Toner and two-component developer

Abstract

To provide a toner that has extremely good fixability even at a low fixing temperature and is excellent in character reproducibility and dot reproducibility, and a two-component developer using the toner.SOLUTION: A toner has a toner particle containing a binder resin. In viscoelasticity measurement that is conducted for a molded sample obtained by performing compression molding of the toner into a disc shape and in which strain in the molded sample is changed at 90°C, a storage elastic modulus G'(1) of the molded sample at a strain of 1% is 7500 Pa to 30000 Pa, and a storage elastic modulus G'(50) of the molded sample at a strain of 50% is 950 Pa to 6000 Pa.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure relates to a toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, a toner jet method, and a two-component developer using the toner.

Background Art

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

[0003] For example, Patent Document 1 discloses a toner containing a crystalline polyester as a main component and a toner using a combination of a crystalline polyester and an amorphous resin.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] ​Toners primarily composed of crystalline resins with sharp melting properties have made it possible to fix toner at lower fixing temperatures than before. However, our research has revealed a new problem: the character and dot reproduction quality of such toners is inferior to that of conventional toners. This disclosure provides a toner that exhibits excellent fixing properties even at low fixing temperatures, as well as excellent character and dot reproduction, and a two-component developer using the toner. [Means for solving the problem]

[0006] The first aspect of this disclosure is, A toner having toner particles containing a binder resin, In a viscoelasticity measurement performed on a molded sample obtained by compressing the toner into a disc shape, while varying the strain of the molded sample at 90°C, The storage modulus G'(1) of the molded sample at a strain of 1% is 7500 Pa to 30000 Pa. This invention relates to a toner characterized in that the storage modulus G'(50) of the molded sample at a strain of 50% is 950 Pa to 6000 Pa.

[0007] Furthermore, a second aspect of this disclosure is: A toner having toner particles containing a binder resin, The binder resin contains a crystalline resin, The crystalline resin, It comprises at least one first monomer unit represented by the following formula (1): Furthermore, it has at least two monomer units selected from the group consisting of a second monomer unit represented by the following formula (2), or Furthermore, it has a second monomer unit represented by the following formula (2) and a third monomer unit represented by the following formula (3). It is a crystalline vinyl resin, This invention relates to a toner characterized in that the proportion of incinerated ash in the tetrahydrofuran-insoluble components of the toner is 5% to 30% by mass, based on the mass of the toner.

[0008] [Chemical formula] (In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms.) In formula (2), R 1 is -C≡N, -C(=O)NHR 10 (R 10 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) a hydroxy group, -COOR 11 (R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) or -NH-C(=O)-N(R 13 )2 (two Rs 13 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), R 2 represents a hydrogen atom or a methyl group.) In formula (3), X represents O or NH, R 2 represents a hydrogen atom or a methyl group, and R 3 represents an alkylene having 2 to 6 carbon atoms.) [Advantages of the Invention]

[0009] According to the present disclosure, it is possible to provide a toner having extremely excellent fixing property even at a low fixing temperature, and excellent character reproducibility and dot reproducibility, and a two-component developer using the toner. [Modes for Carrying Out the Invention]

[0010] 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 endpoints, unless otherwise specified. ((Meth)acrylate means acrylate and / or methacrylate.) When numerical ranges are given in stages, the upper and lower limits of each range can be combined in any way. A "monomer unit" refers to the reacted form of monomer substances in a polymer. For example, in a polymer where vinyl monomers are polymerized, one carbon-carbon bond interval in the main chain is called a "monomer unit." Let's call it T. Vinyl monomers can be represented by the following formula (Z). [ka] (In formula (Z), Z1 represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), and Z2 represents any substituent.) Crystalline resins refer to resins that exhibit a clear endothermic peak in differential scanning calorimeter (DSC) measurements.

[0011] In the following, with respect to the matters described for the toner of the first embodiment and the matters described for the toner of the second embodiment, the matters described for one embodiment of the toner may be replaced with the matters described for the other embodiment of the toner, as necessary.

[0012] The first aspect of this disclosure is, A toner having toner particles containing a binder resin, In a viscoelasticity measurement performed on a molded sample obtained by compressing the toner into a disc shape, while varying the strain of the molded sample at 90°C, The storage modulus G'(1) of the molded sample at a strain of 1% is 7500 Pa to 30000 Pa. This invention relates to a toner characterized in that the storage modulus G'(50) of the molded sample at a strain of 50% is 950 Pa to 6000 Pa.

[0013] The inventors of the present invention considered the following reasons why the aforementioned toner's character and dot reproduction performance is inferior to that of conventional toners. In toners with excellent low-temperature fixing properties, such as those containing a large amount of crystalline resin, the temperature required for the toner to begin deforming is lower than that of conventional toners. Therefore, the toner transferred onto the paper deforms and spreads on the paper due to radiant heat from these components before it is deformed by the heat and pressure it receives from the fixing belt and film during the fixing process. As a result, we believe that character and dot reproduction quality deteriorates. To suppress this phenomenon, we believed it was necessary to give the toner properties such that it would not deform from heat alone during the fixing process, but only deform when subjected to both heat and pressure. The inventors first discovered that the temperature at which toners exhibiting excellent low-temperature fixing properties but reduced reproducibility of characters and dots are fixed is around 90°C. Based on this, they diligently investigated toners with various characteristics at 90°C, leading to the present disclosure.

[0014] In the first embodiment, in viscoelastic measurements performed on a molded sample obtained by compression molding the toner into a disc shape, at 90°C while varying the strain of the molded sample, the storage modulus G'(1) of the molded sample at 1% strain is 7500 Pa to 30000 Pa, and the storage modulus G'(50) of the molded sample at 50% strain is 950 Pa to 6000 Pa. Here, the strain of the molded sample is assumed to be 0% when the stress applied to the molded sample is 0 Pa. The storage modulus obtained by viscoelastic measurement of the molded sample corresponds to the modulus of the toner, as described later. Furthermore, in viscoelasticity measurements where the strain of the molded sample is varied, as described later, the strain value can be set.

[0015] The storage modulus G'(1) of the molded sample at a strain of 1% is considered to correspond to the modulus of the toner when the toner is subjected to almost no pressure during the fixing process. When G'(1) is in the range of 7500Pa to 30000Pa, the reproducibility of characters and dots is good. Preferably it is 8200Pa to 28000Pa, more preferably 10000Pa to 27000Pa, even more preferably 13000Pa to 26000Pa, and particularly preferably 15000Pa to 25000Pa. If G'(1) is less than 7500 Pa, the toner becomes more susceptible to deformation by heat alone, resulting in a decrease in character and dot reproduction quality. On the other hand, if G'(1) exceeds 30000 Pa, it becomes difficult for G'(50), described later, to fall within the scope of this disclosure, and low-temperature fixation performance, in particular, deteriorates.

[0016] The storage modulus G'(50) of the molded sample at 50% strain is thought to correspond to the hardness of the toner when it is subjected to heat and pressure during the fixing process. Our research has shown that the thickness of the toner layer on the paper is approximately halved before and after fixing, so the value of the storage modulus G'(50) of the molded sample measured at 50% strain is important. When G'(50) is in the range of 950 Pa to 6000 Pa, excellent low-temperature fixation can be achieved. Preferably, it is 1000 Pa to 5500 Pa, more preferably 1500 Pa to 4000 Pa, and particularly preferably 1800 Pa to 3000 Pa. If G'(50) is less than 950 Pa, the storage modulus becomes too small when heat and pressure are applied to the toner during the fixing process, resulting in reduced hot offset performance. On the other hand, if G'(50) exceeds 6000 Pa, low-temperature fixing performance decreases. The method for measuring the storage modulus will be described later.

[0017] The toner configuration that achieves the storage moduli G'(1) and G'(50) described above will be explained. By appropriately selecting the binder resin to be used, G'(1) or G'(50) can be set to the above range. Criteria for selecting the binder resin include, for example, appropriately selecting its molecular weight, glass transition temperature, softening point, and monomers constituting the amorphous resin if the binder resin is mainly composed of amorphous resin. If the binder resin is mainly composed of crystalline resin, appropriately selecting its melting point, molecular weight, softening point, and monomers constituting the binder resin. Furthermore, it is possible to adjust the storage modulus G'(1) or G'(50) of the molded sample using other means for adjusting the storage modulus of the toner. Other methods, though not limited to those mentioned above, include methods such as reducing the storage modulus by adding a crystalline resin or plasticizer with a plasticizing effect to a binder resin mainly composed of an amorphous resin, or increasing the storage modulus by adding fine particles or compounds with a filler effect.

[0018] However, it is difficult to set G'(1) and G'(50) within the above range using only the above means. Generally, when viscoelasticity is measured while varying the strain, the storage modulus tends to remain approximately the same or decrease slightly as the strain increases. According to our investigation, in toner configurations using known technologies, G'(50) decreases by at most about 10% compared to G'(1). In other words, simply controlling either G'(1) or G'(50) to the above range using the means described above does not necessarily satisfy the storage modulus of the other.

[0019] Therefore, the inventors conceived of imparting toner properties such that the storage modulus changes significantly depending on the magnitude of the strain, and diligently conducted research on this. As a result, for example, by means of selecting an appropriate monomer for the binder resin, by means of including multiple types of filler components in the toner particles, or by means of combining these means, it is possible to impart toner properties such that the storage modulus changes significantly depending on the magnitude of the strain. We found that... As a result, we were able to define G'(1) and G'(50) within the above range. More specifically, it was found that by using a crystalline resin having a specific monomer unit as the binder resin, and by using a combination of inorganic fine particle filler components or organic pigment filler components with submicron particle sizes, along with the gel component of the binder resin, the storage modulus tends to change significantly depending on the magnitude of the strain.

[0020] The toner contains toner particles. Furthermore, the toner particles contain a binder resin. The binder resin preferably contains a crystalline resin. The crystalline resin content of the binder resin is not particularly limited, but is preferably 35% to 75% by mass, more preferably 40% to 70% by mass, and preferably 50% to 60% by mass. As the crystalline resin, known crystalline resins can be used. Examples include crystalline polyester, crystalline vinyl resin, crystalline polyurethane, and crystalline polyurea. Also, ethylene copolymers such as ethylene-vinyl acetate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methacrylic acid copolymer, and ethylene-acrylic acid copolymer can be used. In particular, crystalline polyester resins and crystalline vinyl resins are preferred from the viewpoint of low-temperature fixation properties. From the viewpoint of electrostatic stability in high-temperature and high-humidity environments, the use of crystalline vinyl resins is even more preferred.

[0021] The crystalline polyester resin is preferably a condensed polymer of a monomer composition mainly comprising an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms. The main component means that its content is 50% by mass or more of the monomer composition. More preferably 70% by mass or more, and even more preferably 90% by mass or more. The aliphatic diol having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but it is preferably a linear (more preferably straight-chain) aliphatic diol. Examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, dodecamethylene glycol, and neopentyl glycol. Among these, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol are preferably exemplified.

[0022] Furthermore, polyhydric alcohol monomers other than the aliphatic diols mentioned above can also be used. Examples of dihydric alcohol monomers among these polyhydric alcohol monomers include aromatic alcohols such as polyoxyethylene-modified bisphenol A and polyoxypropylene-modified bisphenol A; and 1,4-cyclohexanedimethanol. Furthermore, it is preferable to use polyhydric alcohol monomers with a valency of 3 or higher among the polyhydric alcohol monomers. Normally, crystalline polyesters have a hydroxyl group or a carboxyl group at the end of the main chain, but by using these polyhydric alcohol monomers with a valency of 3 or higher, it becomes easier to obtain a crystalline polyester resin having hydroxyl groups that are not directly bonded to the polyester main chain. By using such a crystalline polyester resin, it becomes easier to obtain a binder resin that easily satisfies the physical properties of the first embodiment of this disclosure.

[0023] Among the polyhydric alcohol monomers, those with a valency of 3 or higher include aromatic alcohols such as 1,3,5-trihydroxymethylbenzene; pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl Examples include aliphatic alcohols such as -1,2,4-butanetriol, trimethylolethane, and trimethylolpropane. Furthermore, a monovalent alcohol may be used to the extent that it does not impair the properties of the crystalline polyester resin. Examples of such monovalent alcohols include monofunctional alcohols such as n-butanol, isobutanol, sec-butanol, n-hexanol, n-octanol, lauryl alcohol, 2-ethylhexanol, decanol, cyclohexanol, benzyl alcohol, and dodecyl alcohol.

[0024] On the other hand, the aliphatic dicarboxylic acid compound having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms) is not particularly limited, but it is preferably a linear (more preferably straight-chain) aliphatic dicarboxylic acid. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superiric acid, glutaconic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and also includes hydrolyzed acid anhydrides or lower alkyl esters of these. More preferably, adipic acid, sebacic acid, and 1,10-decanedicarboxylic acid are used.

[0025] Other polycarboxylic acids (hereinafter also referred to as "other polycarboxylic acids") besides the aliphatic dicarboxylic acid compounds with 2 to 22 carbon atoms mentioned above can also be used. Other polycarboxylic acid monomers include divalent carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as n-dodecylsuccinic acid and n-dodecenylsuccinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These also include their acid anhydrides or lower alkyl esters. Furthermore, among other carboxylic acid monomers, polycarboxylic acids with a valency of 3 or higher include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, and pyromellitic acid, as well as aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane. Derivatives such as acid anhydrides or lower alkyl esters of these compounds are also included.

[0026] Furthermore, it is preferable to use polycarboxylic acid monomers with a valency of 3 or higher among the polycarboxylic acid monomers. Normally, crystalline polyesters have a hydroxyl group or a carboxyl group at the end of the main chain, but by using these polycarboxylic acid monomers with a valency of 3 or higher, it becomes easier to obtain a crystalline polyester resin having a carboxyl group that is not directly bonded to the polyester main chain. By using such a crystalline polyester resin, it becomes easier to obtain a binder resin that easily satisfies the physical properties of the first embodiment of this disclosure.

[0027] Furthermore, the material may contain a monovalent carboxylic acid to an extent that does not impair the properties of the crystalline polyester resin. Examples of monovalent carboxylic acids include monocarboxylic acids such as benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, and stearic acid.

