Black toner

Abstract

A black toner that suppresses both cold offset and white spots. [Solution] A black toner having black toner particles having a binder resin, hydrocarbon wax and carbon black, wherein the black toner particles further contain at least one selected from the group consisting of copper phthalocyanine and zinc phthalocyanine, and the binder resin contains a vinyl resin having a specific monomer unit having a linear alkyl group having 8 to 22 carbon atoms.

Description

Technical Field

[0001] The present disclosure relates to a black toner used in an image forming method such as an electrophotographic method.

Background Art

[0002] In recent years, in electrophotographic image forming apparatuses such as multifunction devices and printers, further power consumption reduction has been demanded. In terms of cost reduction, reduction of the amount of heat applied to the fixing device has been particularly studied from the viewpoint of power consumption reduction. Regarding toners, the need for so-called low-temperature fixing toners that can be fixed with less heat has been increasing. In order to meet such requirements, various studies have been conducted on the binder resin used in toners. Among them, studies have been conducted on resins incorporating long-chain alkyl (meth) acrylates as binder resins having excellent melting properties.

[0003] For example, Patent Document 1 discloses a black toner for electrostatic charge image development containing a styrene-acrylic resin having a structural unit derived from an alkyl (meth) acrylate monomer having 8 to 22 carbon atoms in the alkyl group and containing a crystalline ester compound. Patent Document 1 also discloses that paraffin wax can be used as a hydrocarbon wax.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] Patent Document 1 uses a styrene-acrylic resin to control the affinity between the crystalline ester compound and the binder resin, improve the melting properties of the toner, and lower the cold offset generation temperature. Therefore, the inventors used the toner described in Patent Document 1 to output an image onto plain paper that has irregularities on its surface. As a result, the inventors recognized that, particularly in areas where pressure from the fixing film is not easily applied, such as recesses in the paper, the toner adheres to the fixing film and is removed from the paper, causing white dots to appear where the image is missing. This disclosure provides a black toner that suppresses the occurrence of both cold offset and white spots. Specifically, it provides a black toner that can suppress the occurrence of white spots even when printing solid images on plain paper. [Means for solving the problem]

[0006] The inventors investigated a method that could suppress the occurrence of both cold offset and white spots. They found that the following black toner solves the above problems.

[0007] In other words, the present disclosure relates to a black toner having black toner particles having a binder resin, hydrocarbon wax and carbon black, The black toner particles further contain at least one selected from the group consisting of copper phthalocyanine and zinc phthalocyanine. The present invention relates to a black toner in which the binder resin contains a vinyl resin having monomer units represented by the following formula (1). [ka] (In formula (1), R 1 R represents a hydrogen atom or a methyl group. 2 (This represents a linear alkyl group with 8 to 22 carbon atoms.) [Effects of the Invention]

[0008] According to this disclosure, it is possible to provide a toner that suppresses the occurrence of both cold offset and white spots. [Modes for carrying out the invention]

[0009] In this disclosure, descriptions of numerical ranges such as "XX or greater and YY or less" or "XX to YY" mean a numerical range that includes the lower and upper limits, unless otherwise specified. When numerical ranges are described in steps, the upper and lower limits of each numerical range can be any combination. In addition, in this disclosure, a description such as "at least one selected from the group consisting of XX, YY, and ZZ" means any of the following: XX, YY, ZZ, a combination of XX and YY, a combination of XX and ZZ, a combination of YY and ZZ, or a combination of XX, YY, and ZZ. Note that if XX is a group, multiple values ​​may be selected from XX, and the same applies to YY and ZZ.

[0010] A "monomer unit" refers to the reacted form of a monomer substance in a polymer. For example, one carbon-carbon bond in the main chain of a polymer formed by the polymerization of vinyl monomers is considered one unit. Vinyl monomers can be represented by the following formula (V). [ka]

[0011] In formula (V), R A R represents a hydrogen atom or an alkyl group (preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group), B represents any substituent.

[0012] This disclosure relates to a black toner having black toner particles having a binder resin, hydrocarbon wax, and carbon black, The black toner particles further contain at least one selected from the group consisting of copper phthalocyanine and zinc phthalocyanine. The present invention relates to a black toner in which the binder resin contains a vinyl resin having monomer units represented by the following formula (1). [ka] (In formula (1), R 1 R represents a hydrogen atom or a methyl group. 2(This represents a linear alkyl group with 8 to 22 carbon atoms.)

