Toner

Abstract

This invention relates to toners. A toner comprises toner particles containing a binder resin, wherein the binder resin comprises a first resin and a second resin, the first resin being a crystalline resin and the second resin being a non-crystalline resin, and in cross-sectional observations of 100 toner particles using a transmission electron microscope, (i) when the area ratio A (area %) represents the proportion of the area occupied by the first resin in the cross-section of each toner particle, the average value of the area ratio A is 30 to 75 area %, and (ii) when X represents the number of cross-sections of toner particles with an area ratio A of 90 area % or more and Z represents the total number of cross-sections of the observed toner particles, the value of X / Z is 0.15 or more.

Description

Technical Field

[0001] This disclosure relates to toners for use in electrophotographic systems, electrostatic recording systems, electrostatic printing systems, and toner spraying systems. Background Technology

[0002] In recent years, with the surge in the use of full-color electrophotographic copiers, the demand for higher printer speeds and greater energy savings has also increased. To achieve high-speed printing, techniques for faster toner melting during the fixing step have been investigated. Techniques for reducing various control times during and between jobs to improve productivity have also been studied. As an energy-saving strategy, techniques for fixing the toner at lower temperatures to reduce energy consumption during the fixing step have been investigated.

[0003] It is known that using a crystalline resin with rapid melting properties as the main component of a toner achieves superior low-temperature fixing properties compared to toners with a non-crystalline resin as the main component. A toner in which a crystalline polyester or crystalline vinyl resin is used as the resin with rapid melting properties has been proposed.

[0004] For example, Japanese Patent Application Publication No. 2014-130243 discloses a toner that simultaneously achieves both low-temperature fixing and heat-resistant storage stability by using a side-chain crystalline acrylate resin. The toner disclosed in this document can simultaneously achieve both low-temperature fixing and heat-resistant storage stability.

[0005] However, it was found that the viscosity of the toner used as a binder resin in the high-temperature region was too low, resulting in heat contamination and encapsulation, and a narrow temperature range for fixing.

[0006] As a result, the addition of non-crystalline resins to crystalline resins to increase the viscosity of the molten toner has been studied. For example, Japanese Patent Application Publication No. 2014-142632 discloses a toner obtained using a binder resin comprising both crystalline vinyl resins and non-crystalline resins. Summary of the Invention

[0007] The toner disclosed in Japanese Patent Application Publication No. 2014-142632 can ensure a certain fixing temperature range, but it has been found that further improvements are needed in areas such as image durability. This disclosure proposes a toner that exhibits both low-temperature fixing properties and heat-resistant staining during high-speed printing, and also demonstrates good image durability.

[0008] A toner comprising toner particles containing a binder resin, wherein

[0009] The adhesive resin comprises a first resin and a second resin.

[0010] The first resin is a crystalline resin.

[0011] The second resin is a non-crystalline resin, and

[0012] In cross-sectional observations of 100 toner particles using a transmission electron microscope,

[0013] (i) When area ratio A (area %) represents the proportion of the area occupied by the first resin in the cross-section of each toner particle, the average value of area ratio A is 30 to 75% area %, and

[0014] (ii) When X represents the number of cross sections of toner particles with an area ratio of 90% or more to A and Z represents the total number of cross sections of toner particles observed, the value of X / Z is 0.15 or more.

[0015] According to this disclosure, a toner can be provided that exhibits both low-temperature fixing properties and heat-resistant staining during high-speed printing, and also demonstrates good image durability. Further features of the invention will become apparent from the following description of exemplary embodiments. Detailed Implementation

[0016] Unless otherwise stated, descriptions of numerical ranges such as "from XX to YY" or "XX to YY" in this disclosure include the upper and lower limits of the range. In this disclosure, (meth)acrylates refer to acrylates and / or methacrylates. When numerical ranges are described in stages, the upper and lower limits of each range can be arbitrarily combined. The term "monomer unit" describes the reactive form of the monomer material in the polymer. For example, a carbon-carbon bonded portion of the main chain of a vinyl monomer polymerized in the polymer is given as a unit. A vinyl monomer can be represented by the following formula (Z):

[0017]

[0018] In formula (Z), Z1 represents a hydrogen atom or an alkyl group (preferably C). 1-3 Alkyl (or more preferably methyl), and Z2 represents any substituent. Crystalline resin is a resin that exhibits a distinct endothermic peak in differential scanning calorimetry (DSC) measurements.

[0019] This disclosure relates to a toner comprising toner particles containing a binder resin, wherein...

[0020] The adhesive resin comprises a first resin and a second resin.

[0021] The first resin is a crystalline resin.

[0022] The second resin is a non-crystalline resin, and

[0023] In cross-sectional observations of 100 toner particles using a transmission electron microscope,

[0024] (i) When area ratio A (area %) represents the proportion of the area occupied by the first resin in the cross-section of each toner particle, the average value of area ratio A is 30 to 75% area %, and

[0025] (ii) When X represents the number of cross sections of toner particles with an area ratio of 90% or more to A and Z represents the total number of cross sections of toner particles observed, the value of X / Z is 0.15 or more.

[0026] The inventors of this invention have discovered that heat resistance to staining is not necessarily improved when crystalline resins are used extensively as binder resins, or when non-crystalline resins are also used. It is understood that in some cases, both low-temperature fixing and heat resistance to staining decrease.

[0027] Furthermore, images coated on paper, typically called coated paper, obtained by coating the surface of paper with inorganic substances such as calcium carbonate or clay, suffer from problems such as image peeling due to friction between the image and other coated papers. During research into the types and proportions of crystalline and non-crystalline resins, the inventors of this invention discovered that by using toner particles with different contents of crystalline and non-crystalline resins, excellent low-temperature fixing and fixing latitude can be achieved, and image durability tends to improve. The aforementioned toner was obtained through further in-depth research based on these findings.

[0028] The toner is characterized in that it comprises a crystalline resin as a first resin and a non-crystalline resin as a second resin. Furthermore, the toner is characterized in that, in cross-sectional observation of 100 toner particles using a transmission electron microscope, when the area ratio A (area %) represents the proportion of the area occupied by the first resin in the cross-section of each toner particle, the average value of the area ratio A is 30 to 75 area.

[0029] The area ratio A indicates the proportion of crystalline resin present as the first resin in the toner particles. If the average area ratio A is 30 to 75% area, a favorable effect of rapid melting derived from the crystalline resin is observed, resulting in a toner exhibiting excellent low-temperature fixing and heat-resistant staining properties. If the average area ratio A is less than 30% area, the low-temperature fixing properties deteriorate. However, if the average area ratio A exceeds 75% area, the heat-resistant staining properties deteriorate. The average area ratio A is preferably 38 to 73% area.

[0030] Furthermore, the toner is characterized in that, when X represents the number of cross-sections of toner particles with an area ratio of A of 90% or more and Z represents the total number of observed toner particle cross-sections, the value of X / Z is 0.15 or more. This indicates that toner particles with a high proportion of crystalline resin are present in the toner in a certain amount or more. Thus, if a certain amount or more of toner particles with an area ratio A higher than the average value of area ratio A are present in the toner, excellent low-temperature fixing and heat-resistant staining properties can be achieved, and image durability on coated paper can be improved. If the value of X / Z is less than 0.15, excellent low-temperature fixing and heat-resistant staining properties cannot be achieved, and image durability deteriorates. The value of X / Z is preferably 0.17 or more. There is no particular upper limit to the value of X / Z, but it is preferably 0.45 or less, and more preferably 0.37 or less.

[0031] The inventors of this invention believe the mechanism is as follows. Since the average area ratio A of the toner is 30 to 75% of the area, it can be said that the toner particles contain a certain amount of crystalline and non-crystalline resin. It is expected that the rapid melting of the crystalline resin will improve low-temperature fixing performance, and that the non-crystalline resin will provide heat-resistant staining resistance; however, these effects are not achieved solely through these factors. This is believed to be because the crystalline resin present in the toner particles cannot achieve the expected rapid melting during fixing, as the non-crystalline resin also present in the same toner particles inhibits rapid melting.

[0032] However, in toners with an area ratio A of 90% or more, the presence of non-crystalline resin in the toner particles is relatively low. As a result, the overall toner particles exhibit high rapid melting and melt before other toner particles. It is believed that this creates an effect of embedding voids between the toner particles, reducing the proportion of air used as an insulating layer, thus resulting in improved low-temperature fixing properties of the overall toner. Furthermore, it is believed that because the number of voids in the image formed by the voids present between the toner particles is reduced, the number of stress concentration points when external forces are applied is reduced, and image durability is improved.

[0033] As an example of a method for producing a toner in which the area ratio A falls within the aforementioned range, the following method can be provided. A group of toner particles (referred to as toner particle group 1) in which the average area ratio A falls within the range of 30 to 75 area % is produced by controlling the ratio of crystalline resin to non-crystalline resin. Additionally, another group of toner particles (referred to as toner particle group 2) containing toner particles with an area ratio A of 90 area % or more is also produced. Then, a toner can be produced by mixing toner particle group 1 and toner particle group 2, which fall within the aforementioned range.

[0034] Furthermore, it is believed that toner particles produced using conventional toner production methods such as melt kneading, emulsion coagulation, dissolution suspension, and emulsion polymerization exhibit a certain distribution of area ratio A. However, when toners are produced using conventionally known production methods, the variation in area ratio A is within ±5% of the average area.

[0035] From the viewpoint of improving image gloss, the cross-section of toner particles with an average area ratio A of 30 to 75% area % preferably has a matrix-domain structure consisting of a matrix containing a first resin and domains containing a second resin. In this case, the number-average length of the major axis of the domain (the number-average diameter of the major axis of the domain) is preferably 0.1 to 2.0 μm, more preferably 0.5 to 1.4 μm.

[0036] The toner contains a first resin that is a crystalline resin. The inclusion of a crystalline resin improves low-temperature fixing properties. Known crystalline resins can be used as the crystalline resin used in the toner.

[0037] Suitable examples include crystalline polyester resins, crystalline vinyl resins, crystalline polyurethane resins, and crystalline polyurea resins. Other examples include ethylene copolymers, such as ethylene-vinyl acetate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-methacrylic acid copolymers, and ethylene-acrylic acid copolymers.

[0038] From the perspective of low-temperature fixing properties, crystalline polyester resins and crystalline vinyl resins are preferred. Furthermore, hybrid resins in which vinyl resins and polyester resins are combined can be used. Additionally, vinyl resins are polymers or copolymers of compounds containing groups having olefinically unsaturated bonds, such as vinyl bonds. Examples of groups having olefinically unsaturated bonds include vinyl, (meth)allyl, and (meth)acryloyl.

[0039] The crystalline polyester resin is preferably a condensation product of a monomer composition comprising an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms as main components. More preferably, the crystalline polyester resin is a condensation product of a monomer comprising an alcohol component selected from aliphatic diols having 6 to 12 carbon atoms as the main component and a monomer comprising a carboxylic acid component selected from aliphatic dicarboxylic acid compounds having 6 to 12 carbon atoms as the main component.

[0040] There is no particular limitation on aliphatic diols with 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms), but chain-like (more preferably linear) aliphatic diols are preferred. Examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 1,4-butadienediol, trimethylenediol, tetramethylenediol, pentamethylenediol, hexamethylenediol, octamethylenediol, nonamethylenediol, decamethylenediol, dodecamethylenediol, and neopentyl glycol. Among these, 1,6-hexanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred.

[0041] The term "major component" refers to a component with a content of 50% by mass or more. This content is preferably 70% by mass or more, and more preferably 90% by mass or more. Polyol monomers other than the aliphatic diols described above can be used. Examples of diol monomers include aromatic alcohols such as polyoxyethylene-modified bisphenol A and polyoxypropylene-modified bisphenol A; and 1,4-cyclohexanediethanol.

[0042] Examples of polyol monomers with three or more ions include aromatic alcohols such as 1,3,5-tris(hydroxymethyl)benzene; and aliphatic alcohols such as pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane.

[0043] In addition, monohydric alcohols can be used, as long as they do not impair the properties of the crystalline polyester resin. Examples of monohydric 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.

[0044] However, there is no particular limitation on aliphatic dicarboxylic acid compounds having 2 to 22 carbon atoms (more preferably 6 to 12 carbon atoms), but chain-like (more preferably linear) aliphatic dicarboxylic acids are preferred. Specific examples include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, pentenoic acid, azelaic acid, sebacic acid, 1,9-azelaic acid, 1,10-decanoic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, maleic acid, fumaric acid, mesoconic acid, citracic acid, and itaconic acid, and also includes compounds obtained by hydrolyzing their anhydrides and lower alkyl esters. More preferred examples include adipic acid, sebacic acid, and 1,10-decanoic acid.

[0045] Other polycarboxylic acids besides aliphatic dicarboxylic acid compounds with 2 to 22 carbon atoms can be used. Examples of these other polycarboxylic acid monomers include aromatic carboxylic acids such as isophthalic acid and terephthalic acid; aliphatic carboxylic acids such as dodecylsuccinic acid and dodecenylsuccinic acid; and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid, as well as their anhydrides and lower alkyl esters.

