Toner

Abstract

To provide a toner that has very good low temperature fixability, and also has good charge maintainability and storage stability, while achieving both scratch resistance and image sticking resistance.SOLUTION: A toner has a toner particle containing a binder resin. The binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1). The crystalline vinyl resin contains a specific monomer unit having at least two long-chain alkyl groups in an amount of 5.0 mass% or more with respect to the mass of the crystalline vinyl resin. The toner particle contains at least one polyvalent metal selected from the group consisting of Mg, Ca, Al, and Zn. The content ratio of the polyvalent metal in the toner particle is 25-500 ppm based on mass.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, techniques for fixing toner at a lower temperature are 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

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, if the main component of the toner's binder resin is a crystalline resin with sharp melt properties, the image after fixing is brittle. When the output is rubbed while a load is applied with the output stacked, the image may peel off and transfer to the back, resulting in a decrease in abrasion resistance. Patent Document 3 discloses that a polyvalent metal is contained in the toner, and a pseudo-crosslinking is formed between the polar groups of the crystalline resin and the polyvalent metal. According to the study by the present inventors, such pseudo-crosslinking can improve the abrasion resistance.

[0006] As described above, with a toner containing a crystalline vinyl resin such as behenyl acrylate as the main component of the binder resin, it has become possible to fix the toner at a lower fixing temperature than before. Furthermore, the toner contains a polyvalent metal, and the polyvalent metal can form a pseudo-crosslink with the polar groups of the resin, thereby improving the abrasion resistance. However, the present inventors have recognized that such a pseudo-crosslinked toner is more likely to cause image sticking, where the papers adhere to each other due to static electricity when the papers output from the copying machine are stacked, and conveyance failure occurs during conveyance to the subsequent process, compared to conventional toners. The present disclosure provides a toner that is extremely excellent in low-temperature fixability, achieves both abrasion resistance and resistance to image sticking, and is also excellent in charge retention and storage stability.

Means for Solving the Problems

[0007] The present disclosure is a toner having toner particles containing a binder resin, The binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1), The crystalline vinyl resin contains 5.0 mass% or more of the monomer unit represented by the following formula (1) based on the mass of the crystalline vinyl resin, The toner particles contain at least one polyvalent metal selected from the group consisting of Mg, Ca, Al, and Zn, Regarding the toner, the content ratio of the polyvalent metal in the toner particles is 25 to 500 ppm by mass.

Chemical formula

Advantages of the Invention

[0008] According to the present disclosure, it is possible to provide a toner that is extremely excellent in low-temperature fixability, achieves both scratch resistance and image sticking resistance, and is also excellent in charge retention and storage stability.

Embodiments for Carrying Out the Invention

[0009] In the present disclosure, the description of "XX or more and YY or less" or "XX to YY" representing a numerical range means a numerical range including the lower limit and the upper limit which are the endpoints, unless otherwise specified. When the numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined. Further, in the present disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means 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.

[0010] 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

[0011] In the 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 Brepresents an arbitrary substituent. A crystalline vinyl resin refers to a resin synthesized from an arbitrary vinyl monomer and showing a distinct endothermic peak in differential scanning calorimetry (DSC) measurement.

[0012] Regarding the mechanism by which the toner according to the present disclosure can achieve both scratch resistance and anti-image sticking, the inventors of the present invention consider it as follows. Conventionally, crystalline vinyl resins such as behenyl acrylate used in toners have low scratch resistance because their crystal domains are small and brittle. Therefore, a polar group is provided in the crystalline vinyl resin, and a polyvalent metal is contained in the toner to pseudo-crosslink the polar group and the polyvalent metal, making the toner harder and improving the scratch resistance. However, since the formation of a pseudo-crosslink between the polar group and the polyvalent metal makes it difficult for charge diffusion to occur, when an image is output, the papers stick to each other due to static electricity and post-conveyance cannot be performed immediately, etc., leaving room for improvement. Therefore, as a result of intensive studies by the inventors of the present invention, it has been found that the above problems can be solved by using the monomer unit represented by the formula (1) in the crystalline vinyl resin and further containing a polyvalent metal in the toner particles. When the monomer unit represented by the formula (1) is used, a plurality of long-chain alkyls in the monomer unit extend in different directions and crystallize, so that the crystal domain becomes larger and harder.

[0013] When the crystal domain becomes larger, the charge transfer distance becomes longer, and the distance between the crystal domains also increases. Therefore, the charge leakage path becomes longer and it becomes difficult for charges to diffuse. However, since the presence of a polyvalent metal there can improve charge diffusion, it is considered that image sticking can be suppressed.

[0014] ​The crystalline vinyl resin preferably has polar groups such as -C≡N, -COOH, and -OH. Due to the polar groups contained in the crystalline vinyl resin, polyvalent metals can bind to the crystal domains, and charge diffusion can be further improved. Furthermore, since the crystal domains are large, the polar groups on the surface are suppressed, and due to the large distance between the crystal domains, pseudo-crosslinking is less likely to occur, and the polyvalent metals are not completely constrained. Therefore, it is presumed that charge diffusion can be made better and image sticking can be more suppressed.

[0015] The present disclosure relates to a toner having toner particles containing a binder resin, wherein the binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1), the crystalline vinyl resin contains 5.0% by mass or more of the monomer unit represented by the following formula (1) based on the mass of the crystalline vinyl resin, the toner particles contain at least one polyvalent metal selected from the group consisting of Mg, Ca, Al, and Zn, and the content ratio of the polyvalent metal in the toner particles is 25 to 500 ppm by mass.

Chemical formula

[0016] 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, R 1 ~R 4Among them, 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.

[0017] By shortening the distance between the alkyl group side chains of the crystalline vinyl resin with the monomer unit represented by formula (1), the crystal domains in the toner are likely to grow, and good low-temperature fixability can be obtained by improving the sharp melt property. When R 5 exceeds 30, the low-temperature fixability is likely to decrease. Also, when R 5 is less than 16, the storage stability is likely to decrease. Also, among R 1 ~R 4 , if only one is -X-COOR 5 , the crystal domains are unlikely to grow large, and it is difficult to obtain the effect of suppressing the above-described image sticking.

[0018] To form crystal domains grown from 1 ~R 4 in formula (1), it is preferable that at least two of R 5 (R 5 is an alkyl group having 16 to 30 carbon atoms). Also, in formula (1), it is more preferable that either one of R 1 and R 2 , and either one of R 3 and R 4 are each independently -COOR 5 (R 5 is 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 even more preferable that R 5 is a linear alkyl group having 18 carbon atoms or a linear alkyl group having 22 carbon atoms.

[0019] ​In addition, the crystalline vinyl resin contains 5.0% by mass or more of the monomer unit represented by the formula (1) based on the mass of the crystalline vinyl resin. When the content of the monomer unit represented by the formula (1) is 5.0% by mass or more, the low-temperature fixability is improved. Also, the abrasion resistance and the charge retention property are improved. Since the low-temperature fixability improves as the content of the unit of the formula (1) increases, it is preferable that the crystalline vinyl resin contains 30.0% by mass or more of the monomer unit represented by the formula (1). The content of the monomer unit represented by the 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 still more preferably 45.0 to 75.0% by mass.

[0020] Similarly, from the viewpoint of low-temperature fixability, the content ratio of the crystalline vinyl resin based on the mass of the binder resin is preferably 30% or more, and more preferably 50% or more. On the other hand, from the viewpoint of storage stability, the content ratio of the crystalline vinyl resin based on the mass of the binder resin is preferably 80% or less. The content ratio 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 still more preferably 50 to 70% by mass.

[0021] In the toner, the toner particles contain at least one polyvalent metal selected from the group consisting of the binder resin and Mg, Ca, Al, and Zn. And it is necessary that the content ratio of the polyvalent metal is 25 to 500 ppm based on the mass of the toner particles.

[0022] When the amount of the polyvalent metal is within the above range, the charge diffusion becomes appropriate and the image sticking is suppressed. When the amount of the polyvalent metal is less than 25 ppm, the charge diffusion becomes insufficient and the image sticking is likely to occur. Also, when the amount of the polyvalent metal exceeds 500 ppm, the charge diffusion becomes excessive, the charge retention property of the toner under high temperature and high humidity decreases, and when printing again after the print interval is opened, a recovery operation is required until the charge amount of the toner increases.

[0023] The content ratio of the polyvalent metal in the toner particles is preferably 100 to 400 ppm and more preferably 150 to 350 ppm on a mass basis. When producing toner particles by the emulsion aggregation method, the content ratio of the polyvalent metal in the toner particles can be controlled by using a flocculant containing the polyvalent metal in the aggregation step. Even when adopting other production methods of toner particles, the polyvalent metal within the above range can be contained by any method.