[0028] Crystalline polyester resins can be produced according to conventional polyester synthesis methods. For example, a desired crystalline polyester resin can be obtained by esterifying or transesterifying the aforementioned carboxylic acid monomer and alcohol monomer, and then carrying out a condensation polymerization reaction under reduced pressure or by introducing nitrogen gas according to a conventional method. The above esterification or transesterification reactions may be carried out using conventional esterification catalysts such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate, as needed. This can be done using a transesterification catalyst. Furthermore, the above condensation polymerization reaction can be carried out using conventional polymerization catalysts, such as known catalysts like titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, and germanium dioxide. The polymerization temperature and catalyst amount are not particularly limited and can be determined as appropriate. In esterification, transesterification, or condensation polymerization reactions, methods such as charging all monomers at once to increase the strength of the resulting crystalline polyester resin, or first reacting divalent monomers and then adding trivalent or higher monomers to reduce the amount of low molecular weight components, may be used.

[0029] The crystalline resin is more preferably a crystalline vinyl resin, and even more preferably has a first monomer unit represented by the following formula (1) (hereinafter also simply referred to as the first monomer unit). Furthermore, a content ratio of the first monomer unit in the crystalline vinyl resin of 20.0% by mass to 100.0% by mass is preferable because the vinyl resin retains its crystalline properties, making it easier to achieve both low-temperature fixability and hot-off resistance. [ka] In formula (1), R Z1 R represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms. Preferably, R is an alkyl group having 18 to 30 carbon atoms. Furthermore, it is preferable that the alkyl group has a linear structure.

[0030] The first monomer unit has an alkyl group with 18 to 36 carbon atoms, represented by R, in its side chain. The presence of this part makes it easier for crystalline vinyl resins to exhibit crystallinity. If the content of the first monomer unit in the crystalline vinyl resin is less than 20.0% by mass, crystallinity is less likely to occur, and low-temperature fixability tends to decrease. The content of the first monomer unit in the crystalline vinyl resin is preferably 40.0% by mass or more, and more preferably 50.0% by mass or more. There is no particular upper limit, but if other monomer units described later are included, it is preferably 90.0% by mass or less, and more preferably 80.0% by mass or less.

[0031] Furthermore, because crystalline vinyl resin has a structure with crystalline side chains, it exhibits superior static charge retention in high-temperature and high-humidity environments compared to crystalline polyester, a conventionally well-known crystalline resin.

[0032] The first monomer unit is preferably a monomer unit consisting of at least one (first polymerizable monomer) selected from the group consisting of (meth)acrylic acid esters having an alkyl group having 18 to 36 carbon atoms.

[0033] Examples of (meth)acrylic acid esters having an alkyl group with 18 to 36 carbon atoms include (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms. Examples include stearyl acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate, behenyl (meth)acrylate, lignoceryl (meth)acrylate, ceryl (meth)acrylate, octacosyl (meth)acrylate, myricyl (meth)acrylate, dotriacontyl (meth)acrylate, etc., and (meth)acrylate esters having branched alkyl groups with 18 to 36 carbon atoms [such as 2-decyltetradecyl (meth)acrylate].

[0034] Of these, from the viewpoint of the toner's low-temperature fixation properties, at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 36 carbon atoms is preferred. More preferably, at least one selected from the group consisting of (meth)acrylic acid esters having a linear alkyl group with 18 to 30 carbon atoms is preferred. Even more preferably, at least one selected from the group consisting of linear (meth)acrylic acid stearyl and (meth)acrylic acid behenyl. The monomers forming the first monomer unit may be used individually or in combination of two or more types.

[0035] The crystalline vinyl resin may contain other monomer units besides the first monomer unit. Examples of polymerizable monomers that form monomer units other than the first monomer unit include the following. Furthermore, the polymerizable monomers that form the other monomer units may be used individually or in combination of two or more.

[0036] Other monomer units besides the first monomer unit are broadly classified into the second monomer unit represented by formula (2) below (hereinafter also simply referred to as the second monomer unit), the third monomer unit represented by formula (3) below (hereinafter also simply referred to as the third monomer unit), and monomer units other than the first, second, and third monomer units. [ka] In formula (2), R 1 -C≡N, -C(=O)NHR 10 (R 10 (This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) Hydroxyl group, -COOR 11 (R 11 (This represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.) -NH-C(=O)-N(R 13 )2(two R13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 2 represents a hydrogen atom or a methyl group. In equation (3), X represents O or NH, and R 2 R represents a hydrogen atom or a methyl group. 3 teeth This represents alkylenes with 2 to 6 carbon atoms.

[0037] The second monomer unit has a polar group directly bonded to the main chain of the crystalline vinyl resin. Examples of polymerizable monomers that form the second monomer unit include the following polymerizable monomers. Monomers having a nitrile group; for example, acrylonitrile, methacrylonitrile, etc. Monomers having a hydroxyl group; for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.

[0038] 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 known methods.

[0039] Monomers having a urea group: For example, monomers obtained by reacting an amine having 3 to 22 carbon atoms [primary amines (such as n-butylamine, t-butylamine, propylamine, and isopropylamine), secondary amines (such as din-ethylamine, din-propylamine, din-butylamine), aniline, and cycloxylamine)] with an isocyanate having 2 to 30 carbon atoms having an ethylenically unsaturated bond, by known methods. Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylate.

[0040] 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 octolate.

[0041] The third monomer unit has a polar hydroxyl group located away from the main chain. Examples of polymerizable monomers that form the third monomer unit include the following: (meth)acrylate-2-hydroxyethyl, (meth)acrylate-2-hydroxypropyl, (meth)acrylate-2-hydroxyethylamide, (meth)acrylate-2-hydroxypropylamide.

[0042] Examples of polymerizable monomers that form monomer units other than the first, second, and third monomer units include the following polymerizable monomers. Styrene, o-methylstyrene and other styrenes and their derivatives, and (meth)acrylic acid esters such as methyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. Unsaturated monoolefins such as ethylene, propylene, butylene, and isobutylene; unsaturated polyenes such as butadiene and isoprene.

[0043] Aromatic divinyl compounds; diacrylate compounds linked by alkyl chains; diacrylate compounds linked by alkyl chains containing ether bonds; diacrylate compounds linked by chains containing aromatic groups and ether bonds; polyester-type diacrylates; polyfunctional crosslinking agents. Examples of the aromatic divinyl compounds include divinylbenzene and divinylnaphthalene.

[0044] Examples of diacrylate compounds linked by the alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6-hexanediol diacrylate. Diacrylate, neopentyl glycol diacrylate, and compounds in which the acrylate of the above compounds is replaced with methacrylate, etc.

[0045] As the polymerizable monomer that forms monomer units other than the first, second, and third monomer units, styrene is preferred because its electrostatic stability under high temperature and high humidity conditions is easily improved.

[0046] As polymerizable monomers that form monomer units other than the first monomer unit, it is preferable to use monomers having a nitrile group, an amide group, a urethane group, or a urea group. More preferably, the monomer has at least one functional group selected from the group consisting of a nitrile group, an amide group, a urethane group, and a urea group, and an ethylenically unsaturated bond. Using these monomers further improves the rate of charge buildup in low humidity environments.

[0047] The crystalline resin preferably has a second monomer unit, more preferably has at least two monomer units selected from the second monomer unit, more preferably has a second monomer unit and a third monomer unit, and even more preferably has a second monomer unit and a third monomer unit. In these cases, the polymerizable monomer forming the second monomer unit is preferably at least one selected from the group consisting of acrylonitrile, methacrylonitrile, acrylic acid, and methacrylic acid, and the polymerizable monomer forming the third monomer unit is preferably at least one selected from the group consisting of (meth)acrylate-2-hydroxyethyl and (meth)acrylate-2-hydroxypropyl. The polymerizable monomer forming the second monomer unit is even more preferably at least one selected from the group consisting of acrylonitrile and methacrynitrile. By using such polymerizable monomers in combination, it becomes possible to achieve a high level of simultaneous improvement in character reproduction, dot reproduction, and low-temperature fixation.

[0048] As monomers in which a nitrile group or carboxyl group is directly bonded to an ethylenically unsaturated bond, acrylonitrile or methacrylonitrile are more preferred. This configuration allows monomer units having polar groups such as nitrile groups or carboxyl groups directly bonded to the main chain of the crystalline vinyl resin (second monomer units) and monomer units having hydroxyl groups that are not directly bonded to the main chain of the crystalline vinyl resin (third monomer units) to coexist within the resin.

[0049] During toner melting, the polar groups in the crystalline vinyl resin interact with each other via electric dipole interactions, resulting in increased viscosity and elastic modulus of the toner compared to resins without polar groups. In the second monomer unit, polar functional groups are directly bonded to the main chain, which contributes significantly to molecular mobility. Therefore, after toner melting, it has a higher storage modulus compared to resins that do not have polar groups directly bonded to the main chain of crystalline vinyl resin. On the other hand, the third monomer unit has a polar hydroxyl group located away from the main chain. Therefore, after toner melting, the storage modulus is less likely to be high compared to resins with polar groups directly bonded to the main chain of crystalline vinyl resin.

[0050] When the second and third monomer units coexist, and the toner strain is small, it is thought that some of the polar groups of the third monomer unit interact with the polar groups of the second monomer unit. As a result, the polar groups directly bonded to the main chain of the second monomer unit have a strong effect, leading to a higher storage modulus. Furthermore, when pressure is applied from the fixing member, the interaction between the polar groups of the third monomer unit and the polar groups of the second monomer unit decreases, increasing molecular mobility, which is thought to reduce the viscosity of the toner. In other words, the storage modulus can be significantly changed depending on whether only heat is applied or both heat and external force are applied.

[0051] When the crystalline vinyl resin is a vinyl-based resin, it can be manufactured using the polymerizable monomer and polymerization initiator described above. From the viewpoint of efficiency, the polymerization initiator should be used in an amount of 0.05 parts by mass or more and 10.00 parts by mass or less per 100.00 parts by mass of the polymerizable monomer.

[0052] Examples of polymerization initiators 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-cyclohexanecarbonitride), 2-Carbamoylazoisobutyronitrile, 2,2'-Azobis(2,4,4-trimethylpentane), 2-Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-Azobis(2-methylpropane), Methyl ethyl ketone peroxide, Ace Ketone peroxides such as tylacetone peroxide and cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl 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-trioyl 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 peroxy Cyisobutyrate, 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.

[0053] The crystalline resin used as the binder resin in this disclosure is preferably such that, from the viewpoint of electrostatic stability, the acid value is 0 mg KOH / g to 100 mg KOH / g, more preferably 10 mg KOH / g to 60 mg KOH / g, even more preferably 15 mg KOH / g to 50 mg KOH / g, and particularly preferably 20 mg KOH / g to 30 mg KOH / g. Similarly, the hydroxyl value is preferably 0 mg KOH / g to 100 mg KOH / g, more preferably 10 mg KOH / g to 75 mg KOH / g, even more preferably 15 mg KOH / g to 70 mg KOH / g, and particularly preferably 18 mg KOH / g to 60 mg KOH / g.

[0054] In the toner of the first embodiment, it is preferable to further include an amorphous resin as the binder resin. The content of the amorphous resin in the binder resin is not particularly limited, but is preferably 25% to 65% by mass, more preferably 30% to 60% by mass, and even more preferably 40% to 50% by mass. As the amorphous resin, known amorphous resins can be used. For example, the following can be mentioned.

[0055] Polyvinyl chloride, phenolic resin, natural resin-modified phenolic resin, natural resin-modified Murray Polyvinyl acetate 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-based resin, vinyl-based resin. Among these, it is preferable to include at least one resin selected from the group consisting of a hybrid resin in which a vinyl resin and a polyester resin are bonded, a polyester resin, and a vinyl resin. More preferably, an amorphous polyester resin is used. By using an amorphous polyester resin, it becomes easier to increase the value of the storage modulus G'(1). As a result, G'(1) and G'(50) can be set within the above range. Consequently, it becomes easier to achieve a high level of balance between hot offset properties, low-temperature fixing properties, and dot reproducibility.

[0056] As the amorphous polyester resin, polyester resins commonly used in toners can be suitably used. Examples of monomers used in the polyester resin include polyhydric alcohols (dihydric or trihydric or higher alcohols), polyhydric carboxylic acids (dihydric or trihydric or higher carboxylic acids), their acid anhydrides, or their lower alkyl esters.

[0057] Examples of such polyhydric alcohols include the following: Examples of dihydric alcohols 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.

[0058] 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, and 1,3,5-trihydroxymethylbenzene. These polyhydric alcohols can be used individually or in combination.

[0059] Examples of polycarboxylic acids include the following: Examples of divalent carboxylic acids 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-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid, isododecylsuccinic acid, n-octenylsuccinic acid, n-octylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and lower alkyl esters thereof. Of these, maleic acid, fumaric acid, terephthalic acid, n-dodecenylsuccinic acid, and adipic acid are preferably used.

[0060] In particular, when using the aforementioned crystalline vinyl resin as the crystalline resin, it is preferable to use alkenyl succinic acid such as n-dodecenyl succinic acid, isododecenyl succinic acid, n-octenyl succinic acid, and isooctenyl succinic acid as the divalent carboxylic acid. By using succinic acid, amorphous resins can contain monomer units made of alkenyl succinic acid. Since the monomer units made of alkenyl succinic acid have an alkenyl group, they readily interact with the long-chain alkyl units with 18 to 30 carbon atoms in crystalline vinyl resins. This interaction is weaker than the interaction between polar groups. Therefore, when the toner strain is small, this interaction easily produces a filler effect, but when the toner strain is large, this interaction becomes less effective, making it difficult to produce a filler effect. As a result, G'(1) and G'(50) can be set within the above range.

[0061] Examples of trivalent or higher carboxylic acids, their acid anhydrides, or their lower alkyl esters include the following: 1,2,4-Benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalentricarboxylic acid, 1,2,4-naphthalentricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra(methylenecarboxy)methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimeric acid, their acid anhydrides, or their lower alkyl esters.