[0013] The above-mentioned black toner suppresses cold offset and reduces the occurrence of white spots when printing solid images on plain paper. The inventors believe the mechanism by which these effects are achieved is as follows. As described above, vinyl resins having monomer units represented by formula (1) have high melting properties, which suppresses cold offset and improves low-temperature fixation.

[0014] On the other hand, the following mechanism can be considered for suppressing white spots. In a system in which a vinyl resin having monomer units shown in formula (1) and carbon black are used together, an interface exists between the vinyl resin chain containing the monomer units shown in formula (1) and the carbon black. Hydrocarbon waxes that are compatible with carbon black are stabilized at this interface. Due to this stabilization effect, the hydrocarbon waxes become more compatible with toner materials such as binder resins.

[0015] When hydrocarbon waxes become easily compatible with toner materials, they aggregate and crystallize, making it impossible to separate them from the toner, and thus they cannot provide sufficient release during fixing. As a result, when printing on plain paper with an uneven surface, the toner may not be sufficiently pressed against the paper in areas where pressure is not applied, such as recesses in the paper, and may remain attached to the fixing film, resulting in white spots.

[0016] In this disclosure, the black toner particles contain at least one selected from the group consisting of copper phthalocyanine and zinc phthalocyanine (hereinafter also simply referred to as "phthalocyanine compound"). Copper phthalocyanine and zinc phthalocyanine are highly planar metal complexes and possess π electrons derived from phthalocyanine. Furthermore, when considering the surface structure of carbon black, it has a planar structure similar to graphite and is rich in π electrons.

[0017] In the phthalocyanine complex, the phthalocyanine has its π electrons strongly attracted by the central metal ion, resulting in electron deficiency. Therefore, phthalocyanine seeks the π electrons on carbon black and is considered to be more likely to penetrate the interface between the vinyl resin chain and carbon black described above prior to the hydrocarbon wax. The hydrocarbon wax loses its place due to the interface being occupied first, and its compatibility with the toner material decreases. Therefore, in the toner, the hydrocarbon wax tends to aggregate, crystallize, and separate. As a result, during fixing, the releasing effect of the hydrocarbon wax is fully exerted, and the toner remains on the paper side even in the recesses of the paper, and it is considered that the generation of white spots is suppressed.

[0018] The black toner particles contain a vinyl-based resin as a binder resin. The vinyl-based resin has a monomer unit represented by the formula (1). Having the monomer unit represented by the formula (1) The vinyl-based resin includes, for example, at least one resin selected from the group consisting of styrene resin, acrylic resin, styrene-acrylic resin, polyethylene resin, polyethylene vinyl acetate resin, vinyl acetate resin, polybutadiene resin, and the like. The vinyl-based resin having the monomer unit represented by the formula (1) is preferably a styrene-acrylic resin having the monomer unit represented by the formula (1).

[0019] [Chemical formula]

[0020] In the formula (1), R 1 represents a hydrogen atom or a methyl group. R 2 is a linear alkyl group having 8 to 22 carbon atoms. R 2 is preferably a linear alkyl having 12 to 22 carbon atoms. In the structure represented by the formula (1), when R 2 is a 2-ethylhexyl group having a side chain, the interface is likely to have a three-dimensionally crowded structure. Therefore, it is considered that only the hydrocarbon wax having a more flexible structure than phthalocyanines penetrates the interface and is compatible with the toner, and the generation of white spots cannot be suppressed.

[0021] The monomer that forms the monomer unit represented by formula (1) (hereinafter also referred to as the "formula (1) unit monomer") is, for example, an alkyl (meth)acrylate having a linear alkyl group with 8 to 22 carbon atoms (preferably 12 to 22).

[0022] The vinyl resin preferably contains, for example, 0.5 to 20.0% by mass of the monomer unit represented by formula (1), more preferably 1.0 to 15.0% by mass, and more preferably 4.0 to 10.0% by mass.

[0023] By including 1.0% by mass or more of the monomer unit represented by formula (1) in the vinyl resin, the melting characteristics of the toner are improved, enabling toner fixation at lower temperatures. On the other hand, by including 15.0% by mass or less of the monomer unit represented by formula (1), the number of interfaces between the vinyl resin chain containing the monomer unit represented by formula (1) and the carbon black can be kept constant, further suppressing the occurrence of white spots.

