on the FFh image on the paper became desired, and the evaluation described below was performed. FFh is a value representing 256 gradations in hexadecimal notation, where 00h is the first gradation (white background) of the 256 gradations, and FFh is the 256th gradation (solid part) of the 256 gradations. Evaluation was performed based on the following evaluation method, and the results are shown in Table 12.

[0147] <Low-temperature Fixing Property> · Paper: GFC-081 (81.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) · Toner loading amount on the paper: 0.70 mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) · Evaluation image: Place a 2 cm × 15 cm image at the center of the above A4 paper · Test environment: Low-temperature and low-humidity environment: Temperature 15°C / Humidity 10% RH (hereinafter referred to as "L / L") · Fixing temperature: 100°C · Process speed: 300 mm / sec The above evaluation image was output, and the low-temperature fixing property was evaluated. The value of the image density reduction rate was used as the evaluation index for the low-temperature fixing property. The image density reduction rate was measured by the following procedure. Using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite), first, the image density at the center was measured. Next, a load of 4.9 kPa (50 g / cm2) was applied to the portion where the image density was measured, and the fixed image was rubbed (10 round trips) with silicone paper, and the image density was measured again. Then, the reduction rate of the image density before and after rubbing was calculated using the following formula. The obtained reduction rate of the image density was evaluated according to the following evaluation criteria. Reduction rate of image density = (Image density before rubbing - Image density after rubbing) / (Image density before rubbing) × 100 (Evaluation Criteria) A: Image density reduction rate less than 2.0% B: Image density reduction rate of 2.0% or more and less than 4.0% C: Image density reduction rate of 4.0% or more and less than 6.0% D: Image density reduction rate of 6.0% or more and less than 10.0% E: Image density reduction rate of 10.0% or more

[0148] <Hot Offset Resistance> · Paper: CS-064 (64.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) · Toner loading amount on paper: 0.08 mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) · Evaluation image: A 2 cm × 20 cm image is placed on the long side in the paper feed direction of the above A4 paper with a 2 mm margin from the paper tip · Test environment: Normal temperature and low humidity environment: Temperature 23°C / Humidity 5% RH (hereinafter "N / L") · Fixing temperature: The temperature is increased in 10°C increments from 100°C to 130°C, and in 1°C increments from 130°C. · Process speed: 300 mm / sec The above evaluation image was output, and the hot offset resistance was evaluated according to the following criteria at the highest fixing temperature at which no hot offset occurred (Evaluation Criteria) A: 140°C or higher B: 135°C or higher and less than 140°C C: 130°C or higher and less than 135°C D: 120°C or higher and less than 130°C E: 110°C or higher and less than 120°C F: 100°C or higher and less than 110°C G: Less than 100°C

[0149] <Evaluation of Rub Resistance> Paper: Oce Top Coated Plus Silk 270g (270.0 g / m 2 ) Toner loading amount: 0.20 mg / cm 2 Evaluation image: A single-color halftone image (5 cm × 25 cm) was placed on the above A4 paper. Fixing test environment: Normal temperature and humidity environment: Temperature 23°C / Humidity 50%RH Process speed: 450 mm / sec Fixing temperature: 150°C The image obtained under the above conditions was cut into strips and set upward in the following apparatus. Only paper was set in the damper section, and a rubbing test was carried out under the following conditions. Rubbing tester: The Kagaku Shinkou type friction fastness tester (AB-301) Weight: 500 g (0.5 kgf) Stroke: 10 reciprocations Toner has migrated to the rubbed paper (abrasive paper). For this abrasive paper and white paper, L, a, b of the images of each gradation were measured using SpectroScan Transmission (manufactured by GretagMacbeth) (measurement conditions: D50, viewing angle 2°). * a * b * ΔE obtained by the following formula was compared and used as an index for evaluating abrasion resistance. ΔE = (abrasive paper) {(L * ) 2 + (a * ) 2 + (b * ) 2} 0.5 - (white paper) {(L * ) 2 + (a * ) 2 + (b * ) 2} 0.5 The lower the ΔE, the better the abrasion resistance. (Evaluation criteria) A: ΔE is less than 4.0 B: ΔE is 4.0 or more and less than 7.0 C: ΔE is 7.0 or more and less than 10.0 D: ΔE is 10.0 or more