[0062] Of these, 1,2,4-benzenetricarboxylic acid (trimellitic acid) or its acid anhydride derivatives are preferred because they are inexpensive and easy to control the reaction. These polycarboxylic acids can be used individually or in combination.

[0063] The method for producing the polyester resin is not particularly limited, and known methods can be used. For example, the polyhydric alcohol and polyhydric carboxylic acid mentioned above are charged simultaneously, and polymerization is carried out via an esterification reaction or transesterification reaction and a condensation reaction to produce the polyester resin. The polymerization temperature is not particularly limited, but a range of 180°C to 290°C is preferred. When polymerizing the polyester resin, polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used. The polyester resin used in the amorphous resin is preferably one that has been polymerized using at least one of a titanium-based catalyst and a tin-based catalyst.

[0064] Examples of vinyl resins used as amorphous resins include polymers of polymerizable monomers containing ethylenically unsaturated bonds. Ethylenelycol-unsaturated bonds refer to carbon-carbon double bonds that can undergo radical polymerization, such as vinyl groups, propenyl groups, acryloyl groups, and methacryloyl groups.

[0065] Examples of polymerizable monomers include the following: Styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and 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, and other acrylic acid esters; Methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, meth α-methylene aliphatic monocarboxylic acids and their esters, such as dodecyl acrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; Also, acrylonitrile, methacrylonitrile, acrylamide, etc.

[0066] Furthermore, polymerizable monomers having a hydroxyl group, such as acrylic acid or methacrylic acid esters like 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl methacrylate, and 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene. These can be used individually or in combination.

[0067] In particular, it is preferable to use monomers that are condensates of acrylic acid or methacrylic acid with an alcohol 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. These monomers readily interact with the long-chain alkyl units (18-30 carbon atoms) of crystalline vinyl resin. This interaction is weaker than the interaction between polar groups. Therefore, when the toner strain is small, the interaction easily produces a filler effect, but when the toner strain is large, this interaction becomes less effective, making it difficult to produce a filler effect. As a result, G'(1) and G'(50) can be set within the above range.

[0068] In addition to the above, various polymerizable monomers capable of vinyl polymerization may be used in combination with the vinyl resin as needed. Examples of polymerizable monomers 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-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, and Unsaturated dibasic acid anhydrides such as alkeneyl succinic anhydride; half-esters of unsaturated basic 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; unsaturated basic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; acid anhydrides of α,β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; anhydrides of the α,β-unsaturated acid and lower fatty acids; polymerizable monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, their acid anhydrides, and their monoesters.

[0069] Furthermore, the 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 alkyl chains; diacrylate compounds linked by alkyl chains containing ether bonds; containing aromatic groups and ether bonds Chain-linked diacrylate compounds; polyester-type diacrylates; polyfunctional crosslinking agents. Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.

[0070] Examples of diacrylate compounds linked by alkyl chains 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 variations of these compounds in which the acrylate is replaced with methacrylate.

[0071] Vinyl resins include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-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, It is preferable that the polymer is a polymerizable monomer containing at least one selected from the group consisting of 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.

[0072] Furthermore, the vinyl resin may be a copolymer of monomers comprising at least one polymerizable monomer selected from the group, and at least one crosslinkable polymerizable monomer selected from the group consisting of divinylbenzene, divinylnaphthalene, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and neopentyl glycol dimethacrylate. The content of the crosslinkable polymer in the monomer should be approximately 0.5% to 5.0% by mass.

[0073] The vinyl resin may be a resin produced using 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 10.00 parts by mass or less per 100.00 parts by mass of polymerizable monomer. The following are examples of polymerization initiators.

[0074] 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-cyclohexanecarbonitride), 2-Carbamoylazoisobutyronitrile, 2,2'-Azobis(2,4,4-trimethylpentane) ), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2'-azobis(2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, ketone peroxides such as cyclohexanone peroxide, 2,2-bis(tert-butylperoxy)butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-tert-butyl peroxide, tert-butylcumyl 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-trioyl peroxide, diisopropyl peroxydicarbonate, di-2- Ethylhexyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, dimethoxyisopropyl peroxydicarbonate, di(3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl sulfonyl 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.

[0075] The vinyl resin and polyester resin used to form the hybrid resin, which is a combination of vinyl resin and polyester resin, can be the same as those used for the amorphous resin described above.

[0076] One method for producing a hybrid resin in which vinyl resin and polyester resin are bonded together is to polymerize using a compound that can react with either of the monomers that make up both resins (hereinafter referred to as "dual-reactive compound").

[0077] Examples of both reactive compounds include fumaric acid, acrylic acid, methacrylic acid, citraconic acid, maleic acid, and dimethyl fumarate. Of these, fumaric acid, acrylic acid, and methacrylic acid are preferably used.

[0078] When a hybrid resin is used in which vinyl resin and polyester resin are bonded, the content of 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, or 90% by mass or less.

[0079] The amorphous resin used as the binder resin in this disclosure is preferably such that, from the viewpoint of electrostatic stability, the acid value is 0 mg KOH / g to 100 mg KOH / g, more preferably 10 mg KOH / g to 60 mg KOH / g, even more preferably 15 mg KOH / g to 50 mg KOH / g, and particularly preferably 20 mg KOH / g to 30 mg KOH / g. Similarly, the hydroxyl value is preferably 0 mg KOH / g to 100 mg KOH / g, more preferably 10 mg KOH / g to 75 mg KOH / g, even more preferably 15 mg KOH / g to 70 mg KOH / g, and particularly preferably 18 mg KOH / g to 60 mg KOH / g.

[0080] The percentage of tetrahydrofuran (THF)-insoluble content in the binder resin is based on the mass of the binder resin. Preferably, the THF-insoluble content is 0.1% to 60.0% by mass. THF-insoluble content in the binder resin is softer than THF-insoluble content such as inorganic fine particles and has less adverse effect on low-temperature fixability, so it is preferably used. When the THF-insoluble content of the binder resin is within the above range, it tends to result in a toner with excellent character and dot reproduction. Preferably, it is 1.0% to 50.0% by mass, more preferably 1.0% to 40.0% by mass, and even more preferably 5.0% to 30.0% by mass. The THF-insoluble content may be from a crystalline resin or an amorphous resin. From the viewpoint of hot offset properties, it is preferable that it be from an amorphous resin. The THF-insoluble content of the binder resin can be controlled, for example, in the case of polyester resin, by using a trivalent or higher alcohol or acid, or by synthesizing an unsaturated polyester and then crosslinking it with a polymerization initiator. In the case of vinyl resin, it can be controlled by using the crosslinkable monomers mentioned above. The method for measuring the amount and percentage of THF-insoluble components in the binder resin will be described later.

[0081] In toner, the binder resin contained in the toner particles contains a crystalline resin, and in differential scanning calorimetry (DSC) using the toner as a sample, it is preferable that the peak temperature of the endothermic peak corresponding to the crystalline resin during the first heating cycle is 50°C to 70°C, and the endothermic amount ΔH (J / g) of the endothermic peak satisfies ΔH ≥ 5. More preferably, the peak temperature of the endothermic peak is 55°C to 65°C. More preferably, the endothermic amount ΔH of the endothermic peak satisfies ΔH ≥ 7, and even more preferably satisfies ΔH ≥ 10. During the first heating cycle, the peak temperature of the endothermic peak corresponding to the crystalline resin is between 50°C and 70°C, and the amount of heat absorbed by the endothermic peak satisfies ΔH ≥ 5, indicating a high concentration of crystalline resin in the toner particles. As a result, the toner exhibits sharp melt properties and improved low-temperature fixability, which is preferable. Furthermore, it is preferable because the value of the storage modulus G'(50) at 50% strain can be reduced. Furthermore, the peak temperature of the endothermic peak corresponding to the crystalline resin, and the amount of heat absorbed by the endothermic peak, can be appropriately adjusted by changing the type of monomer used as the raw material for the crystalline resin.

[0082] The tetrahydrofuran (THF) insoluble content of the toner is preferably 12% to 60% by mass, more preferably 13% to 55% by mass, even more preferably 15% to 50% by mass, and particularly preferably 18% to 45% by mass, based on the mass of the toner. The method for measuring the amount and content ratio of THF insoluble content in the toner will be described later. The THF-insoluble components in toner obtained by the method described later include inorganic and organic pigments contained as colorants in the toner, fine particles contained in the toner particles, fine particles used as external additives, and THF-insoluble components contained in the binder resin. Therefore, the proportion of THF-insoluble components in the toner can be adjusted by adjusting the content of these components. When the THF-insoluble content of the toner is within the above range, the amount of organic components in the THF-insoluble content of the toner also increases. Organic components have a strong interaction with the binder resin. As a result, even when a crystalline resin is used as the binder resin, it becomes easy to increase the storage modulus of the toner, and G'(1) and G'(50) can be set within the above range.

[0083] The content of tetrahydrofuran (THF)-insoluble incinerated ash (hereinafter also simply referred to as incinerated ash) in the toner is preferably 5% to 30% by mass, more preferably 6% to 23% by mass, and even more preferably 8% to 20% by mass, based on the mass of the toner. The method for measuring the content of incinerated ash will be described later. The solid components of the THF-insoluble toner obtained by the method described later, which are incinerated ash, consist of inorganic and organic pigments contained as colorants in the toner, fine particles used as external additives, and inorganic components contained in the THF-insoluble binder resin. Therefore, the proportion of incinerated ash can be adjusted by adjusting the content of these components. Inorganic components have less interaction with the resin during toner melting compared to organic components. Therefore, the filler effect when the toner is subjected to large strains is reduced. As a result, the change in storage modulus measured by varying the strain of the toner tends to be larger, and G'(1) and G'(50) can be kept within the above ranges.

[0084] The percentage of incinerated ash in the tetrahydrofuran (THF)-insoluble portion of the toner is preferably 24% to 85% by mass, more preferably 26% to 77% by mass, even more preferably 30% to 70% by mass, and particularly preferably 35% to 65% by mass, based on the percentage of THF-insoluble portion in the toner. As mentioned above, the ratio of incinerated ash to the THF-insoluble content of toner indicates the proportion of inorganic components in the THF-insoluble content of the toner. Conversely, the components of the THF-insoluble content of toner excluding incinerated ash can be considered organic components. The organic components in the THF-insoluble content of toner, like the inorganic components, act as fillers when the toner melts. However, because the organic components in the THF-insoluble content of toner have a stronger interaction with the binder resin, they exhibit a stronger filler effect than the inorganic components at low strain. In other words, by setting the ratio of incinerated ash content to the THF-insoluble content of the toner within the above range, it is possible to combine organic components that exhibit a strong filler effect at low strain with inorganic incinerated ash that exhibits a small filler effect at high strain. As a result, G'(1) and G'(50) can be set within the above range.

[0085] It is preferable that the binder resin contained in the toner contains both a crystalline resin and an amorphous resin, and that, when the cross-sectional observation of the toner particles by transmission electron microscopy, it has a domain matrix structure composed of a matrix containing a crystalline resin and domains containing an amorphous resin. The inclusion of crystalline resin in the matrix results in excellent low-temperature fixation. Furthermore, the presence of amorphous resin within the domains allows these amorphous resin domains to act as fillers. Because the toner particles possess a domain-matrix structure, they readily exhibit changes in storage modulus in response to strain. As a result, a toner with excellent low-temperature fixation, character reproduction, and dot reproduction can be achieved. By appropriately changing the composition of crystalline resin and amorphous resin, toner particles can have a domain matrix structure.

[0086] Furthermore, the average number diameter of the domains is preferably 0.05 μm to 3.00 μm, more preferably 0.10 μm to 2.00 μm, and even more preferably 0.10 μm to 1.00 μm. When the average number diameter of the domains is within the above range, the amorphous resin is more likely to act as a filler during toner melting, and is more likely to cause a change in the storage modulus in response to strain, which is preferable. As a result, a toner with excellent low-temperature fixability, character reproduction, and dot reproduction can be obtained. The average number diameter of domains can be controlled by factors such as the composition of monomers constituting crystalline resins, the composition of monomers constituting amorphous resins, and the manufacturing conditions of toner particles.

[0087] In cross-sectional observation of toner particles, the ratio of the domain area to the area of ​​the cross-section of the toner particle (hereinafter also simply referred to as the domain area ratio) is preferably 15% to 80%, more preferably 20% to 70%, even more preferably 30% to 65%, and particularly preferably 38% to 61%.

[0088] In viscoelastic measurements performed at 90°C with varying strains on a molded sample, it is preferable that the storage modulus G'(1) and the loss modulus G''(1) of the molded sample at 1% strain satisfy the condition G'(1) > G''(1). The condition G'(1)>G''(1) indicates that in viscoelastic measurements of a molded sample, the elastic term is greater than the viscous term when the strain is small, meaning that the toner behaves elastically. Therefore, deformation is reduced before large pressures are applied during the fixing process, which is preferable because it improves the reproducibility of characters and dots. Means of achieving toner viscoelasticity such that G'(1)>G''(1) include changing the composition of monomers constituting the crystalline resin, the composition of monomers constituting the amorphous resin, and the type and amount of filler components contained in the toner particles.

[0089] A second aspect of this disclosure is, A toner containing toner particles containing a binder resin, The binder resin contains a crystalline resin, The crystalline resin, It comprises at least one first monomer unit represented by the following formula (1): Furthermore, it has at least two monomer units selected from the group consisting of a second monomer unit represented by the following formula (2), or Furthermore, it has a second monomer unit represented by the following formula (2) and a third monomer unit represented by the following formula (3). It is a crystalline vinyl resin, This invention relates to a toner characterized in that the proportion of incinerated ash in the tetrahydrofuran-insoluble components of the toner is 5% to 30% by mass, based on the mass of the toner. [ka] In formula (1), R Z1 represents a hydrogen atom or a methyl group, and R represents an alkyl group with 18 to 36 carbon atoms. In formula (2), R 1 -C≡N, -C(=O)NHR 10 (R 10 (This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) Hydroxyl group, -COOR 11 (R 11 ) or -NH-C(=O)-N(R13 )2(two R 13 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R 2 represents a hydrogen atom or a methyl group. In equation (3), X represents O or NH, and R 2 R represents a hydrogen atom or a methyl group. 3 This represents alkylenes with 2 to 6 carbon atoms.