[0024] Examples of vinyl resins include homopolymers composed of the following polymerizable monomers, copolymers obtained by combining two or more of these monomers, or mixtures thereof. Styrene monomers such as styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, n-amyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-nonyl (meth)acrylate (Meth)acrylic monomers such as phosphates, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dimethyl phosphate ethyl (meth)acrylate, diethyl phosphate ethyl (meth)acrylate, dibutyl phosphate ethyl (meth)acrylate, and 2-benzoyloxyethyl (meth)acrylate, (meth)acrylonitrile, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid, and maleic acid; Vinyl ether monomers such as vinyl methyl ether and vinyl isobutyl ether; vinyl ketone monomers such as vinyl methyl ketone, vinyl ethyl ketone, and vinyl isopropenyl ketone; Polyolefins such as ethylene, propylene, and butadiene.

[0025] Vinyl resins may use polyfunctional polymerizable monomers as needed. Examples of polyfunctional polymerizable monomers include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 2,2'-bis(4-(meth)acryloxydiethoxy)phenyl)propane, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tetra(meth)acrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

[0026] The vinyl resin is preferably a polymer of a monomer mixture comprising at least one selected from the group consisting of (meth)acrylic monomers, styrene, and a unit monomer of formula (1). More preferably, the vinyl resin is a polymer of a monomer mixture comprising a unit monomer of formula (1), styrene, and n-butyl (meth)acrylate. In vinyl resins, the content of monomer units corresponding to styrene is preferably 50.0 to 95.0% by mass or 60.0 to 85.0% by mass. In vinyl resins, the content of monomer units corresponding to (meth)acrylic monomers (preferably n-butyl (meth)acrylate) is preferably 5.0 to 40.0% by mass and 10.0 to 25.0% by mass.

[0027] Furthermore, known chain transfer agents and polymerization inhibitors can be added to control the degree of polymerization of the vinyl resin. Examples of polymerization initiators for obtaining vinyl resins include organic peroxide-based initiators and azo-based polymerization initiators.

[0028] Examples of organic peroxide initiators include benzoyl peroxide, lauroyl peroxide, di-α-cumyl peroxide, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, bis(4-t-butylcyclohexyl)peroxydicarbonate, 1,1-bis(t-butylperoxy)cyclododecane, t-butylperoxymaleic acid, bis(t-butylperoxy)isophthalate, methyl ethyl ketone peroxide, tert-butylperoxy-2-ethylhexanoate, diisopropyl peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, and tert-butyl-peroxypivalate.

[0029] Examples of azo polymerization initiators include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobismethylbutyronitrile, and 2,2'-azobis-(methyl isobutyrate). These are some examples.

[0030] Furthermore, a redox initiator, which combines an oxidizing substance and a reducing substance, can also be used as a polymerization initiator. Examples of oxidizing substances include hydrogen peroxide, inorganic peroxides such as persulfates (sodium, potassium, and ammonium salts), and oxidizing metal salts of tetravalent cerium salts.

[0031] Examples of reducing substances include reducing metal salts (divalent iron salts, monovalent copper salts, and trivalent chromium salts), ammonia, lower amines (amines with approximately 1 to 6 carbon atoms, such as methylamine and ethylamine), amino compounds such as hydroxylamine, reducing sulfur compounds such as sodium thiosulfate, sodium hydrosulfite, sodium bisulfite, sodium sulfite, and sodium formaldehyde sulfoxylate, lower alcohols (with 1 to 6 carbon atoms), ascorbic acid or its salts, and lower aldehydes (with 1 to 6 carbon atoms).

[0032] Polymerization initiators are selected based on their 10-hour half-life temperature and are used alone or in combination. The amount of polymerization initiator added varies depending on the desired degree of polymerization, but generally, 0.5 to 20 parts by mass are added per 100.0 parts by mass of polymerizable monomer.

[0033] The black toner particles may contain a binder resin other than the vinyl resin having the monomer unit shown in formula (1). The binder resin other than the vinyl resin having the monomer unit shown in formula (1) is not particularly limited, and known ones such as those shown below can be used.