[0024] The content ratio of the polyvalent metal (ppm on a mass basis) based on the mass of the toner particles and the content ratio (mass %) of the monomer unit represented by the formula (1) based on the mass of the toner particles preferably satisfy the following formula (2). It is preferable that (content ratio of polyvalent metal) / (content ratio of monomer unit represented by formula (1)) ≥ 1.0 (ppm / mass %) ··· (2) When the above formula (2) is within the above range, sufficient polyvalent metal exists with respect to the crystal domain, charge diffusion becomes good, and image sticking can be more suppressed. (Content ratio of polyvalent metal) / (content ratio of monomer unit represented by formula (1)) is preferably 1.0 to 25.0 (ppm / mass %), and more preferably 4.0 to 12.0 (ppm / mass %). In the crystalline vinyl resin, the polymerizable monomer capable of forming the monomer unit represented by the formula (1) may be used alone or in combination of two or more.

[0025] The crystalline vinyl resin may contain other monomer units other than the monomer unit represented by the formula (1) to the extent that the effects of the present disclosure are not impaired, if necessary. Examples of the polymerizable monomer forming the other monomer unit include monomers having a nitrile group; acrylonitrile, methacrylonitrile. (2 - hydroxyethyl (meth) acrylate, 2 - hydroxypropyl (meth) acrylate, 2 - hydroxyethylamide (meth) acrylate, 2 - hydroxypropylamide (meth) acrylate, etc.

[0026] ​ Among these, it is preferable to use at least one polymerizable monomer selected from the group consisting of acrylonitrile, methacrylonitrile, acrylic acid, and methacrylic acid. These polymerizable monomers can impart high polarity to the crystalline vinyl resin. When the crystalline vinyl resin has polarity, not only is the adhesion to paper improved and the fixing property becomes better, but also as described above, it contributes to charge diffusion, making it easier to suppress image sticking. Furthermore, since the polar group also interacts with the polyvalent metal, the polyvalent metal in the toner particles is uniformly dispersed, making it even easier to suppress image sticking. 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.

[0027] 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. Also, the crystalline vinyl resin may contain 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, etc. 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 (N).

Chemical formula

[0028] 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 formula (N) in the crystalline vinyl resin is preferably 4.0 to 45.0% by mass, more preferably 5.5 to 35.0% by mass. Further, the crystalline vinyl resin preferably contains the monomer unit represented by formula (H) in an amount of 10.0 to 35.0% by mass, more preferably 15.0 to 35.0% by mass. In addition, the total content of the monomer unit represented by formula (N) and the monomer unit represented by formula (H) in the crystalline vinyl resin is preferably 4.0 to 45.0% by mass, more preferably 5.5 to 35.0% by mass.

[0029] In addition, examples of the polymerizable monomer that forms other monomer units other than the monomer unit represented by formula (1) include the following polymerizable monomers. Monomers having an amide group; for example, acrylamide, monomers obtained by reacting an amine having 1 to 30 carbon atoms with 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, amines having 3 to 22 carbon atoms [primary amines (such as normal butylamine, t-butylamine, propylamine, and isopropylamine), secondary amines (such as dinormal ethylamine, dinormal propylamine, dinormal butylamine, etc.), aniline, and cyclohexylamine, etc.], and monomers obtained by reacting an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond by a known method 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; linked by a chain containing an aromatic group and an ether bond Dialkylate compounds linked by a chain; polyester type dialkylates; polyfunctional crosslinking agents.

[0030] Examples of the aromatic divinyl compound include divinylbenzene, divinylnaphthalene, etc. Examples of the dialkylate compounds linked by the 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.

[0031] 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 a monomer unit corresponding to styrene in an amount of 0.0 to 50.0% by mass, more preferably 20.0 to 40.0% by mass.

[0032] The crystalline vinyl resin can be produced using the exemplified polymerizable monomer and a polymerization initiator. From the viewpoint of efficiency, the polymerization initiator is preferably used in an amount of 0.05 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the polymerizable monomer.

[0033] 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), ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, 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) peroxydicarbonate, 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.,

[0034] From the viewpoint of charging stability, the crystalline vinyl resin preferably has an acid value of 0 mgKOH / g to 100 mgKO H / 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.

[0035] 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 fixing property, the binder resin preferably contains 30 to 80% by mass of the crystalline vinyl resin.

[0036] Examples of known amorphous resins include the following. Polyvinyl chloride, phenolic resin, natural resin-modified phenolic 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.

[0037] 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-level low-temperature fixability and hot offset resistance.

[0038] 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 (diols or triols or higher), polyvalent carboxylic acids (diacids or triacids or higher), their acid anhydrides, or their lower alkyl esters.

[0039] Examples of the polyhydric alcohol include the following. Examples of the diol 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.

[0040] 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.

[0041] Examples of the polycarboxylic 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.

[0042] 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 units of the crystalline vinyl resin. Because 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. Thereby, the low-temperature fixability of the toner may be improved.

[0043] 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(methylene carboxyl)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, Empol trimer acid, acid anhydrides thereof, or lower alkyl esters thereof.

[0044] Among these, derivatives such as 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its acid anhydride are inexpensively available and easy to control in reaction, and thus are preferably used. These polyvalent carboxylic acids can be used alone or in combination of two or more. Moreover, linear saturated fatty acids such as behenic acid may be used.

[0045] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the aforementioned polyhydric alcohol and polyvalent carboxylic acid are charged simultaneously, and polymerized through an esterification reaction or transesterification reaction, and a condensation reaction to produce a polyester resin. 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.

[0046] 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.

[0047] 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, p-nitrostyrene; Acrylic acid esters such as 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 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, and diethylaminoethyl methacrylate; Also, acrylonitrile, methacrylonitrile, acrylamide, etc.

[0048] Furthermore, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and polymerizable monomers having a hydroxy group such as 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene. These can be used alone or in combination of multiple types.

[0049] Among them, styrene, acrylic acid esters, methacrylic acid esters, acrylonitrile, etc. are preferable. Also, monomers that are condensates of acrylic acid or methacrylic acid and alcohols having 6 to 22 carbon atoms, such as n-octyl acrylate, dodecyl acrylate, 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 the filler effect is difficult to be exhibited when the strain is large. Thereby, the low-temperature fixability of the toner may be better.

[0050] For the amorphous vinyl resin, various polymerizable monomers capable of vinyl polymerization may be used in combination as needed in addition to the above. 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.

[0051] Further, 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, divinylnaphthalene, and the like.

[0052] 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.

[0053] The amorphous vinyl resin is preferably a polymer of a polymerizable monomer containing at least one selected from the group consisting of 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, 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.

[0054] 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 monomers may be about 0.5% by mass to 5.0% by mass.

[0055] 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.

[0056] 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), ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, 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.,

[0057] As the vinyl resin and the polyester resin used to form a hybrid resin in which a vinyl resin and a polyester resin are bonded, the same ones as the vinyl resin and the polyester resin used as the amorphous resin described above can be used.

[0058] 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.

[0059] 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 polycondensation resin and the addition polymerization resin. Among these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.

[0060] When using a hybrid resin in which a vinyl resin and a polyester resin are bonded, 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.

[0061] <Colorant> The toner particles may contain a colorant. 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. The colorant may use a pigment alone but it is preferable to use a combination of a dye and a pigment to improve the vividness from the viewpoint of the image quality of the full-color image.

[0062] 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.

[0063] Examples of the dye for magenta toner include the following. Oil-soluble dyes such as 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; C.I. Disperse Violet 1; Basic dyes such as 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; C.I. Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0064] Examples of the pigments for cyan toners 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 toners, there is C.I. Solvent Blue 70.

[0065] Examples of the pigments for yellow toners 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 toners, there is C.I. Solvent Yellow 162.

[0066] 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.

[0067] <Release agent> The toner particles may contain wax as a release agent. 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.

[0068] Furthermore, the following may be mentioned. 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 fatty acid bisamides such as methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, and hexamethylene bisstearic acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N'-dioleyl adipic acid amide, and N,N'-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide and N,N'-distearyl isophthalic acid amide; fatty acid metal salts (commonly referred to as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted with vinyl monomers such as styrene or acrylic acid onto aliphatic hydrocarbon waxes; partial esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having a hydroxy group obtained by hydrogenating vegetable oils.

[0069] ​ The wax content is preferably 2.0 to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0070] <Charge control agent> The toner particles may contain a charge control agent as needed. As the charge control agent, known ones can be used, and in particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high charging speed of the toner, and can stably maintain a certain charge amount is preferable.

[0071] Examples of the negative charge control agent include metal salicylate compounds, metal naphthenate compounds, metal dicarboxylate compounds, polymer compounds having sulfonic acid or carboxylic acid in the side chain, polymer compounds having sulfonate or sulfonic acid esterified products in the side chain, polymer compounds having carboxylate or carboxylic acid esterified products in the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0072] 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 to 10.0 parts by mass with respect to 100 parts by mass of the binder resin.

[0073] <External additive> The toner may contain toner particles and an external additive. As the external additive, 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.

