JP2017134243A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner capable of exhibiting long-term durability by controlling a dispersion state of wax in the toner.SOLUTION: The toner includes toner particles comprising a binder resin, wax and a colorant and has such characteristics that: (1) the binder resin comprises a polyester resin; (2) the wax is a hydrocarbon-based wax; and (3) the toner particles contain a compound represented by general formula (1) below. In formula (1), R, R, and Rrepresent hydrogen or an alkyl group having 1 to 5 carbon atoms; and Rand Rrepresent hydrogen or an alkyl group having 1 to 12 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an electrophotographic system, an electrostatic recording system, an electrostatic printing system, and a toner jet system.

In recent years, when color copiers have been rapidly spread, the use applications of color copiers have been widespread, and the demand for image quality has increased more than ever.
Ordinary full-color toners are designed such that a sharp melt, low molecular weight polyester resin or the like is used as a binder resin, and the color toners of each color are sufficiently mixed in the fixing process. However, such a resin having a sharp melt property has a problem that a self-aggregation force is weak and a high temperature offset phenomenon occurs in which a molten toner adheres to a fixing roller or the like. Therefore, conventionally, a toner in which a low melting point wax is contained in the toner for preventing offset has been proposed.
However, conventionally used hydrocarbon waxes have poor compatibility with the polyester resin and styrene acrylic resin used as the binder resin for the toner, resulting in poor wax dispersion in the toner particles. Since the uniformity is poor and charging cannot be performed uniformly, long-term durability tribodown and fogging occur and become a problem.
As a means for solving this problem, there is a known example of a toner in which a polyester resin and a highly compatible ester wax are combined to improve the uniformity between the toners. (Patent document 1).
On the other hand, a toner containing a binder resin made of polyester, an aromatic petroleum resin, and a synthetic hydrocarbon wax is known (Patent Document 2).
However, development of a toner having high coloring power and high density stability has been demanded due to the recent trend toward high speed and high image quality, but it is still insufficient and there is room for improvement.

JP 2002-221822 A JP 2007-264222 A

  An object of the present invention is to provide a toner that solves the above problems. Specifically, an object of the present invention is to provide a toner having high coloring power and high density stability by controlling the dispersion state of the wax in the toner.

The present invention is a toner having toner particles containing a binder resin, a wax and a colorant,
(1) The binder resin contains a polyester resin,
(2) The wax is a hydrocarbon wax,
(3) The toner particles include a compound represented by the following general formula (1).

（式（１）中、Ｒ¹、Ｒ²およびＲ³は、Ｈまたは炭素数１以上５以下であるアルキル基を表わし、Ｒ⁴およびＲ⁵は水素または炭素数１以上１２以下のアルキル基を表わす。）

(In the formula (1), R ¹ , R ² and R ³ represent H or an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ represent hydrogen or an alkyl group having 1 to 12 carbon atoms. Represents.)

  According to the present invention, a toner having high coloring power and high density stability can be provided.

  Hereinafter, embodiments for carrying out the present invention will be described in detail.

The toner of the present invention having toner particles containing a binder resin, a wax and a colorant,
(1) The binder resin contains a polyester resin (2) The wax is a hydrocarbon wax (3) The toner particles contain a compound represented by the following general formula (1) Yes.

（式（１）中、Ｒ¹、Ｒ²およびＲ³は、Ｈまたは炭素数１以上５以下であるアルキル基を表わし、Ｒ⁴およびＲ⁵は水素または炭素数１以上１２以下のアルキル基を表わす。）

(In the formula (1), R ¹ , R ² and R ³ represent H or an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ represent hydrogen or an alkyl group having 1 to 12 carbon atoms. Represents.)

  It is important that the compound represented by the general formula (1) of the present invention has a cyano group in the polar part and an alkyl chain in the nonpolar part.

  In the present invention, in a toner having toner particles having a polyester resin containing a hydrocarbon wax and a compound of the above general formula (1), the wax concentration in the toner is finely dispersed, and at the same time, the toner density stability is improved. It was possible. As a result of studies by the present inventors, the following mechanism is presumed.

  In the case of a polyester toner containing a hydrocarbon wax, the wax in the toner particles cannot be finely dispersed because the compatibility between the highly polar polyester resin and the nonpolar hydrocarbon wax is poor. There are large domains of wax in the particles. In the pulverization step, the particles having a large domain are easily pulverized. Therefore, if there is a large domain of wax in the toner particles, the wax part is cracked and the wax domain is exposed on the toner particle surface. As a result, it is presumed that the uniformity of the material on the surface of the toner particles is impaired, the toner particles cannot be uniformly charged, and the toner concentration durability is lowered.

  Since the compound of the above formula (1) has a nonpolar alkyl chain, the affinity with the nonpolar hydrocarbon wax is improved. At the same time, since it has a cyano polar group, it has a high affinity with a highly polar polyester resin. Therefore, it is considered that the compound of the general formula (1) can finely disperse the wax in the toner particles.

  From the viewpoint of finely dispersing the wax in the polyester resin, it is produced through a step of melt-kneading a mixture containing the polyester resin, the hydrocarbon wax and the compound of the general formula (1), and pulverizing the obtained kneaded product. As a result, the above-described effect is more easily exhibited.

  In the present invention, a preferable toner configuration for achieving the object will be described in detail below.

  The details of the compound having the structure represented by the following general formula (1) in the present invention will be described.

The alkyl group in R ¹ , R ² and R ³ is not particularly limited, but is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl. Group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group Examples thereof include saturated linear or branched primary to quaternary alkyl groups having 1 to 5 carbon atoms.

The alkyl group in R ⁴ and R ⁵ is not particularly limited, but is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group. N-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 1,3-dimethylpropyl group N-hexyl group, cyclohexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1,1-dimethylbutyl group 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3-dimethylbutyl group Saturated straight chain such as til group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, 1-methylhexyl group, 2-ethylhexyl group , Branched or cyclic primary to quaternary alkyl groups having 1 to 12 carbon atoms.

Among them, it is particularly preferable that R ¹ is a methyl group, R ² is an ethyl group, and R ⁴ and R ⁵ are 2-ethylhexyl groups, because the wax is finely dispersed in the polyester and the concentration stability is improved.

  The compound represented by the general formula (1) is preferably used in an amount of 0.5 parts by mass or more and 10 parts by mass or less based on 100 parts by mass of the binder resin of the toner in order to obtain a fine dispersion effect of wax.