[0090] The second aspect of this disclosure is described below. The toner of the second embodiment has toner particles. The toner particles also contain a binder resin. The binder resin contains a crystalline resin. The crystalline resin is a crystalline vinyl resin and has a first monomer unit represented by the following formula (1). Furthermore, the content of the first monomer unit in the crystalline vinyl resin is 20.0% by mass. A concentration of 100.0% by mass is preferable because it allows the vinyl resin to have crystalline properties, making it easier to achieve both low-temperature fixability and hot-off resistance. [ka] In formula (1), R Z1 R represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms. Preferably, R is an alkyl group having 18 to 30 carbon atoms. Furthermore, it is preferable that the alkyl group has a linear structure.

[0091] The first monomer unit has an alkyl group with 18 to 36 carbon atoms, represented by R, in its side chain. The presence of this part makes it easier for crystalline vinyl resins to exhibit crystallinity. If the content of the first monomer unit in the crystalline vinyl resin is less than 20.0% by mass, crystallinity is less likely to occur, and low-temperature fixability tends to decrease. The content of the first monomer unit in the crystalline vinyl resin is preferably 40.0% by mass or more, and more preferably 50.0% by mass or more. There is no particular upper limit, but it is preferably 90.0% by mass or less, and more preferably 80.0% by mass or less. Furthermore, because crystalline vinyl resin has a structure with crystalline side chains, it exhibits superior static charge retention in high-temperature and high-humidity environments compared to crystalline polyester, a conventionally well-known crystalline resin.

[0092] The first monomer unit represented by formula (1) in the second embodiment may be preferably the same as that shown in the first embodiment for the same reasons, and the polymerizable monomer forming the first monomer unit in the second embodiment may be preferably the same as that shown in the first embodiment for the same reasons.

[0093] The crystalline resin of the second embodiment has at least two monomer units selected from the group consisting of a second monomer unit represented by formula (2) (hereinafter also simply referred to as the second monomer unit), or has a second monomer unit and a third monomer unit represented by formula (3) (hereinafter also simply referred to as the third monomer unit). Preferably, it has a second monomer unit represented by formula (2) and a third monomer unit represented by formula (3). The second monomer unit has a polar group directly bonded to the main chain of the crystalline vinyl resin. The third monomer unit has an alkylene group with 2 to 6 carbon atoms between the main chain of the crystalline vinyl resin and the hydroxyl group, and the polar hydroxyl group is located away from the main chain.

[0094] Having at least two monomer units selected from the group consisting of a second monomer unit, or having a second monomer unit and a third monomer unit, increases the viscosity of the toner during toner melting compared to when these monomer units are not present. This is due to the electric dipole interaction of polar groups in the crystalline vinyl resin. The second monomer unit has polar functional groups directly bonded to the main chain, which greatly contributes to molecular mobility. Therefore, after toner melting, the main chain of the crystalline vinyl resin is directly bonded to it. Compared to resins that do not have bonded polar groups, it has a higher storage modulus. During the fixing process, when the toner is only receiving heat from the fixing material, the effect of the second monomer unit minimizes deformation of the toner. On the other hand, the third monomer unit has a polar hydroxyl group located away from the main chain. Therefore, after toner melting, the storage modulus is less likely to be high compared to resins with polar groups directly bonded to the main chain of crystalline vinyl resin.

[0095] When the second and third monomer units coexist, and the toner distortion is small, it is thought that some of the polar groups of the third monomer unit interact with the polar groups of the second monomer unit. In this case, when the toner is only receiving heat from the fixing member, the deformation of the toner can be minimized due to the effect of the second monomer unit described above. Furthermore, when pressure is applied from the fixing member, the interaction between the polar groups of the third monomer unit and the polar groups of the second monomer unit decreases, increasing molecular mobility, which is thought to reduce the viscosity of the toner. In other words, the storage modulus can be significantly changed depending on whether only heat is applied or both heat and external force are applied. As a result, a high level of low-temperature fixing, character reproduction, and dot reproduction can be achieved simultaneously.

[0096] The content ratio W2 of the second monomer unit in the crystalline vinyl resin is preferably 1.0% by mass or more, more preferably 5.0% by mass or more. Furthermore, it is preferably 70.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 20.0% by mass or less. The content ratio W3 of the third monomer unit in the crystalline vinyl resin is preferably 1.0% by mass or more, more preferably 5.0% by mass or more. Furthermore, it is preferably 70.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 20.0% by mass or less. The ratio W2 / W3 of the content of the second monomer unit to the third monomer unit is preferably 0.1 to 10.0, and more preferably 0.5 to 5.0.

[0097] For the same reasons, the polymerizable monomers that form the second and third monomer units can be those shown in the first embodiment. The crystalline resin of the toner in the second embodiment may optionally contain monomer units other than the first, second, and third monomer units, to the extent that it does not impair the effects of the present disclosure. The polymerizable monomers that form the monomer units other than the first, second, and third monomer units are those shown in the first embodiment and can be suitably used for similar reasons. The content of monomer units other than the first, second, and third monomer units in the crystalline resin is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0098] In the second embodiment, the toner contains 5% to 30% by mass of tetrahydrofuran (THF) insoluble incinerated ash (hereinafter also simply referred to as incinerated ash) based on the mass of the toner. Preferably, the incinerated ash content is 6% to 23% by mass, and more preferably 8% to 20% by mass. The method for measuring the incinerated ash content will be described later. The solid components of the THF-insoluble toner obtained by the method described later, which are incinerated ash, consist of inorganic and organic pigments contained as colorants in the toner, fine particles used as external additives, and inorganic components contained in the THF-insoluble binder resin. Therefore, the proportion of incinerated ash can be adjusted by adjusting the content of these components. Inorganic components have less interaction with the resin during toner melting compared to organic components. Therefore, the filler effect when the toner is subjected to large stresses is reduced. As a result, when the toner is not subjected to pressure from the fixing material during the fixing process, it is less likely to melt due to the filler effect, and the fixing material... The material melts under pressure. This makes it possible to achieve a high level of simultaneous reproduction of characters, dots, and low-temperature fixation.

[0099] In the toner of the second embodiment, for the same reasons as in the toner of the first embodiment, the content of tetrahydrofuran (THF) insoluble matter in the binder resin is preferably 0.1% to 60.0% by mass, more preferably 1.0% to 50.0% by mass, even more preferably 1.0% to 40.0% by mass, and particularly preferably 5.0% to 30.0% by mass, based on the mass of the binder resin.

[0100] In the second embodiment of the toner, the tetrahydrofuran (THF) insoluble content of the toner is preferably 12% to 60% by mass, more preferably 13% to 55% by mass, even more preferably 15% to 50% by mass, and particularly preferably 18% to 45% by mass, based on the mass of the toner. The method for measuring the amount and content ratio of THF insoluble content in the toner will be described later. The THF-insoluble components in toner obtained by the method described later include inorganic and organic pigments contained as colorants in the toner, fine particles contained in the toner particles, fine particles used as external additives, and THF-insoluble components contained in the binder resin. Therefore, the proportion of THF-insoluble components in the toner can be adjusted by adjusting the content of these components. When the THF-insoluble content of the toner falls within the above range, the organic component of the THF-insoluble toner also increases. The organic component strongly interacts with the binder resin. Therefore, it exhibits a strong filler effect at low strain levels. As a result, it becomes possible to achieve a high level of balance between character reproduction, dot reproduction, and low-temperature fixation.

[0101] In the second embodiment of the toner, the incinerated ash content of the tetrahydrofuran (THF) insoluble portion of the toner is preferably 24% to 85% by mass, more preferably 26% to 77% by mass, even more preferably 30% to 70% by mass, and particularly preferably 35% to 65% by mass, based on the THF insoluble portion content of the toner. As mentioned above, the ratio of incinerated ash to the THF-insoluble content of toner indicates the proportion of inorganic components in the THF-insoluble content of the toner. Conversely, the components of the THF-insoluble content of toner excluding incinerated ash can be considered organic components. The organic components in the THF-insoluble content of toner, like the inorganic components, act as fillers when the toner melts. However, because the organic components in the THF-insoluble content of toner have a stronger interaction with the binder resin, they exhibit a stronger filler effect than the inorganic components at low strain. In other words, by setting the ratio of incinerated ash to the THF-insoluble content of the toner within the above range, it is possible to combine organic components that exhibit a strong filler effect at low distortion with inorganic incinerated ash that exhibits a small filler effect at high distortion. As a result, it becomes possible to achieve a high level of balance between character reproduction, dot reproduction, and low-temperature fixing performance.

[0102] In the toner of the second embodiment, it is preferable to further include an amorphous resin as the binder resin. The amorphous resin in the second embodiment can be the same as that shown in the first embodiment for the same reasons.

[0103] For the same reasons as the toner of the first embodiment, the toner of the second embodiment preferably has a domain matrix structure composed of a matrix containing a crystalline resin and domains containing an amorphous resin, as observed in cross-sectional view of the toner particles using a transmission electron microscope.

[0104] Furthermore, the average number diameter of the domains is preferably 0.05 μm to 3.00 μm, and more preferably 0.10 μm to 2.00 μm, for the same reasons as in the toner of the first embodiment. It is preferable that the particle size be between 0.10 μm and 1.00 μm.

[0105] In the second embodiment of the toner, it is preferable that, in cross-sectional observation of the toner, the ratio of the domain area to the area of ​​the cross-section of the toner particles (hereinafter also simply referred to as the domain area ratio) is 15% to 80%.

[0106] For the same reasons as the toner of the first embodiment, it is preferable that the storage modulus G'(1) of the toner at 1% strain and the loss modulus G''(1) of the toner at 1% strain, obtained in viscoelastic measurements with varying strains of the toner at 90°C, satisfy the relationship G'(1)>G''(1).

[0107] The following describes matters common to the first and second aspects of this disclosure. The binder resin may contain resins other than the crystalline resin and amorphous resin described above, to the extent that it does not impair the effects of the present disclosure, for purposes such as improving pigment dispersibility. Examples of such 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-based resin.

[0108] Toner particles may contain colorants. Examples of colorants include the following: Examples of black colorants include carbon black; and black produced by mixing yellow, magenta, and cyan colorants. While pigments may be used alone as colorants, it is preferable to use dyes and pigments in combination to improve clarity, which enhances the image quality of full-color images.

[0109] Examples of pigments used for magenta toner include the following: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; CI Pigment Violet 19; CI Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

[0110] Examples of dyes used for magenta toner include the following: Oil-soluble dyes such as CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, 27; CI Disperse Violet 1; basic dyes such as CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

[0111] Examples of pigments used for cyan toner include the following: CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; CI Bat Blue 6; CI Acid Blue 45; copper phthalocyanine pigments in which 1 to 5 phthalimidomethyl groups are substituted onto the phthalocyanine skeleton. CI Solvent Blue 70 is a dye used for cyan toner.

[0112] Examples of pigments for yellow toner include the following: CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; CI Bat Yellow 1, 3, 20. CI Solvent Yellow 162 is a dye used for yellow toner.

[0113] The colorant content is preferably 0.1 to 30.0 parts by mass, and more preferably 0.1 to 20.0 parts by mass, per 100.0 parts by mass of the binder resin. By setting the content within this range, it is possible to easily achieve the viscoelastic properties of this disclosure. When using pigments as colorants, the number-average diameter of the primary particles of the pigment is preferably 30 nm to 300 nm, and more preferably 40 nm to 200 nm. Within this range, the change in storage modulus tends to be large when measuring viscoelasticity by varying the strain. The number-average diameter of the primary particles of the pigment can be measured using known means such as a scanning electron microscope.

[0114] The toner particles may contain wax. Examples of such wax include the following: Hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; waxes mainly composed of fatty acid esters such as carnauba wax; and deoxidized fatty acid esters such as deoxidized carnauba wax, which have been partially or completely deoxidized.

[0115] Furthermore, the following can be listed: Saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinalic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; polyhydric alcohols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid with alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylenebisstearate amide, ethylenebiscaprate amide, ethylenebislaurate amide, hexamethylene Saturated fatty acid bisamides such as bis-stearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'dioleyl adipic acid amide, and N,N'dioleyl sebacinamide; aromatic bisamides such as m-xylenebis-stearamide and N,N'distearyl isophthalamide; aliphatic metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene or acrylic acid; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; methyl ester compounds having hydroxyl groups obtained by hydrogenation of vegetable oils and fats.

[0116] The wax content is preferably 2.0 to 30.0 parts by mass per 100.0 parts by mass of the binder resin.

[0117] The toner particles may contain a charge control agent as needed. The charge control agent may include public While any known material can be used, metal compounds of aromatic carboxylic acids that are colorless, have a fast toner charging speed, and can stably maintain a constant charge are particularly preferred.

[0118] Examples of negative charge control agents include salicylate metal compounds, naphthoate metal compounds, dicarboxylic acid metal compounds, polymer compounds having sulfonic acid or carboxylic acid as a side chain, polymer compounds having sulfonate salts or sulfonic acid esters as a side chain, polymer compounds having carboxylate salts or carboxylic acid esters as a side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0119] The charge control agent may be added internally or externally to the toner particles. The charge control agent content is preferably 0.2 to 10.0 parts by mass per 100.0 parts by mass of the binder resin.

[0120] Inorganic microparticles can be added to the toner as needed. These microparticles may be internally added to the toner particles or mixed with them as an external additive. In particular, internally adding them to the toner particles makes it easier to control the change in storage modulus due to the magnitude of strain, enabling a high level of simultaneous low-temperature fixation, character reproduction, and dot reproduction. Preferred inorganic fine particles to be added to the toner particles include silica, titanium dioxide, aluminum oxide, metal titanates such as strontium titanate and calcium titanate, and calcium carbonate.

[0121] The number-average diameter of the primary inorganic fine particles embedded in the toner particles is preferably 40 nm to 800 nm, more preferably 80 nm to 600 nm, even more preferably 100 nm to 500 nm, and particularly preferably 150 nm to 450 nm. Within this range, the change in storage modulus when measuring viscoelasticity with varying strain tends to be large. The number-average diameter of the primary inorganic fine particles can be measured using known means such as a scanning electron microscope.