[0074] 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 durability stabilization, those having a specific surface area of 10 m 2 / g or more and 50 m 2It is preferably an inorganic fine particle of / g or less. In order to achieve both fluidity improvement and durability stabilization, inorganic fine particles having a specific surface area within the above range may be used in combination. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used. The content of the external additive is preferably 0.1 part by mass to 10.0 parts by mass, more preferably 1.0 part by mass to 5.0 parts by mass, based on 100 parts by mass of the toner particles.

[0075] <Developer> 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.

[0076] 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 substances such as ferrite; a magnetic substance-dispersed resin carrier (so-called resin carrier) containing the magnetic substance and a binder resin for holding the magnetic substance in a dispersed state; and the like, and generally known ones can be exemplified. When the toner is mixed with the 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.

[0077] <Method for manufacturing toner> The method for manufacturing the toner is not particularly limited, and known methods such as a pulverization method, a suspension polymerization method, a dissolution suspension method, an emulsion aggregation method, a dispersion polymerization method, etc. can be used. The toner is preferably manufactured by an emulsion aggregation method. That is, the toner particles are preferably emulsion aggregation toner particles.

[0078] <Emulsion aggregation method> The emulsion aggregation method is a method of preparing in advance an aqueous dispersion of fine particles made of the constituent materials of toner particles that are sufficiently small for the target particle size, aggregating the fine particles in an aqueous medium until they reach the particle size of the toner particles, and fusing the resin by heating or the like to produce toner particles. That is, in the emulsion aggregation method, a dispersion step of preparing a fine particle dispersion made of the constituent materials of toner particles, an aggregation step of aggregating the fine particles made of the constituent materials of toner particles and controlling the particle size until it reaches the particle size of the toner particles, a fusion step of fusing the resin contained in the obtained aggregated particles, a subsequent cooling step, a metal removal step of filtering the obtained toner and removing excessive polyvalent metal ions, a filtration / washing step of washing with ion-exchanged water or the like, and a step of removing the moisture of the washed toner particles and drying them are carried out to produce toner particles.

[0079] <Step of preparing a resin fine particle dispersion (dispersion step)> The resin fine particle dispersion can be prepared by known methods, but is not limited to these methods. Examples of known methods include emulsion polymerization method, self-emulsification method, phase inversion emulsification method of emulsifying the resin by adding an aqueous medium to a resin solution dissolved in an organic solvent, or forced emulsification method of forcibly emulsifying the resin by high-temperature treatment in an aqueous medium without using an organic solvent. Specifically, the binder resin is dissolved in an organic solvent capable of dissolving them, and a surfactant and a basic compound are added. At this time, if the binder resin is a crystalline resin having a melting point, it may be heated above the melting point and dissolved. Subsequently, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate resin fine particles. Then, the solvent is removed by heating or reducing the pressure to prepare an aqueous dispersion of resin fine particles. As the organic solvent used to dissolve the resin, any organic solvent capable of dissolving the resin can be used, but it is preferable to use an organic solvent that forms a homogeneous phase with water, such as toluene, from the viewpoint of suppressing the generation of coarse powder.

[0080] The surfactant used during the above emulsification is not particularly limited. For example, anionic surfactants such as sulfate ester salts, sulfonates, carboxylates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts ; nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols, etc. may be mentioned. The surfactant may be used alone or in combination of two or more. Examples of the basic compound used during the dispersion step include inorganic bases such as sodium hydroxide and potassium hydroxide; and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The basic compound may be used alone or in combination of two or more. Also, the 50% particle size (D50) based on the volume distribution of the fine particles of the binder resin in the aqueous dispersion of the resin fine particles is preferably from 0.05 μm to 1.0 μm, more preferably from 0.05 μm to 0.4 μm. By adjusting the 50% particle size (D50) based on the volume distribution within the above range, it becomes easier to obtain toner particles having a volume average particle size of 3 μm to 10 μm, which is an appropriate volume average particle size as toner particles. For the measurement of the 50% particle size (D50) based on the volume distribution, a dynamic light scattering particle size distribution analyzer NanoTrack UPA - EX150 (manufactured by Nikkiso Co., Ltd.) is used.

[0081] <Colored pigment fine particle dispersion> The colored pigment fine particle dispersion that is used as needed can be prepared by known methods listed below, but is not limited to these techniques. It can be prepared by mixing a colored pigment, an aqueous medium, and a dispersant using a mixer such as a known stirrer, emulsifier, and disperser. The dispersant used here can be a known one such as a surfactant and a polymer dispersant. Both the surfactant and the polymer dispersant can be removed in the washing step described later. From the viewpoint of washing efficiency, the surfactant is preferred. Examples of surfactants include anionic surfactants such as sulfate salts, sulfonates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, nonionic surfactants or anionic surfactants are preferred. Also, a nonionic surfactant and an anionic surfactant may be used in combination. The surfactant may be used alone or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5% by mass to 5% by mass.

[0082] The content of the colorant fine particles in the colorant fine particle dispersion is not particularly limited, but is preferably 1% by mass to 30% by mass based on the total mass of the colorant fine particle dispersion. Also, from the viewpoint of the dispersibility of the colorant in the finally obtained toner, the dispersed particle diameter of the colorant fine particles in the aqueous dispersion of the colorant is preferably such that the 50% particle diameter (D50) based on the volume distribution is 0.5 μm or less. Also, for the same reason, the 90% particle diameter (D90) based on the volume distribution is preferably 2 μm or less. The dispersed particle diameter of the colorant fine particles dispersed in the aqueous medium is measured with a dynamic light scattering particle size distribution analyzer (NanoTrack UPA-EX150: manufactured by Nikkiso Co., Ltd.). Examples of mixers such as known stirrers, emulsifiers, and dispersers used when dispersing the colorant in the aqueous medium include ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint shakers. These may be used alone or in combination.

[0083] <Release agent (aliphatic hydrocarbon compound) fine particle dispersion> A release agent fine particle dispersion may be used as necessary. The release agent fine particle dispersion can be prepared by known methods listed below, but is not limited to these techniques. The release agent fine particle dispersion is prepared by adding a release agent to an aqueous medium containing a surfactant, heating the mixture to a temperature equal to or higher than the melting point of the release agent, and then dispersing the mixture into particles using a homogenizer having a strong shearing ability (e.g., "ClearMix W Motion" manufactured by M Technique Co., Ltd.) or a pressure discharge type disperser (e.g., "Gorin Homogenizer" manufactured by Gorin Co., Ltd.). After that, the mixture is cooled to a temperature lower than the melting point. In the aqueous dispersion of the release agent, the dispersion particle size of the release agent fine particle dispersion preferably has a volume distribution-based 50% particle size (D50) of 0.03 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm. Further, it is preferable that there are no coarse particles of 1 μm or more. When the dispersion particle size of the release agent fine particle dispersion is within the above range, the release agent can be finely dispersed and present in the toner, maximizing the bleeding effect during fixing and enabling good separability. The dispersion particle size of the release agent fine particle dispersion dispersed in the aqueous medium can be measured using a dynamic light scattering particle size distribution analyzer (NanoTrack UPA-EX150: manufactured by Nikkiso Co., Ltd.).

[0084] <Mixing step> In the mixing step, a mixed liquid is prepared by mixing a resin fine particle dispersion and at least one of a release agent fine particle dispersion and a colorant fine particle dispersion as required. This can be carried out using a known mixing device such as a homogenizer and a mixer.

[0085] <Step of forming aggregate particles (aggregation step)> In the aggregation step, the fine particles contained in the mixed liquid prepared in the mixing step are aggregated to form aggregates having a target particle size. At this time, a flocculant is added and mixed, and at least one of heating and mechanical power is appropriately applied as required to form aggregates in which resin fine particles and at least one of release agent fine particles and colorant fine particles are aggregated. The flocculant is a flocculant containing metal ions of a polyvalent metal, and the polyvalent metal is at least one selected from the group consisting of Mg, Ca, Al, and Zn.

[0086] The content ratio of the polyvalent metal in the toner particles can be controlled by the addition amount of the flocculant containing the metal ions of the polyvalent metal. The addition amount of the flocculant is not particularly limited, and may be in the range where the content ratio of the polyvalent metal in the toner particles is 25 to 500 ppm on a mass basis.

[0087] The flocculant containing the metal ions of the polyvalent metal has a high flocculation power and can achieve the purpose with a small amount of addition. These flocculants can ionically neutralize the ionic surfactants contained in the resin fine particle dispersion, the release agent fine particle dispersion, and the colorant fine particle dispersion. As a result, due to the effects of salting out and ion crosslinking, the binder resin fine particles, the release agent fine particles, and the colorant fine particles are flocculated. Furthermore, the flocculant containing the metal ions of the polyvalent metal can be uniformly dispersed in the toner particles. Furthermore, when the crystalline vinyl resin has a polar group, the metal ions can interact with the polar group, thereby having better charge diffusibility and effectively suppressing image sticking.