  The binder resin used in the toner of the present invention needs to contain a polyester resin, and the main component of the binder resin is a polyester resin (the polyester resin contains 50 parts by mass or more in 100 parts by mass of the binder resin). ). Monomers used in the polyester unit of the polyester resin include polyhydric alcohols (divalent or trivalent or higher alcohols), polyvalent carboxylic acids (divalent or trivalent or higher carboxylic acids), acid anhydrides thereof or lower ones thereof. Alkyl esters are used.

  Here, when preparing a branched polymer, it is effective to partially crosslink in the molecule | numerator of binder resin, and it is preferable to use the polyfunctional compound more than trivalence for that purpose. Therefore, it is preferable to include a trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester, and / or a trivalent or higher alcohol as a raw material monomer for the polyester unit.

  As the polyhydric alcohol monomer used in the polyester unit of the polyester resin, the following polyhydric alcohol monomers can be used.

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by formula (A) and derivatives thereof;

（式中、Ｒはエチレンまたはプロピレン基であり、ｘ及びｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０以上１０以下である。）
式（Ｂ）で示されるジオール類；

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 or more and 10 or less.)
Diols represented by formula (B);

が挙げられる。

Is mentioned.

  Examples of the trivalent or higher alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Can be mentioned. Of these, glycerol, trimethylolpropane, and pentaerythritol are preferably used. These dihydric alcohols and trihydric or higher alcohols can be used alone or in combination.

  As the polyvalent carboxylic acid monomer used in the polyester unit of the polyester resin, the following polyvalent carboxylic acid monomers can be used.

  Examples of the divalent carboxylic acid component 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 These lower alkyl esters are mentioned. Of these, maleic acid, fumaric acid, terephthalic acid, and n-dodecenyl succinic acid are preferably used.

  Examples of the trivalent or higher carboxylic acid, its acid anhydride or its lower alkyl ester include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid. 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra ( Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, acid anhydrides thereof, or lower alkyl esters thereof. Among these, in particular, 1,2,4-benzenetricarboxylic acid, that is, trimellitic acid or its derivative, is inexpensive and easy to control, so that it is preferably used. These divalent carboxylic acids and trivalent or higher carboxylic acids can be used alone or in combination.

  In the present invention, the binder resin may be a hybrid resin containing other resin components as long as the polyester resin is a main component. For example, a hybrid resin of a polyester resin and a vinyl resin can be given. As a method of obtaining a reaction product of a vinyl resin or a vinyl copolymer unit and a polyester resin, such as a hybrid resin, a monomer component capable of reacting with each of the vinyl resin, the vinyl copolymer unit and the polyester resin is included. Where a polymer is present, a method of performing a polymerization reaction of one or both resins is preferable.

  For example, among the monomers constituting the polyester resin component, those capable of reacting with the vinyl copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, or anhydrides thereof. It is done. Among the monomers constituting the vinyl copolymer component, those capable of reacting with the polyester resin component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  The polyester resin preferably has an acid value of 1 mgKOH / g or more and 10 mgKOH / g or less from the viewpoint of charging stability. When it is 10 mgKOH / g or less, the chargeability of the magnetic toner is easily stabilized, so that development efficiency particularly in a high temperature and high humidity environment is likely to be improved.

  Examples of the wax used in the toner of the present invention include the following. Examples of hydrocarbon waxes include low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax.

  The wax content is preferably 1.0 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the binder resin. When the content of the wax is within this range, it becomes easy to efficiently exhibit the durability of the toner at a high temperature. The peak temperature of the maximum endothermic peak of the wax is preferably 50 ° C. or higher and 110 ° C. or lower.

  The toner in the present invention preferably contains a resin composition in which an aliphatic hydrocarbon unit and a vinyl polymerization unit are chemically bonded in order to further improve the dispersibility of the wax in the resin. Among these, it is preferable to further contain a graft polymer having a structure in which a polyolefin which is an aliphatic hydrocarbon unit is grafted to the vinyl polymer unit or a graft polymer in which a vinyl monomer is graft polymerized to a polyolefin.

  When the resin composition is contained, it is possible to follow the wax in which the resin composition is dispersed, and to disperse the resin composition in the binder resin, thereby suppressing a decrease in charge due to carrier or member contamination. Moreover, it is preferable that content of this resin composition is 1.0 to 15 mass parts with respect to 100 mass parts of binder resin. When the content is in this range, the above effect is easily exhibited.

  Regarding the graft polymer having a structure in which a polyolefin is grafted to a vinyl-based polymerization unit, the polyolefin is not particularly limited as long as it is a polymer or copolymer of an unsaturated hydrocarbon having one double bond, and various polyolefins are used. be able to. In particular, polyethylene and polypropylene are preferably used.

Examples of the monomer constituting the vinyl polymerization unit include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichloro. Styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, p -Styrenic units such as styrene and derivatives thereof such as n-decylstyrene and pn-dodecylstyrene.
Amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; vinyl-based units containing N atoms such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.
Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half-esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; Acrylic acid, Methacrylic acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, and anhydrous α and β-unsaturated acids and lower fatty acids. A vinyl-based unit containing a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof, and monoesters thereof.
Acrylic acid or methacrylic acid ester such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) (Hexyl) Vinyl-based units containing hydroxyl groups such as styrene.
Methyl acrylate, ethyl acrylate, acrylate-n-butyl, acrylate isobutyl, propyl acrylate, acrylate-n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylate-2- An ester unit comprising an acrylic ester such as chloroethyl and acrylic ester such as phenyl acrylate.
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylate-n-butyl, methacrylate isobutyl, methacrylate-n-octyl, methacrylate-decyl, methacrylate-2-ethylhexyl, stearyl methacrylate, phenyl methacrylate, methacryl Examples thereof include ester units composed of methacrylic acid esters such as α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl acid, diethylaminoethyl methacrylate, and cyclohexyl methacrylate.

  As a constituent unit of the vinyl-based polymerization unit, it is preferable to include styrene, and further acrylonitrile, methacrylonitrile, or cyclohexyl methacrylate.

  The following are preferably used as the colorant.

  Examples of the black colorant include carbon black; those prepared by using a yellow colorant, a magenta colorant, and a cyan colorant and adjusting the color to black.

  Examples of the magenta colored pigment 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; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

  The following are mentioned as a cyan coloring pigment. C. I. Pigment blue 2, 3, 15: 2, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

  The following are mentioned as a yellow coloring pigment. 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; I. Bat yellow 1, 3, 20

  Particularly effectively, C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. Pigment Yellow 155, carbon black, C.I. I. Pigment blue 15: 3, C.I. I. Pigment red 122, C.I. I. This is the case when used in combination with Pigment Red 57 and the like. These pigments may be used alone or in combination of two or more.