[0150] <Storage stability> 5 g of toner was placed in a 100 mL resin cup and left in a temperature- and humidity-variable thermostat (50 °C, 54%) for 72 hours. After leaving, the cohesiveness of the toner was evaluated. The cohesiveness was evaluated using the remaining ratio of the toner as an evaluation index when shaken for 10 seconds at an amplitude of 0.5 mm with a 150-μm mesh opening using a Powder Tester PT-X manufactured by Hosokawa Micron Corporation. (Evaluation Criteria) A: Remaining ratio less than 2.0% B: Remaining ratio of 2.0% or more and less than 10.0% C: Remaining ratio of 10.0% or more

[0151] <Image Glossiness> · Paper: GFC-081 (81.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) · Toner loading amount on paper: 0.40 mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) · Evaluation image: A 2 cm × 5 cm image was placed in the center of the above A4 paper · Test environment: Temperature 23 °C / Humidity 50% RH · Fixing temperature: 160 °C · Process speed: 400 mm / sec The above evaluation image was output, and the image glossiness was evaluated. The evaluation of the image glossiness was performed using a handy gloss meter ("PG-1M" manufactured by Tokyo Denshoku Co., Ltd.), measuring the value at a single angle of 60°, and evaluating the measured value as the gloss value. (Image Glossiness Evaluation Criteria) A: Gloss value of 10 or more B: Gloss value of 5 or more and less than 10 C: Gloss value less than 5

[0152] <Examples 2 to 40 and Comparative Examples 1 to 8> Evaluation was performed in the same manner as in Example 1, except that two-component developers 2 to 48 were used instead of the two-component developer 1. The evaluation results are shown in Table 9.

[0153]

Table 9

[0154] The present disclosure relates to the following configurations. (Configuration 1) A toner having toner particles containing a binder resin and inorganic fine particles, wherein the binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1), the content of the monomer unit represented by the following formula (1) is 5.0% by mass or more based on the mass of the crystalline vinyl resin, the inorganic fine particles have an alkyl group on the surface, and the content of the inorganic fine particles is 0.10 to 15.00% by mass based on the mass of the toner particles. The toner is characterized by this. TIFF2025094904000014.tif28153 (In formula (1), among R 1 ~R 4 at least two are each independently -X-COOR 5 , the rest are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a single bond or an alkylene group having 1 or 2 carbon atoms, and R 5 is an alkyl group having 16 to 30 carbon atoms.) (Configuration 2) In the cross-sectional observation of the toner by a transmission electron microscope, the toner particles contain the inorganic fine particles in a region 0.3 μm or more inside from the surface of the toner particles. The toner according to Configuration 1. (Configuration 3) The content of the crystalline vinyl resin based on the mass of the binder resin is 30 to 80% by mass. The toner according to Configuration 1 or 2. (Configuration 4) In the formula (1), among R 1 ~R 4 at least two are each independently -COOR 5 (R 5 is an alkyl group having 16 to 30 carbon atoms). The toner according to any one of Configurations 1 to 3. (Configuration 5) In the formula (1), R 1 and R 2 either one of them, and R 3 and R 4 either one of them are each independently -COOR 5 (R 5 is an alkyl group having 16 to 30 carbon atoms), the toner according to any one of Configurations 1 to 4. (Configuration 6) The toner according to any one of Configurations 1 to 5, wherein the content of the monomer unit represented by the formula (1) is 30.0% by mass or more based on the mass of the crystalline vinyl resin. (Configuration 7) The toner according to any one of Configurations 1 to 6, wherein the number average particle diameter of the primary particles of the inorganic fine particles is 10 to 500 nm. (Configuration 8) The toner according to any one of Configurations 1 to 7, wherein the content of the alkyl group on the surface of the inorganic fine particles is 0.10 to 5.00% by mass based on the mass of the inorganic fine particles. (Configuration 9) The toner according to any one of Configurations 1 to 8, wherein the content (% by mass) of the monomer unit represented by the formula (1) based on the mass of the toner particles is 20 times or more the content (% by mass) of the alkyl group possessed on the surface by the inorganic fine particles based on the mass of the toner particles. (Configuration 10) The toner according to any one of Configurations 1 to 9, wherein the difference between the number of carbon atoms of the alkyl group on the surface of the inorganic fine particles and the number of carbon atoms of R 5 in the formula (1) is 5 or less. (Configuration 11) R 5 in the formula (1) is a linear alkyl group having 18 carbon atoms or a linear alkyl group having 22 carbon atoms, the toner according to any one of Configurations 1 to 10. (Configuration 12) The toner according to any one of Configurations 1 to 11, wherein the inorganic fine particles contain calcium carbonate. (Configuration 13) The toner according to any one of Configurations 1 to 12, wherein the crystalline vinyl resin contains at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (N) and a monomer unit represented by the following formula (H). TIFF2025094904000015.tif68153 In formula (N), R 6 is a hydrogen atom or a methyl group. In formula (H), R 7 is an alkylene group having 1 to 4 carbon atoms, and R 8 is a hydrogen atom or a methyl group.