[0046] Among these other carboxylic acid monomers, examples of polycarboxylic acids with three or more nucleotides include aromatic carboxylic acids such as 1,2,4-benzenetricarboxylic acid (triphenyltriic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and pyromellitic acid; aliphatic carboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane; and their derivatives such as acid anhydrides and lower alkyl esters.

[0047] In addition, monocarboxylic acids may be included, as long as they do not impair the properties of the crystalline polyester resin. Examples of monocarboxylic acids include benzoic acid, naphtholic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, and stearic acid.

[0048] Crystalline polyester resins can be produced using conventional polyester synthesis methods. For example, the desired crystalline polyester resin can be obtained by subjecting the aforementioned carboxylic acid monomers and alcohol monomers to esterification or transesterification, followed by polycondensation under reduced pressure or with the introduction of nitrogen using conventional methods.

[0049] Esterification or transesterification reactions can be carried out using conventional esterification or transesterification catalysts such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, or magnesium acetate, as needed. Alternatively, polycondensation reactions 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. There are no particular limitations on the polymerization temperature and the amount of catalyst, and these should be determined at the discretion of the individual.

[0050] To improve the strength of crystalline polyester resins obtained in esterification, transesterification, or polycondensation reactions, all monomers can be added at once, or a method can be used such as first reacting the binary monomers to reduce the amount of low molecular weight components, and then adding ternary or higher monomers and reacting them.

[0051] Furthermore, the first resin is more preferably a vinyl-based resin, and preferably contains a first monomer unit represented by formula (1). More preferably, the first resin represented by formula (1) is a vinyl-based resin having a first monomer unit represented by formula (1). Additionally, the content of the first monomer unit in the first resin is preferably 20.0 to 100.0% by mass. Within this range, low-temperature fixing and heat-resistant staining are desirable. The weight-average molecular weight (Mw) of the first resin is preferably 5,000 to 100,000, more preferably 15,000 to 70,000.

[0052]

[0053] In equation (1), R Z1 R represents a hydrogen atom or a methyl group, and R represents an alkyl group having 18 to 36 carbon atoms. R is preferably an alkyl group having 18 to 30 carbon atoms. In addition, the alkyl group preferably has a straight-chain structure.

[0054] The first monomer unit represented by formula (1) has an alkyl group (represented by R) with 18 to 36 carbon atoms in its side chain. By having this moiety, the first resin tends to exhibit crystallinity. If the content of the first monomer unit in the first resin is 20.0 to 100.0% by mass, the first resin exhibits crystallinity and its low-temperature fixing properties tend to be further improved. This content is preferably 40.0% by mass or more, more preferably 50.0% by mass or more. There is no particular limitation on the upper limit of this content, but when other monomer units described later are included, it is preferably 90.0% by mass or less, more preferably 80.0% by mass or less.

[0055] In addition, compared with crystalline polyester, which is a known crystalline resin in the past, crystalline resin having a first monomer unit represented by formula (1) exhibits excellent charge retention under high temperature and high humidity conditions, which may be due to the structure in which the side chain exhibits crystalline properties.

[0056] The first monomer unit represented by formula (1) is preferably a monomer unit derived from at least one of the group consisting of alkyl (meth)acrylates selected from alkyl groups having 18 to 36 carbon atoms.

[0057] Each has C 18-36 Examples of alkyl (meth)acrylates include those each having a C 18-36 Straight-chain alkyl (meth)acrylates [(meth)stearyl acrylate, (meth)nonadecanyl acrylate, (meth)eicosyl acrylate, (meth)dodecyl acrylate, (meth)benzyl acrylate, (meth)tetradecyl acrylate, (meth)hexadecyl acrylate, (meth)octadecyl acrylate, (meth)triacyl acrylate, (meth)triacyl acrylate, (meth)dodecyl acrylate, etc.] and each having C18-36 Branched alkyl (meth)acrylates [(meth)acrylate 2-decyltetradecyl ester, etc.].

[0058] From the viewpoint of low-temperature fixing properties of the toner, at least one of the group consisting of (meth)acrylates having a straight-chain alkyl group having 18 to 36 carbon atoms is preferred, at least one of the group consisting of (meth)acrylates having a straight-chain alkyl group having 18 to 30 carbon atoms is more preferred, and at least one of the group consisting of stearyl (meth)acrylate and benzyl (meth)acrylate is even more preferred. As the monomer forming the first monomer unit, one may be used alone, or two or more may be used in combination.

[0059] In addition to the first monomer unit represented by formula (1), the first resin may also contain other monomer units. In the case that the first resin is a vinyl-based resin, examples of polymerizable monomers used to form these other monomer units include those listed below. Furthermore, the polymerizable monomers forming the other monomer units may be a single monomer or a combination of two or more monomers.

[0060] Acrylonitrile monomers; for example, acrylonitrile and methacrylonitrile.

[0061] Hydroxyl monomers; for example, 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0062] Monomers having an amide group; for example, acrylamide and monomers obtained by reacting an amine having 1 to 30 carbon atoms with a carboxylic acid (such as acrylic acid and methacrylic acid) having 2 to 30 carbon atoms and an olefinic unsaturated bond by known methods.

[0063] Monomers having a urea group; for example, monomers obtained by reacting amines having 3 to 22 carbon atoms [primary amines (n-butylamine, tert-butylamine, propylamine, and isopropylamine, etc.), secondary amines (di-n-ethylamine, di-n-propylamine, and di-n-butylamine, etc.), aniline, and cyclohexylamine, etc.] with isocyanates having 2 to 30 carbon atoms and olefinic unsaturated bonds by known methods.

[0064] Monomers having a carboxyl group; for example, methacrylic acid, acrylic acid, and 2-carboxyethyl (meth)acrylic acid.

[0065] Vinyl esters; for example, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl caprylate, vinyl decanoate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl pentanoate, and vinyl octanoate.

[0066] In addition, styrene and its derivatives, such as styrene and o-methylstyrene; (meth)acrylates, such as methyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; unsaturated monoenes such as ethylene, propylene, butene and isobutylene; and unsaturated polyenes such as butadiene and isoprene.

[0067] Aromatic divinyl compounds; diacrylate compounds linked by alkyl chains; diacrylate compounds linked by alkyl chains containing ether bonds; diacrylate compounds linked by chains including aromatic groups and ether bonds; polyester-type diacrylate compounds; and multifunctional crosslinking agents. Examples of such aromatic divinyl compounds include divinylbenzene and divinylnaphthalene.

[0068] Examples of such diacrylate compounds linked by alkyl chains include ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentanediol diacrylate, and compounds in which the acrylate portion of the above compounds is replaced by the methacrylate portion.

[0069] Monomers having nitrile, amide, urethane, hydroxyl, or urea groups are preferred. More preferably, monomers having an olefinic unsaturated bond and at least one functional group selected from the group consisting of nitrile, amide, urethane, hydroxyl, and urea groups are preferred. Using these monomers can further improve charge rise performance in low humidity environments.

[0070] The first resin preferably comprises monomer units represented by formula (A) obtained by polymerizing styrene and monomer units represented by formula (B) obtained by polymerizing (meth)acrylic acid. The content of monomer units represented by formula (A) is preferably 5.0 to 80.0% by mass, more preferably 8.0 to 70.0% by mass. The content of monomer units represented by formula (B) is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 2.0% by mass.

[0071]

[0072] In the formula, R 3 This indicates a hydrogen atom or a methyl group. When the first resin is a vinyl-based resin, the above-described polymerizable monomer and polymerization initiator can be used to produce the resin. From an efficiency point of view, the polymerization initiator can be used in an amount of 0.05 to 10 parts by mass relative to 100 parts by mass of the polymerizable monomer.

[0073] Examples of polymerization initiators include the following types: 2,2'-azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), 2,2'-azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis(1-cyclohexanenitrile), 2-carbamoylazoisobutyronitrile, 2,2'-azobis(2,4,4-trimethylpentane), 2-phenylazobis(2,2'-azobisisobutyronitrile). 2,4-Dimethyl-4-methoxypentanilonitrile, 2,2'-azobis(2-methylpropane), ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide, 2,2-di(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, Octyl peroxide, Decanoyl peroxide, Lauroyl peroxide, 3,5,5-Trimethylhexanoyl peroxide, Benzoyl peroxide, Toluyl peroxide, Diisopropyl peroxide, Di-2-Ethylhexyl peroxide, Di-n-propyl peroxide, Di-2-Ethoxyethyl peroxide, Dimethoxyisopropyl peroxide, Di(3-methyl-3-methoxybutyl) peroxide, Acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-pentyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, and di-tert-butyl peroxyazelate.

[0074] The adhesive resin includes a second resin, and the second resin is a non-crystalline resin. Known non-crystalline resins can be used as non-crystalline resins. Examples include the types listed below.

[0075] The resin comprises poly(vinyl chloride), phenolic resin, natural resin-modified phenolic resin, natural resin-modified maleic acid resin, poly(vinyl acetate) resin, silicone resin, polyester resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, poly(vinyl butyral) resin, terpene resin, coumarone-indene resin, petroleum-based resin, and vinyl-based resin. The second resin preferably comprises at least one resin selected from the group consisting of a hybrid resin in which vinyl-based resin and polyester resin are combined, and polyester resin and vinyl-based resin.

[0076] As the polyester resin, polyester resins commonly used in toners are preferred. Monomers used in polyester resins include polyols (di- or tri- or higher alcohols), polycarboxylic acids (di- or tri- or higher carboxylic acids), their anhydrides, or their lower alkyl esters.

[0077] Examples of polyols include the following. Examples of diols 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, and polyoxypropylene-(6)-2,2-bis(4-hydroxyphenyl)propane, etc.

[0078] Examples of other polyols 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-cyclohexanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polybutanediol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trimethylolbenzene. These polyols can be used alone or in combination of two or more.

[0079] Examples of polycarboxylic acids include the following. Examples of dicarboxylic acids include maleic acid, fumaric acid, citracic acid, itaconic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, dodecenylsuccinic acid, isododecenylsuccinic acid, dodecylsuccinic acid, isododecylsuccinic acid, octenylsuccinic acid, octylsuccinic acid, isoctenylsuccinic acid, isooctenylsuccinic acid, isooctylsuccinic acid, anhydrides of these acids, and their lower alkyl esters. Among these, maleic acid, fumaric acid, terephthalic acid, and dodecenylsuccinic acid are preferred.

[0080] Examples of trivalent or higher carboxylic acids, their anhydrides, or their lower alkyl esters include the following: 1,2,4-benzenetricarboxylic acid (triphenyltricarboxylic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic 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 anhydrides, or their lower alkyl esters.

[0081] Among these, 1,2,4-benzenetricarboxylic acid (triphenyltriacyl) or its anhydrides are preferred because they are low in cost and easy to control in reaction. These polycarboxylic acids can be used alone or in combination of two or more.

[0082] There are no particular limitations on the production method of polyester resin, and known methods can be used. For example, polyester resin can be produced by simultaneously adding the aforementioned polyol and polycarboxylic acid, followed by polymerization via esterification, transesterification, or condensation. Furthermore, there are no particular limitations on the polymerization temperature, but a range of 180°C to 290°C is preferred. Polymerization catalysts such as titanium-based catalysts, tin-based catalysts, zinc acetate, antimony trioxide, or germanium dioxide can be used when polymerizing the polyester resin. Polyester resins used for non-crystalline resins are preferably obtained by polycondensation using titanium-based and / or tin-based catalysts.

[0083] Examples of vinyl resins used as second resins include polymers of polymerizable monomers having olefinic unsaturated bonds. Olefinic unsaturated bonds are carbon-carbon double bonds capable of free radical polymerization, and examples include vinyl, propylene, acryloyl, and methacryloyl groups.

[0084] Examples of polymerizable monomers include the following types: styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene; and acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, and propylene. Acrylic acids and acrylates such as dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; α-methylene aliphatic monocarboxylic acids and their esters such as 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, and diethylaminoethyl methacrylate; as well as acrylonitrile, methacrylonitrile, and acrylamide.

[0085] In addition, acrylic and methacrylate esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and 2-hydroxypropyl (meth)acrylate; and hydroxyl-containing polymeric monomers such as 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene. One or more of these polymeric monomers can be used alone or in combination.

[0086] In addition to the monomers mentioned above, various other polymerizable monomers capable of vinyl polymerization may be used in vinyl-based resins as needed. Examples of such polymerizable monomers include the types listed below: unsaturated monoolefins such as ethylene, propylene, butene, and isobutene; unsaturated polyolefins such as butadiene and isoprene; halogenated vinyl compounds 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; vinylnaphthalene compounds; unsaturated dicarboxylic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid compounds, fumaric acid, and mesocarboxylic acid; and unsaturated dicarboxylic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid compounds, fumaric acid, and mesocarboxylic acid. Anhydrides of unsaturated dicarboxylic acids, such as anhydrides of citrate, itaconic acid, and alkenyl succinic anhydride compounds; half-esters of unsaturated dicarboxylic acids, such as methyl maleate half-ester, ethyl maleate half-ester, butyl maleate half-ester, methyl citrate half-ester, ethyl citrate half-ester, butyl citrate half-ester, methyl itaconic acid half-ester, methyl alkenyl succinate half-ester, methyl fumarate half-ester, and ethyl citrate half-ester; unsaturated dicarboxylic acid esters, such as dimethyl maleate and dimethyl fumarate; anhydrides of α,β-unsaturated acids, such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; anhydrides of these α,β-unsaturated acids and lower fatty acids; and carboxylic acid-containing polymerizable monomers, such as alkenyl malonic acid compounds, alkenyl glutaric acid compounds, alkenyl adipic acid compounds, their anhydrides, and monoesters.