[0088] Examples of the flocculant containing the metal ions of the polyvalent metal include metal salts of polyvalent metals or polymers of metal salts. Specifically, divalent inorganic metal salts such as calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, and zinc chloride can be mentioned. Also, trivalent metal salts such as iron(III) chloride, iron(III) sulfate, aluminum sulfate, and aluminum chloride can be mentioned. Also, inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide can be mentioned, but are not limited thereto. These may be used alone or in combination of two or more. The flocculant may be added in either the form of a dry powder or an aqueous solution dissolved in an aqueous medium, but in order to cause uniform flocculation, it is preferably added in the form of an aqueous solution. Also, the addition and mixing of the flocculant are preferably carried out at a temperature equal to or lower than the glass transition temperature or the melting point of the resin contained in the mixed solution. By mixing under this temperature condition, flocculation proceeds relatively uniformly. The mixing of the flocculant into the mixed solution is carried out using known devices such as a homogenizer and a mixer. It can be carried out using a mixing device. The aggregation step is a step of forming aggregates of toner particle size in an aqueous medium. The volume average particle diameter of the aggregates produced in the aggregation step is preferably 3 μm or more and 10 μm or less. The volume average particle diameter can be measured with a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter) by the Coulter method.

[0089] <Step of obtaining a dispersion liquid containing toner particles (fusion step)> In the fusion step, a flocculation inhibitor may be added to the dispersion liquid containing the aggregates obtained in the aggregation step under the same stirring as in the aggregation step. Examples of the flocculation inhibitor include chelating agents that partially dissociate the ionic crosslink between the acidic polar group of the surfactant and the metal ions that are the flocculant, and form a coordination bond with the metal ions to stabilize the flocculated particles. By the action of the flocculation inhibitor, after the dispersion state of the flocculated particles in the dispersion liquid becomes stable, it is heated to a temperature equal to or higher than the glass transition temperature or melting point of the binder resin to fuse the flocculated particles.

[0090] The chelating agent is not particularly limited as long as it is a known water-soluble chelating agent. Specifically, oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, and their sodium salts; iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA), and their sodium salts; can be mentioned. The chelating agent can change the environment in the dispersion liquid from a state that is electrostatically unstable and prone to aggregation to a state that is electrostatically stable and less likely to cause further aggregation by coordinating with the metal ions of the flocculant present in the dispersion liquid of the flocculated particles. Thereby, further aggregation of the flocculated particles in the dispersion liquid can be suppressed, and the flocculated particles can be stabilized. The chelating agent is effective even in a small addition amount, and since toner particles with a sharp particle size distribution can be obtained, it is preferably an organic metal salt having a carboxylic acid of trivalent or higher. In addition, from the perspective of achieving both stabilization from the agglomerated state and washing efficiency, the addition amount of the chelating agent is preferably 1 to 30 parts by mass, more preferably 2.5 to 15 parts by mass, based on 100 parts by mass of the binder resin. Note that the volume-based median particle size (D50) of the toner particles is preferably 3 μm or more and 10 μm or less.

[0091] <Step of promoting crystallization> From the perspective of increasing the crystallinity of crystalline materials such as crystalline vinyl resins, annealing treatment may be performed near the crystallization temperature of the crystalline material (for example, in the range of the crystallization temperature ± 10°C, preferably in the range of the crystallization temperature ± 5°C). The preferred range of the holding time is 30 minutes or more, more preferably 60 minutes or more, and even more preferably 100 minutes or more. The upper limit of the holding time is about 24 hours or less due to manufacturing efficiency.

[0092] <Cooling step> If necessary, in the cooling step, the temperature of the dispersion containing the toner particles obtained in the fusion step can also be cooled to a temperature lower than at least one of the crystallization temperature and the glass transition temperature of the binder resin. By cooling to a temperature lower than at least one of the crystallization temperature and the glass transition temperature, the generation of coarse particles can be prevented. The specific cooling rate can be 0.1°C / min to 50°C / min.

[0093] <Washing step> If necessary, in the washing step, impurities in the toner particles can be removed by repeating the washing and filtration of the toner particles obtained in the cooling step. Specifically, it is preferable to wash the toner particles with an aqueous solution containing a chelating agent such as ethylenediaminetetraacetic acid (EDTA) and its Na salt, and then wash with pure water. By repeating the washing and filtration with pure water a plurality of times, metal salts, surfactants, etc. in the toner particles can be removed. The number of filtration times is preferably 3 to 20 times, more preferably 3 to 10 times, from the perspective of manufacturing efficiency.

[0094] <Drying step> In the drying process, if necessary, the toner particles obtained in the above process are dried.

[0095] <External addition process> In the external addition process, if necessary, inorganic fine particles are externally added to the toner particles obtained in the drying process. Specifically, it is preferable to add inorganic fine particles such as silica and resin fine particles such as vinyl resin, polyester resin, and silicone resin by applying a shearing force in a dry state.

[0096] The measurement methods for various physical properties of the toner and raw materials will be described below. <Method for measuring the metal content in toner particles> The metal content in the toner particles is measured using a multi-element simultaneous ICP emission spectrometer Vista-PRO (manufactured by Hitachi High-Technologies Corporation). Sample: 50 mg Solvent: 6 mL of nitric acid Weigh the above and perform a decomposition process using a microwave sample pretreatment device ETHOS UP (manufactured by Milestone General). Temperature: Heat up from 20°C to 230°C and hold at 230°C for 30 min After passing the decomposition solution through filter paper (5C), transfer it to a 50 mL volumetric flask and make up to 50 mL with ultrapure water. By measuring the aqueous solution in the volumetric flask with a multi-element simultaneous ICP emission spectrometer Vista-PRO under the following conditions, the content of polyvalent metal elements (such as Mg, Ca, Al, and Zn) in the toner particles can be quantified. The quantification of the content is calculated based on a calibration curve prepared using a standard sample of the element to be quantified. Conditions: RF power 1.20 kW, Ar gas: Plasma flow 15.0 L / min, Auxiliary flow: 1.50 L / min, MFC: 1.50 L / min, Nebulizer flow: 0.90 L / min, Liquid delivery pump speed: 15 rpm, Measurement repetition: 3 times, Measurement time: 1.0 s

[0097] (When measuring a toner to which inorganic fine particles containing at least one metal selected from the group consisting of Mg, Ca, Al, and Zn are externally added) When measuring the content of a metal in toner particles of a toner to which inorganic fine particles containing at least one metal selected from the group consisting of Mg, Ca, Al, and Zn are externally added, in order to prevent calculation of the content of the metal derived from the inorganic fine particles in addition to the polyvalent metal in the toner particles, the measurement is performed after separating the inorganic fine particles from the toner.

[0098] (Method for separating inorganic fine particles from toner) The inorganic fine particles can be separated from the toner by utilizing the difference in solubility of each material contained in the toner in a solvent. The toner is dissolved in methyl ethyl ketone (MEK) at 100 °C to separate the soluble components (crystalline vinyl resin, amorphous resin other than crystalline vinyl resin, release agent) and the insoluble components (colorant, inorganic fine particles, etc.). By measuring the obtained soluble components and insoluble components respectively, the amount of polyvalent metal in the toner particles can be measured.

[0099] <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. 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is added to 100 mL of ion-exchanged water and dissolved while stirring to prepare a thick sucrose solution. 31 g of the above thick sucrose solution and 6 mL of Contaminon N (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.) are placed in 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. Place the centrifuge tube on a shaker (sold by AS ONE Corporation) and shake 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 additives 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 through a pressure filtration device, dry it in a dryer for 1 hour or more to obtain toner particles. Repeat this operation multiple times to ensure the required amount.

[0100] <Method for Separating Crystalline Vinyl Resin and Amorphous Resin from Toner Particles> Separation of crystalline vinyl resin and amorphous resin from toner particles can be achieved by known methods, and an example is shown below. As a method for separating the resin component from toner particles, gradient LC is used. In this analysis, separation can be performed according to the polarity of the resin in the binder resin regardless of the molecular weight. First, dissolve the toner particles in chloroform. The sample was adjusted to a sample concentration of 0.1 mass% with chloroform, and the solution filtered through a 0.45 μm PTFE filter was used for measurement. The gradient polymer LC measurement conditions are shown below. Apparatus: UlTIMATE3000 (manufactured by Thermo Fisher Scientific) Mobile phase: A Chloroform (HPLC), B Acetonitrile (HPLC) Gradient: 2 min (A / B = 0 / 100) → 25 min (A / B = 100 / 0) (Note that the gradient of the change in the mobile phase was made linear.) Flow rate: 1.0 mL / min Injection: 0.1 mass% × 20 μL Column: Tosoh TSKgel ODS (4.6 mmφ x 150 mm x 5 μm) Column temperature: 40 °C Detector: Corona charged particle detector (Corona - CAD) (manufactured by Thermo Fisher Scientific) Regarding the time - intensity graph obtained by measurement, the resin components can be separated into two peaks according to polarity. Then, by performing the above measurement again and fractionating at the time corresponding to the valley of each peak, it is possible to separate into two types of resins. For the separated resins, DSC measurement is performed, and the resin with a melting point peak is defined as crystalline vinyl resin (A) (mass W11 [g]), and the resin without a melting point peak is defined as amorphous resin (mass W12 [g]).