[0122] The toner may contain external additives other than the inorganic fine particles mentioned above. For example, toner particles may be made by adding external additives. Preferred external additives are inorganic fine particles such as silica, titanium dioxide, aluminum oxide, and metal titanate salts. The inorganic fine particles used as external additives are preferably hydrophobized with a hydrophobic agent such as a silane compound, silicone oil, or a mixture thereof. As an external additive for improving liquidity, a BET specific surface area of ​​50m² is used. 2 / g~400m 2 Inorganic fine particles of / g are preferred, and for durability stabilization, a BET specific surface area of ​​10m² is desirable. 2 / g~50m 2 It is preferable that the inorganic fine particles weigh / g. To achieve both improved fluidity and stable durability, inorganic fine particles with a BET specific surface area within the above range may be used in combination. Mixing the toner particles and external additives can be done using a known mixer such as a Henschel mixer.

[0123] The total content ratio of inorganic fine particles contained in the toner particles and inorganic fine particles added externally to the toner particles is preferably 0.1% to 30.0% by mass relative to the toner particles.

[0124] Toner can be used as a one-component developer, but it is preferable to mix it with a magnetic carrier and use it as a two-component developer in order to obtain stable images over a long period of time. In other words, a two-component developer containing toner and a magnetic carrier is preferable, where the toner is the toner described above.

[0125] Examples of magnetic carriers include iron powder or iron powder with an oxidized surface; metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, their alloy particles or oxide particles; magnetic materials such as ferrite; and the magnetic material. Examples of commonly known materials include magnetic material dispersion resin carriers (so-called resin carriers) containing a binder resin that holds the magnetic material in a dispersed state. When toner is mixed with a magnetic carrier and used as a two-component developer, the toner content in the two-component developer is preferably 2% to 15% by mass, and more preferably 4% to 13% by mass.

[0126] The method for producing toner particles is not particularly limited, and conventionally known methods such as suspension polymerization, emulsification and agglutination, melt kneading, and dissolution and suspension can be employed. The following explanation will use the melt-mixing method as an example, but it is not limited to this method.

[0127] First, in the raw material mixing process, a predetermined amount of crystalline resin and amorphous resin, or a binder resin containing crystalline resin and amorphous resin, as well as other components such as wax, colorants, and charge control agents as needed, are weighed, blended, and mixed to form the materials that make up the toner particles. Examples of mixing equipment include double-con mixers, V-type mixers, drum-type mixers, super mixers, Henschel mixers, Nauta mixers, and Mechanohybrid (manufactured by Nippon Coke Industries Co., Ltd.).

[0128] Next, the mixed materials are melt-kneaded to disperse the other components in a binder resin containing crystalline and amorphous resins. In the melt-kneading process, batch-type kneaders such as pressure kneaders and Banbury mixers, or continuous kneaders can be used, and single-screw or twin-screw extruders are the mainstream due to their advantage of being able to produce continuously. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel, Ltd.), the TEM twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.), the PCM kneader (manufactured by Ikegai Iron Works, Ltd.), the twin-screw extruder (manufactured by KCK Co., Ltd.), the Co-kneader (manufactured by Buss Co., Ltd.), and the Nidex (manufactured by Nippon Coke Industries, Ltd.). Furthermore, the resin composition obtained by melt-kneading may be rolled with two rolls or the like and cooled with water in a cooling process.

[0129] By controlling the mixing temperature and screw rotation speed during the melt-mixing process, it is possible to control the dispersion state of crystalline and amorphous resins, as well as the average number diameter of domains.

[0130] Alternatively, crosslinking may be performed using a polymerization initiator while kneading a mixture of crystalline resin and uncrosslinked amorphous resin. This makes it possible to control the amount and proportion of THF-insoluble components in the binder resin while improving the dispersion state of the crystalline resin and amorphous resin.

[0131] Furthermore, effective methods for finely dispersing amorphous resin within crystalline resin include, in which a mixture of crystalline resin and uncrosslinked amorphous resin is kneaded before toner production while crosslinking the amorphous resin with a polymerization initiator, or in which a system in which crystalline resin and uncrosslinked amorphous resin are dissolved in a solvent and coexist, and a polymerization initiator is added while stirring to carry out the crosslinking reaction.

[0132] Next, the cooled resin composition is pulverized to the desired particle size in a pulverization process. In the pulverization process, the material is coarsely pulverized using a pulverizer such as a crusher, hammer mill, or feather mill, and then further finely pulverized using a fine pulverizer such as a Kryptron system (manufactured by Kawasaki Heavy Industries), Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), Turbo Mill (manufactured by Turbo Industries Co., Ltd.), or an air jet type pulverizer.

[0133] Subsequently, the toner particles can be obtained by classifying or sieving them using classifiers or sieving machines such as the inertial classifier Elbow Jet (manufactured by Nippon Steel Mining Co., Ltd.), the centrifugal classifier Turboplex (manufactured by Hosokawa Micron Corporation), the TSP separator (manufactured by Hosokawa Micron Corporation), or the Faculty (manufactured by Hosokawa Micron Corporation), as needed.

[0134] The following describes methods for measuring various physical properties of toner and raw materials. <Viscoelasticity measurement of molded samples with varying strain> The measuring device used is a rotary plate rheometer "ARES" (manufactured by TA INSTRUMENTS). The sample used for measurement is a molded sample prepared by weighing 0.1 g of toner and compressing it into a disc shape with a diameter of 8.0 mm and a thickness of 1.5 ± 0.3 mm at 10 MPa for 60 seconds using a tablet molding compressor at room temperature (25°C). The molded sample is mounted on an 8.0 mm diameter parallel plate, heated from room temperature (25°C) to 90°C in 5 minutes, held for 10 minutes, and then measurement begins. At this time, the sample is set so that the initial normal force is 0. Furthermore, as described below, the effect of the normal force can be canceled out in subsequent measurements by turning on automatic tension adjustment.

[0135] The measurement will be performed under the following conditions. (1) Use a parallel plate with a diameter of 8.0 mm. (2) Frequency: 1 Hz. (3) Measure the strain at six points: 0.1%, 1%, 5%, 10%, 50%, and 100%. The measurement will be performed using the following automatic adjustment mode settings. (4) Set the maximum torque (Max Allowed Torque) to 200.0 [g·cm] and the minimum torque (Min Allowed Torque) to 0.2 [g·cm]. (5) Set Auto Tension Direction to Compression. (6) Set the Initial Static Force to 10g and the Auto Tension Sensitivity to 10.0g. (7) The operating conditions for Auto Tension are: Sample Modulus: 1.00 × 10 6 The value must be Pa or higher.

[0136] Under the above conditions, the storage modulus G'(1) of the molded sample at a strain of 1%, the loss modulus G''(1) of the molded sample at a strain of 1%, and the storage modulus G'(50) of the molded sample at a strain of 50% are measured at a temperature of 90°C and a frequency of 1 Hz.

[0137] <Calculation of the percentage of THF-insoluble matter and incinerated ash content in toner or binder resin> 1.0 g of toner (0.7 g if measuring the THF-insoluble content and percentage of the resin alone) is weighed accurately (w1 [g]), placed in a pre-weighed cylindrical filter paper (product name: No. 86R, size 28 x 100 mm, manufactured by Advantec), and set in the Soxhlet extractor. Extraction was performed for 18 hours using 200 mL of tetrahydrofuran (THF) as the solvent, at a reflux rate such that the solvent extraction cycle occurred approximately once every 5 minutes. After extraction is complete, the cylindrical filter paper is removed and air-dried, then vacuum-dried at 40°C for 8 hours. The mass of the cylindrical filter paper containing the extraction residue is weighed, and the mass of the extraction residue (w2 [g]) is calculated by subtracting the mass of the cylindrical filter paper. Calculate w2 / w1 to determine the percentage of THF-insoluble content in the toner or binder resin.

[0138] The amount of incinerated ash w3 [g] in the THF insoluble matter is calculated as follows: Place the cylindrical filter paper containing the extraction residue described above into a pre-weighed 30 mL magnetic crucible. A magnetic crucible is placed in an electric furnace and heated at approximately 900°C for approximately 3 hours. After cooling in the electric furnace, it is allowed to cool further in a desiccator at room temperature for at least 1 hour. The mass of the crucible containing the incineration residue is weighed, and the amount of incineration ash (w3 [g]) is calculated by subtracting the mass of the cylindrical filter paper from the mass of the crucible. Then, the w3 / w2 ratio is used to calculate the percentage of insoluble THF in the incinerated ash.

[0139] <Method for measuring the acid value of crystalline and amorphous resins> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 gram of a sample. The acid value of crystalline and amorphous resins is measured according to JIS K 0070-1992, specifically following the procedure below.

[0140] (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add deionized water to make 100 mL, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 mL of water, add ethyl alcohol (95% by volume) to make 1 L. Place the solution in an alkali-resistant container, keeping it away from carbon dioxide, and let it stand for 3 days. Then filter it to obtain a potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by taking 25 mL of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0141] (2) Operation (A) Main examination Accurately weigh 2.0 g of a pulverized crystalline or amorphous resin sample into a 200 mL Erlenmeyer flask, add 100 mL of a toluene / ethanol (2:1) mixture, and dissolve over 5 hours. Then, add a few drops of the phenolphthalein solution as an indicator, and titrate with the potassium hydroxide solution. The titration endpoint is reached when the indicator turns a pale pink color for approximately 30 seconds. (B) Blank test The titration procedure is the same as described above, except that no sample is used (i.e., only a mixed solution of toluene / ethanol (2:1) is used).

[0142] (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: volume of potassium hydroxide solution added in the blank test (mL), C: volume of potassium hydroxide solution added in the main test (mL), f: factor of the potassium hydroxide solution, and S: mass of the sample (g).

[0143] <Method for measuring the hydroxyl value of crystalline and amorphous resins> The hydroxyl value is the number of milligrams of potassium hydroxide required to neutralize the acetic acid bonded to the hydroxyl group when acetylating 1 g of a sample. This hydroxyl value is measured according to JIS K 0070-1992, and specifically, the following procedure is followed.

[0144] (1) Preparation of reagents Place 25 g of special grade acetic anhydride into a 100 mL volumetric flask, add pyridine to bring the total volume to 100 mL, and shake thoroughly to obtain the acetylation reagent. Store the obtained acetylation reagent in a brown bottle, keeping it away from moisture, carbon dioxide, etc. Dissolve 1.0 g of phenolphthalein in 90 mL of ethyl alcohol (95% by volume), add deionized water to make a total volume of 100 mL, and obtain a phenolphthalein solution. Dissolve 35 g of special grade potassium hydroxide in 20 mL of water, and add ethyl alcohol (95 vol%) to make 1 L. Place in an alkali-resistant container, taking care not to come into contact with carbon dioxide, etc., and leave for 3 days. After filtration, obtain potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by taking 25 mL of 0.5 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. L-hydrochloric acid shall be prepared in accordance with JIS K 8001-1998.

[0145] (2) Operation (A) Main examination Accurately weigh 1.0 g of the pulverized crystalline or amorphous resin sample into a 200 mL round-bottom flask, and precisely add 5.0 mL of the acetylation reagent to it using a volumetric pipette. If the sample is difficult to dissolve in the acetylation reagent, add a small amount of special grade toluene to dissolve it. Place a small funnel over the mouth of the flask and immerse about 1 cm of the bottom of the flask in a glycerin bath at approximately 97°C and heat. At this time, it is preferable to cover the base of the flask's neck with a piece of cardboard with a round hole cut out to prevent the temperature of the flask's neck from rising due to the heat of the bath. After 1 hour, remove the flask from the glycerin bath and allow it to cool. After cooling, add 1 mL of water from the funnel and shake to hydrolyze the acetic anhydride. To further complete hydrolysis, heat the flask again in the glycerin bath for 10 minutes. After cooling, wash the funnel and the walls of the flask with 5 mL of ethyl alcohol. Add a few drops of the phenolphthalein solution as an indicator, and titrate with the potassium hydroxide solution. The endpoint of the titration is when the indicator remains faintly pink for approximately 30 seconds. (B) Blank test The titration procedure is the same as described above, except that a crystalline or amorphous resin sample is not used. (3) Substitute the obtained results into the following formula to calculate the hydroxyl value. A = [{(BC) × 28.05 × f} / S] + D Here, A: hydroxyl value (mgKOH / g), B: volume of potassium hydroxide solution added in the blank test (mL), C: volume of potassium hydroxide solution added in the main test (mL), f: factor of the potassium hydroxide solution, S: mass of the sample (g), and D: acid value of the sample (mgKOH / g).

[0146] <Cross-sectional observation of toner particles> First, a thin section is prepared to serve as a reference sample for the amount of the substance present. Crystalline resin is thoroughly dispersed in a visible light-curable resin (Arronix LCR series D800), and then cured by irradiation with short-wavelength light. The resulting cured material is cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin-section samples. Thin-section samples are prepared in the same manner for amorphous resins.

[0147] Furthermore, crystalline resin and amorphous resin are mixed by mass in ratios of 0 / 100, 30 / 70, 70 / 30, and 0 / 100, and then melt-kneaded to produce a compound. These are also dispersed in a visible light-curable resin, cured, and then cut to produce thin flake samples. Next, the cut samples are observed in cross-section using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX), and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen. The mapping conditions are as follows: Acceleration voltage: 200kV Electron beam irradiation size: 1.5 nm Live time limit: 600 sec Dead time: 20-30 Mapping resolution: 256×256

[0148] Based on the average spectral intensity of each element (over a 10 nm square area), the (oxygen intensity / carbon intensity) and (nitrogen intensity / carbon intensity) ratios are calculated, and a calibration curve is created for the mass ratio of crystalline resin to amorphous resin. If nitrogen atoms are present in the monomer units of the crystalline resin, the (nitrogen intensity / carbon intensity) calibration curve will be used for future quantification.