[0087] Additionally, as needed, vinyl resins can be polymers crosslinked using crosslinkable polymerizable monomers as exemplified below. Examples of crosslinkable polymerizable monomers include the following types: aromatic divinyl compounds; diacrylate compounds linked by alkyl chains; diacrylate compounds linked by alkyl chains containing ether bonds; diacrylate compounds linked by chains including aromatic groups and ether bonds; polyester-type diacrylate compounds; and multifunctional crosslinking agents. Examples of such aromatic divinyl compounds include divinylbenzene and divinylnaphthalene.

[0088] Examples of such diacrylate compounds linked by alkyl chains include ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentanediol diacrylate, and compounds in which the acrylate portion of the above compounds is replaced by the methacrylate portion.

[0089] Vinyl resins are preferably polymers comprising at least one polymerizable monomer selected from the group consisting of: styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, and dodecyl acrylate. Esters, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-(1-hydroxy-1-methylbutyl)styrene and 4-(1-hydroxy-1-methylhexyl)styrene.

[0090] Additionally, vinyl resins can be copolymers of at least one polymerizable monomer selected from the group above and at least one crosslinkable polymerizable monomer selected from the group consisting of: divinylbenzene, divinylnaphthalene, ethylene glycol diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentanediol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and neopentanediol dimethacrylate. The content of the crosslinkable monomer in the monomer can be approximately 0.5 to 5.0% by mass.

[0091] Vinyl resins can be produced using polymerization initiators. From an efficiency standpoint, polymerization initiators can be used in amounts of 0.05 to 10 parts by mass relative to 100 parts by mass of polymerizable monomers. Examples of polymerization initiators include the following types.

[0092] 2,2'-Azobisisobutyronitrile, 2,2'-Azobis(4-methoxy-2,4-dimethylpentanitrile), 2,2'-Azobis(2,4-dimethylpentanitrile), 2,2'-Azobis(2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-Azobis(1-cyclohexanenitrile), 2-carbamoylazoisobutyronitrile, 2,2'-Azobis(2,4,4-trimethylpentane), 2-phenylazo- 2,4-Dimethyl-4-methoxypentanilonitrile, 2,2'-azobis(2-methylpropane), ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, and cyclohexanone peroxide, 2,2-di(tert-butylperoxide)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-butylperoxide)isopropyl (Benzo)benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-toluyl peroxide, diisopropyl peroxide, di-2-ethylhexyl peroxide, di-n-propyl peroxide, di-2-ethoxyethyl peroxide, dimethoxyisopropyl peroxide, di(3-methyl-3-methoxybutyl) peroxide, etc. Acetylcyclohexylsulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxyneodecanate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, tert-butyl peroxyisopropylcarbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, tert-pentyl peroxy-2-ethylhexanoate, di-tert-butyl peroxyhexahydroterephthalate, and di-tert-butyl peroxyazelate.

[0093] Vinyl resins and polyester resins similar to those used as second resins can be used as vinyl resins and polyester resins for forming hybrid resins in which vinyl resins and polyester resins are combined with each other.

[0094] One example of a method for manufacturing a hybrid resin that combines vinyl resins and polyester resins is a method that involves polymerization using a compound (hereinafter referred to as a "bireactive compound") capable of reacting with the monomers that produce both resins.

[0095] Examples of bireactive compounds include fumaric acid, acrylic acid, methacrylic acid, citrate, maleic acid, and dimethyl fumarate. Fumaric acid, acrylic acid, and methacrylic acid are particularly advantageous.

[0096] When using a hybrid resin in which vinyl resin and polyester resin are combined, 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, or 80% by mass or more, and preferably 100% by mass or less or 90% by mass or less.

[0097] From the viewpoint of improving the charge-carrying performance under high temperature and high humidity conditions, the acid value AVA of the second resin is preferably 50.0 mg KOH / g or less, more preferably 30.0 mg KOH / g or less. There is no particular limitation on the lower limit, but it is preferably 0 mg KOH / g or more. From the viewpoint of improving charge-carrying performance, it is preferably 0.5 mg KOH / g or more, more preferably 1.0 mg KOH / g or more.

[0098] When observing the cross-section of 100 toner particles using a transmission electron microscope, the area ratio B (area %) represents the proportion of the area occupied by the second resin in the cross-section of the toner particles. When Y represents the number of cross-sections of toner particles with an area ratio B of 90% or more, the value of Y / Z is preferably 0.10 or more, more preferably 0.14 or more. There is no particular upper limit to the Y / Z value, but it is preferably 0.25 or less, more preferably 0.20 or less. If the value of Y / Z is 0.10 or more, the toner particles, in which a high proportion of non-crystalline resin acts as the second resin, act as fillers in the image, resulting in improved image strength and thus further improved image durability. Furthermore, the average area ratio B is preferably 25 to 70% (area %), more preferably 27 to 62% (area %).

[0099] As an example of a method for producing a toner in which the area ratio B falls within the aforementioned range, the following method can be provided. By controlling the ratio of crystalline resin to non-crystalline resin, a group of toner particles (referred to as toner particle group 1) in which the average area ratio A falls within the range of 30 to 75 area %. In addition, another group of toner particles (referred to as toner particle group 2) containing toner particles with an area ratio A of 90 area % or more is produced. Further, another group of toner particles (referred to as toner particle group 3) containing toner particles with an area ratio B of 90 area % or more is produced. Then, toner particle groups 1 to 3 are mixed to achieve the aforementioned range.

[0100] For the purpose of improving pigment dispersibility, the binder resin may include a third resin in addition to the first and second resins, to the extent that it does not impair the effects of this disclosure. Examples of such resins include the following: polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, and petroleum-based resins.

[0101] Toner particles may contain waxes. Examples of waxes include: hydrocarbon waxes such as microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as polyethylene oxide wax, and their block copolymers; waxes such as carnauba wax, which is mainly composed of fatty acid esters; and waxes such as deoxycarnauba wax, which is composed of partially or completely deoxygenated fatty acid esters.

[0102] Other examples include: saturated straight-chain fatty acids such as palmitic acid, stearic acid, and linoleic acid; unsaturated fatty acids such as brassinolic acid, tungstic acid, and octadecanoic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, betaine alcohol, carbamate alcohol, wax alcohol, and beeswax alcohol; polyols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, betaine acid, and linoleic acid with alcohols such as stearyl alcohol, aralkyl alcohol, betaine alcohol, carbamate alcohol, wax alcohol, and beeswax alcohol; fatty acid amides such as linoleamide, oleamide, and lauramide; and saturated fatty acids such as methylene bis-stearamide, ethylene bis-decamide, ethylene bis-laurate, and hexamethylene bis-stearamide. Fatty acid diamides; such as ethylene dioleamide, hexamethylene dioleamide, N,N'-dioleylhexadiamide, N,N'-dioleyl sebacamide and other unsaturated fatty acid amides; such as m-xylene bis-stearamide and N,N'-distearate isophthalamide and other aromatic diamides; such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate and other aliphatic metal salts (commonly known as metal soaps); waxes obtained by grafting vinyl monomers such as styrene and acrylic acid onto aliphatic hydrocarbon waxes; partial esterification products of polyols and fatty acids, such as betaine monoglycerides; and methyl ester compounds with hydroxyl groups obtained by hydrogenation of vegetable oils.

[0103] The wax content is preferably 2.0 to 30.0 parts by weight relative to 100 parts by weight of adhesive resin.

[0104] Toner particles may also contain coloring agents. Examples of coloring agents include the following.

[0105] Examples of black colorants include carbon black and black colorants obtained by blending yellow, magenta, and cyan colorants. Pigments can be used alone as colorants, but from the perspective of image quality in panchromatic images, it is desirable to combine dyes and pigments to improve sharpness.

[0106] Examples of magenta pigments for toners include 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 and 282; CI Pigment Violet 19; and CI Vat Red 1,2,10,13,15,23,29 and 35.

[0107] Examples of magenta toner dyes include CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, and 121; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; oil-soluble dyes such as CI Disperse Violet 1, and CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40; and basic dyes such as CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28.

[0108] Examples of pigments for cyan colorants include CI Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16 and 17; CI Vat Blue 6; and CI Acid Blue 45, and copper phthalocyanine pigments having 1 to 5 phthalimide methyl substituents in the phthalocyanine skeleton. Examples of dyes for cyan colorants include CI Solvent Blue 70.

[0109] Examples of pigments for yellow toners include 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, and 185; and CI Vat Yellow 1, 3, and 20. Examples of dyes for yellow toners include CI Solvent Yellow 162. The colorant content is preferably from 0.1 parts by weight to 30.0 parts by weight relative to 100 parts by weight of binder resin.

[0110] Depending on the requirements, the toner particles may contain a charge control agent. Known substances can be used as charge control agents, but colorless metal compounds of aromatic carboxylic acids that have a fast charging rate and can stably maintain a certain charge are particularly preferred.

[0111] Examples of negative charge control agents include metal compounds of salicylic acid, metal compounds of naphthoic acid, metal compounds of dicarboxylic acid, polymeric compounds having sulfonic acid or carboxylic acid in the side chain, polymeric compounds having sulfonate or sulfonated products in the side chain, polymeric compounds having carboxylate or carboxylic acid esterified products in the side chain, boron compounds, urea compounds, silicon compounds, and calixarenes.

[0112] The charge control agent can be added internally or externally to the toner particles. The preferred content of the charge control agent is 0.2 parts by weight to 10.0 parts by weight.

[0113] The toner may contain external additives. For example, the toner can be obtained by externally adding external additives to the toner particles. Preferably, the external additives are inorganic fine particles such as silica fine particles, titanium dioxide fine particles, and alumina fine particles. Preferably, the external additive used to improve flowability has a specific surface area of ​​50–400 m². 2 The inorganic fine particles have a specific surface area of ​​10–50 m² / g for durability. 2 / g of inorganic fine particles.

[0114] To improve both flowability and durability, various combinations of inorganic fine particles with specific surface areas falling within the aforementioned range can be used. The content of external additives is preferably 0.1 to 10.0 parts by weight relative to 100 parts by weight of toner particles. When mixing the toner particles with the external additives, a known mixer, such as a Henschel mixer, can be used.

[0115] Toners can also be used as single-component developers, but from the perspective of providing stable images over the long term, it is preferable to use toners as two-component developers mixed with a magnetic carrier to further improve point reproducibility. That is, a two-component developer comprising a toner and a magnetic carrier is preferred, wherein the toner is the aforementioned toner.

[0116] The magnetic carrier can be a generally known carrier, such as iron powder or surface-oxidized iron powder; particles of metals such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, or rare earth elements, or particles of alloys or oxides of these metals; magnetic materials such as ferrites; or a magnetic material dispersion resin carrier (so-called resin carrier), which contains magnetic material and a binder resin that holds the magnetic material in a dispersed state. When a toner is used as a two-component developer mixed with the magnetic carrier, the toner content in the two-component developer is preferably 2 to 15% by mass, more preferably 4 to 13% by mass.

[0117] There are no particular restrictions on the production method of toner granules, and well-known production methods such as suspension polymerization, emulsion aggregation, melt kneading, and dissolution suspension can be used. The melt kneading method will now be used as an example, but the production method of toner granules is not limited to these.

[0118] First, in the raw material mixing process, a specified amount of first resin and second resin, or binder resin containing first resin and second resin, are weighed and mixed together with other components as needed, such as wax, colorant, charge control agent, etc., as materials constituting the toner particles. Examples of mixing devices include double cone mixers, V-type mixers, drum mixers, super mixers, Henschel mixers, Nauta mixers, and Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.).

[0119] Next, the mixture is melt-kneaded to disperse other components in the binder resin comprising the first and second resins. In the melt-kneading step, intermittent kneaders such as pressure kneaders or Banbury mixers, or continuous kneaders, can be used. From the viewpoint of enabling continuous production, single-screw and twin-screw extruders have become mainstream. Examples include the KTK twin-screw extruder (manufactured by Kobe Steel Ltd.), the TEM twin-screw extruder (manufactured by ToshibaMachine Co., Ltd.), the PCM kneader (manufactured by Ikegai Corp.), the twin-screw extruder (manufactured by KCK), the co-kneader (manufactured by Buss), and Kneadex (manufactured by Nippon Coke & Engineering Co., Ltd.). Furthermore, the resin composition obtained by melt-kneading is rolled using a twin-roll mill or similar device, and can be cooled with water or the like in the cooling step.

[0120] The dispersion state and number-average diameter of the first and second resins can be controlled by adjusting the kneading temperature and screw speed during the melt kneading step.

[0121] Then, the cooled product of the resin composition is pulverized to the desired particle size in a pulverizing step. In the pulverizing step, after coarse pulverization using a pulverizer such as a crusher, hammer mill, or milling mill, it is further finely pulverized using, for example, a Cryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), a SuperRotor (manufactured by Nisshin Engineering Co., Ltd.), a turbomill (manufactured by Turbo Industries Co., Ltd.), or an air jet system.