[0101] When the toner particles contain a release agent, it is necessary to separate the release agent from the toner particles in advance. The separation of the release agent is carried out by recycling HPLC to separate components with a molecular weight of 3000 or less as the release agent. Note that the molecular weight at the time of separation can be changed according to the molecular weight of the release agent. The measurement method is shown below. First, prepare a chloroform solution of the toner by the method described above. Then, filter the obtained 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 components soluble in chloroform is 1.0 mass%. Using this sample solution, measurement is performed under the following conditions. · Equipment: LC - Sakura NEXT (manufactured by Japan Analytical Industry Co., Ltd.) · Column: JAIGEL2H, 4H (manufactured by Japan Analytical Industry Co., Ltd.) · Eluent: Chloroform · Flow rate: 10.0 ml / min · Oven temperature: 40.0 °C · Sample injection volume: 1.0 ml When calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (for example, 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. From the molecular weight curve thus obtained, components with a molecular weight of 3000 or less are repeatedly fractionated to remove the release agent (mass W3 [g]) from the toner particles.

[0102] <Measurement of the content ratio of each component in the toner particles> From each mass described in the <Method for Separating Crystalline Vinyl Resin and Amorphous Resin from Toner Particles> described above, the content ratio of each component in the toner particles is calculated as follows. 〔Content ratio of crystalline vinyl resin based on the mass of the binder resin: (unit: mass%)〕=(W11 / (W11 + W12))×100

[0103] <Identification of Monomer Units Constituting Crystalline Vinyl Resin and Amorphous Resin and Method for Measuring the Content Ratio of Monomer Units> The identification of the monomer units constituting the crystalline vinyl resin and the amorphous resin and the measurement of the content ratio of the monomer units are 1 performed by 1H-NMR under the following conditions. 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 later can be used. The following will be described based on an example using a crystalline vinyl resin. The obtained 1 From the 1H-NMR chart, a peak independent of the peaks attributed to the components of the monomer unit represented by the formula (1) contained in the crystalline vinyl resin is selected from among the peaks attributed to the components of the monomer unit, and the integral value S1 of this peak is calculated. Similarly, for each of 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 units constituting the crystalline vinyl resin are the monomer unit represented by the formula (1) and one other monomer unit, the content ratio of the monomer unit represented by the formula (1) is determined as follows using the above integral values S1 and S2. Here, n1 and n2 are the number of hydrogens in the components to which the peaks focused on for each site are attributed. Content ratio (mol%) of the monomer unit represented by the 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 (a) 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 also be calculated in the same manner. In the case where a polymerizable monomer containing no hydrogen atom in the components other than the vinyl group is used, 13 using 13C-NMR to set the measurement nucleus to 13 13C and performing the measurement in the single pulse mode, 1 it 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, R in the formula (1) 5The number of carbon atoms in an alkyl group, etc., can be calculated from the integration ratio of proton peaks in the H-NMR chart. 1 It can be calculated from the integration ratio of proton peaks in the H-NMR chart.

[0106] <Method for measuring the weight average molecular weight (Mw) of resins, etc., using gel permeation chromatography (GPC)> The weight average molecular weight (Mw) of the tetrahydrofuran (THF)-soluble component of a 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" with a pore size of 0.2 μm (manufactured by Tosoh Corporation) 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, the measurement is performed under the following conditions. Apparatus: HLC8220 GPC (Detector: RI) (manufactured by Tosoh Corporation) Column: 7-series 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] When calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (product 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 the toner (particles) is measured 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 attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data. The measurement is carried out with an effective number of measurement channels of 25,000 channels, and the measurement data is analyzed and calculated. The electrolytic aqueous solution used for the measurement is 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 the measurement and analysis, the settings of the dedicated software are made as follows.

[0109] On the "Change Screen of 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.). Threshold / noise Press the measurement button of the bell to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check 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 about 200 mL of the electrolytic aqueous solution into a 250 mL round-bottom glass beaker dedicated to Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Flash of Aperture Tube" function of the dedicated software to remove dirt and bubbles in the aperture tube. (2) Put about 30 mL of the electrolytic aqueous solution into a 100 mL glass flat-bottom beaker, and add about 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.) 3-fold by mass with ion-exchanged water as a dispersant. (3) Put a predetermined amount of ion-exchanged water into the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.) with an electric output of 120 W, which incorporates two oscillators with an oscillation frequency of 50 kHz and a 180-degree phase shift, and add about 2 mL of Contaminon N into 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 about 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. In ultrasonic dispersion, appropriately adjust so that the water temperature in the water tank is between 10°C and 40°C. (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 about 5%. Then, perform the measurement until the number of measured particles reaches 50,000. (7) Analyze the measurement data using the dedicated software attached to the device to calculate the weight average particle diameter (D4). 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 diameter (D4).

[0111] <Method for Measuring the Average Circularity of Toner> The average circularity of the toner is measured by a flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation. The measurement principle of the flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) is to capture flowing particles as still images and perform image analysis. The sample added to the sample chamber is sent into the flat sheath flow cell by the sample suction syringe. The sample sent into the flat sheath flow forms a flat flow sandwiched between the sheath fluids. The sample passing through the flat sheath flow cell is irradiated with stroboscopic light at intervals of 1 / 60 second, and it is possible to capture the flowing particles as still images. Also, because it is a flat flow, imaging is performed in a focused state. The particle images are captured by a CCD camera, and the captured images are processed at an image processing resolution of 512×512 pixels (0.37×0.37 μm per pixel), the contour of each particle image is extracted, and the projected area S, perimeter L, etc. of the particle image are measured. Next, the equivalent circle diameter and circularity are obtained using the above area S and perimeter L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is defined as the value obtained by dividing the perimeter of the circle obtained from the equivalent circle diameter by the perimeter of the particle projection image, and is calculated by the following formula. Circularity C = 2×(π×S) 1 / 2 / L When the particle image is circular, the circularity becomes 1.000, and the greater the degree of unevenness of the outer periphery of the particle image the smaller the circularity value becomes. After calculating the circularity of each particle, the range of circularity from 0.200 to 1.000 is divided into 800 parts, the additive average value of the obtained circularities is calculated, and this value is taken as the average circularity.

[0112] The specific measurement method is as follows. First, put about 20 mL of ion-exchanged water from which impurities and solids have been removed in advance into a glass container. Add about 0.2 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.) about 3 times by mass with ion-exchanged water as a dispersant. Further, add about 0.02 g of the measurement sample and perform dispersion treatment for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. At this time, appropriately cool the dispersion so that the temperature of the dispersion becomes 10°C to 40°C. As the ultrasonic disperser, use a tabletop ultrasonic cleaner disperser (model "VS-150" (manufactured by Verwo Clear)) with an oscillation frequency of 50 kHz and an electrical output of 150 W. Put a predetermined amount of ion-exchanged water in the water tank, and add about 2 mL of this contaminant N into this water tank. For the measurement, use the flow-type particle image analyzer equipped with a standard objective lens (10x), and use Particle Sheath "PSE-900A" (manufactured by Sysmex) as the sheath liquid. Introduce the dispersion prepared according to the above procedure into the flow-type particle image analyzer, and measure 3000 toner particles in the total count mode in the HPF measurement mode. Then, set the binarization threshold value at the time of particle analysis to 85%, set the analysis particle diameter to an equivalent circle diameter of 1.98 μm to 39.96 μm, and obtain the average circularity of the toner. At the time of measurement, perform automatic focus adjustment using standard latex particles (for example, "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific diluted with ion-exchanged water) before starting the measurement. Thereafter, it is preferable to perform focus adjustment every 2 hours from the start of the measurement.

[0113] <Method for Measuring the 50% Particle Size (D50) Based on Volume Distribution of Polymer Fine Particles, Amorphous Resin Fine Particles Other than Polymer A, Aliphatic Hydrocarbon Compound Fine Particles, and Colorant Fine Particles> For the measurement of the 50% particle size (D50) based on volume distribution of polymer fine particles, amorphous resin fine particles other than polymer A, aliphatic hydrocarbon compound fine particles, and colorant fine particles, use a dynamic light scattering particle size distribution meter NanoTrack UPA-EX150 (manufactured by Nikkiso Co., Ltd.). Specifically, measure according to the following procedure. To prevent aggregation of the measurement sample, pour the dispersion in which the measurement sample is dispersed into an aqueous solution containing Family Fresh (manufactured by Kao Corporation) and stir. After stirring, inject the measurement sample into the above device and perform two measurements to obtain the average value. As measurement conditions, the measurement time is set to 30 seconds, the refractive index of the sample particles is set to 1.49, the dispersion medium is water, and the refractive index of the dispersion medium is set to 1.33. Measure the volume particle size distribution of the measurement sample, and from the measurement results, the particle size at which the cumulative volume from the small particle size side in the cumulative volume distribution reaches 50% is defined as the 50% particle size (D50) based on the volume distribution of each fine particle.