[0149] Next, we will analyze the toner sample. After thoroughly dispersing toner in a visible light-curable resin (Arronix LCR series D800), the resin is cured by irradiation with short-wavelength light. The resulting cured material is then cut using an ultramicrotome equipped with a diamond knife to prepare 250 nm thin-section samples. Next, the excised sample is observed using a transmission electron microscope (JEOL JEM-2800) (TEM-EDX). Cross-sectional images of the toner particles are obtained, and elemental mapping is performed using EDX. The elements to be mapped are carbon, oxygen, and nitrogen.

[0150] The toner particle cross-sections to be observed are selected as follows: First, the cross-sectional area of ​​the toner particle is determined from the toner particle cross-sectional image, and the diameter of a circle with an area equal to that cross-sectional area (equivalent circle diameter) is determined. Only toner particle cross-sectional images where the absolute value of the difference between this equivalent circle diameter and the weight-average particle size (D4) of the toner is 1.0 μm or less are observed.

[0151] For the observed image, the toner particle cross-section is divided into 10 nm square areas. In each area, the (oxygen element intensity / carbon element intensity) and / or (nitrogen element intensity / carbon element intensity) are calculated based on the (average) spectral intensity of each element in the 10 nm square area, and crystalline resin and amorphous resin are distinguished by comparing these values ​​with the calibration curve. If crystalline resin or amorphous resin is present in an amount of 80% by mass or more, the 10 nm square area is considered to be occupied by that crystalline resin or amorphous resin. Here, when the group of areas occupied by amorphous resin is surrounded by the group of areas of crystalline resin and exists in isolation, the area occupied by amorphous resin is identified as an amorphous domain. Also, when the group of areas of crystalline resin exists as a continuous phase, it is identified as a matrix. Because it has such a matrix and domains, it is identified that the toner particle has a domain matrix structure composed of a matrix containing crystalline resin and domains containing amorphous resin.

[0152] Subsequently, the images are binarized, and the domain particle size is measured in the toner particle cross-sectional images. The particle size is defined as the major axis of the domain. For 10 toner particle cross-sections in the toner particle cross-sectional image, the domain particle size is measured at 10 points per toner particle cross-section, and the arithmetic mean of the total 100 domain particle sizes is taken as the domain number-average diameter (μm). On the other hand, for the domain area, the total area is calculated by summing the areas of all domains present in a single toner cross-sectional image, and this is defined as S1. Ten measurements are taken for each toner sample, and the total area of ​​the 10 domains in the toner (i.e., S1 + S2... + S100) is calculated, and the arithmetic mean of these is defined as the "domain area". To determine the area of ​​the toner particle cross-section, the total cross-sectional area of ​​the toner obtained from the toner particle cross-sectional images used to determine the domain area (10 points per toner sample, and 10 toners) is calculated, and the arithmetic mean of these is taken as the "area of ​​the toner particle cross-section." Then, [domain area] / [area of ​​the toner cross-section] × 100 is taken as the ratio of the domain area to the area of ​​the toner particle cross-section (domain area ratio (%)). Image Pro PLUS (manufactured by Roper Japan Co., Ltd.) was used for binarization and area ratio calculation.

[0153] <Identification of monomer units constituting crystalline resins and amorphous resins, and method for measuring the content ratio of monomer units> Identification of monomer units constituting crystalline and amorphous resins, and measurement of the monomer unit content, 1 The procedure is performed using H-NMR under the following conditions. Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Measurement temperature: 30℃ Sample: Place 50 mg of the sample to be measured into a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve in a constant temperature bath at 40°C to prepare the sample.

[0154] obtained 1 From the H-NMR chart, select a peak from among the peaks attributed to the components of monomer unit A that is independent of the peaks attributed to the components of other monomer units, and calculate the integral value S1 of this peak. Similarly, if the resin has further monomer units X, such as monomer unit C, select a peak independent of the peaks attributed to the components of other monomer units, and calculate the integral value S2 of this peak. x Calculate.

[0155] The content ratio of monomer unit A is determined using the above integral value as follows. Note that n1, n2, n x This represents the number of hydrogen atoms in the constituent element to which the peak observed in each region belongs. Percentage of monomer unit A (mol %) = {(S1 / n1) / ((S1 / n1)+(S2 / n2)...+(S x / n x ))}×100 Similarly, the content of monomer unit B is determined as follows. Percentage of monomer unit B (mol %) = {(S2 / n2) / ((S1 / n1)+(S2 / n2)...+(S x / n x ))}×100 Similarly, if monomer unit X is present, the content ratio of monomer unit X is determined.

[0156] Furthermore, in the case of crystalline resins and amorphous resins, for example, when polymerizable monomers are used in which components other than vinyl groups do not contain hydrogen atoms, 13 The atomic nuclei to be measured using C-NMR 13 Let C be used, and the measurement will be performed in single-pulse mode. 1 The calculation is performed in the same manner as with 1H-NMR. Based on the molecular weight of the monomer unit, it is possible to convert from mol% to weight%.

[0157] <Method for measuring the weight-average molecular weight (Mw) of resins and other materials using gel permeation chromatography (GPC)> The weight-average molecular weight (Mw) of tetrahydrofuran (THF)-soluble components in resins and other materials is measured using gel permeation chromatography (GPC) as follows. First, the resin and other materials are dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. Then, the resulting solution is filtered through a solvent-resistant membrane filter, "Myshoridisk" (manufactured by Tosoh Corporation), with a pore diameter of 0.2 μm, to obtain the sample solution. The sample solution is adjusted so that the concentration of components soluble in THF is approximately 0.8% by mass. This sample solution is then used for measurement under the following conditions. Equipment: HLC8220 GPC (Detector: RI) (Manufactured by Tosoh Corporation) Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (7 columns, manufactured by Showa Denko) Eluent: Tetrahydrofuran (THF) Flow rate: 1.0mL / min Oven temperature: 40.0℃ Sample injection volume: 0.10 mL

[0158] In calculating the molecular weight of the sample, standard polystyrene resin (product name "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) is used. A molecular weight calibration curve created using "-1000, A-500" (manufactured by Tosoh Corporation) will be used.

[0159] <Method for measuring the melting point, endothermic peak, and endothermic amount of toner and resin, etc.> The melting points of toners and resins, as well as the endothermic peaks and endothermic amounts, are measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10℃ / min Measurement start temperature: 20℃ Measurement end temperature: 180℃

[0160] The temperature correction for the device's detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. Specifically, approximately 5 mg of the sample is accurately weighed, placed in an aluminum pan, and differential scanning calorimetry is performed. An empty silver pan is used as a reference. The peak temperature of the maximum endothermic peak during the first heating process is defined as the melting point. The maximum endothermic peak is the peak with the largest amount of endothermic energy when there are multiple peaks. Furthermore, the amount of endothermic energy of this maximum endothermic peak is determined. The assignment of each peak can be determined by performing DSC measurements on each individual material separated from the toner as described above.

[0161] (Measurement of BET specific surface area of ​​inorganic microparticles) The BET specific surface area of ​​inorganic fine particles will be measured in accordance with JIS Z8830 (2001). The specific measurement method is as follows: The measuring device used is the "Automatic Specific Surface Area and Pore Distribution Measurement Device TriStar3000 (manufactured by Shimadzu Corporation)," which employs a gas adsorption method based on constant volume. The setting of measurement conditions and analysis of measurement data are performed using the dedicated software "TriStar3000 Version 4.00" included with the device, and the device is connected to a vacuum pump, nitrogen gas piping, and helium gas piping. Nitrogen gas is used as the adsorption gas, and the value calculated by the BET multipoint method is used as the BET specific surface area of ​​inorganic fine particles in this disclosure. The BET specific surface area is calculated as follows. First, nitrogen gas is adsorbed onto inorganic microparticles, and the equilibrium pressure P (Pa) in the sample cell and the amount of nitrogen adsorbed by the inorganic microparticles Va (moles / g) are recorded. -1 The nitrogen adsorption amount Va (moles / g) is measured. The relative pressure Pr, which is the value obtained by dividing the equilibrium pressure P (Pa) in the sample cell by the saturated vapor pressure Po (Pa) of nitrogen, is plotted on the horizontal axis. -1 Obtain an adsorption isotherm with ) as the vertical axis. Next, the amount of adsorption required to form a monolayer on the surface of inorganic nanoparticles is the monolayer adsorption amount Vm (moles·g). -1 ) is calculated by applying the following BET formula. Pr / Va(1-Pr)=1 / (Vm×C)+(C-1)×Pr / (Vm×C) (Here, C is the BET parameter, which is a variable that varies depending on the type of sample being measured, the type of adsorbed gas, and the adsorption temperature.) The BET formula can be interpreted as a straight line with a slope of (C-1) / (Vm×C) and an intercept of 1 / (Vm×C), where the X-axis is Pr and the Y-axis is Pr / Va(1-Pr) (this straight line is called a BET plot). The slope of a straight line = (C-1) / (Vm×C) Intercept of a line = 1 / (Vm × C) By plotting the measured values ​​of Pr and Pr / Va(1-Pr) on a graph and drawing a straight line using the least squares method, the slope and intercept of that line can be calculated. Solving the simultaneous equations for the slope and intercept using these values ​​allows us to calculate Vm and C. Furthermore, the Vm calculated therein and the molecular occupied cross-section of the nitrogen molecule (0.162 nm) 2From the following formula, the BET specific surface area S (m 2 / g) of the inorganic fine particles is calculated. S = Vm × N × 0.162 × 10 -18 (Here, N is Avogadro's number (mol -1 ).)

[0162] The measurement using this apparatus follows the "TriStar3000 Instruction Manual V4.0 " attached to the apparatus. Specifically, the measurement is performed according to the following procedure. The tare of a dedicated glass sample cell (stem diameter 3 / 8 inch, volume approximately 5 ml) that had been thoroughly cleaned and dried was precisely weighed. Then, using a funnel, approximately 0.1 g of inorganic fine particles was placed into this sample cell. The sample cell containing the inorganic fine particles was set in a "pretreatment apparatus, Vacuprep 061 (manufactured by Shimadzu Corporation)" connected to a vacuum pump and a nitrogen gas pipe, and vacuum degassing was continued at 23°C for approximately 10 hours. When performing vacuum degassing, gradually degas while adjusting the valve so that the inorganic fine particles are not sucked into the vacuum pump. The pressure inside the cell gradually decreases during degassing and finally reaches approximately 0.4 Pa (approximately 3 millitorr). After the completion of vacuum degassing, nitrogen gas was gradually injected to return the inside of the sample cell to atmospheric pressure, and the sample cell was removed from the pretreatment apparatus. Then, the mass of this sample cell was precisely weighed, and the exact mass of the inorganic fine particles was calculated from the difference from the tare. At this time, during weighing, cover the sample cell with a rubber stopper so that the inorganic fine particles inside the sample cell are not contaminated by moisture in the air, etc. Next, a dedicated "isothermal jacket" was attached to the stem part of the sample cell containing the inorganic fine particles. Then, a dedicated filler rod was inserted into this sample cell, and the sample cell was set in the analysis port of the apparatus. The isothermal jacket is a cylindrical member composed of a porous material on the inner surface and an impermeable material on the outer surface, which can suck up liquid nitrogen to a certain level by capillary action. Subsequently, the free space of the sample cell including the connection device is measured. The free space is calculated by measuring the volume of the sample cell using helium gas at 23°C, and then measuring the volume of the sample cell after cooling it with liquid nitrogen using helium gas in the same manner, and converting it from the difference between these volumes. In addition, the saturated vapor pressure Po (Pa) of nitrogen is automatically measured separately using the Po tube built into the device. Next, after performing vacuum degassing in the sample cell, the sample cell is cooled with liquid nitrogen while continuing the vacuum degassing. Then, nitrogen gas is introduced into the sample cell step by step to adsorb nitrogen molecules onto the inorganic fine particles. At this time, the adsorption isotherm is obtained by measuring the equilibrium pressure P (Pa) at any time, and this adsorption isotherm is converted into a BET plot. Note that the points of the relative pressure Pr for collecting data are set to a total of 6 points of 0.05, 0.10, 0.15, 0.20, 0.25, and 0.30. A straight line is drawn for the obtained measurement data by the least squares method, and Vm is calculated from the slope and intercept of the straight line. Furthermore, using this value of Vm, the BET specific surface area of the inorganic fine particles is calculated as described above.

[0163] <Method for Measuring the Number-Average Diameter of Primary Particles of Inorganic Fine Particles and Pigments> The measurement of the number-average diameter of primary particles of inorganic fine particles and pigments is carried out by combining a scanning electron microscope "S-4800" (trade name; manufactured by Hitachi, Ltd.) and elemental analysis by energy-dispersive X-ray spectroscopy (EDS). Observe the toner containing inorganic fine particles and pigments, and take pictures of the inorganic fine particles and pigments in a field of view magnified up to 200,000 times. From the taken images, select the inorganic fine particles and pigments, randomly measure the major diameters of 100 primary particles of the inorganic fine particles and pigments respectively, and obtain the number-average diameters of the inorganic fine particles and pigments. The observation magnification is appropriately adjusted according to the sizes of the inorganic fine particles and pigments.

[0164] <Method for Measuring the Weight-Average Particle Size (D4) of Toner (Particles)> The weight-average particle size (D4) of toner (particles) is measured using the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method with a 100 μm aperture tube, and the accompanying dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data, with an effective measurement channel count of 25,000. The measurement data is then analyzed and calculated. The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of approximately A device that achieves a 1% mass value, such as the "ISOTON II" (manufactured by Beckman Coulter), can be used. Before performing measurements and analysis, configure the dedicated software as follows.

[0165] In the dedicated software's "Change Standard Measurement Method (SOM)" screen, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the Threshold / Noise Level measurement button to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the "Flush Aperture Tube After Measurement" option. In the dedicated software's "Pulse to Particle Size Conversion Settings" screen, set the bottle spacing to logarithmic particle size, the particle size bottle to 256 particle size bottle, and the particle size range to 2 μm or more and 60 μm or less. The specific measurement method is as follows.