  The amount of the pigment used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner may contain a charge control agent as necessary. As the charge control agent contained in the toner, known ones can be used. In particular, a metal compound of an aromatic carboxylic acid that is colorless, has a high toner charging speed, and can stably maintain a constant charge amount is preferable.

  Negative charge control agents include salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, sulfonates or sulfonated compounds in the side chain. Examples thereof include a polymer compound, a polymer compound having a carboxylate or a carboxylic acid ester in the side chain, a boron compound, a urea compound, a silicon compound, and calixarene. Examples of the positive charge control agent include quaternary ammonium salts, polymer compounds having the quaternary ammonium salt in the side chain, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles. The addition amount of the charge control agent is preferably 0.2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the binder resin.

  The toner of the present invention may contain inorganic fine particles as necessary. The inorganic fine particles may be added internally to the toner particles or may be mixed with the toner particles as an external additive. As the external additive, inorganic fine powders such as silica, titanium oxide and aluminum oxide are preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane compound, silicone oil or a mixture thereof.

As an external additive for improving fluidity, an inorganic fine powder having a specific surface area of 50 m ² / g or more and 400 m ² / g or less is preferable. For stabilization of durability, the specific surface area is 10 m ² / g or more and 50 m or less. An inorganic fine powder of ² / g or less is preferable. In order to achieve both improvement in fluidity and stabilization of durability, an inorganic fine powder having a specific surface area in the above range may be used in combination.

  The external additive is preferably used in an amount of 0.1 to 10.0 parts by mass with respect to 100 parts by mass of the toner particles. For mixing the toner particles and the external additive, a known mixer such as a Henschel mixer can be used.

  Although the toner of the present invention can be used as a one-component developer, it is preferably mixed with a magnetic carrier and used as a two-component developer in order to further improve dot reproducibility. Moreover, it is also preferable in that a stable image can be obtained over a long period of time.

  Examples of the magnetic carrier include iron powder whose surface is oxidized, non-oxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, and the like Magnetic material dispersed resin carriers (so-called resin carriers) containing magnetic materials such as alloy particles, oxide particles, ferrite, and the like, and magnetic materials and binder resins that hold the magnetic materials in a dispersed state are generally known. Things can be used.

  When the toner of the present invention is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio at that time is 2% by mass or more and 15% by mass or less, preferably as a toner concentration in the two-component developer. In general, good results are obtained when the content is from 4% by mass to 13% by mass.

  The method for producing the toner of the present invention is not particularly limited as long as it is a conventionally known toner production method such as an emulsion aggregation method, a melt kneading method, a dissolution suspension method, but the melt kneading method is preferable from the viewpoint of dispersion of raw materials.

<Manufacturing method>
The melt-kneading method is characterized in that a toner composition that is a raw material of toner particles is melt-kneaded, and the obtained kneaded product is pulverized. An example of the manufacturing method will be described.

  In the raw material mixing step, a predetermined amount of other components such as a binder resin, a wax, a colorant, and, if necessary, a charge control agent are weighed and mixed as materials constituting the toner particles and mixed. Examples of the mixing apparatus include a double-con mixer, a V-type mixer, a drum-type mixer, a super mixer, a Henschel mixer, a Nauta mixer, and a mechano-hybrid (manufactured by Nippon Coke Industries, Ltd.).

  Next, the mixed material is melt-kneaded to disperse other raw materials and the like in the binder resin. In the melt-kneading process, a batch kneader such as a pressure kneader or a Banbury mixer, or a continuous kneader can be used. From the advantage that continuous production is possible, a single-screw or twin-screw extruder has become the mainstream. Yes. For example, KTK type twin screw extruder (manufactured by Kobe Steel Co., Ltd.), TEM type twin screw extruder (manufactured by Toshiba Machine Co., Ltd.), PCM kneader (manufactured by Ikekai Tekko), twin screw extruder (manufactured by Kay Sea Kay Co., Ltd.) ), Co-kneader (manufactured by Buss), kneedex (manufactured by Nippon Coke Industries Co., Ltd.), and the like. Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water or the like in the cooling step.

  Next, the cooled product of the resin composition is pulverized to a desired particle size in the pulverization step. In the pulverization step, for example, after coarse pulverization with a pulverizer such as a crusher, a hammer mill, or a feather mill, for example, a kryptron system (manufactured by Kawasaki Heavy Industries), a super rotor (manufactured by Nisshin Engineering), a turbo mill Finely pulverized with a fine pulverizer (Freund Turbo Kogyo) or air jet type.

  Then, if necessary, classification such as inertial class elbow jet (manufactured by Nippon Steel & Mining Co., Ltd.), centrifugal classification turboplex (manufactured by Hosokawa Micron), TSP separator (manufactured by Hosokawa Micron), Faculty (manufactured by Hosokawa Micron) The toner particles are obtained by classification using a machine or a sieving machine.

  In addition, if necessary, after pulverization, a hybridization system (manufactured by Nara Machinery Co., Ltd.), a mechano-fusion system (manufactured by Hosokawa Micron), a faculty (manufactured by Hosokawa Micron), or Meteole Inbo MR Type (manufactured by Nippon Pneumatic Co., Ltd.) is used. Thus, the toner particles can be subjected to a surface treatment such as a spheroidizing treatment.

  Next, methods for measuring physical properties related to the present invention will be described.

<Measurement method of softening point of resin>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). Then, the temperature of the flow curve when the piston descending amount is X in the flow curve is the melting temperature in the 1/2 method.

  As a measurement sample, about 1.0 g of resin is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 40 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measurement of acid value of polyester resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

  Titration is performed using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titrator (potential difference titrator AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). 100 mL of 0.100 mol / L hydrochloric acid is placed in a 250 mL tall beaker, titrated with the potassium hydroxide ethyl alcohol solution, and determined from the amount of the potassium hydroxide ethyl alcohol solution required for neutralization. As the 0.100 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

The measurement conditions for the acid value measurement are shown below.
Titration device: potentiometric titration device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.)
Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.)
Titrator control software: AT-WIN
Titration analysis software: Tview

The titration parameters and control parameters at the time of titration are as follows.
Titration parameters Titration mode: Blank titration Titration style: Total titration Maximum titration: 20 mL
Waiting time before titration: 30 seconds Titration direction: Automatic control parameter end point judgment potential: 30 dE
End point determination differential value: 50 dE / dmL
End point detection range setting: Not set Control speed mode: Standard gain: 1
Data collection potential: 4 mV
Data collection titration: 0.1 mL
main exam;
0.100 g of a measurement sample is precisely weighed in a 250 mL tall beaker, and 150 mL of a mixed solution of toluene / ethanol (3: 1) is added and dissolved over 1 hour. Titrate with the potassium hydroxide ethyl alcohol solution using the potentiometric titrator.
Blank test;
Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene / ethanol (3: 1) is used).