[0114] <Measurement method for melting point of crystalline vinyl resin; peak top Tm> The melting point of the crystalline vinyl resin is measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10 °C / min Measurement start temperature: 20 °C Measurement end temperature: 180 °C For temperature correction of the device detection part, the melting points of indium and zinc are used, and for heat quantity correction, the heat of fusion of indium is used. Specifically, 5 mg of the sample is precisely weighed and placed in an aluminum pan, and differential scanning calorimetry is performed. As a reference, a silver empty 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.

Example

[0115] 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.

[0116] <Production example of monomer 1 capable of forming monomer unit represented by formula (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. · Behenyl alcohol 883 parts (66 mol% based on the total 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 while stirring, and stirring was carried out 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 while removing the distillate water at 21 kPa for 3 hours to obtain monomer 1.

[0117] <Production examples of monomers 2 - 10 capable of forming monomer units represented by formula (1)> 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 2 to obtain monomers 2 - 10.

[0118]

Table 1

[0119] <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, and styrene in the following ratios) 〔Monomer 1: 60.0 parts〕 〔Acrylonitrile: 16.0 parts〕 〔Styrene: 24.0 parts〕 · Polymerization initiator: 0.5 part [t - butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV)] Into a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube, the above materials were charged under a nitrogen atmosphere. While stirring the inside of the reaction vessel at 200 rpm, heating was carried out at 70 °C for 12 hours to carry out a polymerization reaction to obtain a solution in which the polymer of the monomer composition was dissolved in toluene.​ Subsequently, after cooling the above-mentioned solution to 25°C, the solution was added to 1000.0 parts of methanol with stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered off, washed further 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 2.

[0120] <Production Examples of Crystalline Vinyl Resins 2 to 21> 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 21. The physical properties are shown in Table 3.

[0121] When the monomer using fumaric acid as the carboxylic acid in Table 1 is used, in formula (1), R 1 and R 2 either one of them and R 3 and R 4 either one of them is a monomer unit containing -COOR 5 to obtain a crystalline vinyl resin. When the monomer using methylene malonic acid is selected, R 1 and R 2 and (or R 3 and R 4 ) are -COOR 5 to obtain a vinyl resin containing a monomer unit. When the monomer using itaconic acid is selected, R 1 and R 2 (or R 3 and R 4 ) either one of them is -X-COOR5 (X is a methylene group with 1 carbon atom), and the other is -COOR 5 to obtain a vinyl resin containing a monomer unit. When acrylic acid is selected, R 1 、R 2 、R 3 、R 4 at least one of them is -COOR 5 to obtain a crystalline vinyl resin containing a monomer unit.

[0122]

Table 2

[0123] [Table 3]

[0124] [Production Example of Amorphous Resin 1] In 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. · Terephthalic acid: 633 parts · Behenic acid: 31 parts · 1,2 - Propanediol: 173 parts (24.8 mol% based on the total number of moles of polycarboxylic acids) · Neopentyl glycol: 251 parts (26.3 mol% based on the total number of moles of polycarboxylic 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. Thereafter, vacuum esterification was carried out at 4 kPa or less, 161 parts of 1,2 - propanediol was recovered, and it was cooled to 180°C. 2 parts of 2,6 - di - tert - butyl - 4 - methylphenol was added and homogenized for 30 minutes. Then, 68 parts of fumaric acid was added, and normal pressure esterification was carried out at 180°C for 2 hours. Thereafter, 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).

[0125] [Production Example of Amorphous Resin 2] 50.0 parts of xylene was charged into an autoclave, replaced with nitrogen, and then heated to 185°C with stirring under a sealed state. Here, a mixed solution 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, and 1.0 part of di - tert - butyl peroxide and 40.0 parts of xylene was added to the o While controlling the temperature inside the autoclave at 190 °C, it was continuously dropped for 3 hours and polymerized. It was further kept at the same temperature for 1 hour to complete the polymerization, and the solvent was removed to obtain the amorphous resin 2.

[0126] <Production Example of Crystalline Vinyl Resin Fine Particle Dispersion 1> · Toluene (manufactured by Wako Pure Chemical Industries, Ltd.): 300 parts · Crystalline vinyl resin 1: 100 parts The above materials were weighed and mixed, and dissolved at 90 °C. Separately, 5.0 parts of sodium dodecylbenzenesulfonate and 10.0 parts of sodium laurate were added to 700 parts of ion-exchanged water, and heated and dissolved at 90 °C. Next, the toluene solution and the aqueous solution were mixed, and stirred at 7000 rpm using an ultra-high speed stirrer T.K. Robomix (manufactured by Primix). Further, it was emulsified at a pressure of 200 MPa using a high-pressure impact type disperser Nanomizer (manufactured by Yoshida Kikai Kogyo). Then, using an evaporator, toluene was removed, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (crystalline vinyl resin fine particle dispersion 1) with a concentration of 20% by mass of the crystalline vinyl resin fine particles 1. When the volume distribution-based 50% particle size (D50) of the crystalline vinyl resin fine particles 1 was measured using a dynamic light scattering particle size distribution meter Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.40 μm.

[0127] <Production Example of Crystalline Vinyl Resin Fine Particle Dispersions 2 to 21> In the production example of the crystalline vinyl resin fine particle dispersion 1, emulsification was carried out in the same manner except that each crystalline vinyl resin was changed as shown in Table 4 to obtain crystalline vinyl resin fine particle dispersions 2 to 21. The physical properties of the crystalline vinyl resin fine particle dispersions 2 to 21 are shown in Table 4.

[0128]

Table 4

[0129] <Production Example of Amorphous Resin Fine Particle Dispersion> · Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.): 300 parts · Amorphous resin 1: 100 parts · Anionic surfactant Neogen RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 0.5 part The above materials were weighed, mixed, and dissolved. Next, 20.0 parts of 1 mol / L aqueous ammonia was added, and the mixture was stirred at 4000 rpm using an ultra-high speed stirrer T.K. Robomix (manufactured by Primix). Further, 700 parts of ion-exchanged water was added at a rate of 8 g / min to precipitate amorphous resin fine particles. Thereafter, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (amorphous resin fine particle 1 dispersion) having a concentration of amorphous resin fine particles 1 of 20% by mass. The volume distribution-based 50% particle size (D50) of amorphous resin fine particles 1 was 0.13 μm.

[0130] <Production Example of Amorphous Resin Fine Particle 2 Dispersion> · Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.): 300 parts · Amorphous resin 2: 100 parts The above materials were weighed, mixed, and dissolved. Separately, 5.0 parts of sodium dodecylbenzenesulfonate was added to 700 parts of ion-exchanged water and dissolved. Next, the toluene solution and the aqueous solution were mixed and stirred at 7000 rpm using an ultra-high speed stirrer T.K. Robomix (manufactured by Primix). Further, emulsification was performed at a pressure of 200 MPa using a high-pressure impact type disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). Thereafter, tetrahydrofuran was removed using an evaporator, and the concentration was adjusted with ion-exchanged water to obtain an aqueous dispersion (amorphous resin fine particle 2 dispersion) having a concentration of amorphous resin fine particles 2 of 20% by mass. The volume distribution-based 50% particle size (D50) of amorphous resin fine particles 2 was 0.13 μm.

[0131] <Production Example of Release Agent (Aliphatic Hydrocarbon Compound) Fine Particle Dispersion> · Aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro Co., Ltd.) 100 parts · Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 5 parts · Ion-exchanged water 395 parts The above materials were weighed and put into a mixing container equipped with a stirring device, then heated to 90 °C and circulated through a Clear Mix W motion (manufactured by M Technique) for 60 minutes for dispersion treatment. The conditions for the dispersion treatment were as follows. · Rotor outer diameter: 3 cm · Clearance: 0.3 mm · Rotor rotation speed: 19000 r / min · Screen rotation speed: 19000 r / min After the dispersion treatment, it was cooled to 40 °C under the cooling treatment conditions of a rotor rotation speed of 1000 r / min, a screen rotation speed of 0 r / min, and a cooling rate of 10 °C / min, to obtain an aqueous dispersion (release agent (aliphatic hydrocarbon compound) fine particle dispersion) with a concentration of 20% by mass of release agent (aliphatic hydrocarbon compound) fine particles. When the 50% particle size (D50) based on the volume distribution of the release agent (aliphatic hydrocarbon compound) fine particles was measured using a dynamic light scattering particle size distribution analyzer Nano Track UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.15 μm.