[0122] Subsequently, as needed, colorant particles can be obtained by classifying the particles using classifiers or sieves such as the inertial classifier Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), the centrifugal classifier Turboplex (manufactured by Hosokawa Micron Corporation), the TSP separator (manufactured by Hosokawa Micron Corporation), and the Faculty (manufactured by Hosokawa Micron Corporation).

[0123] Furthermore, the production of toner particles using the emulsion aggregation method will now be described. In the emulsion aggregation method, the toner is produced by performing the following steps: a dispersion step for producing a fine particulate dispersion of the constituent material containing the toner; an aggregation step for agglomerating the fine particles of the constituent material containing the toner to control the particle size until it reaches the particle size of the toner; a fusion step for melt adhesion of the resin contained in the resulting aggregated particles; a subsequent cooling step; a metal removal step for filtering the obtained toner and removing excess polyvalent metal ions; a filtration / washing step for filtering the obtained toner and washing it with ion-exchanged water, etc.; and a step for removing water from the washed toner and drying it.

[0124] Preparation steps of resin fine particle dispersion (dispersion step)

[0125] Resin fine particle dispersions can be prepared using known methods, but are not limited to these methods. Examples of known methods include emulsification polymerization, self-emulsification, phase inversion emulsification in which an aqueous medium is added to a resin solution dissolved in an organic solvent to emulsify the resin, or forced emulsification in which the resin is subjected to high-temperature treatment in an aqueous medium without the use of an organic solvent to force emulsification of the resin.

[0126] Specifically, binder resins such as the first and second resins are dissolved in an organic solvent, and surfactants or alkaline compounds are added as needed. In this case, if the binder resin is a crystalline resin with a melting point, the resin can be dissolved after heating to at least its melting point. Next, a fine resin particle is precipitated by slowly adding an aqueous medium while stirring with a homogenizer or similar device. Then, an aqueous solution of the fine resin particle dispersion is prepared by heating or reducing the pressure to remove the solvent.

[0127] As an organic solvent for dissolving the resin, any solvent capable of dissolving the aforementioned resin can be used, but from the viewpoint of suppressing the formation of coarse particles, it is preferable to use an organic solvent such as toluene that forms a homogeneous phase with water.

[0128] There are no particular restrictions on the types of surfactants, but examples include anionic surfactants such as sulfate salts, sulfonates, carboxylates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycols, adducts of ethylene oxide and alkylphenols, and polyols. One of these surfactants may be used alone or in combination of two or more.

[0129] Examples of basic compounds include inorganic bases such as sodium hydroxide and potassium hydroxide, and organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. One of these basic compounds may be used alone, or in combination of two or more.

[0130] Furthermore, the volume-based 50% particle size (D50) of the resin fine particles in the aqueous dispersion is preferably 0.05 to 1.00 μm, more preferably 0.05 to 0.40 μm. By adjusting the volume-based 50% particle size (D50) within the above range, it is easy to obtain toner particles with a diameter of 3 to 10 μm that is a suitable weight-average particle size for toner particles. Moreover, the volume-based 50% particle size (D50) can be measured using a dynamic light scattering particle size analyzer (Ninotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).

[0131] Preparation of colorant fine particle dispersion

[0132] The desired fine-particle dispersion of colorant can be prepared using, but is not limited to, the methods described below. The fine-particle dispersion of colorant can be prepared by mixing the colorant, aqueous medium, and dispersant using a known mixer such as a stirrer, emulsifier, or disperser. As the dispersant used in this case, known dispersants such as surfactants or polymeric dispersants can be used. Regardless of whether the dispersant is a surfactant or a polymeric dispersant, the dispersant can be removed by the washing step described later; however, from the viewpoint of washing efficiency, surfactants are preferred.

[0133] Examples of surfactants include anionic surfactants such as sulfate esters, sulfonates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; and nonionic surfactants such as polyethylene glycol surfactants, ethylene oxide and alkylphenol adducts, and polyol surfactants.

[0134] Nonionic and anionic surfactants are preferred. Furthermore, nonionic and anionic surfactants can be used in combination. One of these surfactants can be used alone, or in combination of two or more. The concentration of the surfactant in the aqueous medium is preferably 0.5% to 5% by mass. There is no particular limitation on the content of colorant fine particles in the colorant fine particle dispersion, but it is preferably 1% to 30% by mass relative to the total mass of the colorant fine particle dispersion.

[0135] Furthermore, from the viewpoint of the dispersibility of the colorant in the final obtained toner particles, the dispersed particle size of the colorant fine particles in the aqueous dispersion is preferably such that the 50% volumetric particle size (D50) is 0.50 μm or less. For the same reason, the 90% volumetric particle size (D90) is preferably 2 μm or less. Moreover, the 50% volumetric particle size (D50) of the colorant fine particles dispersed in the aqueous medium can be measured using a dynamic light scattering particle size distribution analyzer (Ninotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).

[0136] Examples of known mixers used for dispersing colorants in aqueous media include agitators, emulsifiers, and dispersers, such as ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint mixers. These mixers can be used individually or in combination.

[0137] Preparation of wax fine particle dispersion

[0138] Wax fine particle dispersions can be used as needed. Wax fine particle dispersions can be prepared using, but are not limited to, the known methods given below. A wax fine particle dispersion can be prepared by adding wax to an aqueous medium containing a surfactant, heating to a temperature above the melting point of the wax, dispersing it in particulate form using a high-shear homogenizer (e.g., "Clearmix W-Motion", manufactured by MTechnique Co., Ltd.) or a pressure-discharge disperser (e.g., "Gaulin homogenizer", manufactured by Gaulin), and then cooling to a temperature below the melting point of the wax.

[0139] Furthermore, the dispersion particle size of the wax particles in the wax particle dispersion is such that the 50% particle size based on volume (D50) is preferably 0.03 to 1.0 μm, more preferably 0.10 to 0.50 μm. In addition, it is preferable that there are no coarse wax particles with a diameter of 1 μm or more.

[0140] If the dispersed particle size in the wax fine particle dispersion falls within the above-mentioned range, the wax can be finely dispersed in the toner particles, maximizing the outward migration effect during fixing and achieving good separation. Furthermore, the 50% volume particle size (D50) of the wax fine particle dispersion in an aqueous medium can be measured using a dynamic light scattering particle size analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).

[0141] Mixing steps

[0142] In the mixing step, a mixture is prepared by mixing a first fine resin particle dispersion, a second fine resin particle dispersion, and, if necessary, a fine wax particle dispersion and a fine colorant particle dispersion. Known mixing equipment such as a homogenizer or mixer can be used.

[0143] The step used to form aggregated particles (aggregation step)

[0144] In the aggregation step, the fine particles contained in the mixture prepared in the mixing step are aggregated to form aggregates of the target particle size. Here, aggregates are formed by adding and mixing flocculants as needed and applying heat and / or mechanical force appropriately, through the aggregation of resin fine particles and, as needed, wax fine particles and colorant fine particles. If necessary, flocculants containing divalent or higher metal ions can be used as flocculants.

[0145] Flocculants containing divalent or higher metal ions exhibit high cohesive strength and achieve the desired effect even with small amounts. These flocculants can ion neutralize ionic surfactants in resin, wax, and colorant particle dispersions. Salting out and ionic cross-linking facilitate the aggregation of resin, wax, and colorant particles.

[0146] The aggregation step is a step of forming aggregates of the toner particle size in an aqueous medium. The weight-average particle size of the aggregates formed in the aggregation step is preferably 3 to 10 μm. Furthermore, this weight-average particle size can be measured using a particle size distribution analyzer utilizing the Coulter principle (Coulter Multisizer III: manufactured by Beckman Coulter, Inc.).

[0147] Fusion Steps

[0148] In the fusion step, an aggregation-stopping agent can be added to the dispersion containing the aggregates obtained in the aggregation step while stirring in the same manner as in the aggregation step. Examples of aggregation-stopping agents include basic compounds that shift the equilibrium of acidic polar groups in the surfactant to the dissociation side and stabilize the aggregated particles. Other examples include chelating agents that partially dissociate the acidic polar groups in the surfactant and the metal ions acting as flocculants through ionic crosslinking and form coordination bonds with the metal ions, thereby stabilizing the aggregated particles.

[0149] After the dispersion of aggregated particles in the dispersion is stabilized by the aggregation-stopping agent, the aggregated particles can be fused together by heating to a temperature above the glass transition temperature or melting point of the binder resin. The number-average diameter of the particles can be controlled by adjusting the temperature during the fusion step. The weight-average particle size of the resulting toner particles is preferably 3–10 μm.

[0150] Filtration, washing, drying and grading steps

[0151] Next, toner particles can be obtained by filtering the solid toner particles and, if necessary, by washing, drying, and grading to adjust particle size. The obtained toner particles can be used as a toner. Toner can also be obtained by mixing the obtained toner particles with inorganic fine particles and other external additives as needed. The toner particles, inorganic fine particles, and other external additives can be mixed using mixing equipment such as a double cone mixer, V-type mixer, drum mixer, super mixer, Henschel mixer, Nauta mixer, Mechano Hybrid (manufactured by Nippon Coke and Engineering Co., Ltd.), or Nobilta (manufactured by Hosokawa Micron Corp.).

[0152] The methods for measuring the various physical properties of toners and raw materials will now be explained.

[0153] Toner cross-section observation

[0154] First, sections were prepared as reference samples for the presence ratio. First, the first resin (crystalline resin) was completely dispersed in a visible-light curable resin (Aronix LCR series D800) and cured by exposure to short-wavelength light. The cured resin was cut using an ultramicrotome equipped with a diamond blade to prepare 250nm sample sections. Samples of the second resin (non-crystalline resin) were prepared in the same manner.

[0155] The first and second resins were mixed in ratios of 30 / 70 and 70 / 30, and then melt-kneaded to prepare a kneaded mixture. These were similarly dispersed in a visible-light-curable resin and cut to prepare sample slices.

[0156] Next, the cross-sections of these reference samples were observed using a transmission electron microscope (JEOL Ltd., JEM-2800 electron microscope) via TEM-EDX, and elemental mapping was performed using EDX. The mapped elements were carbon, oxygen, and nitrogen. The mapping conditions were as follows.

[0157] Accelerating voltage: 200kV

[0158] Electron beam exposure size: 1.5nm

[0159] Usage time limit: 600 seconds

[0160] Dead zone time: 20-30

[0161] Mapping resolution: 256×256

[0162] The (oxygen intensity / carbon intensity) and (nitrogen intensity / carbon intensity) values ​​are calculated based on the spectral intensity of each element (average value over a 10 nm square region), and calibration curves are constructed for the mass ratio of the first and second resins. When the monomer units of the first resin contain nitrogen, the (nitrogen intensity / carbon intensity) calibration curve is used for subsequent determinations.

[0163] Next, the toner samples were analyzed. First, the toner was thoroughly dispersed in a visible-light-curable resin (Aronix LCR series D800), and then cured by exposure to short-wavelength light. The cured resin was cut using an ultramicrotome equipped with a diamond blade to prepare 250 nm sample sections. The cut samples were then observed using a transmission electron microscope (JEOL Ltd., JEM-2800 electron microscope) via TEM-EDX. Cross-sectional images of the toner particles were obtained, and elemental mapping was performed using EDX. The mapped elements were carbon, oxygen, and nitrogen.

[0164] Furthermore, the cross-sections of the toner particles to be observed are selected as follows: First, the cross-sectional area of ​​the toner particle is determined from the cross-sectional image of the toner particle, and the diameter (equivalent diameter of the circle) of the same area is determined. Only cross-sectional images of toner particles for which the absolute value of the difference between the equivalent diameter of the circle and the weight-average particle size (D4) of the toner is within 1.0 μm are observed.

[0165] For the observed images, the cross-sections of the toner particles were divided into regions with a size of 10 nm on each side. For each region, the values ​​of (oxygen intensity / carbon intensity) and / or (nitrogen intensity / carbon intensity) were calculated based on the spectral intensity of the elements (the average value of the 10 nm square region), and the first and second resins were distinguished from each other by comparison with the calibration curves described above. When the content of the first or second resin is 80% by mass or more, it is presumed that the 10 nm square region is occupied by either the first or second resin. One hundred toner particle cross-sections were observed, and the area ratios A, B, and X / Z and Y / Z values ​​were calculated based on the analysis results of these regions. For area ratios A and B, the arithmetic mean of the 100 cross-sections was used. Furthermore, binarization and area ratio calculations were performed using Image Pro PLUS (manufactured by Nippon Roper Kabushiki Kaisha).

[0166] Confirmation of matrix-domain structure

[0167] The cross-sections of toner particles were observed in the manner described above. Among the 100 observed toner particle cross-sections, the structure of toner particle cross-sections with an area ratio A of 30–70% was confirmed. If, among the toner particle cross-sections with an area ratio A of 30–70%, the proportion of cross-sections in which the toner particles exhibit a matrix-domain structure was 80% or more, the measured toner particle cross-sections were evaluated as having a matrix-domain structure.