The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.611] / S
(In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in blank test (mL), C: addition amount of potassium hydroxide ethyl alcohol solution in this test (mL), f: Factor of potassium hydroxide solution, S: Sample (g))

<Measurement of Volume Average Particle Size (D4) of Toner>
The volume average particle diameter (D4) of the toner is determined based on a precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a pore electric resistance method equipped with an aperture tube of 100 μm and measurement conditions. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analyze and calculate. As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in deionized water to a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software is set as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked. In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

Specific measurement methods are as follows (1) to (7).
(1) About 200 ml of the electrolytic solution is placed in a 250 ml round bottom beaker made exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. The dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is placed in a glass 100 ml flat bottom beaker, and “Contaminone N” (nonionic surfactant, anionic surfactant, organic builder having a pH of 7 is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for cleaning precision instruments (made by Wako Pure Chemical Industries, Ltd.) 3 times by weight with deionized water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A fixed amount of deionized water is added, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) In the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. To do. Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the volume average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the volume average particle diameter (D4).

<Measurement of Glass Transition Point (Tg) of Toner>
The glass transition temperature of the resin is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 5 mg of resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure in min. The temperature is raised to 180 ° C. and held for 10 minutes, then the temperature is lowered to 30 ° C., and then the temperature is raised again. In the second temperature raising process, a specific heat change is obtained in the temperature range of 30 to 100 ° C. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature (Tg) of the resin.

<Measuring method of 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 a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is picked up by a CCD camera, and the picked-up image is image-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 particle image The projected area S, the peripheral length L, etc. are measured.

Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length 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 a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.
Circularity C = 2 × (π × S) 1/2 / L

  When the particle image is circular, the circularity is 1.000, and the greater the degree of unevenness around the particle image, the smaller the circularity. After calculating the circularity of each particle, the range of the circularity of 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is put in, and about 2 ml of the contamination N is added to the water tank.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the total count mode in the HPF measurement mode. Then, by setting the binarization threshold at the time of particle analysis to 85% and specifying the analysis particle diameter, the number ratio (%) of particles in the range and the average circularity can be calculated. The average circularity of the toner was set to an equivalent circle diameter of 1.98 μm to 39.96 μm, and the average circularity of the toner was determined.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “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 two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.98 μm or more and less than 39.69 μm.

<Measurement of weight average molecular weight of resin>
The molecular weight distribution of the THF soluble part of the resin is measured by gel permeation chromatography (GPC) as follows.

The column is stabilized in a 40 ° C. heat chamber, and tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is suitably used. The detector uses an RI (refractive index) detector. In addition, as a column, it is good to combine several commercially available polystyrene gel columns, for example, the following combinations are mentioned. A combination of Shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ) manufactured by Tosoh Corporation , G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), TSKgourd column combination.

  Moreover, a sample is produced as follows.

  Place 50 mg of the sample in 10 ml of THF, leave it at 25 ° C. for several hours, shake well, mix well with THF (until the sample is no longer integrated), and let stand for more than 12 hours. Note that the total standing time in THF is 24 hours. Then, a sample processing filter (pore size of 0.2 μm or more and 0.5 μm or less, for example, Myssho Disc H-25-2 (manufactured by Tosoh Corporation)) can be used as a GPC sample.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further in detail, this invention is not limited to these Examples.

  <Synthesis of Compound D1>

  According to the above scheme, a methanol (MeOH) 20 mL solution of 0.721 g of an amine compound was cooled to 5 ° C., and 2 mL of concentrated sulfuric acid and 1.4 mL of nitrosylsulfuric acid (40 mass%) were added dropwise (diazotized A solution). Separately, a solution of 0.496 g of pyridone compound (P1) in 20 mL of methanol (MeOH) is cooled to 5 ° C., and the diazotized A solution is slowly added dropwise to maintain the temperature at 5 ° C. or lower. Stir in for 20 minutes. After completion of the reaction, an aqueous sodium carbonate solution was added dropwise to neutralize the pH to 6, followed by stopping with chloroform. Thereafter, the solid obtained by distilling off the solvent was purified by column chromatography (developing solvent: heptane / ethyl acetate), and further recrystallized with a heptane solution to obtain 0.8 g of the compound of the above formula (S1). D1 was obtained.

  The obtained compound D1 was identified by an analysis method using MALDI MS (autoflex apparatus, manufactured by Bruker Daltonics). In MALDI MS, a negative mode was adopted as a detection ion.

  Mass spectrometry by MALDI MS: m / z = 618.612 (M−H)

  <Synthesis of Compound D2>

  Compound D2 having the structure of the above formula (S2) was obtained in the same manner as Compound 1, except that the pyridone compound (P1) was changed to the pyridone compound (P2).

<Compounds D3 to D6>
Compounds D3 to D6 were synthesized as compound D1 by selecting an amine compound and a pyridone compound so that R ^{1 to} R ⁵ of the following general formula 1 are as shown in Table 1.

<Example of production of amorphous polyester resin>
[Production Example of Amorphous Low Molecular Weight Polyester Resin L1]
Bisphenol A propylene oxide 2 mol adduct 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-28.0 parts by mass of terephthalic acid; 100.0 mol% based on the total number of polyvalent carboxylic acids
-Tin 2-ethylhexanoate (esterification catalyst) 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised in a normal pressure environment while stirring, and the mixture was reacted for 4 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was allowed to proceed for 1.5 hours while maintaining the temperature at 180 ° C., and the softening point measured according to ASTM D36-86 reached 96 ° C. After confirming the above, the temperature was lowered to stop the reaction (second reaction step) to obtain an amorphous low molecular weight polyester resin L1. The obtained amorphous low molecular weight resin L1 had an acid value of 4.5 mgKOH / g, a weight average molecular weight of 5,000, a softening point (Tm) of 96 ° C., and a glass transition temperature (Tg) of 57 ° C.

[Production Example of Amorphous Low Molecular Weight Polyester Resin L2]
Bisphenol A propylene oxide 2 mol adduct 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-28.0 parts by mass of terephthalic acid (0.17 mol; 100.0 mol% based on the total number of polycarboxylic acids)
-Tin 2-ethylhexanoate (esterification catalyst) 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised in a normal pressure environment while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was carried out for 1.5 hours while maintaining the temperature at 180 ° C., and the softening point measured according to ASTM D36-86 reached 87 ° C. After confirming the above, the temperature was lowered to stop the reaction (second reaction step) to obtain an amorphous low molecular weight polyester resin L2. The obtained amorphous low molecular weight resin L2 had an acid value of 4.5 mgKOH / g, a weight average molecular weight of 4,000, a softening point (Tm) of 87 ° C., and a glass transition temperature (Tg) of 55 ° C.