[0132] <Production of colorant fine particle dispersion> · Colorant 50.0 parts (Cyan pigment manufactured by Dainichi Seika Kogyo Co., Ltd.: Pigment Blue 15:3) · Anionic surfactant Neogen RK (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 7.5 parts · Ion-exchanged water 442.5 parts The above materials were weighed, mixed, dissolved, and dispersed for 1 hour using a high-pressure impact type disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.) to obtain an aqueous dispersion (colorant fine particle dispersion) with a concentration of 10% by mass of colorant fine particles in which the colorant was dispersed. When the 50% particle size (D50) based on the volume distribution of the colorant fine particles was measured using a dynamic light scattering particle size distribution analyzer Nano Track UPA-EX150 (manufactured by Nikkiso Co., Ltd.), it was 0.20 μm.

[0133] <Production example of toner 1> · 300 parts of a dispersion of crystalline vinyl resin fine particles · 200 parts of a dispersion of amorphous resin fine particles · 50 parts of a dispersion of mold release agent (aliphatic hydrocarbon compound) fine particles · 80 parts of a dispersion of colorant fine particles · 160 parts of ion-exchanged water Each of the above materials was put into a round stainless steel flask and mixed, and then 40 parts of a 5% aqueous magnesium sulfate solution was added. Subsequently, it was dispersed at 5000 r / min for 10 minutes using a homogenizer Ultra-Turrax T50 (manufactured by IKA). Then, it was heated to 58 °C while appropriately adjusting the rotation speed such that the mixed solution was stirred using a stirring blade in a water bath for heating. The volume average particle diameter of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III. When aggregated particles with a volume average particle diameter of about 6.00 μm were formed, 300 parts of a 5% aqueous sodium ethylenediaminetetraacetate solution was added, and then it was heated to 75 °C while continuing stirring. Then, the aggregated particles were fused by holding at 75 °C for 1 hour. Thereafter, it was cooled to 50 °C and held for 3 hours to promote the crystallization of the polymer. Thereafter, it was cooled to 25 °C, filtered and solid-liquid separated, and then washed with ion-exchanged water. After the washing was completed, it was dried using a vacuum dryer to obtain toner particles 1 with a weight average particle diameter (D4) of about 6.07 μm.

[0134] · 100 parts of toner particles 1 · 3 parts of large particle size silica fine particles surface-treated with hexamethyldisilazane with an average particle diameter of 130 nm · 1 part of small particle size silica fine particles surface-treated with hexamethyldisilazane with an average particle diameter of 20 nm Each of the above materials was mixed using a Henschel mixer FM-10C type (manufactured by Mitsui Miike Kakoki Co., Ltd.) at a rotation speed of 30 s -1 and a rotation time of 10 minutes to obtain toner 1. The constituent materials of toner 1 are shown in Table 5. The weight average particle diameter (D4) of toner 1 was 6.1 μm, and the average circularity was 0.975. The physical properties of toner 1 are shown in Table 6.

[0135]

Table 5

[0136]

Table 6

[0137] <Production Examples of Toners 2 to 36> In the production example of Toner 1, the same operations as in the production example of Toner 1 were carried out except that the type and addition amount of the crystalline vinyl resin fine particle dispersion liquid, the type and addition amount of the amorphous resin fine particle dispersion liquid, the type and addition amount of the aggregating agent, and the type and addition amount of the terminating agent were changed as shown in Table 5 above, and Toners 2 to 36 were obtained. The physical properties are shown in Table 6. In addition, when the obtained toner was analyzed by the method described above, the content ratio of each monomer unit in the crystalline vinyl resin was in agreement with the formulation shown in Table 2.

[0138] <Production Example of Toner 37> · Crystalline vinyl resin 1: 60.0 parts · Amorphous resin 1: 40.0 parts · Aliphatic hydrocarbon compound HNP-51 (manufactured by Nippon Seiro Co., Ltd.): 10.0 parts · Colorant: 8.0 parts (Cyan pigment manufactured by Dainichi Seika Kogyo Co., Ltd.: Pigment Blue 15:3) · Aluminum 3,5 - di - t - butylsalicylate compound: 0.03 parts Using a Henschel mixer (FM - 75 type, manufactured by Mitsui Mining Co., Ltd.), the above materials were mixed at a rotation speed of 20 s -1 and a rotation time of 5 min, and then melt - kneaded in a twin - screw kneader (PCM - 30 type, manufactured by Ikegai Corporation) with the temperature set at 130°C. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less using a hammer mill to obtain a coarsely pulverized product. The obtained coarsely pulverized product was finely pulverized using a mechanical pulverizer (T - 250, manufactured by Turbo Industry Co., Ltd.). Furthermore, classification was performed using a Faculity F - 300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 37 with a weight - average particle size (D4) of about 6.07 μm. The operating conditions were a classification rotor rotation speed of 130 s -1 and a dispersion rotor rotation speed of 120 s -1 as specified.

[0139] · 100 parts of toner particles 37 · 3 parts of large - particle - size silica fine particles surface - treated with hexamethyldisilazane with an average particle size of 130 nm · 1 part of small - particle - size silica fine particles surface - treated with hexamethyldisilazane with an average particle size of 20 nm The above - mentioned respective materials were mixed using a Henschel mixer FM - 10C type (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at a rotation speed of 30 s -1 and a rotation time of 10 min to obtain toner 37. The weight - average particle size (D4) of toner 37 was 6.1 μm, and the average circularity was 0.960. The physical properties of toner 37 are shown in Table 6.

[0140] <Production Example of Magnetic Carrier 1> · Magnetite 1 with a number - average particle size of 0.30 μm and a magnetization strength of 65 A·m 2 / kg under a magnetic field of 1000 / 4π (kA / m) · Magnetite 2 with a number - average particle size of 0.50 μm and a magnetization strength of 65 A·m 2 / kg under a magnetic field of 1000 / 4π (kA / m) 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% by mass · Formaldehyde solution: 6% by mass (formaldehyde 40% by mass, methanol 10% by mass, water 50% by mass) · Magnetite 1 treated with the above silane compound: 58% by mass · Magnetite 2 treated with the above silane compound: 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, and the temperature was raised to 85 °C in 30 minutes while stirring and mixing, and held for 3 hours to cause a polymerization reaction to cure the resulting phenol resin. Thereafter, the cured phenol resin was cooled to 30 °C, water was further added, then the supernatant was removed, the precipitate was washed with water and air-dried. Then, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60 °C to obtain a magnetic carrier 1 in the form of spherical magnetic carriers dispersed. The volume-based 50% particle size (D50) of the magnetic carrier 1 was 34.2 μm.

[0141] <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 by a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain a binary developer 1.

[0142] <Production Examples of Binary Developers 2 to 37> 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 7 to obtain binary developers 2 to 37.

[0143]

Table 7

[0144] <Example 1> Evaluation was carried out using the above binary developer 1. As an image forming apparatus, a modified Canon digital commercial printer imageRUNNER ADVANCE C7770 was used, and the two-component developer 1 was put into the cyan developer. As the modification points of the apparatus, the fixing temperature, the process speed, the DC voltage VDC of the developer carrier, 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 as desired, and the evaluation described below was performed. FFh is a value representing 256 gradations in hexadecimal notation, where 00h is the first gradation of 256 gradations and FFh is the 256th gradation (solid part) of 256 gradations. Evaluation was performed based on the following evaluation method, and the results are shown in Table 8.

[0145] <Low-temperature Fixing Property> Paper: GFC-081 (81.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner loading amount on paper: 0.90 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 × 15 cm image was placed 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: 120°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 an 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, for the part where the image density was measured, 4.9 kPa (50 g / cm 2A load of was applied, and the fixed image was rubbed (10 round trips) with Sylvon 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: Reduction rate of image density less than 2.0% B: Reduction rate of image density 2.0% or more and less than 4.0% C: Reduction rate of image density 4.0% or more and less than 6.0% D: Reduction rate of image density 6.0% or more and less than 10.0% E: Reduction rate of image density 10.0% or more

[0146] <Evaluation of rubbing resistance> Paper: OK Top Coat Matt N (128.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) Tonner loading amount on paper: 0.05 mg / cm 2 (2Fh image) (DC voltage V of the developer carrier DC , charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) Evaluation image: A 3 m × 15 cm image was placed at the center of the above A4 paper Fixing test environment: Normal temperature and humidity environment (temperature 23 °C / humidity 50% RH (hereinafter N / N)) Fixing temperature: 100 °C Process speed: 132 mm / sec The above evaluation image was output, and the rubbing resistance was evaluated. The difference value of the reflectance was used as the evaluation index of the rubbing resistance. First, for the image part of the evaluation image, using a Kagaku Shinkou type friction fastness tester (AB-301: manufactured by Tester Sangyo Co., Ltd.), a load of 0.5 kgf was applied, and it was rubbed (10 round trips) with a new evaluation paper. Then, a reflectometer (REFLECTOMETER MODEL Using TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the portion where friction was applied and the reflectance of the portion where no friction was applied were measured using a new evaluation paper. Then, using the following formula, the difference in reflectance between the portion where friction was applied and the portion where no friction was applied was calculated. The obtained difference in reflectance was evaluated according to the following evaluation criteria. If the evaluation was A to C, it was judged as good. Difference in reflectance = Reflectance of the portion where no friction was applied - Reflectance of the portion where friction was applied (Evaluation criteria) A: Less than 1.0% difference in reflectance B: 1.0% or more and less than 2.0% difference in reflectance C: 2.0% or more and less than 4.0% difference in reflectance D: 4.0% or more difference in reflectance