[0034] Styrene resin, acrylic resin, styrene-acrylic resin, polyethylene resin, polyethylene vinyl acetate resin, vinyl acetate resin, polybutadiene resin, phenolic resin, polyurethane resin, polybutyral resin, polyester resin, epoxy resin, polyamide resin, cellulose resin, polyether resin, and mixed resins and composite resins of these. Among these, styrene-based resins, acrylic resins, and styrene-acrylic resins are preferred from the viewpoint of toner properties.

[0035] The binder resin preferably contains 50% by mass or more of a vinyl resin having monomer units represented by formula (1), more preferably 70% by mass or more, and even more preferably 80% by mass or more. Furthermore, the binder resin preferably contains 50 to 100% by mass of a vinyl resin having monomer units represented by formula (1), more preferably 70 to 95% by mass, and even more preferably 80 to 95% by mass.

[0036] The toner particles are black toner particles containing carbon black. The carbon black content is, for example, 3.0 to 30.0 parts by mass, preferably 5.0 to 25.0 parts by mass, and more preferably 5.0 to 17.0 parts by mass, per 100 parts of binder resin. When the carbon black content is 5.0 parts by mass or more, the toner's coloring power is particularly excellent, and a high-density image can be formed. On the other hand, when the carbon black content is 25.0 parts by mass or less, the amount of hydrocarbon wax drawn into the interface is minimized, the release effect is fully exhibited, and the occurrence of white spots can be further suppressed.

[0037] Carbon black is carbon black obtained by methods such as furnace black, gas black, thermal black, acetylene black, lamp black, etc., and is not limited to any particular method. In other words, carbon black is obtained from furnace black, gas black, thermal black, acetylene black, lamp black, etc. It is preferable that it be at least one selected from the group.

[0038] The black toner particles contain at least one selected from the group consisting of copper phthalocyanine and zinc phthalocyanine. The total content of copper phthalocyanine and zinc phthalocyanine is, for example, 0.05 to 12.00 parts by mass, preferably 0.10 to 8.00 parts by mass, and more preferably 0.15 to 8.00 parts by mass, per 100 parts by mass of the binder resin.

[0039] When the copper phthalocyanine and zinc phthalocyanine content is 0.10 parts by mass or more, a sufficient amount of phthalocyanine complex is supplied to the interface, further suppressing the occurrence of white spots. On the other hand, when the copper phthalocyanine and zinc phthalocyanine content is 8.00 parts by mass or less, carbon black with excessively bound phthalocyanine complexes seeks electrons and does not aggregate with other carbon black, allowing for the output of high-density images.

[0040] Let a (mass%) be the carbon black content based on the mass of the black toner particles, and let b (mass%) be the total content of copper phthalocyanine and zinc phthalocyanine based on the mass of the black toner particles. In this case, a / b is, for example, 0.5 to 120.0. Furthermore, it is preferable that a and b satisfy the following formula (2). 2.0 ≤ a / b ≤ 30.0 ···(2)

[0041] When the a / b value falls within the range given by equation (2), the carbon black and phthalocyanine complex interact more efficiently with each other, maximizing the effect of suppressing white spots. a / b is more preferably 5.0 to 20.0.

[0042] The black toner particles contain hydrocarbon wax. The hydrocarbon wax content is, for example, 0.5 to 18.0 parts by mass, preferably 1.5 to 15.0 parts by mass, per 100 parts of binder resin. A hydrocarbon wax content of 1.5 parts by mass or more allows for sufficient deformability during fixing, making it easier to suppress both cold offset and white spots. On the other hand, a hydrocarbon wax content of 15.0 parts by mass or less makes it easier to suppress the stabilization of some of the hydrocarbon wax at the interface and its compatibility with the toner. Therefore, the wax is less likely to crystallize in the image after fixing, resulting in better gloss.

[0043] Hydrocarbon waxes include at least one selected from the group consisting of paraffin wax, microcrystalline wax, petroleum-based waxes such as petrolatum, and Fischer-Tropsch wax. Hydrocarbon waxes include, for example, paraffin wax.

[0044] Furthermore, the black toner particles may contain release agents other than hydrocarbon waxes. Examples of other release agents include alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid, or their acid amides, esters, and ketones; hydrogenated castor oil and its derivatives, plant waxes, and animal waxes.