[0168] Furthermore, the state in which domains, as discontinuous phases, are dispersed within a matrix, which is a continuous phase, is taken as the matrix-domain structure. Here, the first resin or the second resin is taken as the continuous phase if more than 90% of the area occupied by the first resin or the area occupied by the second resin in the cross-section of the toner particles exists as a continuous region. In addition, the major axis of the domains is measured, and the number-average diameter of all cross-sections present in the observed cross-section of the toner particles is calculated.

[0169] <Methods for separating materials from toners>

[0170] By taking advantage of the differences in solubility of each material in a solvent, the various materials contained in the toner can be separated from the toner itself.

[0171] First separation: The colorant is dissolved in methyl ethyl ketone (MEK) at 23°C to separate the soluble components (second resin) from the insoluble components (first resin, wax, colorant, inorganic fine particles, etc.).

[0172] Second separation: The insoluble components (first resin, wax, colorant, inorganic particles, etc.) obtained from the first separation are dissolved in MEK at 100°C to separate the soluble components (first resin, wax) from the insoluble components (colorant, inorganic fine particles, etc.).

[0173] Third separation: The soluble components (first resin, wax) obtained from the second separation are dissolved in chloroform at 23°C to separate into soluble components (first resin) and insoluble components (wax).

[0174] Methods for identifying and measuring the content of monomer units constituting the first and second resins

[0175] The method for identifying and determining the content of monomer units constituting the first and second resins is as follows: 1 H-NMR was performed under the following conditions.

[0176] Measurement equipment: FT NMR equipment (JNM-EX400, manufactured by JEOL Ltd.)

[0177] Measurement frequency: 400MHz

[0178] Pulse condition: 5.0 μs

[0179] Frequency range: 10,500Hz

[0180] Total number of times: 64

[0181] Temperature measured: 30℃

[0182] Sample: Place 50 mg of the test sample in a sample tube with an inner diameter of 5 mm, add deuterated chloroform (CDCl3) as a solvent, and dissolve the test sample in a constant temperature bath at 40 °C.

[0183] From what was obtained 1 In the H-NMR spectrum, among the peaks belonging to the constituent elements of the first monomer unit, a peak independent of the peaks belonging to the constituent elements of other monomer units is selected, and the integral value S1 of this peak is calculated. Similarly, when the resin has a second monomer unit, among the peaks belonging to the constituent elements of the second monomer unit, a peak independent of the peaks belonging to the constituent elements of other monomer units is selected, and the integral value S2 of this peak is calculated. When the resin also has an x-th monomer unit, such as a third monomer unit, the integral value S is calculated in the same manner. x .

[0184] The content of the first monomer unit is calculated using these integral values ​​in the following manner. Furthermore, n1, n2, and n... x This indicates the amount of hydrogen in the constituent elements that can be attributed to the peaks observed at each location.

[0185] The content (mol%) of the first monomer unit = {(S1 / n1) / ((S1 / n1)+(S2 / n2)···+(S x / n x ))}×100

[0186] Similarly, the content of the second monomer unit is determined in the following manner.

[0187] The content (mol%) of the second monomer unit = {(S2 / n2) / ((S1 / n1)+(S2 / n2)···+(S x / n x ))}×100

[0188] For example, when polymerizable monomers other than vinyl groups that do not contain hydrogen atoms are used in the first and second resins, 13 C is used as the measurement nucleus, and the measurement is performed in single-pulse mode. 13 C-NMR measurements, and compared with 1 The same calculations are performed using H-NMR measurements. Mole % can be converted to mass % using the molecular weight of the monomer unit.

[0189] <Method for measuring the weight-average molecular weight (Mw) of resins, etc. using gel permeation chromatography (GPC)>

[0190] The weight-average molecular weight (Mw) of tetrahydrofuran (THF) soluble components such as resins was measured by gel permeation chromatography (GPC) as follows.

[0191] First, the sample, such as resin, was dissolved in tetrahydrofuran (THF) at room temperature for 24 hours. The resulting solution was then filtered through a solvent-resistant membrane filter (Maishori Disk, Tosoh Corp.) with a pore size of 0.2 μm to obtain the sample solution. The concentration of the THF-soluble component in the sample solution was adjusted to approximately 0.8% by mass. Measurements were then performed using this sample solution under the following conditions.

[0192] System: HLC8120 GPC (Detector: RI) (Tosoh Corp.)

[0193] Columns: Shodex KF-801, 802, 803, 804, 805, 806, 807 (Total 7) (Showa Denko)

[0194] Eluent: Tetrahydrofuran (THF)

[0195] Flow rate: 1.0 mL / min

[0196] Oven temperature: 40.0℃

[0197] Sample injection volume: 0.10 mL

[0198] The molecular weight calibration curves prepared using standard polystyrene resins (product names: TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500, Tosoh Corp.) were used to calculate the molecular weight of the samples.

[0199] Methods for measuring the melting point, endothermic peak, and heat of heat in toners and resins, etc.

[0200] The melting point, endothermic peak, and heat of endothermic agents or resins are measured using a DSC Q1000 (manufactured by TA Instruments) under the following conditions.

[0201] Heating rate: 10℃ / min

[0202] Measurement start temperature: 20℃

[0203] Measurement termination temperature: 180℃

[0204] Temperature calibration of the detector in the device was performed using the melting points of indium and zinc, and thermal calibration was performed using the heat of fusion of indium. Specifically, approximately 5 mg of sample was weighed, placed in an aluminum pan, and differential scanning calorimetry (DSC) was performed. An empty silver pan was used as a reference. The melting point was taken as the peak temperature of the maximum endothermic peak during the first heating step. Furthermore, in the case of multiple peaks, the maximum endothermic peak was taken as the peak with the largest endothermic heat. The heat of endothermic absorption at this maximum endothermic peak was also measured. Peak assignment could be determined by performing DSC measurements on the individual unit materials separated from the aforementioned toner.

[0205] Methods for measuring acid value

[0206] Acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1g of sample. Acid value is measured according to JIS K0070-1992, but the following steps are used for specific measurement.

[0207] (1) Preparation of reagents

[0208] A phenolphthalein solution was obtained by dissolving 1.0 g of phenolphthalein in 90 mL of ethanol (95 vol%) and adding deionized water to a volume of 100 mL. A potassium hydroxide solution was obtained by dissolving 7 g of high-grade potassium hydroxide in 5 mL of water and adding ethanol (95 vol%) to a volume of 1 L. The resulting solution was placed in an alkali-resistant container to prevent contact with carbon dioxide gas, etc., and allowed to stand for 3 days, then filtered to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution was stored in an alkali-resistant container. The factor of the potassium hydroxide solution was determined as follows: 25 mL of 0.1 mol / L hydrochloric acid was placed in an Erlenmeyer flask, a few drops of phenolphthalein solution were added, and titrated with potassium hydroxide solution. The factor was determined by the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid was produced according to JIS-K8001-1998.

[0209] (2) Operation

[0210] (A) Main Experiment

[0211] Accurately weigh 2.0 g of the pulverized sample into a 200 mL Erlenmeyer flask, add 100 mL of a toluene / ethanol (2:1) mixture, and allow the sample to dissolve for 5 hours. Next, add a few drops of phenolphthalein solution as an indicator and titrate with potassium hydroxide solution. The endpoint of the titration is considered to be the point where the indicator remains a pale red color for approximately 30 seconds.

[0212] (B) Blank test

[0213] The titration was performed in the same manner as described above, except that no sample was used (i.e., only a toluene / ethanol (2:1) mixture was used).

[0214] (3) The acid value is calculated by substituting the obtained result into the following formula.

[0215] A = [(CB) × f × 5.61] / S

[0216] Here, A represents the acid value (mgKOH / g), B represents the amount of potassium hydroxide solution added in the blank test (mL), C represents the amount of potassium hydroxide solution added in the main test (mL), f represents the potassium hydroxide solution factor, and S represents the sample mass (g).

[0217] <Method for measuring resin softening temperature (Tm)>

[0218] The softening temperature of the resin was measured using a constant-load extrusion capillary rheometer (Shimadzu Corporation, CFT-500D Flowtester flow property evaluation device) according to the accompanying manual. Using this device, the temperature of the sample in the barrel was increased to melt it, while a constant load was applied to the sample from above using a piston. The molten sample was then extruded through a die at the bottom of the barrel. A flow curve showing the relationship between temperature and piston descent during this process was obtained. The "melting temperature of the 1 / 2 method" described in the manual accompanying the CFT-500D Flowtester flow property evaluation device is given as the softening temperature.

[0219] The melting temperature of the 1 / 2 method is calculated as follows.

[0220] Determine half the difference between the piston descent at the end of the outflow (the outflow endpoint, given as "Smax") and the piston descent at the beginning of the outflow (the minimum point, given as "Smin"), and give it as X (X = (Smax - Smin) / 2). The temperature in the flow profile where the piston descent is the sum of X and Smin is the melting temperature of the 1 / 2 method.

[0221] For the test sample, about 1.0 g of resin was compressed at about 10 MPa for about 60 seconds at 25°C using a tableting compressor (e.g., NPaSystems Co., Ltd., NT-100H) to obtain a cylindrical sample with a diameter of about 8 mm.

[0222] The specific measurement operations should be performed in accordance with the device manual.

[0223] The measurement conditions for the CFT-500D are as follows.

[0224] Measurement mode: Heating method

[0225] Starting temperature: 50℃

[0226] Reaching temperature: 200℃

[0227] Measurement interval: 1.0℃

[0228] Heating rate: 4.0℃ / min

[0229] Piston cross-sectional area: 1.000 cm² 2

[0230] Test load (piston load): 10.0 kgf / cm 2 (0.9807MPa)

[0231] Warm-up time: 300 seconds

[0232] Mold bore diameter: 1.0mm

[0233] Mold length: 1.0mm

[0234] <Method for measuring the weight-average particle size (D4) of toner particles>

[0235] A Multisizer 3CoulterCounter precision particle size distribution analyzer based on pore resistance method and equipped with a 100 μm inlet tube, along with the accompanying dedicated Beckman Coulter Multisizer 3 Version 3.51 software (Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data, was used to measure 25,000 effective measurement channels and analyze the measurement data to calculate the weight-average particle size (D4) of the toner particles (or toner). The electrolyte aqueous solution used in the measurement can be a solution of super-grade sodium chloride dissolved in ion-exchanged water to a concentration of approximately 1% by mass, for example, ISOTON II (Beckman Coulter, Inc.). The dedicated software settings are performed as follows prior to measurement and analysis.

[0236] On the "Standard Measurement Method (SOM) Change" interface of the dedicated software, set the total count in the 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" (Beckman-Coulter, Inc.). The threshold noise level is automatically set by pressing the "Threshold / Noise Level Measurement Button". Additionally, set the current to 1600 μA, the gain to 2, and the electrolyte solution to ISOTON II; and check the rinsing tube after measurement. On the "Pulse to Particle Size Conversion Setting" interface of the dedicated software, set the element spacing to logarithmic particle size, the particle size element to 256, and the particle size range to 2 μm to 60 μm. The specific measurement method is as follows.

[0237] (1) Add approximately 200 mL of electrolyte solution to a 250 mL round-bottom beaker specifically designed for Multisizer3. Place the beaker in the sample holder and stir counterclockwise with a stir bar at a speed of 24 rpm. Then, remove any contaminants and air bubbles from the beaker using the "Flush" function in the dedicated software.

[0238] (2) Place 30 mL of the same electrolyte aqueous solution into a 100 mL flat-bottomed glass beaker, and add 0.3 mL of a diluted solution made by diluting “Contaminon N” (a 10% by mass aqueous solution of a neutral detergent for precision measuring instruments with a pH of 7, consisting of nonionic surfactants, anionic surfactants and organic detergent builders, manufactured by Wako PureChemical Industries) with deionized water by 3 times by mass.

[0239] (3) Place a specific amount of ion-exchanged water into the water tank of an ultrasonic disperser (Ultrasonic Dispersion SystemTetora 150, Nikkaki Bios). The ultrasonic disperser has a power output of 120W and is equipped with two built-in oscillators with a phase shift of 180° and an oscillation frequency of 50kHz. Add about 2mL of Contaminon N to the water tank.

[0240] (4) Place the beaker from (2) above into the beaker fixing hole of the ultrasonic disperser and start the ultrasonic disperser. Adjust the height of the beaker to maximize the resonance state of the electrolyte aqueous solution surface in the beaker.

[0241] (5) While exposing the electrolyte solution in the beaker from (4) above to ultrasound, add 10 mg of toner (granules) little by little to the electrolyte solution and disperse it. Then, continue ultrasonic dispersion for an additional 60 seconds. During ultrasonic dispersion, adjust the water temperature in the bath appropriately from 10°C to 40°C.

[0242] (6) Using a pipette, add the electrolyte aqueous solution in (5) above, in which the toner (particles) are dispersed, dropwise into the round-bottom beaker in (1) placed in the sample holder, and adjust the measurement concentration to about 5%. Then, perform the measurement until the number of particles measured reaches 50,000.

[0243] (7) Use the dedicated software provided with the equipment to analyze the measurement data and calculate the weight-average particle size (D4). The weight-average particle size (D4) is the "average diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" interface when the chart / volume % is set in the dedicated software.