[0166] (1) Place approximately 200 mL of electrolytic solution into a 250 mL round-bottom glass beaker specifically designed for the Multisizer 3, set it on the sample stand, and stir the mixture with the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Tube Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tubes. (2) Place approximately 30 mL of the electrolytic aqueous solution into a 100 mL flat-bottomed glass beaker, and add approximately 0.3 mL of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted three times by mass with deionized water as a dispersant. (3) Two oscillators with an oscillation frequency of 50 kHz are built in with a phase difference of 180 degrees, and a predetermined amount of deionized water is placed in the water tank of an ultrasonic dispersion device called "Ultrasonic Dispersion System Tetora150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120 W, and approximately 2 mL of Contaminon N is added to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add approximately 10 mg of toner (particles) to the electrolytic aqueous solution in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank as appropriate so that it is between 10°C and 40°C. (6) Using a pipette, the electrolytic aqueous solution from (5) containing dispersed toner (particles) is dropped into the round-bottom beaker from (1) placed in the sample stand, and the concentration is adjusted to approximately 5%. The measurement is then continued until the number of particles to be measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device, and the weight-average particle size (D4) is calculated. Note that the "Average Diameter" on the Analysis / Volume Statistics (Arithmetic Mean) screen when the dedicated software is set to Graph / Volume % is the weight-average particle size (D4). [Examples]

[0167] This disclosure will be specifically illustrated by the following embodiments. However, these embodiments are not intended to limit this disclosure in any way. Unless otherwise specified, all "parts" in the following formulations refer to mass. Note that Example 34 below is considered Reference Example 34.

[0168] <Example of manufacturing crystalline resin 1> • Solvent: Toluene 100.0 parts • Monomer composition 100.0 parts (The monomer composition is a mixture of behenyl acrylate, acrylonitrile, acrylic acid, and styrene in the proportions shown below.) Behenyl acrylate 50.0 parts 30.0 parts styrene Acrylonitrile 15.0 parts 2-hydroxyethyl acrylate 5.0 parts • Polymerization initiator 0.5 part [t-butyl peroxypivalate (manufactured by NOF Corporation: Perbutyl PV)]

[0169] The above materials were placed in a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. The reaction vessel was heated to 70°C while stirring at 200 rpm, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the monomer composition polymer was dissolved in toluene. Subsequently, the solution was cooled to 25°C, and then added to 1000.0 parts methanol while stirring to precipitate the methanol-insoluble components. The obtained methanol-insoluble components were filtered off, washed with methanol, and then vacuum-dried at 40°C for 24 hours to obtain the first resin 1 (crystalline resin 1). The physical properties are shown in Table 2.

[0170] <Manufacturing examples of crystalline resins 2-12, 14-16> In the example of producing crystalline resin 1, the reaction was carried out in the same manner except that the monomers and parts by mass were changed as shown in Table 1, to obtain crystalline resins 2-12 and crystalline resins 14-16. The physical properties are shown in Table 2. [Table 1]

[0171] The abbreviations in Table 1 are as follows: BEA: Behenyl Acrylate STA: Stearyl acrylate MYA: Myricyl Acrylate HDA: Hexadecyl acrylate St: Styrene ACN: Acrylonitrile MCN: Methacrylonitrile HEA: 2-Hydroxyethyl acrylate HPA: 2-Hydroxypropyl acrylate HEMA: 2-Hydroxyethyl methacrylate HPMA: 2-Hydroxypropyl methacrylate HEAA: 2-Hydroxyethyl acrylamide AA: Acrylic acid HDDA: 1,6-Hexanediol diacrylate

[0172] <Production Example of Crystalline Resin 13> · 33.9 parts of 1,10-decanediol (100.0 mol% based on the total molar amount of polyhydric alcohol) · 66.1 parts of dodecanedioic acid (100.0 mol% based on the total molar amount of polyvalent carboxylic acid) · 0.5 part of tin 2-ethylhexanoate The above materials were weighed into a reaction vessel equipped with a condenser, a stirrer, a nitrogen inlet tube, and a thermocouple. After replacing the inside of the flask with nitrogen gas, the temperature was gradually increased with stirring, and the reaction was carried out for 3 hours while stirring at a temperature of 140 °C. Next, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 200 °C. Thereafter, the pressure in the reaction vessel was reduced to 5 kPa or less and the reaction was carried out at 200 °C for 3 hours to obtain Crystalline Resin 13. The physical properties are shown in Table 2. [Table 2] In the table, AV represents the acid value, OHV represents the hydroxyl value, T p represents the peak temperature of the endothermic peak corresponding to the crystalline resin, Mw represents the weight average molecular weight, and the THF insoluble content represents the content ratio of the tetrahydrofuran insoluble content of the crystalline resin.

[0173] <Production Example of Amorphous Resin 1> The following materials were added to a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet tube under a nitrogen atmosphere. • Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 71.4 parts by mass (100.0 mol% of the total number of moles of polyhydric alcohols) • Terephthalic acid: 14.7 parts by mass (50.0 mol% of the total number of moles of polycarboxylic acids) • Adipic acid: 5.2 parts by mass (20.0 mol% of the total number of moles of polycarboxylic acids) • Fumaric acid: 4.1 parts by mass (20.0 mol% relative to the total number of moles of polycarboxylic acids) Dodecenyl succinic anhydride: 4.7 parts by mass (10.0 mol% relative to the total number of moles of polycarboxylic acid) Titanium tetrabutoxide: 2.0 parts by mass Next, the flask was purged with nitrogen gas, and the temperature was gradually increased while stirring. The mixture was then stirred at 200°C and allowed to react for 2 hours while distilling off the water produced. Furthermore, the pressure in the reaction vessel was reduced to 8.3 kPa and maintained for 1 hour, after which it was cooled to 180°C and returned to atmospheric pressure (first reaction step). • Trimellitus anhydride: 8.2 parts by mass (0.02 moles; 5.0 mol% of the total number of moles of polycarboxylic acids) • tert-butylcatechol (polymerization inhibitor): 0.1 parts by mass Subsequently, the above materials were added, the pressure in the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining the temperature at 150°C. The reaction was then stopped by lowering the temperature (second reaction step), and the second resin 1 was obtained. The physical properties are shown in Table 4.

[0174] <Manufacturing examples of amorphous resins 2-6> In the example of the production of amorphous resin 1, the reaction was carried out in the same manner except that the monomers and parts by mass were changed as shown in Table 3, to obtain amorphous resins 2 to 6. The physical properties are shown in Table 4. [Table 3]

[0175] The abbreviations in Table 3 are as follows: BPO-EO: Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane TPA: Terephthalic acid FA: Fumaric acid AA: Adipic acid DSA: Dodecenyl succinic anhydride

[0176] <Example of manufacturing amorphous resin 7> 50.0 parts by mass of xylene were placed in an autoclave, and after purging with nitrogen, the temperature was raised to 185°C under stirring and in a sealed state. A mixed solution of 70.0 parts by mass of styrene, 20.0 parts by mass of n-butyl acrylate, 3.0 parts by mass of methyl methacrylate, 5.0 parts by mass of acrylic acid, 2.0 parts by mass of divinylbenzene, 1.0 part of di-tert-butyl peroxide, and 20.0 parts of xylene was added dropwise continuously for 3 hours while controlling the autoclave temperature to 190°C, and polymerization was carried out. The temperature was then maintained at the same temperature for another hour to complete polymerization, and the solvent was removed to obtain amorphous resin 7. The physical properties are shown in Table 4.

[0177] <Example of manufacturing amorphous resin 8> 50.0 parts by mass of xylene were placed in an autoclave, and after purging with nitrogen, the temperature was raised to 185°C under stirring and in a sealed state. A mixed solution of 30.0 parts by mass of styrene, 40.0 parts by mass of n-butyl acrylate, 23.0 parts by mass of stearyl acrylate, 5.0 parts by mass of acrylic acid, 2.0 parts by mass of divinylbenzene, 1.0 part of di-tert-butyl peroxide, and 20.0 parts of xylene was added dropwise continuously for 3 hours while controlling the autoclave temperature to 190°C, and polymerization was carried out. The temperature was then maintained at the same temperature for another hour to complete polymerization, and the solvent was removed to obtain amorphous resin 8. The physical properties are shown in Table 4. [Table 4] In the table, AV represents the acid value, OHV represents the hydroxyl value, and Mw represents the weight-average molecular weight.

[0178] <Example of manufacturing of binder resin 1> In a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet, 140 parts of amorphous resin and 160 parts of crystalline resin were mixed and homogenized at 170°C. Then, 2 parts of di-t-butyl peroxide were added and the reaction was carried out at 170°C for 1 hour. After that, the reaction was carried out at 170°C under reduced pressure of 1.0 kPa for 2 hours to remove decomposition products by the initiator. The resulting mixture was cooled to obtain binder resin 1.

[0179] <Manufacturing examples of binder resins 2-22> In the example of the production of binder resin 1, the reaction was carried out in the same manner except that the types and mass parts of the amorphous resin and crystalline resin were changed as shown in Table 5, and binder resins 2 to 22 were obtained. [Table 5]

[0180] <Example of manufacturing inorganic fine particles 1> A double-tube hydrocarbon-oxygen mixed burner capable of forming both an inner and outer flame was used as the combustion furnace. A two-fluid nozzle for slurry injection was mounted in the center of the burner, and the silicon compound raw material was introduced. A combustible hydrocarbon-oxygen gas was injected from around the two-fluid nozzle to form an inner flame and an outer flame, creating a reducing atmosphere. The atmosphere, temperature, and flame length were adjusted by controlling the amount and flow rate of flammable gas and oxygen. Silica nanoparticles were formed from the silicon compound in the flame and further fused until the desired particle size was achieved. After cooling, the silica nanoparticles were collected using a bag filter or the like. Hexamethylcyclotrisiloxane was used as the raw material silicon compound to produce the silica nanoparticles. Next, 100 parts of the obtained silica nanoparticles were surface-treated with 4 parts of hexamethyldisilazane to obtain inorganic nanoparticles 1, which had a primary particle number average diameter of 100 nm.

[0181] <Examples of manufacturing inorganic fine particles 4-5> In the example of producing inorganic fine particles 1, the number-average diameter of primary particles was adjusted by controlling the amount and flow rate of flammable gas and oxygen to obtain inorganic fine particles 4 and 5.

[0182] <Example of manufacturing inorganic fine particles 2> A 200 mL solution of 50% ethanol / water was cooled to -20°C to 10°C, and 160 g of Ca(OH)2 was added to form a slurry. While vigorously stirring, a mixed gas of 30% carbon dioxide / nitrogen gas was introduced from the bottom of the container at a flow rate of 500 mL / min to 5000 mL / min, and the reaction was continued until the pH of the slurry began to decrease. At this time, the reaction temperature and the rate of introduction of carbon dioxide gas were adjusted so that the number average diameter of the primary particles was 200 nm, and a synthetic calcium carbonate slurry was obtained. Furthermore, this dispersion was filtered while still at a low temperature, thoroughly washed with pure water, and dried to obtain synthetic calcium carbonate. Water adjusted to 70°C to a solid content of 10% by mass was added to the obtained synthetic calcium carbonate, and a slurry was formed using a stirring disperser. 1 kg of this synthetic calcium carbonate slurry was stirred in the disperser, and 1.0 g of saponified stearic acid was added. After stirring for 20 minutes, the slurry was pressed and dehydrated. At this time, the amount of fatty acid added and the stirring time were varied to obtain hydrophobized calcium carbonate slurries with different fatty acid treatment amounts and distributions. After drying the obtained dehydrated cake, it was crushed and powdered to obtain approximately 100 g of calcium carbonate with a fatty acid hydrophobized surface treatment as inorganic fine particles 2.

[0183] <Example of manufacturing inorganic fine particles 3> In the example of producing inorganic fine particles 2, inorganic fine particles 3 were obtained by the same method except that the reaction temperature and the rate of carbon dioxide introduction were changed.

[0184] <Example of toner particle 1 manufacturing> • Binding resin 1 80 parts by mass • Hydrocarbon wax (manufactured by the Fischer-Tropsch process with a melting point of 90°C) 5 parts by mass • Coloring agent (cyan pigment, manufactured by Dainichi Seika: Pigment Blue 15:3) 5 parts by mass • Inorganic fine particles 1 (silica fine particles shown in Table 5) 10 parts by mass

[0185] The above materials were mixed using a Henschel mixer (FM-75 model, manufactured by Nippon Coke Industries Co., Ltd.) at a rotation speed of 20 seconds.-1 The mixture was mixed for a rotation time of 3 minutes. It was kneaded in a twin-screw mixer (PCM-30 model, manufactured by Ikegai Co., Ltd.) set to a temperature of 120°C, with a screw rotation speed of 250 rpm and a discharge temperature of 110°C. The resulting mixture was cooled and coarsely ground to less than 1 mm in a hammer mill to obtain coarse material. The obtained coarse material was then ground in a mechanical grinder (T-250, Freund Turbo Co., Ltd.) It was finely ground using a (manufacturing) process. Furthermore, classification was performed using a Faculty F-300 (manufactured by Hosokawa Micron Corporation) to obtain toner particles 1a with a weight-average particle size of approximately 6.0 μm. The operating conditions were a classification rotor rotation speed of 130 s. -1 , the distributed rotor rotation speed is 120s -1 That's what I decided.

[0186] <Manufacturing example of toner particles 2-44> In the example of manufacturing toner particle 1, the manufacturing process was carried out in the same manner as in Tables 6-1, 6-2, 7, and 8, except that the types and quantities of the binder resin, crystalline resin, amorphous resin, inorganic fine particles, and colorant used were changed. Toner particles 2 to 44 were obtained. [Table 6-1] In the table, C / H indicates the proportion of crystalline resin in the binder resin. [Table 6-2] [Table 7] [Table 8]

[0187] <Example of Toner 1 manufacturing> • Toner particles 1 100 copies ·Inorganic fine particles 1 3 parts The above ingredients were mixed in a Henschel FM-10C mixer (manufactured by Mitsui Miike Chemical Machinery) at a rotation speed of 50 seconds. -1The mixture was then mixed for a rotation time of 10 minutes to obtain toner 1. The physical properties of toner 1 are shown in Table 9.