[0045] The black toner particles consist of a first ester compound which is at least one ester compound selected from the group consisting of the ester compound represented by formula (3), the ester compound represented by formula (4), and the ester compound represented by formula (5), and It is preferable to contain a second ester compound, which is at least one ester compound selected from the group consisting of ester compounds represented by the following formula (6), ester compounds represented by the following formula (7), and ester compounds represented by the following formula (8). [ka]

[0046] In formula (3), R 3 and R4 Each of these is independently, for example, a linear alkyl group having 15 to 22 carbon atoms, preferably a linear alkyl group having 16 to 22 carbon atoms (however, R 3 When the carbon number is 18-22, R 4 This represents the case where the carbon number is between 19 and 22. In formula (4), R 5 R represents, for example, a linear alkylene group having 1 to 7 carbon atoms, preferably a linear alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4 or 1 to 3 carbon atoms), 6 and R 7 Each of these independently represents, for example, a linear alkyl group having 14 to 24 carbon atoms, preferably a linear alkyl group having 14 to 22 carbon atoms (more preferably 16 to 22 carbon atoms). In formula (5), R 5 R represents, for example, a linear alkylene group having 1 to 7 carbon atoms, preferably a linear alkylene group having 1 to 6 carbon atoms (more preferably 1 to 4 or 1 to 3 carbon atoms), 6 and R 7 Each of these independently represents, for example, a linear alkyl group having 14 to 24 carbon atoms, preferably a linear alkyl group having 14 to 22 carbon atoms (more preferably 16 to 22 carbon atoms).

[0047] In formula (6), R 8 R represents a linear alkyl group with 21 carbon atoms. 9 This represents a linear alkyl group with 22 carbon atoms. In formula (7), R 10 R represents, for example, a linear alkylene group having 8 to 14 carbon atoms, preferably a linear alkylene group having 8 to 12 carbon atoms. 11 and R 12 Each of these independently represents, for example, a linear alkyl group having 18 to 24 carbon atoms, preferably a linear alkyl group having 18 to 22 carbon atoms. In formula (8), R 10 R represents, for example, a linear alkylene group having 8 to 14 carbon atoms, preferably a linear alkylene group having 8 to 12 carbon atoms. 11 and R 12 Each of these independently represents, for example, a linear alkyl group having 18 to 24 carbon atoms, preferably a linear alkyl group having 18 to 22 carbon atoms.

[0048] The presence of the ester compounds shown in formulas (3) to (5) improves the melting properties of the toner, enabling toner fixation at lower temperatures. On the other hand, the presence of the ester compounds shown in formulas (6) to (8) improves the release properties of the toner, and is particularly effective in suppressing the occurrence of white spots. Furthermore, it acts on the ester compounds shown in formulas (3) to (5) to prevent the ester compounds shown in formulas (3) to (5) from crystallizing on the image after fixation, which reduces gloss. It is possible.

[0049] The black toner particles preferably contain polyvalent metal elements. The polyvalent metal elements preferably contain at least one selected from the group consisting of aluminum and magnesium. The mass concentration of the polyvalent metal elements in the black toner particles is, for example, 5 to 700 ppm, and preferably 5 to 500 ppm.

[0050] Aluminum and magnesium interact with hydroxyl groups on the carbon black surface, attracting electrons. This makes the electron-deficient carbon black more likely to attract phthalocyanine complexes to the interface, thus aiding in the separation of hydrocarbon waxes. When the mass concentration of polyvalent metal elements in the toner particles is 5 ppm or higher, aluminum or magnesium acts on the carbon black and works effectively to aid in the separation of hydrocarbon waxes. On the other hand, when the mass concentration of polyvalent metal elements in the toner particles is 500 ppm or lower, the aluminum or magnesium that has acted excessively on the carbon black does not hinder the penetration of phthalocyanine complexes to the interface, allowing for the effective separation of hydrocarbon waxes.

[0051] These polyvalent metal elements can be introduced into black toner particles by using metal salts as flocculants when manufacturing toner particles by emulsification and flocculation, or by adding them as organometallic compounds to the oil layer when manufacturing toner particles by suspension polymerization.

[0052] As a means of introducing polyvalent metal elements, it is preferable to use aluminum distearate. That is, it is preferable that the black toner particles contain aluminum distearate. Aluminum distearate disperses well in the binder resin and can act on the pigment to improve the dispersibility of the pigment, thereby improving the coloring power of the toner.