[0244] Method for measuring the 50% particle size (D50) based on volume of fine resin particles, fine wax particles, and fine colorant particles.

[0245] The volume-based 50% particle size (D50) of fine particles was measured using a dynamic light scattering particle size distribution analyzer (Ninotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.). Specifically, the measurements were performed using the following steps: To prevent aggregation of the measurement sample, a dispersion obtained by dispersing the measurement sample in an aqueous solution containing Family Fresh (manufactured by Kao Corporation) was introduced and stirred. After stirring, the measurement sample was introduced into the instrument, and two measurements were performed, and the average value was calculated.

[0246] Regarding the measurement conditions, the measurement time was 30 seconds, the refractive index of the sample particles was 1.49, the dispersion medium was water, and the refractive index of the dispersion medium was 1.33. The volume-based particle size distribution of the measured sample was determined, and based on the measurement results, the particle size that accounts for 50% of the cumulative value from the smallest particle size side in the volume-based particle size distribution was taken as the volume-based 50% particle size (D50) of the fine particles.

[0247] Example

[0248] The present disclosure will now be described in more detail using the examples given below. However, these examples are in no way limiting of the present disclosure. In the following formulations, "parts" always refers to parts by weight unless otherwise expressly stated.

[0249] Production Example of First Resin 1 (Crystallized Resin 1)

[0250] Solvent: Toluene: 100.0 parts

[0251] • Monomer composition: 100.0 parts

[0252] (The monomer composition is obtained by mixing benzyl acrylate, acrylic acid and styrene in the proportions shown below)

[0253] (Bezoar acrylate: 40.0 parts)

[0254] (Acrylic acid: 1.0 part)

[0255] (Styrene: 59.0 parts)

[0256] • Polymerization initiator: 0.5 parts

[0257] tert-butyl peroxypentanoate (Perbutyl PV, manufactured by NOF Corp.)

[0258] The above materials were placed in a reaction vessel equipped with a reflux condenser, stirrer, thermometer, and nitrogen inlet under a nitrogen atmosphere. While stirring at 200 rpm, the interior of the reaction vessel was heated to 70°C, and the polymerization reaction was carried out for 12 hours to obtain a solution in which the polymer of the monomer composition was dissolved in toluene. Subsequently, after the solution temperature was lowered to 25°C, the solution was poured into 1000 parts of methanol while stirring to precipitate the methanol-insoluble matter. The obtained methanol-insoluble matter was filtered out, further washed with methanol, and then vacuum dried at 40°C for 24 hours to obtain the first resin 1 (crystalline resin 1).

[0259] Production examples of first resins 2-5 (crystalline resins 2-5)

[0260] Except for changing the monomers and their proportions as shown in Table 1-1, first resins 2 to 12 (crystalline resins 2 to 12) are obtained by carrying out the same reaction as used in the production example of first resin 1. The physical properties are shown in Table 2.

[0261] [Table 1-1]

[0262]

[0263] The abbreviations used in the table are as follows.

[0264] BEA: Betaine Acrylate

[0265] ODA: Octadecyl acrylate

[0266] AA: Acrylic acid

[0267] St: Styrene

[0268] Production Example of First Resin 6 (Crystallized Resin 6)

[0269] ·1,6-Hexanediol: 33.9 parts

[0270] (Relative to the total molar percentage of polyols: 100.0 mol%)

[0271] • Dodecanoic acid: 66.1 parts

[0272] (Relative to the total molar percentage of polycarboxylic acids, which is 100.0 mol%)

[0273] · Tin 2-ethylhexanoate: 0.5 parts

[0274] The above materials were weighed into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet pipe, and thermocouple. The flask was purged with nitrogen, and while stirring the contents of the flask, the temperature was gradually increased, and the reaction was carried out for 3 hours at 140°C while stirring the contents of the flask. Next, the pressure inside 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. Then, by reducing the pressure inside the reaction vessel to below 5 kPa and reacting at 200°C for 3 hours, the first resin 6 (crystalline resin 6) was obtained.

[0275] Production examples of first resins 7-9 (crystalline resins 7-9)

[0276] Except for changing the alcohol and carboxylic acid components to the monomers shown in Tables 1-2, the first resins 7-9 were obtained by producing them in the same manner as in the production example of the first resin 6. Their physical properties are shown in Table 2.

[0277] [Table 1-2]

[0278]

[0279] The abbreviations used in the table are as follows.

[0280] EG: Ethylene glycol

[0281] BO: Butanediol

[0282] HO: Hexanediol

[0283] DA: Sebacic acid

[0284] DDA: dodecanedioic acid

[0285] TDA: Tetradecanedioic acid

[0286] [Table 2]

[0287]

[0288] AVc represents the acid value and Tp represents the melting point.

[0289] Production Example of Second Resin 1 (Non-crystalline Resin 1)

[0290] In a nitrogen atmosphere, place the following materials in a reaction vessel equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet pipe.

[0291] • Polyoxypropylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 73.2 parts (0.25 mol; 100.0 mol% relative to the total moles of polyols)

[0292] • Terephthalic acid: 25.1 parts (0.24 mol; 95.0 mol% relative to the total moles of polycarboxylic acids)

[0293] Tetrabutoxytitanium: 2.0 parts

[0294] Next, the flask was purged with nitrogen. While stirring the contents of the flask, the temperature was gradually increased, and the reaction was carried out for 2 hours while stirring the contents of the flask and distilling off the generated water. Then, the pressure inside the reaction vessel was reduced to 8.3 kPa and maintained at this pressure for 1 hour. After that, the contents of the reaction vessel were cooled to 180°C and the reaction vessel was restored to atmospheric pressure (first reaction step).

[0295] Trimeric triglyceride: 8.2 parts (0.02 mol; 5.0 mol% relative to the total moles of polycarboxylic acids)

[0296] • Tert-butylcatechol (polymerization inhibitor): 0.1 parts

[0297] Next, the above materials were added, the pressure inside the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining a temperature of 150°C. The temperature was then lowered to terminate the reaction (second reaction step) to obtain the second resin 1. The physical properties are shown in Table 4.

[0298] Production Example of Second Resin 2 (Non-crystalline Resin 2)

[0299] In a nitrogen atmosphere, place the following materials in a reaction vessel equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet pipe.

[0300] • Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 81.0 parts (0.20 mol; 50.0 mol% relative to the total moles of polyols)

[0301] • Polyoxypropylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 115.0 parts (0.25 mol; 40.0 mol% relative to the total moles of polyols)

[0302] Ethylene glycol: 3.1 parts (0.05 mol; 10.0 mol% relative to the total moles of polyols)

[0303] • Terephthalic acid: 49.8 parts (0.30 mol; 60.0 mol% relative to the total moles of polycarboxylic acids)

[0304] • Adipic acid: 21.9 parts (0.15 mol; 30.0 mol% relative to the total moles of polycarboxylic acids)

[0305] Tetrabutoxytitanium: 2.5 parts

[0306] Weigh the materials listed above and introduce them into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet, and thermocouple. Next, purge the flask with nitrogen, and while stirring the contents, gradually increase the temperature. Continue the reaction for 2 hours at 230°C, stirring the contents and distilling off the generated water. Then, react under reduced pressure of 8.3 kPa for 1 hour, after which raise the temperature to 180°C and restore the pressure to atmospheric pressure (first reaction step).

[0307] Trimeric triglyceride: 13.3 parts (0.05 mol; 10.0 mol% relative to the total moles of polycarboxylic acids)

[0308] • tert-butylcatechol (polymerization inhibitor): 1 part

[0309] Next, the above materials were added, the pressure inside the reaction vessel was reduced to 8.3 kPa, and the reaction was carried out for 4 hours while maintaining a temperature of 150°C. The temperature was then lowered to terminate the reaction (second reaction step) to obtain non-crystalline resin 2.

[0310] Production Example of Second Resin 3 (Non-crystalline Resin 3)

[0311] 50.0 parts of xylene were placed in an autoclave, then purged with nitrogen. The autoclave temperature was then raised to 185°C under stirring and a sealed environment. While maintaining the autoclave temperature at 190°C, a mixed solution of 74.6 parts of styrene, 24.7 parts of n-butyl acrylate, 0.7 parts of acrylic acid, 1.0 part of di-tert-butyl peroxide, and 20.0 parts of xylene was continuously added dropwise over 3 hours and polymerized. The polymerization was completed by maintaining this temperature for another hour and removing the solvent, yielding the second resin 3 (amorphous resin 3).

[0312] Production example of the second resin 4 (non-crystalline resin 4)

[0313] In a nitrogen atmosphere, place the following materials in a reaction vessel equipped with a reflux condenser, stirrer, thermometer and nitrogen inlet pipe.

[0314] • Polyoxyethylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 23.0 parts (0.05 mol; 10.0 mol% relative to the total moles of polyols)

[0315] • Polyoxypropylene (2.0)-2,2-bis(4-hydroxyphenyl)propane: 182.0 parts (0.45 mol; 90.0 mol% relative to the total moles of polyols)

[0316] • Terephthalic acid: 49.8 parts (0.30 mol; 60.0 mol% relative to the total moles of polycarboxylic acids)

[0317] • Adipic acid: 21.9 parts (0.15 mol; 30.0 mol% relative to the total moles of polycarboxylic acids)

[0318] Tetrabutoxytitanium: 2.5 parts

[0319] Weigh the materials listed above and introduce them into a reaction vessel equipped with a condenser, stirrer, nitrogen inlet, and thermocouple. Next, purge the flask with nitrogen, and while stirring the contents, gradually increase the temperature. Continue the reaction for 2 hours at 230°C, stirring the contents and distilling off the generated water. Then, react under reduced pressure of 8.3 kPa for 1 hour, after which raise the temperature to 180°C, and then restore the pressure to atmospheric pressure (first reaction step).

[0320] Trimeric triglyceride: 13.3 parts (0.05 mol; 10.0 mol% relative to the total moles of polycarboxylic acids)

[0321] • tert-butylcatechol (polymerization inhibitor): 1 part

[0322] Next, the materials listed above are added, the pressure inside the reaction vessel is reduced to 8.3 kPa, the reaction is carried out for 4 hours while maintaining a temperature of 150°C, and the temperature is lowered to terminate the reaction (second reaction step) to obtain non-crystalline resin 4.

[0323] Production Example of Second Resin 5 (Non-crystalline Resin 5)

[0324] (Formulation of polyester resin 1)

[0325] • 50.0 molar amount of the (2.2 mol) adduct of ethylene oxide and bisphenol A.

[0326] • 50.0 molar amount of the (2.2 mol) adduct of propylene oxide and bisphenol A.

[0327] • Terephthalic acid: 65.0 moles

[0328] Trimeric trioxide: 25.0 moles

[0329] Acrylic acid: 10.0 moles

[0330] Ninety parts of the monomer mixture used to produce polyester resin 1 were placed in a four-necked flask. A vacuum device, a water separator, a nitrogen inlet device, a temperature measuring device, and a stirrer were connected to the flask, and the mixture was stirred at 160°C under a nitrogen atmosphere. Then, after 4 hours, 10 parts of vinyl polymerizable monomers used to produce vinyl-based resins (81.0 parts styrene, 17.0 parts n-butyl acrylate, 0.9 parts acrylic acid, and 1.1 parts divinylbenzene) and 1 part benzoyl peroxide as a polymerization initiator were added dropwise through a dropping funnel, and the reaction was carried out at 160°C for 5 hours. Then, the temperature was raised to 230°C, and tetrabutoxytitanium was added in an amount of 0.2 parts relative to the total amount of monomers used to produce the polyester resin, and polymerization was carried out until a softening point of 105°C was reached. After the reaction was complete, the polymer was removed from the container, cooled, and pulverized to obtain the second resin 5 (amorphous resin 5). The physical properties are shown in Table 4.

[0331] Production example of the second resin 6 (non-crystalline resin 6)

[0332] • Uniol DA-400 (manufactured by NOF Corp.): 60.8 units

[0333] • Dimethylolbutyric acid: 2.5 parts

[0334] • Diphenylmethane-4,4'-diisocyanate: 38.5 parts

[0335] • Dioctyltin dilaurate: 0.04 parts

[0336] The monomers listed above were placed in a flask equipped with a stirrer, a nitrogen inlet pipe, a temperature sensor, and a distillation column, and reacted at 130°C for 5 hours to obtain the second resin 6, which serves as a polyurethane resin. The physical properties are shown in Table 4.

[0337] [Table 3]

[0338]

[0339] AVA represents the acid value, Tg represents the glass transition temperature, and Tm represents the softening point.

[0340] Production example of colorant granules 1a

[0341] • First resin 1:50 parts

[0342] • Second resin 1:50 parts

[0343] • Hydrocarbon wax 1 (Fischer-Tropsch wax; peak temperature of the maximum endothermic peak in DSC: 92℃): 10.0 parts

[0344] • Pigment (cyan pigment, pigment blue 15:3, produced by Dainichiseika Color and Chemicals Mfg. Co., Ltd.): 6.5 parts

[0345] Using a Henschel mixer (FM-75 model, manufactured by Nippon Coke and Engineering Co., Ltd.), at 20 seconds -1 The materials listed above were mixed at a certain speed for 3 minutes. Then, they were kneaded at a screw speed of 250 rpm and a discharge temperature of 125°C using a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corporation) set to a temperature of 120°C. The resulting kneaded product was cooled and then coarsely pulverized to a size of less than 1 mm using a hammer mill to obtain a coarsely pulverized product. The coarsely pulverized product was then finely pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Corporation). The finely pulverized product was then classified using a Faculty F-300 (manufactured by Hosokawa Micron Corp.) to obtain toner particles 1a with a weight average particle size of approximately 6.0 μm. The operating conditions were a classification rotor speed of 130 s. -1 The rotational speed of the dispersed rotor is 120s. -1 .