[Production Example of Amorphous Low Molecular Weight Polyester Resin L3]
Bisphenol A propylene oxide 2 mol adduct 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-28.0 parts by mass of terephthalic acid (0.17 mol; 100.0 mol% based on the total number of polycarboxylic acids)
-Tin 2-ethylhexanoate (esterification catalyst) 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised in a normal pressure environment while stirring, and the reaction was performed for 6 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, then cooled to 180 ° C. and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 3 parts by mass (0.01 mol; 4.0 mol% based on the total number of polyvalent carboxylic acids)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was allowed to proceed for 1.5 hours while maintaining the temperature at 180 ° C., and the softening point measured according to ASTM D36-86 reached 103 ° C. After confirming the above, the reaction was stopped by lowering the temperature (second reaction step) to obtain an amorphous low molecular weight polyester resin L3. The obtained amorphous low molecular weight resin L3 had an acid value of 4.5 mgKOH / g, a weight average molecular weight of 6,000, a softening point (Tm) of 103 ° C., and a glass transition temperature (Tg) of 58 ° C.

[Production Example of Amorphous High Molecular Weight Polyester Resin H1]
Bisphenol A propylene oxide 2 mol adduct 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-23.0 parts by mass of terephthalic acid (0.14 mol; 70.0 mol% based on the total number of polycarboxylic acids)
Adipic acid 5.0 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polyvalent carboxylic acids)
-Tin 2-ethylhexanoate (esterification catalyst) 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised in a normal pressure environment while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 6.5 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polycarboxylic acids)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was continued for 18 hours while maintaining the temperature at 160 ° C., and the softening point measured according to ASTM D36-86 reached 155 ° C. Then, the temperature was lowered to stop the reaction (second reaction step), and an amorphous high molecular weight polyester resin H1 was obtained. The obtained amorphous high molecular weight resin H1 had an acid value of 20.0 mgKOH / g, a weight average molecular weight of 200,000, a softening point (Tm) of 155 ° C., and a glass transition temperature (Tg) of 61 ° C.

[Production Example of Amorphous High Molecular Weight Polyester Resin H2]
Bisphenol A propylene oxide 2 mol adduct 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-23.0 parts by mass of terephthalic acid (0.14 mol; 70.0 mol% based on the total number of polycarboxylic acids)
Adipic acid 5.0 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polyvalent carboxylic acids)
-Tin 2-ethylhexanoate (esterification catalyst) 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 1 hour while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 6.5 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polycarboxylic acids)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was continued for 18 hours while maintaining the temperature at 160 ° C., and it was confirmed that the softening point measured according to ASTM D36-86 reached 150 ° C. Then, the temperature was lowered to stop the reaction (second reaction step), and an amorphous high molecular weight polyester resin H2 was obtained. The obtained amorphous high molecular weight resin H2 had an acid value of 20.5 mgKOH / g, a weight average molecular weight of 150,000, a softening point (Tm) of 150 ° C., and a glass transition temperature (Tg) of 59 ° C.

[Production Example of Amorphous High Molecular Weight Polyester Resin H3]
Bisphenol A propylene oxide 2 mol adduct 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-23.0 parts by mass of terephthalic acid (0.14 mol; 70.0 mol% based on the total number of polycarboxylic acids)
Adipic acid 5.0 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polyvalent carboxylic acids)
-Tin 2-ethylhexanoate (esterification catalyst) 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 6.5 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polycarboxylic acids)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was continued for 18 hours while maintaining the temperature at 160 ° C., and it was confirmed that the softening point measured according to ASTM D36-86 reached 160 ° C. Then, the temperature was lowered to stop the reaction (second reaction step), and an amorphous high molecular weight polyester resin H3 was obtained. The obtained amorphous high molecular weight resin H3 had an acid value of 19.5 mgKOH / g, a weight average molecular weight of 250,000, a softening point (Tm) of 160 ° C., and a glass transition temperature (Tg) of 62 ° C.

[Production Example of Amorphous High Molecular Weight Polyester Resin H4]
Bisphenol A propylene oxide 2 mol adduct 72.0 parts by mass (0.20 mol; 100.0 mol% with respect to the total number of polyhydric alcohols)
-23.0 parts by mass of terephthalic acid (0.14 mol; 70.0 mol% based on the total number of polycarboxylic acids)
Adipic acid 5.0 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polyvalent carboxylic acids)
-Tin 2-ethylhexanoate (esterification catalyst) 0.5 part by mass The above materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 0.5 hour while stirring at a temperature of 200 ° C. Further, the pressure in the reaction vessel was lowered to 8.3 kPa, maintained for 1 hour, cooled to 180, and returned to atmospheric pressure (first reaction step).

Trimellitic anhydride: 6.5 parts by mass (0.03 mol; 15.0 mol% with respect to the total number of polycarboxylic acids)
Thereafter, the above materials were added, the pressure in the reaction vessel was lowered to 8.3 kPa, the reaction was continued for 18 hours while maintaining the temperature at 160 ° C., and the softening point measured according to ASTM D36-86 reached 135 ° C. Then, the temperature was lowered to stop the reaction (second reaction step), and an amorphous high molecular weight polyester resin H4 was obtained. The obtained amorphous high molecular weight resin H4 had an acid value of 21.0 mgKOH / g, a weight average molecular weight of 130,000, a softening point (Tm) of 135 ° C., and a glass transition temperature (Tg) of 58 ° C.

<Resin composition B1 having a structure in which a vinyl resin component and a hydrocarbon compound are chemically bonded>
・ 20.0 parts by mass of low density polyethylene (Mw 1400, Mn 850, DSC has a maximum endothermic peak of 100 ° C.)
Styrene 50.0 parts by mass n-butyl acrylate 10.0 parts by mass Acrylonitrile 20.0 parts by mass were charged into an autoclave and the system was replaced with N ₂ , and then maintained at 180 ° C. while stirring at elevated temperature. A resin composition in which 50 parts by mass of a 2% by mass t-butyl hydroperoxide xylene solution was continuously dropped into the system for 5 hours, and after cooling, the solvent was separated and removed, and the vinyl resin component reacted with the low-density polyethylene. Product B1 was obtained.