[0188] <Manufacturing examples for toners 2-44> In the example of manufacturing toner 1, the toner particles used as materials were designated as toner particles 2 to 44, and the type and mass of inorganic fine particles were as described in the "External Additive Formulation" section of Table 6-2. The same manufacturing procedure was followed to obtain toners 2 to 44. The physical properties of the obtained toners 2 to 44 are shown in Table 9. [Table 9] In the table, THF-insoluble content indicates the proportion of tetrahydrofuran-insoluble content in the toner, and incineration ash content indicates the proportion of incineration ash content of tetrahydrofuran-insoluble content in the toner. Furthermore, no domains containing amorphous resin were observed in the cross-sectional observation of toner 44.

[0189] <Manufacturing example of magnetic carrier 1> • Number-average particle size 0.30 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite 1 ( / kg) • Number-average particle size 0.50 μm, magnetization strength 65 Am under a magnetic field of (1000 / 4π (kA / m)) 2 Magnetite 2 ( / kg) To each of the above materials, 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) was added, and the mixture was rapidly mixed and stirred in a container at over 100°C to treat the respective fine particles.

[0190] • Phenolic: 10% by mass Formaldehyde solution: 6% by mass (40% formaldehyde by mass, 10% methanol by mass, 50% water by mass) • Magnetite treated with the above silane compound 1:58 mass% • Magnetite treated with the above silane compound: 2:26% by mass 100 parts of the above material, 5 parts of a 28% by mass aqueous ammonia solution, and 20 parts of water were placed in a flask. The mixture was stirred and heated to 85°C for 30 minutes and maintained there, and the polymerization reaction was carried out for 3 hours to cure the resulting phenolic resin. After that, the cured phenolic resin was cooled to 30°C, water was added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Next, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60°C to obtain spherical magnetic carrier 1 in the form of a dispersed magnetic material. The volume-based 50% particle size (D50) of magnetic carrier 1 was 34.2 μm.

[0191] <Example of manufacturing a two-component developer 1> 92.0 parts of magnetic carrier 1 were mixed with 8.0 parts of toner 1 using a V-type mixer (V-20, manufactured by Seishin Corporation) to obtain a two-component developer 1.

[0192] <Manufacturing examples of two-component developers 2-44> In the example of manufacturing two-component developer 1, the manufacturing process was carried out in the same manner except that the toner was changed as shown in Table 10, and two-component developers 2 to 44 were obtained. [Table 10]

[0193] <Example 1> The evaluation was performed using the two-component developer 1 described above. A modified Canon imageRUNNER ADVANCE C7770 digital commercial printer was used as the image forming apparatus, and the two-component developer 1 was placed in the cyan developer unit. The modifications to the apparatus included allowing free setting of the fixing temperature, process speed, DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power. For image output evaluation, a solid fill image (FFh image) with the desired image ratio was output, and the VDC, VD, and laser power were adjusted so that the amount of toner on the FFh image on the paper was as desired, and the evaluation described below was performed. FFh is a hexadecimal value representing 256 gradations, where 00h is the first gradation (white area) of the 256 gradations, and FFh is the 256th gradation (solid area). The evaluation was performed based on the following evaluation method, and the results are shown in Table 11.

[0194] <Low temperature retention> ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner amount on paper: 0.70 mg / cm² 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) • Evaluation image: Place a 2cm x 15cm image in the center of the A4 paper shown above. • Test environment: Low temperature and low humidity environment: Temperature 15°C / Humidity 10%RH (hereinafter referred to as "L / L") Fixing temperature: 100℃ Process speed: 300 mm / sec

[0195] The above evaluation images were output, and the low-temperature fixability was evaluated. The image density reduction rate was used as the evaluation index for low-temperature fixability. The image density reduction rate was measured using an X-Rite color reflectance densitometer (500 series: manufactured by X-Rite). First, the image density of the central part was measured. Next, 4.9 kPa (50 g / cm³) was applied to the area where the image density was measured. 2 The image was rubbed (10 times back and forth) with a load of ) using Silbon paper, and the image density was measured again. Then, the rate of decrease in image density before and after friction was calculated using the following formula. The obtained rate of decrease in image density was evaluated according to the evaluation criteria below. Image density reduction rate = (Image density before friction - Image density after friction) / (Image density before friction) × 100 (Evaluation Criteria) A: Image density reduction rate less than 2.0% B: Image density reduction rate of 2.0% or more and less than 5.0% C: Image density reduction rate of 5.0% or more and less than 10.0% D: Image density decrease rate of 10.0% or more

[0196] <Hot offset resistance> ·Paper:CS-064(64.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Toner amount on paper: 0.08 mg / cm² 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 2cm x 20cm image is placed on the long edge of the A4 paper in the direction of paper feeding, with a 2mm margin from the leading edge of the paper. • Test environment: Normal temperature and low humidity environment: Temperature 23°C / Humidity 5%RH (hereinafter referred to as "N / L") • Fixing temperature: Increase temperature in 5°C increments starting from 100°C. Process speed: 300 mm / sec The above evaluation image was output, and the hot offset resistance was evaluated at the highest fixing temperature at which no hot offset occurred, according to the following criteria. (Evaluation Criteria) A: Above 140℃ B: 120℃ or higher, but less than 140℃ C: 100℃ or higher, less than 120℃ D: Below 100℃

[0197] <Character reproducibility> ·Paper: GFC-081 (81.0g / m 2 ) (Sold by Canon Marketing Japan Inc.) • Amount of toner on paper: 0.40 mg / cm² 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) • Test environment: Temperature 23℃ / Humidity 50%RH Fixing temperature: 100℃ Process speed: 300 mm / sec

[0198] Under the above conditions, the following evaluation images were output. An image was output with a 5 mm margin at the front and rear and a 5 mm margin on the left and right, in which 100 (10 × 10) Chinese characters "電" (6 points, Ming typeface) were arranged at intervals of 10 mm. Then, the 100 "電" characters were observed with a magnifying glass, the number of characters with chips was counted, and the character reproducibility was determined according to the following criteria. A. The number of character chips is less than 3. B. The number of character chips is 3 or more and less than 6. C. The number of character chips is 6 or more and less than 10. D. The number of character chips is 10 or more.

[0199] <Dot reproducibility> · Paper: GFC-081 (81.0 g / m 2 ) (Sold by Canon Marketing Japan Inc.) · Toner loading amount on paper: 0.40 mg / cm 2 (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power) · Test environment: Temperature 23°C / Humidity 50%RH · Fixing temperature: 100°C · Process speed: 300 mm / sec

[0200] Under the above conditions, the following evaluation images were output. A halftone image formed by isolated dots was output with a 5 mm margin at the front and rear and a 5 mm margin on the left and right (dot printing rate 10%). Using a magnifying glass, 100 isolated dots in the image were randomly observed, the minor diameter and major diameter of each dot were measured, and the ratio of the major diameter to the minor diameter (value obtained by dividing the major diameter by the minor diameter) was determined. Then, using the maximum value of the ratio of the major diameter to the minor diameter among the 100 isolated dots, the dot reproducibility was determined according to the following criteria. A. The maximum value of the ratio of the major diameter to the minor diameter is less than 1.10. B. The maximum value of the ratio of the major diameter to the minor diameter is 1.10 or more and less than 1.20. C. The maximum value of the ratio of the major diameter to the minor diameter is 1.20 or more and less than 1.30. D. The maximum ratio of the major axis to the minor axis is 1.30 or greater.

[0201] <Charging properties (static retention) under high temperature and high humidity environments> The amount of triboelectric charge on toner was calculated by collecting toner on an electrostatic latent image carrier using a metal cylindrical tube and a cylindrical filter. Specifically, the amount of triboelectric charge on the toner on the electrostatic latent image carrier was measured using a Faraday cage. A Faraday cage is a coaxial double cylinder with the inner and outer cylinders insulated. If a charged object with charge Q is placed inside the inner cylinder, electrostatic induction makes it as if a metal cylinder with charge Q were present. This induced charge was measured using an electrometer (Kessley 6517A, manufactured by Kessley), and the amount of charge Q (mC) divided by the toner mass M (kg) in the inner cylinder (Q / M) was defined as the amount of triboelectric charge on the toner. The amount of triboelectric charge on toner (mC / kg) = Q / M

[0202] First, an evaluation image used for hot offset resistance was formed on the electrostatic latent image carrier. Before it was transferred to the intermediate transfer medium, the rotation of the electrostatic latent image carrier was stopped, and the toner on the electrostatic latent image carrier was collected by suction using a metal cylindrical tube and cylindrical filter, and the [initial Q / M] was measured. Subsequently, the developer was left inside the evaluation machine for two weeks in a high temperature and high humidity (H / H) environment (32°C, 80%RH). After that, the same procedure as before was performed, and the charge amount Q / M (mC / kg) per unit mass on the electrostatic latent image carrier after standing was measured. The Q / M per unit mass on the electrostatic latent image carrier before standing was defined as the [initial Q / M], and the Q / M per unit mass on the electrostatic latent image carrier after standing was defined as the [Q / M after standing]. The charge retention rate was calculated as ([Q / M after standing] / [initial Q / M] × 100), and judged according to the following criteria. (Evaluation Criteria) A: Maintenance rate of 85% or higher B: Maintenance rate is 80% or more but less than 85% C: Maintenance rate is between 70% and 80% D: Maintenance rate less than 70%

[0203] <Storability> 5g of toner was placed in a 100mL plastic cup and left in a temperature and humidity-controlled constant temperature bath (50°C, 54%) for 72 hours. After the period, the toner's cohesiveness was evaluated. Cohesiveness was evaluated using a Hosokawa Micron PT-X powder tester, sifted through a 150μm mesh with a 0.5mm amplitude for 10 seconds. The remaining toner percentage was used as the evaluation index. A score of C or higher was considered good. (Evaluation Criteria) A: Survival rate less than 2.0% B: Survival rate between 2.0% and less than 5.0% C: Survival rate between 5.0% and less than 10.0% D: Survival rate 10.0% or more

[0204] <Examples 2 to 35, and Comparative Examples 1 to 9> The evaluation was carried out in the same manner as in Example 1, except that two-component developers 2 to 44 were used instead of two-component developer 1. The evaluation results are shown in Table 11. [Table 11]

Claims

1. A toner having toner particles containing a binder resin, The binder resin contains an amorphous polyester resin and a crystalline resin. In a viscoelasticity measurement performed on a molded sample obtained by compressing the toner into a disc shape, while varying the strain of the molded sample at 90°C, The storage modulus G'(1) of the molded sample at a strain of 1% is 10,000 Pa to 30,000 Pa. The storage modulus G'(50) of the molded sample at a strain of 50% is 950 Pa to 5500 Pa. A toner characterized in that the content of tetrahydrofuran-insoluble components is 12% by mass to 60% by mass, based on the mass of the toner.

2. The toner according to claim 1, wherein the proportion of incinerated ash in the tetrahydrofuran-insoluble portion of the toner is 5% by mass to 30% by mass, based on the mass of the toner.

3. A toner having toner particles containing a binder resin, The binder resin contains an amorphous polyester resin and a crystalline resin. In a viscoelasticity measurement performed on a molded sample obtained by compressing the toner into a disc shape, while varying the strain of the molded sample at 90°C, The storage modulus G'(1) of the molded sample at a strain of 1% is 10,000 Pa to 30,000 Pa. The storage modulus G'(50) of the molded sample at a strain of 50% is 950 Pa to 5500 Pa. A toner characterized in that the proportion of incinerated ash in the tetrahydrofuran-insoluble portion of the toner is 5% to 30% by mass, based on the mass of the toner.

4. In differential scanning calorimetry using the toner as a sample, During the first heating cycle, the peak temperature of the endothermic peak corresponding to the crystalline resin is 50°C to 70°C, and the amount of heat absorbed by the endothermic peak ΔH (J / g) is, ΔH≧5 A toner according to any one of claims 1 to 3, which satisfies the requirements.

5. A toner having toner particles containing a binder resin, The binder resin contains an amorphous polyester resin and a crystalline resin. In a viscoelasticity measurement performed on a molded sample obtained by compressing the toner into a disc shape, while varying the strain of the molded sample at 90°C, The storage modulus G'(1) of the molded sample at a strain of 1% is 10,000 Pa to 30,000 Pa. The storage modulus G'(50) of the molded sample at a strain of 50% is 950 Pa to 5500 Pa. In differential scanning calorimetry using the toner as a sample, During the first heating cycle, the peak temperature of the endothermic peak corresponding to the crystalline resin is 50°C to 70°C, and the amount of heat absorbed at the endothermic peak ΔH (J / g) is, ΔH≧5 A toner characterized by satisfying the following conditions.

6. In cross-sectional observation of the toner particles using a transmission electron microscope, The toner according to any one of claims 1 to 5, having a domain matrix structure composed of a matrix containing the crystalline resin and domains containing the amorphous polyester resin.

7. A toner having toner particles containing a binder resin, The binder resin contains an amorphous polyester resin and a crystalline resin. In a viscoelasticity measurement performed on a molded sample obtained by compressing the toner into a disc shape, while varying the strain of the molded sample at 90°C, The storage modulus G'(1) of the molded sample at a strain of 1% is 10,000 Pa to 30,000 Pa. The storage modulus G'(50) of the molded sample at a strain of 50% is 950 Pa to 5500 Pa. In cross-sectional observation of the toner particles using a transmission electron microscope, A toner characterized by having a domain matrix structure composed of a matrix containing the crystalline resin and domains containing the amorphous polyester resin.

8. The toner according to any one of claims 1 to 7, wherein the amorphous polyester resin contains monomer units of alkenyl succinic acid.

9. In viscoelasticity measurements performed at 90°C, where the strain of the molded sample is varied, The above G'(1) and the loss modulus of elasticity G''(1) of the molded sample at a strain of 1% are, G'(1)>G"(1) A toner according to any one of claims 1 to 8, which satisfies the requirements.

10. The toner according to any one of claims 1 to 9, wherein G'(50) is 1500 Pa to 4800 Pa.

11. The toner according to any one of claims 1 to 10, wherein the crystalline resin is a crystalline polyester resin or a crystalline vinyl resin.

12. A two-component developer containing toner and a magnetic carrier, A two-component developer wherein the toner is the toner described in any one of claims 1 to 11.

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