[0346] Production examples of toner granules 1b and 1c

[0347] Except for changing the proportions of the first resin and the second resin as shown in Table 4, toner particles 1b and 1c are obtained by producing them in the same manner as in the production example of toner particles 1a.

[0348] Production examples of colorant granules 2a-12a, 16a-28a, 2b-12b and 16b-22b

[0349] Except for changing the type and amount of the first and second resins as shown in Table 4, toner particles 2a-12a, 16a-28a, 2b-12b and 16b-22b are obtained by producing them in the same manner as in the production example of toner particles 1a.

[0350] Production example of colorant granules 13

[0351] Production Example of First Resin 6 Fine Particle Dispersion

[0352] • Toluene (produced by Wako Pure Chemical Industries, Ltd.): 300 parts

[0353] • First resin 6: 100 parts

[0354] Weigh out the materials listed above, mix them, and dissolve them at 90°C. Additionally, add 5.0 parts sodium dodecylbenzenesulfonate and 10.0 parts sodium laurate to 700 parts deionized water and dissolve them by heating at 90°C. Next, mix the above toluene solution and aqueous solution together and stir at 7000 rpm using a TK Robomix ultra-high-speed stirrer (manufactured by Primix Corporation). Then, emulsify the obtained mixture at a pressure of 200 MPa using a Nanozer high-pressure impact disperser (manufactured by Yoshida Kikai Co., Ltd.). Then, remove the toluene using an evaporator and adjust the concentration using deionized water to obtain an aqueous dispersion containing 20% ​​by mass of fine particles of the first resin 6 (first resin 6 fine particle dispersion solution). The volume-based 50% particle size (D50) of the first resin 6 was measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.) and was found to be 0.40 μm.

[0355] Example of production of fine particle dispersion of second resin 4

[0356] Tetrahydrofuran (produced by Wako Pure Chemical Industries, Ltd.): 300 parts

[0357] • Second resin 4: 100 parts

[0358] • Anionic surfactant (Neogen RK, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): 0.5 parts

[0359] Weigh out the materials listed above, mix and dissolve them. Next, add 20.0 parts of 1 mol / L ammonia solution and stir at 4000 rpm using a TK Robomix ultra-high-speed stirrer (manufactured by Primix Corporation). Then, add 700 parts of deionized water at a rate of 8 g / min to precipitate fine particles of the second resin 4. Then, remove tetrahydrofuran by using an evaporator and adjust the concentration with deionized water to obtain an aqueous dispersion containing fine particles of the second resin 4 at a concentration of 20% by mass (second resin 4 fine particle dispersion). The volume-based 50% particle size (D50) of the second resin 4 fine particles is 0.14 μm.

[0360] Production example of wax fine particle dispersion

[0361] - Hydrocarbon wax 1 100.0 parts

[0362] (Fischer-Tropsch wax; DSC: peak temperature of the maximum endothermic peak 92℃)

[0363] - 5 parts of anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0364] - 395 portions of ion-exchanged water

[0365] Weigh out the above materials and place them in a mixing container equipped with a stirrer. Heat to 90°C, circulate to CLEAREMIX W-MOTION (manufactured by M-Technique Co., Ltd.), and disperse for 60 minutes. The dispersion conditions are as follows.

[0366] - Rotor outer diameter: 3cm

[0367] - Gap: 0.3mm

[0368] - Rotor speed: 19000 r / min

[0369] - Screen rotation speed: 19000 r / min

[0370] After dispersion, the mixture was cooled to 40°C under the following conditions: rotor speed 1000 r / min, screen speed 0 r / min, and cooling rate 10°C / min, to obtain an aqueous dispersion of 20% by mass of fine wax particles (fine wax particle dispersion). The 50% particle size (D50) based on the volume distribution of the fine wax particles was measured using a dynamic light scattering particle side profile meter NANOTRACK UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and determined to be 0.15 μm.

[0371] <Production Example of Colorant Fine Particle Dispersion>

[0372] -Colorant 1 50.0 parts

[0373] (Cyan pigment: Pigment blue 15:3, manufactured by Dainichiseika Color & Chem MFG Co., Ltd.)

[0374] - 7.5 parts of anionic surfactant NEOGEN RK (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)

[0375] - 442.5 parts of ion-exchanged water

[0376] The above materials were weighed, mixed, dissolved, and dispersed for approximately 1 hour using a high-pressure impact disperser NANOMIZER (manufactured by Yoshida Kikai Co., Ltd.) to obtain an aqueous dispersion (colorant fine particle dispersion) in which the colorant is dispersed and the concentration of colorant fine particles is 10% by mass. The 50% particle size (D50) of the colorant fine particles based on the volume distribution was measured using a dynamic light scattering particle side distribution meter NANOTRACK UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and determined to be 0.20 μm.

[0377] Production example of colorant granules 13a

[0378] • First resin 6 fine particle dispersion: 300 parts

[0379] • Second resin 4 fine particle dispersion: 200 parts

[0380] • Colorant fine particle dispersion: 65 parts

[0381] • Fine wax particle dispersion: 50 parts

[0382] • Ion-exchanged water: 160 parts

[0383] Place the materials listed above into a round stainless steel flask and mix. Next, disperse the resulting mixture for 10 minutes at 5000 rpm using a homogenizer (Ultratarax T50, manufactured by IKA). Add 1.0% nitric acid aqueous solution to adjust the pH to 3.0, then heat the mixture to 58°C in a heated water bath while adjusting the speed of the stirrer blades appropriately. Use a Coulter Multisizer III to appropriately confirm the formation of aggregated particles. When aggregated particles with a weight-average particle size (D4) of approximately 6.00 μm are formed, adjust the pH to 9.0 using a 5% sodium hydroxide aqueous solution.

[0384] The solution was then heated to 75°C while continuing stirring. The aggregated particles were fused together by maintaining the temperature at 75°C for 1 hour. Crystallization of the resin was then promoted by cooling to 50°C and maintaining that temperature for 3 hours. The mixture was then cooled to 25°C, filtered, and subjected to solid-liquid separation, followed by washing with deionized water. After washing, the toner particles 13a with a weight-average particle size (D4) of approximately 6.0 μm were obtained by drying using a vacuum dryer.

[0385] Production example of colorant granules 13b

[0386] Except for changing the number of parts of the first resin 6 fine particle dispersion from 300 parts to 475 parts and the number of parts of the second resin 4 fine particle dispersion from 200 parts to 25 parts, the toner particles 13b are obtained by producing them in the same manner as in the production example of toner particles 13a.

[0387] Production Example of First Resin 8 Fine Particle Dispersion

[0388] Except for changing the first resin 6 to the first resin 8, the first resin 8 fine particle dispersion was obtained by producing it in the same manner as the production example of the first resin 6 fine particle dispersion. The volume-based 50% particle size (D50) of the first resin 6 was measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.) and was found to be 0.40 μm.

[0389] Example of production of fine particle dispersion of second resin 3

[0390] Except for changing the second resin 4 to the second resin 3, the second resin 3 fine particle dispersion was obtained by producing it in the same manner as the production example of the second resin 4 fine particle dispersion. The volume-based 50% particle size (D50) of the second resin 3 was measured using a dynamic light scattering particle size distribution analyzer (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.) and was found to be 0.40 μm.

[0391] Production example of colorant granules 15a

[0392] Except for changing the fine particle dispersion of the first resin 6 to the fine particle dispersion of the first resin 8 and the fine particle dispersion of the second resin 4 to the fine particle dispersion of the second resin 3, the toner particles 15a are obtained by producing them in the same manner as in the production example of the toner particles 13a.

[0393] Production example of colorant granules 15b

[0394] Except for changing the fine particle dispersion of the first resin 6 to the fine particle dispersion of the first resin 8 and the fine particle dispersion of the second resin 4 to the fine particle dispersion of the second resin 3, the toner particles 15b are obtained by producing them in the same manner as in the production example of the toner particles 13b.

[0395] Production example of colorant granules 14a

[0396] ·First Resin 7: 60.0 parts

[0397] • Second resin 1: 40.0 parts

[0398] • Hydrocarbon wax (Fischer-Tropsch wax; peak temperature of the maximum endothermic peak in DSC: 92℃): 10.0 parts

[0399] Pigment Blue 15:3 (produced by Dainichiseika Color and Chemicals Mfg.Co.,Ltd.): 5.0 parts

[0400] Toluene: 150.0 parts

[0401] An oil phase was prepared by adding the solution to a container and stirring / dispersing at 2000 rpm for 5 minutes using a homogenizer (manufactured by Tokushu Kika Kogyo Co., Ltd.). In another container, 390.0 parts of a 0.1 mol / L sodium phosphate (Na3PO4) aqueous solution were added to 1152.0 parts of ion-exchanged water, and the temperature was raised to 70°C while stirring with a Clearmix (manufactured by M Technique Co., Ltd.). Then, a dispersion stabilizer containing tricalcium phosphate (Ca3(PO4)2) was prepared by adding 58.0 parts of a 1.0 mol / L calcium chloride (CaCl2) aqueous solution and continuing stirring, thus preparing an aqueous medium.

[0402] Next, the oil phase was added to the aqueous phase, and granulation was performed by stirring at 10,000 rpm for 10 minutes at 60°C under a nitrogen atmosphere using a Clearmix (manufactured by M Technique Co., Ltd.). Then, while stirring the suspension with a paddle mixer at 150 rpm, the resulting suspension was desolvated under reduced pressure at 80°C and 400 mbar for 5 hours. Then, toner slurry 14a was obtained by cooling the suspension to 25°C and adding deion-exchanged water to achieve a solid content of 20% by mass in the dispersion. Toner slurry 14a was cooled to 25°C, hydrochloric acid was added until the pH reached 1.5, and the slurry was stirred for 2 hours. Then, toner particles 14a were obtained by thoroughly washing the slurry with deion-exchanged water, filtering, drying, and classifying.

[0403] Production example of colorant granules 14b

[0404] Except for changing the amount of the first resin 7 from 60.0 parts to 95.0 parts and the amount of the second resin 1 from 40.0 parts to 5.0 parts, the toner particles 14b are obtained by producing them in the same manner as in the production example of toner particles 14a.

[0405] [Table 4]

[0406]

[0407] Production example of colorant 1

[0408] • Toner granules 1a: 64 parts

[0409] • Toner granules 1b: 20 parts

[0410] • Toner granules 1c: 16 parts

[0411] · Fine silica particles 1:0.5 parts

[0412] (Hydrophobicated silica fine particles with a number-average primary particle size of 15 nm)

[0413] · Fine silica particles 2:1.0 parts

[0414] (Hydrophobicated silica fine particles with a number-average primary particle size of 80 nm)

[0415] Toner 1 was mixed in an FM-10C Henschel mixer (manufactured by Mitsui Miike Kakoki Corporation) for 50 seconds. -1 The mixture was obtained by combining the materials listed above with a rotational speed and a rotation time of 10 minutes. The physical properties are shown in Table 5.

[0416] Production examples of colorants 2-28

[0417] Except for changing the toner particle composition as shown in Table 4, toners 2 to 28 were obtained by producing them in the same manner as in the production example of toner 1. The physical properties of the obtained toners are shown in Table 5.

[0418] [Table 5]

[0419]

[0420] The number-average diameter of a field is the number-average length of its major axis.

[0421] Production Example of Magnetic Carrier 1

[0422] • Magnetite 1; Number average particle size: 0.30 μm (1000 / 4π (kA / m)); Magnetization under a magnetic field: 65 Am 2 / kg)

[0423] • Magnetite 2; Number average particle size: 0.50 μm (1000 / 4π (kA / m)); Magnetization under a magnetic field: 65 Am 2 / kg)

[0424] 4.0 parts of a silane compound (3-(2-aminoethylaminopropyl)trimethoxysilane) were added to more than 100 parts of each of the listed materials, and the mixture was subjected to high-speed mixing and stirring in a container at a temperature above 100°C to process fine particles.

[0425] Phenol: 10% by mass

[0426] • Formaldehyde solution: 6% by mass (40% by mass formaldehyde, 10% by mass methanol and 50% by mass water)

[0427] Magnetite treated with the above silane compound 1:58 by mass

[0428] • Magnetite treated with the above silane compound 2:26% by mass

[0429] More than 100 parts of the listed materials, 5 parts of a 28% by mass ammonia solution, and 20 parts of water were placed in a flask. While stirring and mixing, the temperature was raised to 85°C and maintained at this temperature for 30 minutes, allowing the polymerization reaction to proceed for 3 hours, and the resulting phenolic resin to cure. The cured phenolic resin was then cooled to 30°C, water was added, the supernatant was removed, and the resulting precipitate was washed with water and air-dried. Next, the precipitate was dried at 60°C under reduced pressure (not exceeding 5 mmHg) to obtain spherical magnetic carrier 1 in the form of a magnetic material dispersion. The volume-based 50% particle size (D50) of magnetic carrier 1 was 34.2 μm.