[0053] This section will provide a more detailed explanation of each component that makes up the black toner and the manufacturing method for the black toner. <Binding resin> The black toner particles have a vinyl resin as a binder resin, which has monomer units represented by the following formula (1). As described above, the black toner particles may also contain other binder resins as needed. Examples of other binder resins include polyester resins.

[0054] Polyester resins can be obtained by selecting and combining suitable polycarboxylic acids, polyols, hydroxycarboxylic acids, etc., and synthesizing them using known methods such as transesterification or polycondensation. Polycarboxylic acids are compounds that contain two or more carboxyl groups in one molecule. Among these, dicarboxylic acids are compounds that contain two carboxyl groups in one molecule and are preferably used.

[0055] Examples of dicarboxylic acids include oxalic acid, succinic acid, glutaric acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, superiric acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylenediacetic acid, m-phenylenediacetic acid, o-phenylenediacetic acid, diphenylacetic acid, diphenyl-p,p'-dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, and cyclohexanedicarboxylic acid.

[0056] Examples of polycarboxylic acids other than dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalentricarboxylic acid, naphthalenetetracarboxylic acid, pyrentricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, glutaconic acid, n-dodecylsuccinic acid, n-dodecenylsuccinic acid, isododecylsuccinic acid, isododecenylsuccinic acid, n-octylsuccinic acid, and n-octenylsuccinic acid. These may be used individually or in combination of two or more.

[0057] Polyols are compounds that contain two or more hydroxyl groups in one molecule. Among these, diols are compounds that contain two hydroxyl groups in one molecule and are preferably used.

[0058] Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, diethylene glycol, Examples include triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, 1,4-cyclohexanediol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, and alkylene oxide adducts (ethylene oxide, propylene oxide, butylene oxide, etc.) of the above bisphenols.

[0059] Of these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, with particular preference being alkylene oxide adducts of bisphenols and combinations thereof with alkylene glycols having 2 to 12 carbon atoms.

[0060] Examples of polyols with a trivalent or higher valent valent valent valent valent valent var. 3 include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, tetraethylolbenzoguanamine, sorbitol, trisphenol PA, phenol novolac, cresol novolac, and alkylene oxide adducts of the above trivalent or higher valent polyphenols. These may be used individually or in combination of two or more. The polyester resin may also be a polyester resin containing urea groups. It is preferable that the carboxyl groups at the ends of the polyester resin are not capped.

[0061] Furthermore, the binder resin may also contain crystalline polyester. Examples of crystalline polyester include condensate polymers of aliphatic diols and aliphatic dicarboxylic acids.

[0062] It is preferable that the product is a condensation polymer of an aliphatic diol having 2 to 12 carbon atoms and an aliphatic dicarboxylic acid having 2 to 12 carbon atoms. Examples of aliphatic diols with 2 to 12 carbon atoms include the following compounds: 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.

[0063] Additionally, aliphatic diols containing double bonds can be used. Examples of aliphatic diols containing double bonds include the following compounds: 2-butene-1,4-diol, 3-hexene-1,6-diol, and 4-octen-1,8-diol.

[0064] Examples of aliphatic dicarboxylic acids having 2 to 12 carbon atoms include the following compounds: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,11-undecanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, and lower alkyl esters and acid anhydrides of these aliphatic dicarboxylic acids.

[0065] Of these, sebacic acid, adipic acid, and 1,10-decanedicarboxylic acid, as well as their lower alkyl esters and acid anhydrides, are preferred. These may be used individually or in combination of two or more.

[0066] Aromatic dicarboxylic acids can also be used. Examples of aromatic dicarboxylic acids include the following compounds: terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4'-biphenyldicarboxylic acid. Among these, terephthalic acid is preferred due to its availability and its tendency to form low-melting-point polymers. Furthermore, dicarboxylic acids having double bonds can also be used. Dicarboxylic acids having double bonds can be suitably used to suppress hot offset during fixing because they can crosslink the entire resin using the double bond.

[0067] Examples of such dicarboxylic acids include fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Lower alkyl esters and acid anhydrides of these are also examples. Among these, fumaric acid and maleic acid are more preferred.