<Resin composition 2 having a structure in which a vinyl resin component and a hydrocarbon compound are chemically bonded>
300 parts by mass of xylene hydrocarbon wax (maximum absorption peak 90 ° C.) 10 parts by mass was placed in an autoclave reaction vessel equipped with a thermometer and a stirrer and dissolved sufficiently.
Styrene 76.5 parts by mass Cyclohexyl methacrylate 13.5 parts by mass Xylene 250 parts by mass of a mixed solution was added dropwise at 180 ° C. for 3 hours for polymerization, and the temperature was further maintained for 30 minutes. Next, the solvent was removed to obtain a resin composition B2.

<Styrene acrylic resin (resin A)>
850 g of xylene was placed in a 2 liter glass four-necked flask equipped with a thermometer, a stainless steel stir bar, a falling condenser and a nitrogen inlet tube, and the temperature was raised to 150 ° C. after nitrogen substitution.

Styrene 1700 parts by mass n-butyl acrylate 250 parts by mass Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 50 parts by mass Dicumyl peroxide 80 parts by mass The mixture of materials was dropped from the dropping funnel over 4 hours and aged for 4 hours at 150 degrees. Thereafter, the temperature was raised to 200 ° C., and xylene was distilled off under reduced pressure to obtain a styrene acrylic resin (resin A). (Copolymer of styrene: n-butyl acrylate = 75: 25 (mass ratio)) (Mw = 30,000, Tg = 55 ° C.)

[Example 1]
<Production Example of Toner 1>
Amorphous low molecular weight polyester resin L1 70.0 parts by mass Amorphous high molecular weight polyester resin H1 30.0 parts by mass Hydrocarbon wax 5.0 parts by mass (Fischer-Tropsch wax, maximum endothermic peak 90 ° C)
-Resin composition B1 5.0 mass parts-Compound D1 (compound of Table 1) 1.0 mass part-C.I. I. Pigment Yellow 180 6.0 parts by mass, 3,5-di-t-butylsalicylic acid aluminum compound 0.5 part by mass Using the Henschel mixer (FM-75 type, manufactured by Nippon Coke Co., Ltd.) as the raw material shown in the above formulation Then, after mixing at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, the mixture was kneaded by a biaxial kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 130 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Industry Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified at a classifying rotor rotational speed of 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.9 μm.

  To 100.0 parts by mass of the obtained toner particles, 0.5 parts by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm surface-treated with 15.0% by mass of isobutyltrimethoxysilane and 20.0% by mass of hexamethyldisilazane. 1.0 parts by mass of hydrophobic silica fine particles having a primary average particle diameter of 15 nm and surface-treated with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Kogyo Co., Ltd.) are mixed, and an ultrasonic vibrating sieve having an aperture of 54 μm is added. Toner 1 was obtained.

<Example of production of magnetic core particle 1>
-Process 1 (weighing / mixing process):
Fe ₂ O ₃ 62.7 parts by mass MnCO ₃ 29.5 parts by mass Mg (OH) ₂ 6.8 parts by mass SrCO ₃ 1.0 parts by mass The ferrite raw materials were weighed so that the above composition ratio was the above. Thereafter, the mixture was pulverized and mixed for 5 hours in a dry vibration mill using 1/8 inch diameter stainless steel beads.
-Process 2 (temporary baking process):
The obtained pulverized product was formed into pellets of about 1 mm square using a roller compactor. After removing the coarse powder from the pellets with a vibrating sieve having a mesh opening of 3 mm, and then removing the fine powders with a vibrating sieve having a mesh opening of 0.5 mm, using a burner-type firing furnace, under a nitrogen atmosphere (oxygen concentration of 0.1. And calcined at a temperature of 1000 ° C. for 4 hours to prepare calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO) _a (MgO) _b (SrO) _c (Fe ₂ O ₃ ) _d
In the above formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393
-Step 3 (grinding step):
After pulverizing to about 0.3 mm with a crusher, 30 parts by mass of water was added to 100 parts by mass of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and pulverized with a wet ball mill for 1 hour. The slurry was pulverized for 4 hours by a wet ball mill using alumina beads having a diameter of 1/16 inch to obtain a ferrite slurry (a finely pulverized product of calcined ferrite).
-Process 4 (granulation process):
To the ferrite slurry, 1.0 part by mass of ammonium polycarboxylate as a dispersant and 100 parts by mass of polyvinyl alcohol as a binder are added to 100 parts by mass of the calcined ferrite, and a spray dryer (manufacturer: Okawara Kako) is used. Granulated into spherical particles. After adjusting the particle size of the obtained particles, using a rotary kiln, it was heated at 650 ° C. for 2 hours to remove the organic components of the dispersant and the binder.
-Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300 ° C. in a nitrogen atmosphere (oxygen concentration: 1.00 vol%) in an electric furnace in 2 hours, and then fired at a temperature of 1150 ° C. for 4 hours. Thereafter, the temperature was lowered to 60 ° C. over 4 hours, returned from the nitrogen atmosphere to the atmosphere, and taken out at a temperature of 40 ° C. or lower.
-Process 6 (screening process):
After crushing the agglomerated particles, the low-magnetic force product is cut by magnetic separation, and the coarse particles are removed by sieving with a sieve having an opening of 250 μm, and a 50% particle size (D50) of 37.0 μm based on volume distribution. Magnetic core particles 1 were obtained.

<Preparation of coating resin 1>
Cyclohexyl methacrylate monomer 26.8 parts by mass Methyl methacrylate monomer 0.2 part by mass Methyl methacrylate macromonomer 8.4 parts by mass (macromonomer having a methacryloyl group at one end and a weight average molecular weight of 5000)
Toluene 31.3 parts by mass Methyl ethyl ketone 31.3 parts by mass Azobisisobutyronitrile 2.0 parts by mass Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, methyl ethyl ketone, reflux condenser, thermometer Into a four-necked separable flask equipped with a nitrogen introduction tube and a stirrer, nitrogen gas was introduced and the system was replaced with nitrogen gas. Thereafter, the mixture was heated to 80 ° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate a copolymer, and the precipitate was filtered off and dried under vacuum to obtain coating resin 1. 30 parts by mass of the obtained coating resin 1 was dissolved in 40 parts by mass of toluene and 30 parts by mass of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

<Preparation of coating resin solution 1>
Polymer solution 1 (resin solid concentration 30%) 33.3 parts by mass Toluene 66.4 parts by mass Carbon black 0.3 parts by mass (primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² / g, DBP oil absorption 75 ml / 100g)
Was dispersed with a paint shaker for 1 hour using zirconia beads having a diameter of 0.5 mm. The obtained dispersion was filtered through a 5.0 μm membrane filter to obtain a coating resin solution 1.