[0430] <Production Example of Two-Component Developer 1>

[0431] A total of 8.0 parts of toner 1 were added to 92.0 parts of magnetic carrier 1 and mixed using a V-type mixer (V-20, manufactured by Seishin Enterprise Co., Ltd.) to obtain two-component developer 1.

[0432] Production examples of two-component developer 2-28

[0433] Except for changing the toner as shown in Table 6, two-component developers 2 to 28 were obtained by producing them in the same manner as in the production example of two-component developer 1.

[0434] [Table 6]

[0435] Two-component developer Toner granules carrier Two-component developer 1 Toner 1 Carrier 1 Two-component developer 2 Toner 2 Carrier 1 Two-component developer 3 Toner 3 Carrier 1 Two-component developer 4 Toner 4 Carrier 1 Two-component developer 5 Toner 5 Carrier 1 Two-component developer 6 Toner 6 Carrier 1 Two-component developer 7 Toner 7 Carrier 1 Two-component developer 8 Toner 8 Carrier 1 Two-component developer 9 Toner 9 Carrier 1 Two-component developer 10 Toner 10 Carrier 1 Two-component developer 11 Toner 11 Carrier 1 Two-component developer 12 Toner 12 Carrier 1 Two-component developer 13 Toner 13 Carrier 1 Two-component developer 14 Toner 14 Carrier 1 Two-component developer 15 Toner 15 Carrier 1 Two-component developer 16 Toner 16 Carrier 1 Two-component developer 17 Toner 17 Carrier 1 Two-component developer 18 Toner 18 Carrier 1 Two-component developer 19 Toner 19 Carrier 1 Two-component developer 20 Toner 20 Carrier 1 Two-component developer 21 Toner 21 Carrier 1 Two-component developer 22 Toner 22 Carrier 1 Two-component developer 23 Toner 23 Carrier 1 Two-component developer 24 Toner 24 Carrier 1 Two-component developer 25 Toner 25 Carrier 1 Two-component developer 26 Toner 26 Carrier 1 Two-component developer 27 Toner 27 Carrier 1 Two-component developer 28 Toner 28 Carrier 1

[0436] <Example 1>

[0437] Evaluation was conducted using a two-component developer 1. As the image forming device, a modified Canon imageRUNNER ADVANCE C5560 printer for digital commercial printing was used, and the two-component developer 1 was placed in the cyan developing unit. The printer was modified to allow free setting of the fixing temperature, processing speed, DC voltage VDC of the developer carrier, charging voltage VD of the electrostatic latent image carrier, and laser power. In the image output evaluation, an FFh image (solid image) with the desired image ratio was output. VDC, VD, and laser power were adjusted to obtain the desired toner load on the FFh image on paper, and the following evaluation was performed. FFh is a hexadecimal display of 256 gray levels, where 00h is the first gray level (white background portion) of the 256 gray levels, and FFh is the 256th gray level (solid portion) of the 256 gray levels. The evaluation was based on the following evaluation method, and the results are shown in Table 7.

[0438] <Low-temperature fixing properties>

[0439] -Paper: GFC-081 (81.0g / m³) 2 )

[0440] (Sold by Canon Marketing Japan Inc.)

[0441] -Toner carrying capacity on paper: 0.70 mg / cm³ 2

[0442] (Adjusted by the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power)

[0443] -Evaluate the image: A 2cm x 15cm image placed in the center of an A4 sheet of paper.

[0444] - Test environment: Low temperature and low humidity environment: temperature 15℃ / humidity 10%RH (hereinafter referred to as "L / L")

[0445] - Fixing temperature: 140℃

[0446] - Processing speed: 400mm / sec

[0447] Output the above evaluation images and evaluate the low-temperature fixing performance. The image density reduction rate is used as an indicator to evaluate the low-temperature fixing performance. First, the image density reduction rate in the central part of the image is measured using an X-Rite color reflectance densitometer (500 series, manufactured by X-Rite). Then, under an application of 4.9 kPa (50 g / cm³), the image density reduction rate is measured. 2While applying a load, the fixed image on the area where the image density was measured was rubbed (reciprocated 10 times) with lens cleaning paper, and then the image density was measured again. Next, the rate of image density reduction before and after rubbing was calculated using the following formula. The obtained rate of image density reduction was evaluated according to the evaluation criteria shown below.

[0448] Image density reduction rate = (Image density before friction – Image density after friction) / (Image density before friction) × 100

[0449] Evaluation Criteria

[0450] A: Image density reduction rate is less than 1.0%.

[0451] B: Image density reduction rate is greater than 1.0% but less than 5.0%.

[0452] C: Image density reduction rate is greater than 5.0% but less than 8.0%.

[0453] D: Image density reduction rate is above 8.0%

[0454] Heat resistance to staining

[0455] • Paper: CS-064 (64.0g / m³) 2 )

[0456] (Sold by Canon Marketing Japan KK)

[0457] • Toner carrying capacity on paper: 0.08 mg / cm³ 2

[0458] (Adjusted by changing the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power)

[0459] • Image evaluation: Place an image measuring 2cm × 20cm along the long side of the A4 paper in the paper-passing direction, leaving a 2mm white border from the edge of the paper.

[0460] • Test environment: Normal temperature and low humidity environment (Temperature: 23℃, Humidity: 5%RH) (hereinafter referred to as "N / L")

[0461] • Fixing temperature: The temperature is increased in 5°C increments from 140°C.

[0462] Processing speed: 400mm / sec

[0463] Output the above evaluation images, and evaluate heat stain resistance based on the highest fixing temperature at which no heat staining occurs, considering the following criteria.

[0464] Evaluation Criteria

[0465] A: Above 170℃

[0466] B: Temperature above 160℃ but below 170℃

[0467] C: Temperatures above 145℃ but below 160℃

[0468] D: Below 145℃

[0469] Image gloss

[0470] • Paper: GFC-081 (81.0g / m³) 2 )

[0471] (Sold by Canon Marketing Japan KK)

[0472] • Toner carrying capacity on paper: 0.40 mg / cm³ 2

[0473] (Adjusted by changing the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power)

[0474] • Image evaluation: Place the image, measuring 2cm x 5cm, in the center of the A4 paper mentioned above.

[0475] • Test environment: Temperature: 23℃, Humidity: 50%RH

[0476] Fixing temperature: 160℃

[0477] Processing speed: 400mm / sec

[0478] Output the above evaluation image and evaluate its glossiness. The image glossiness is evaluated by measuring at a single angle of 60° using a handheld gloss meter (PG-1M, manufactured by Tokyo Denshoku Co., Ltd.), and this measurement value is used as the gloss value.

[0479] Evaluation criteria for image gloss

[0480] A: 8 or more

[0481] B: 5 or higher but less than 8

[0482] C: 2 or higher but less than 5

[0483] D: Less than 2

[0484] Electrical properties (charge retention) under high temperature and high humidity environments

[0485] Toner on the electrostatic latent image carrier is collected by suction using a cylindrical metal tube and a cylindrical filter, and the triboelectric charge of the toner is calculated. Specifically, a Faraday cage is used to measure the triboelectric charge of the toner on the electrostatic latent image carrier. The Faraday cage is a coaxial double cylinder, with the inner cylinder insulated from the outer cylinder. When a charged body with charge Q is placed inside the inner cylinder, it appears that a metal cylinder with charge Q is present due to electrostatic induction. This induced charge is measured using an electrometer (Keithley 6517A, manufactured by Keithley), and the triboelectric charge of the toner, i.e., (Q / M), is determined by dividing the charge Q (mC) by the mass M (kg) of the toner in the inner cylinder.

[0486] The triboelectric charge of the toner (mC / kg) = Q / M

[0487] First, an evaluation image for heat-resistant staining is formed on the electrostatic latent image carrier. The rotation of the electrostatic latent image carrier is stopped before transferring the image to the intermediate transfer component. Toner on the electrostatic latent image carrier is collected by suction using a cylindrical metal tube and a cylindrical filter, and the "initial Q / M" is measured. Next, the developing apparatus is placed in the evaluation equipment for two weeks in a high-temperature, high-humidity (H / H) environment (32°C, 80% RH). Afterward, the same steps as before placement are performed, and the charge per unit mass (Q / M (mC / kg)) on the electrostatic latent image carrier is measured. The Q / M value per unit mass on the electrostatic latent image carrier before placement is expressed as "initial Q / M," and the Q / M value per unit mass on the electrostatic latent image carrier after placement is expressed as "post-placement Q / M." The value of ("post-placement Q / M" / "initial Q / M" × 100) is calculated as the charge retention rate and evaluated according to the criteria shown below.

[0488] Evaluation Criteria

[0489] A: The charge retention rate is above 85%.

[0490] B: Charge retention rate is above 80% but less than 85%.

[0491] C: Charge retention rate is above 70% but less than 80%.

[0492] D: Charge retention rate is less than 70%.

[0493] Abrasion resistance (image intensity)

[0494] • Evaluation paper: Image Coat Gloss 158 (158.0g / m²) 2 )

[0495] (Sold by Canon Marketing Japan KK)

[0496] • Toner carrying capacity on paper: 0.10 mg / cm³ 2

[0497] (Adjusted by changing the DC voltage VDC of the developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power)

[0498] • Image evaluation: Place the image, measuring 3cm x 15cm, in the center of the A4 paper mentioned above.

[0499] • Fixing test environment: normal temperature and humidity environment (temperature: 23℃, humidity: 50%RH) (hereinafter referred to as "N / N")

[0500] Fixing temperature: 160℃

[0501] Processing speed: 400mm / sec

[0502] Output the above evaluation image and evaluate its abrasion resistance. The difference in reflectance is used as an indicator of abrasion resistance. First, apply a 0.5 kgf load to the image portion of the evaluation image using a color fastness abrasion tester (AB-301, manufactured by Tester Sangyo Co., Ltd.) and rub a new evaluation paper (ten times). Next, use a reflectometer (REFLECTOMETER MODEL TC-6DS, manufactured by Tokyo Denshoku Co., Ltd.) to measure the reflectance of the rubbed and non-rubbed areas using the new evaluation paper. Then, calculate the difference in reflectance before and after rubbing using the following formula. Evaluate the obtained difference in reflectance according to the evaluation criteria shown below.

[0503] Difference in reflectivity = Reflectivity before friction - Reflectivity after friction

[0504] Evaluation Criteria

[0505] A: Less than 2.0%

[0506] B: Above 2.0% but less than 4.0%

[0507] C: Above 4.0% but less than 6.0%

[0508] D: 6.0% or higher

[0509] Examples 2-22 and Comparative Examples 1-6

[0510] Except that two-component developer 2-28 were used instead of two-component developer 1, the evaluation was conducted in the same manner as in Example 1. The evaluation results are shown in Table 7.

[0511] [Table 7]

[0512]

[0513] While the invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the claims is to be interpreted in the broadest sense to cover all such modifications and equivalent structures and functions.

Claims

1. A toner comprising toner particles containing a binder resin, characterized in that, The adhesive resin comprises a first resin and a second resin. The first resin is a crystalline resin. The second resin is a non-crystalline resin, and In cross-sectional observations of 100 toner particles using a transmission electron microscope, (i) When area ratio A, expressed as area % (%), represents the proportion of the area occupied by the first resin in the cross-section of each of the toner particles, the average value of area ratio A is 30 to 75% area %, and (ii) When X represents the number of cross sections of the toner particles whose area ratio A is 90% or more and Z represents the total number of cross sections of the observed toner particles, the value of X / Z is 0.15 or more and 0.45 or less.

2. The toner according to claim 1, wherein the second resin is at least one resin selected from the group consisting of a hybrid resin combining polyester resin and vinyl resin, polyester resin and vinyl resin.

3. The toner according to claim 1 or 2, wherein the first resin comprises a first monomer unit represented by the following formula (1): In equation (1), R Z1 R represents a hydrogen atom or a methyl group, and R represents an alkyl group with 18 to 36 carbon atoms.

4. The toner according to claim 3, wherein the first resin is a vinyl resin having the first monomer unit.

5. The toner according to claim 3, wherein the content of the first monomer unit in the first resin is 20.0 to 100.0% by mass.

6. The toner according to claim 1 or 2, wherein... In cross-sectional observation of the toner particles using a transmission electron microscope, The cross-section of the toner particles with an area ratio A of 30 to 70 area% has a matrix-domain structure consisting of a matrix containing the first resin and a domain containing the second resin.

7. The toner according to claim 6, wherein the number-average length of the major axis of the domain is 0.5 to 1.4 μm.

8. The toner according to claim 1 or 2, wherein In cross-sectional observations of 100 toner particles using a transmission electron microscope, When the area ratio B, expressed as a percentage of area, represents the proportion of the area occupied by the second resin in the cross-section of each toner particle, and When Y represents the number of cross-sections of the toner particles whose area ratio B is 90% or more. Then the value of Y / Z is greater than 0.10 and less than 0.25.

Images