[0147] (Evaluation of image adhesion strength) Paper: OK Top Coat + (128.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) Toner loading amount on 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: An image was placed on the entire surface of the above A3 paper. Test environment: Normal temperature and low humidity environment: Temperature 23°C / Humidity 10% RH Fixing temperature: 100°C Process speed: 132 mm / sec 100 sheets of the above evaluation images were output double-sided, and the image adhesion strength was evaluated. Tape was attached to the center of the short side and the tip of the long side of the top sheet of the stacked evaluation images so that it protruded vertically. The lower evaluation image was fixed to the table, and the image adhesion strength was measured when pulling horizontally at 300 mm / min with a digital force gauge (FGJN-2: manufactured by Nidec-Shimpo Corporation). The obtained image adhesion strength was evaluated according to the following evaluation criteria. B or above was judged as good. A: Less than 0.5 N B: 0.5 N or more and less than 1.0 N C: 1.0 N or more

[0148] <Charge retention rate under high temperature and high humidity environment> Paper: GFC-081 (81.0 g / m 2 )(Canon Marketing Japan Inc.) Toner loading amount on paper: 0.35 mg / cm 2 (DC voltage V of the developer carrier DC , charging voltage V of the electrostatic latent image carrier D , and adjusted by laser power) Evaluation image: Place a 2 cm × 5 cm image at the center of the above A4 paper Fixing test environment: High temperature and high humidity environment: Temperature 30°C / Humidity 80% RH (hereinafter referred to as "H / H") Process speed: 377 mm / sec The triboelectric charge amount of the toner was calculated by sucking and collecting the toner on the electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter. Specifically, the triboelectric charge amount of the toner on the electrostatic latent image carrier was measured by a Faraday-Cage. A Faraday-Cage is a coaxial double cylinder, and the inner cylinder and the outer cylinder are insulated. Suppose a charged body with a charge amount Q is placed in this inner cylinder. Then, due to electrostatic induction, it becomes the same as if there is a metal cylinder with a charge amount Q. The induced charge amount is measured with an electrometer (Keithley 6517A manufactured by Keithley Instruments, Inc.), and the value obtained by dividing the charge amount Q (mC) by the toner mass M (kg) in the inner cylinder (Q / M) is defined as the triboelectric charge amount of the toner. Triboelectric charge amount of toner (mC / kg) = Q / M First, form the above evaluation image on the electrostatic latent image carrier. Before transferring it to the intermediate transfer body, stop the rotation of the electrostatic latent image carrier, and suck and collect the toner on the electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter, and measure [initial Q / M]. Subsequently, in the H / H environment, after leaving the developing device in the evaluation machine for two weeks, the same operations as before leaving were performed, and the charge amount Q / M (mC / kg) per unit mass on the electrostatic latent image carrier after leaving was measured. Taking the Q / M per unit mass on the above-mentioned initial electrostatic latent image carrier as 100%, the retention rate of Q / M per unit mass on the electrostatic latent image carrier after leaving ([Q / M after leaving] / [initial Q / M]×100) was calculated and judged according to the following criteria. If the evaluation was A to C, it was judged as good. Q / M] / [initial Q / M]×100) was calculated and judged according to the following criteria. If the evaluation was A to C, it was judged as good. (Evaluation criteria) A: The charge retention rate is 90% or more B: The charge retention rate is 85% or more and less than 90% C: The charge retention rate is 80% or more and less than 85% D: The charge retention rate is less than 80%

[0149] <Storage stability> 5 g of toner was placed in a 100 mL resin cup and left in a temperature and humidity variable constant temperature bath (50 °C, 54%) for 72 hours, and the agglomeration property of the toner was evaluated after leaving. The agglomeration property was evaluated using the remaining rate of the remaining toner as an evaluation index when shaken with a 150 μm mesh opening for 10 seconds at an amplitude of 0.5 mm with a powder tester PT-X manufactured by Hosokawa Micron Corporation. If it was B or higher, it was judged as good. (Evaluation criteria) A: The remaining rate is less than 2.0% B: The remaining rate is 2.0% or more and less than 10.0% C: The remaining rate is 10.0% or more

[0150] <Examples 2 to 29 and Comparative Examples 1 to 8> Evaluation was performed in the same manner as in Example 1 except that two-component developer 2 to two-component developer 37 were used instead of two-component developer 1. The evaluation results are shown in Table 8.

[0151]

Table 8

[0152] The present disclosure relates to the following configuration. (Configuration 1) A toner having toner particles containing a binder resin, The binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1), The crystalline vinyl resin contains 5.0% by mass or more of the monomer unit represented by the following formula (1) based on the mass of the crystalline vinyl resin, The toner particles contain at least one polyvalent metal selected from the group consisting of Mg, Ca, Al, and Zn, A toner characterized in that the content ratio of the polyvalent metal in the toner particles is 25 to 500 ppm by mass. TIFF2025094800000013.tif28153 (In the formula (1), R 1 ~R 4 Among them, 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.) (Constitution 2) The toner according to Constitution 1, wherein the content ratio of the crystalline vinyl resin based on the mass of the binder resin is 30 to 80% by mass. (Constitution 3) In the formula (1), R 1 ~R 4 Among them, at least two are each independently -COOR 5 (R 5 Is an alkyl group having 16 to 30 carbon atoms), the toner according to Constitution 1 or 2. (Constitution 4) In the formula (1), either one of R 1 and R 2 , and either one of R 3 and R 4 are each independently -COOR 5 (R 5 Is an alkyl group having 16 to 30 carbon atoms), the toner according to any one of Constitutions 1 to 3. (Constitution 5) The toner according to any one of Configurations 1 to 4, wherein the crystalline vinyl resin contains 30.0% by mass or more of the monomer unit represented by the formula (1) based on the mass of the crystalline vinyl resin. (Configuration 6) The toner according to any one of Configurations 1 to 5, wherein the content ratio (ppm based on mass) of the polyvalent metal based on the mass of the toner particles and the content ratio (% by mass) of the monomer unit represented by the formula (1) based on the mass of the toner particles satisfy the following formula (2). (Content ratio of polyvalent metal) / (Content ratio of monomer unit represented by formula (1)) ≥ 1.0 (ppm / mass%) ··· (2) (Configuration 7) The toner according to any one of Configurations 1 to 6, wherein the content ratio of the crystalline vinyl resin based on the mass of the binder resin is 50 to 80% by mass. (Configuration 8) R in the formula (1) 5 is a linear alkyl group having 18 carbon atoms or a linear alkyl group having 22 carbon atoms, and the toner according to any one of Configurations 1 to 7. (Configuration 9) The toner according to any one of Configurations 1 to 8, wherein the crystalline vinyl resin 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 (N). TIFF2025094800000014.tif68153 In the formula (N), R 6 is a hydrogen atom or a methyl group. In the 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, wherein the binder resin contains a crystalline vinyl resin having a monomer unit represented by the following formula (1), the crystalline vinyl resin contains 5.0% by mass or more of the monomer unit represented by the following formula (1) based on the mass of the crystalline vinyl resin, the toner particles contain at least one polyvalent metal selected from the group consisting of Mg, Ca, Al, and Zn, and the content ratio of the polyvalent metal in the toner particles is 25 to 500 ppm by mass. The toner is characterized by this. (In the formula (1), R １ to R ４ Among them, 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.)

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

3. In the formula (1), R １ ~R ４ Among them, at least two are each independently -COOR ５ (R ５ is an alkyl group having 16 to 30 carbon atoms), the toner according to claim 1 or 2.

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

5. The toner according to claim 1 or 2, wherein the crystalline vinyl resin contains 30.0% by mass or more of the monomer unit represented by the formula (1) based on the mass of the crystalline vinyl resin.

6. The toner according to claim 1 or 2, wherein the content ratio (ppm by mass) of the polyvalent metal based on the mass of the toner particles and the content ratio (% by mass) of the monomer unit represented by the formula (1) based on the mass of the toner particles satisfy the following formula (2). (Content ratio of polyvalent metal) / (Content ratio of monomer unit represented by formula (1)) ≥ 1.0 (ppm / mass%)... (2)

7. The toner according to claim 1 or 2, wherein the content ratio of the crystalline vinyl resin based on the mass of the binder resin is 50 to 80% by mass.

8. R in the formula (1) above ５ The toner according to claim 1 or 2, wherein R is a linear alkyl group having 18 carbon atoms or a linear alkyl group having 22 carbon atoms.

9. The toner according to claim 1 or 2, 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 (N) The toner according to claim 1 or 2, which 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 (N). 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.

Images