<Example of production of magnetic carrier 1>
(Resin coating process):
The coating resin solution 1 was charged into a vacuum degassing kneader maintained at room temperature so that the resin component was 2.5 parts by mass with respect to 100 parts by mass of the magnetic core particles 1. After the addition, the mixture was stirred for 15 minutes at a rotation speed of 30 rpm, and after the solvent was volatilized above a certain level (80% by mass), the temperature was raised to 80 ° C. while mixing under reduced pressure, and toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier is separated by low-magnetization by magnetic separation, passed through a sieve having an opening of 70 μm, and then classified by an air classifier, and a magnetic carrier having a 50% particle size (D50) of 38.2 μm based on volume distribution. 1 was obtained.

<Example of production of two-component developer 1>
To 92.0 parts by mass of magnetic carrier 1, 8.0 parts by mass of toner 1 was added and mixed with a V-type mixer (Dalton Co., Ltd.) to obtain a two-component developer 1.

  The performance of the toner was evaluated according to the following methods (1) to (3). The evaluation results are shown in Table 3.

(1) Evaluation method of fog after endurance Using a remodeling machine (continuous copying speed: A4 65 sheets / min) of Canon's full-color copying machine imageRUNNER ADVANCE C5255 as an image forming apparatus, two-component development in the cyan station developer Agent 1 was added and evaluated. The evaluation environment is a normal temperature and humidity environment (NN; 23 ° C., 50% RH) and a high temperature and high humidity environment (HH; 30 ° C., 80% RH). The evaluation paper is copy paper GF-640 (A4, tsubo) Amount 64.0 g / m ² ) (available from Canon Marketing Japan Inc.).

  The fog on the white background before and after endurance in each environment was measured.

  The average reflectance Dr (%) of the evaluation paper before image printing was measured by a reflectometer (“REFECTOMETER MODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.).

The reflectance Ds (%) of the 00H image portion (white background portion) after durability (5000th sheet) was measured using a chart with an image ratio of 40%. From the obtained Dr and Ds, fog (%) was calculated using the following formula. The obtained fog was evaluated according to the following evaluation criteria.
Fog (%) = Dr (%) − Ds (%)

(Evaluation criteria)
A: Less than 0.35 (very good)
B: 0.35 or more and less than 0.55 (good)
C: 0.55 or more (prior art level)

(2) Evaluation Method of Toner Coloring Strength Using a remodeling machine of Canon full color copier “imageRUNNER ADVANCE C5255” as an image forming apparatus, the fixing temperature is changed to 150 ° C. The system developer 1 was added for evaluation.

The evaluation environment is a normal temperature and humidity environment (23 ° C., 50% RH), and the evaluation paper is copy paper GF-640 (A4, basis weight 64.0 g / m ² ) sold by Canon Marketing Japan Inc. It was.

  First, in the evaluation environment, automatic gradation correction was performed twice to adjust the image density on the paper.

  600 g of toner 1 was put in a toner bottle for imageRUNNER ADVANCE C5255 and set in the main body. A chart with an image ratio of 40% was output on the evaluation paper, and the number of output sheets was counted [× 1000 sheets].

(Evaluation criteria)
A: 9.0 or higher (very good)
B: 8.0 or more and less than 9.0 (good)
C: 7.0 or more and less than 8.0 (this is a problem-free level in the present invention)
D: Less than 7.0 (prior art level)

[Examples 2 to 16 and 21]
As shown in Table 2, toners 2 to 16 and 21 were prepared by changing the type of material and the number of added parts of the material, and two-component developers 2 to 16 and 21 were prepared in the same manner as in Example 1. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 17
<Binder resin fine particle dispersion (1)>
100 parts by mass of amorphous low molecular weight polyester resin L1 was dissolved in 150 parts by mass of tetrahydrofuran. An ion in which 5 parts by mass of potassium hydroxide and 10 parts by mass of sodium dodecylbenzene-sulfonate were added as surfactants while stirring this tetrahydrofuran solution at 10,000 rpm for 2 minutes with a homogenizer (IKA Japan: Ultra Tarax) at room temperature. 1000 parts by mass of exchange water was dropped. The mixed solution was heated to about 75 ° C. to remove tetrahydrofuran. Then, it diluted with ion-exchange water so that solid content might be 8%, and the binder resin fine particle dispersion (1) with a volume average particle diameter of 0.09 micrometer was obtained.

<Binder resin fine particle dispersion (2)>
100 parts by mass of amorphous high molecular weight polyester resin H1 was dissolved in 150 parts by mass of tetrahydrofuran. An ion in which 5 parts by mass of potassium hydroxide and 10 parts by mass of sodium dodecylbenzene-sulfonate were added as surfactants while stirring this tetrahydrofuran solution at 10000 rpm for 2 minutes with a homogenizer (IKA Japan: Ultra Tarax) at room temperature. 1000 parts by mass of exchange water was dropped. The mixed solution was heated to about 75 ° C. to remove tetrahydrofuran. Then, it diluted with ion-exchange water so that solid content might be 8%, and the binder resin fine particle dispersion (2) with a volume average particle diameter of 0.09 micrometer was obtained.

<Manufacture of colorant fine particles>
・ C. I. Pigment Yellow 180 8.0 parts by mass, anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1.5 parts by mass, ion-exchanged water 88.5 parts by mass An aqueous dispersion of colorant fine particles was prepared by dispersing the colorant for about 1 hour using a disperser Nanomizer (manufactured by Yoshida Kikai Kogyo Co., Ltd.). The volume-based median diameter was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso Co., Ltd.), and was 0.20 μm.

<Manufacture of release agent fine particles>
Hydrocarbon wax 10 parts by mass (Fischer-Tropsch wax, maximum endothermic peak 90 ° C)
-Compound D1 (compound described in Table 1) 2.0 parts by mass-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) 1 part by mass-89 parts by mass of ion-exchanged water And then heated to 90 ° C. and circulating to Claremix W Motion (M Technique Co., Ltd.), the rotor rotation speed is 19000 r / min at the shear stir site where the rotor outer diameter is 3 cm and the clearance is 0.3 mm. The mixture was stirred at a screen rotation speed of 19000 r / min, dispersed for 60 minutes, and then cooled to 40 ° C. under cooling 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. By cooling, an aqueous dispersion of release agent fine particles was obtained. The volume-based median diameter was measured using a dynamic light scattering particle size distribution diameter (Nanotrack: manufactured by Nikkiso), and was 0.15 μm.