Claims

1. A toner having toner particles containing a binder resin and inorganic fine particles, The binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1): The content of the monomer unit represented by the following formula (1) is 5.0% by mass or more based on the mass of the crystalline vinyl resin, The inorganic fine particles have alkyl groups on the surface thereof, The toner is characterized in that the content of the inorganic fine particles is 0.10 to 15.00% by mass based on the mass of the toner particles. In formula (1), R １ ~R ４ At least two of the groups are independently -X-COOR ５ the remainders are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X is a single bond or an alkylene group having 1 or 2 carbon atoms, R ５ is an alkyl group having 16 to 30 carbon atoms.

2. 2. The toner according to claim 1, wherein, in cross-sectional observation of the toner with a transmission electron microscope, the toner particles contain the inorganic fine particles in an area 0.3 μm or more inward from the surface of the toner particles.

3. 3. The toner according to claim 1, wherein the content of the crystalline vinyl resin is 30 to 80% by mass based on the mass of the binder resin.

4. In the formula (1), R １ ~R ４ At least two of the groups are independently -COOR ５ (R ５ The toner according to claim 1 or 2, wherein: is an alkyl group having 16 to 30 carbon atoms.

5. In the formula (1), R １ and R ２ Either one of the above and R ３ and R ４ and each independently represents -COOR ５ (R ５ The toner according to claim 1 or 2, wherein: is an alkyl group having 16 to 30 carbon atoms.

6. 3. The toner according to claim 1, wherein the content of the monomer unit represented by the formula (1) is 30.0% by mass or more based on the mass of the crystalline vinyl resin.

7. 3. The toner according to claim 1, wherein the inorganic fine particles have a number average particle size of primary particles of 10 to 500 nm.

8. 3. The toner according to claim 1, wherein the content of the alkyl group on the surface of the inorganic fine particles is 0.10 to 5.00% by mass based on the mass of the inorganic fine particles.

9. 3. The toner according to claim 1, wherein the content (mass %) of the monomer unit represented by formula (1) based on the mass of the toner particles is 20 times or more the content (mass %) of the alkyl groups on the surfaces of the inorganic fine particles based on the mass of the toner particles.

10. The number of carbon atoms of the alkyl group on the surface of the inorganic fine particles and R ５ The toner according to claim 1 or 2, wherein the difference between the number of carbon atoms of

11. R in the above formula (1) ５ 3. The toner according to claim 1, wherein is a linear alkyl group having 18 carbon atoms or a linear alkyl group having 22 carbon atoms.

12. The toner according to claim 1 , wherein the inorganic fine particles contain calcium carbonate.

13. 3. The toner according to claim 1, wherein the crystalline vinyl resin comprises at least one monomer unit selected from the group consisting of a monomer unit represented by the following formula (N) and a monomer unit represented by the following formula (H): In formula (N), R ６ is a hydrogen atom or a methyl group. ７ is an alkylene group having 1 to 4 carbon atoms, R ８ is a hydrogen atom or a methyl group.

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