<Production Example of Toner 17>
-Binder resin fine particle dispersion (1) 70 parts by mass (resin L1 equivalent)
-Binder resin fine particle dispersion (2) 30 parts by mass (resin H1 equivalent)
・ 6 parts by mass of colorant fine particles (equivalent to colorant)
・ 5 parts by weight of release agent fine particles (equivalent to release agent)
-1.5 mass% magnesium sulfate aqueous solution 10 mass parts The above was disperse | distributed using the homogenizer (IKA company_made: Ultra Tarrax T50). Subsequently, the pH was adjusted to 8.1 with a 0.1N sodium hydroxide aqueous solution. Then, it heated, stirring with a stirring blade to 45 degreeC in the water bath for heating. After maintaining at 45 ° C. for 1 hour, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 5.4 μm were formed. After adding 40 parts by mass of a 5 mass% trisodium citrate aqueous solution, the temperature was raised to 85 ° C. while maintaining stirring, and maintained for 90 minutes to fuse the core particles. Next, while stirring was continued, water was placed in the water bath and cooled to 25 ° C. Further, when the particle size of the core particles was measured by a particle size distribution analyzer (Coulter Multisizer III: manufactured by Coulter, Inc.) by the Coulter method, the volume-based median diameter was 5.5 μm.

  Thereafter, after filtration and solid-liquid separation, 800 parts by mass of ion-exchanged water whose pH was adjusted to 8 with sodium hydroxide was added to the solid content, followed by stirring and washing for 30 minutes. Thereafter, filtration and solid-liquid separation were performed again. Subsequently, 800 parts by mass of ion-exchanged water was added to the solid content and washed with stirring for 30 minutes. Thereafter, filtration and solid-liquid separation were performed again, and this was repeated 5 times. Next, the obtained solid content was dried to obtain toner particles.

To 100 parts by mass of the toner particles, 1.0 part by mass of silica fine particles having a primary average particle diameter of 15.0 nm is added, and mixed with a Henschel mixer (FM-75 type) at a rotation speed of 31.6 s ⁻¹ and a rotation time of 5 minutes. The toner 17 was obtained by passing through an ultrasonic vibration sieve having a mesh size of 54 μm. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Examples 18 to 20]
Toners 18 to 20 were produced in the same manner as in Example 1 except that the amorphous polyester resin and the colorant were changed as shown in Table 2, and two-component developers 18 to 20 were produced in the same manner. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 1]
As shown in Table 2, a toner 22 was prepared by changing the type of material and the number of added parts of the material, and a two-component developer 22 was prepared in the same manner as in Example 1. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Comparative Example 2]
Amorphous low molecular weight polyester resin L1 70.0 parts by mass Amorphous high molecular weight polyester resin H1 30.0 parts by mass Ester wax (maximum absorption peak temperature 70 ° C) 5.0 parts by mass Resin composition B1 5.0 parts by mass-Compound D1 (compounds described in Table 1) 1.0 part by mass-C.I. I. Pigment Yellow 180 6.0 parts by mass, 3,5-di-t-butylsalicylic acid aluminum compound 0.5 part by mass Using the Henschel mixer (FM-75 type, manufactured by Nippon Coke Co., Ltd.) as the raw material shown in the above formulation Then, after mixing at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, the mixture was kneaded by a biaxial kneader (PCM-30 type, manufactured by Ikegai Co., Ltd.) set at a temperature of 130 ° C. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Industry Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified at a classifying rotor rotational speed of 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 5.9 μm.

  To 100.0 parts by mass of the obtained toner particles, 0.5 parts by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm surface-treated with 15.0% by mass of isobutyltrimethoxysilane and 20.0% by mass of hexamethyldisilazane. 1.0 parts by mass of hydrophobic silica fine particles having a primary average particle diameter of 15 nm and surface-treated with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Kogyo Co., Ltd.) are mixed, and an ultrasonic vibrating sieve having an aperture of 54 μm is added. The toner 23 was passed through. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

[Production Example of Comparative Example 3]
Styrene acrylic resin (resin A) 95.0 parts by mass (styrene: n-butyl acrylate = 75: 25 (mass ratio) copolymer) (Mw = 30,000, Tg = 55 ° C.)
-Hydrocarbon wax 5.0 parts by mass-Compound D1 (compound described in Table 1) 1.0 part by mass-C.I. I. Pigment Yellow 180 6.0 parts by mass The raw materials shown in the above recipe were mixed using a Henschel mixer (FM-75 type, manufactured by Nippon Coke Co., Ltd.) at a rotation speed of 20 s ⁻¹ and a rotation time of 5 minutes, and then a temperature of 130. It knead | mixed with the biaxial kneader (PCM-30 type | mold, Ikegai Co., Ltd.) set to ℃. The obtained kneaded material was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized material. The resulting coarsely pulverized product was finely pulverized with a mechanical pulverizer (T-250, manufactured by Freund Turbo Industry Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Corporation) were classified at a classifying rotor rotational speed of 50.0 s ⁻¹ . The obtained toner particles had a weight average particle diameter (D4) of 6.0 μm.

  To 100.0 parts by mass of the obtained toner particles, 0.5 parts by mass of titanium oxide fine particles having a primary average particle diameter of 50 nm surface-treated with 15.0% by mass of isobutyltrimethoxysilane and 20.0% by mass of hexamethyldisilazane. 1.0 parts by mass of hydrophobic silica fine particles having a primary average particle diameter of 15 nm and surface-treated with a Henschel mixer (FM-75 type, manufactured by Nippon Coke Kogyo Co., Ltd.) are mixed, and an ultrasonic vibrating sieve having an aperture of 54 μm is added. The toner 24 was passed through. Furthermore, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 3.

Claims (4)

A toner having toner particles containing a binder resin, a wax and a colorant,
(1) The binder resin contains a polyester resin,
(2) The wax is a hydrocarbon wax,
(3) The toner, wherein the toner particles contain a compound represented by the following general formula (1).

(In the formula (1), R ¹ , R ² and R ³ represent H or an alkyl group having 1 to 5 carbon atoms, and R ⁴ and R ⁵ represent hydrogen or an alkyl group having 1 to 12 carbon atoms. Represents.)   The toner particles contain a resin composition, and the resin composition contains a resin in which an aliphatic hydrocarbon unit and a vinyl polymerization unit are chemically bonded. The vinyl polymerization unit is made of styrene or styrene. The toner according to claim 1, further comprising a derivative.   The colorant contains a pigment, and the pigment contains C.I. I. Pigment Yellow 74, C.I. I. Pigment Yellow 180, C.I. I. Pigment Yellow 185, C.I. I. The toner according to claim 1, wherein the toner is one or more pigments selected from the group of Pigment Yellow 155.   4. The toner particles according to claim 1, wherein the toner particles are produced through a step of melt-kneading a mixture containing the binder resin, wax, and colorant, and pulverizing the obtained kneaded product. The toner according to item 1.