[0068] There are no particular restrictions on the method for producing crystalline polyester; it can be produced by general polyester polymerization methods that involve reacting a dicarboxylic acid component with a diol component. For example, it can be produced using either a direct polycondensation method or a transesterification method, depending on the type of monomer. The content of crystalline polyester in the binder resin is preferably 1.0% by mass or more and 30.0% by mass or less, and more preferably 3.0% by mass or more and 25.0% by mass or less.

[0069] The peak temperature of the maximum endothermic peak measured using a differential scanning calorimeter (DSC) for crystalline polyester is preferably 50.0°C to 100.0°C, and more preferably 60.0°C to 90.0°C from the viewpoint of low-temperature fixation.

[0070] The binder resin may contain an acid group-containing resin. The acid value of the acid group-containing resin is, for example, 2 to 30 mg KOH / g, preferably 3 to 25 mg KOH / g.

[0071] The acid group-containing resin is not particularly limited, and known resins such as those listed below can be used, but at least one selected from the group consisting of styrene-acrylic resins and polyester resins is preferred.

[0072] The acid group-containing resin preferably includes a styrene-acrylic resin. Examples of styrene-acrylic resins include polymers of a monomer mixture containing at least one selected from the group consisting of the (meth)acrylic monomers described above, and styrene. The acid value can be controlled by using monomers having acid groups, such as (meth)acrylic acid and maleic acid, in the monomer mixture. The acid group-containing resin may be a polyester resin as a polar resin. The fat can be selected from the monomers mentioned above, and it is preferable to select monomers such that the acid value is 2 to 30 mgKOH / g. The content of the acid group-containing resin in the binder resin is preferably 2 to 20% by mass and 4 to 15% by mass.

[0073] The molecular weight of the binder resin is preferably such that its peak molecular weight Mp is 5,000 or more and 100,000 or less, and more preferably 10,000 or more and 40,000 or less. The glass transition temperature Tg of the binder resin is preferably such that it is 40°C or more and 70°C or less.

[0074] <Crosslinking agent> To control the molecular weight of the binder resin, a crosslinking agent may be added during the polymerization of polymerizable monomers.

[0075] For example, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol diacrylate, divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol #200, #400, and #600 diacrylates, dipropylene glycol diacrylate, polypropylene glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and those in which the above acrylates are replaced with methacrylates.

[0076] The amount of crosslinking agent added is preferably 0.001 parts by mass or more and 15.000 parts by mass or less per 100 parts by mass of polymerizable monomer.

[0077] <Charge control agents and charge control resins> Black toner particles may contain a charge control agent or a charge control resin. Known charge control agents can be used, and those with a fast triboelectric charging speed and the ability to stably maintain a constant triboelectric charge are particularly preferred. Furthermore, when toner particles are manufactured by suspension polymerization, charge control agents with low polymerization inhibitory properties and substantially no solubilizers in aqueous media are particularly preferred.

[0078] Examples of materials that control the toner's charge characteristics include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic and dicarboxylic acid-based metal compounds, aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarenes, and charge-controlling resins.

[0079] Examples of charge-controlled resins include polymers or copolymers having sulfonic acid groups, sulfonic acid bases, or sulfonic acid ester groups. Among polymers having sulfonic acid groups, sulfonic acid bases, or sulfonic acid ester groups, polymers containing 2% by mass or more of a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in copolymerization ratio are particularly preferred, and more preferably polymers containing 5% by mass or more.

[0080] Preferably, the charge-controlled resin has a glass transition temperature (Tg) of 35°C to 90°C, a peak molecular weight (Mp) of 10,000 to 30,000, and a weight-average molecular weight (Mw) of 25,000 to 50,000. When this is used, desirable triboelectric properties can be imparted without affecting the thermal properties required for toner particles. Furthermore, if the charge-controlled resin contains sulfonic acid groups, for example, the dispersibility of the charge-controlled resin itself in polymerizable monomer compositions, as well as the dispersibility of colorants, can be improved, further enhancing coloring power, transparency, and triboelectric properties.

[0081] These charge control agents or charge control resins may be added individually or in combination of two or more types. The amount of charge control agent or charge control resin added is preferably 0.01 parts by mass or more and 20.0 parts by mass or less, and more preferably 0.5 parts by mass or more and 10.0 parts by mass or less, per 100.0 parts by mass of the binder resin.

[0082] <Method for manufacturing black toner particles> The method for producing black toner particles is not particularly limited and known means can be used, including kneading and grinding methods and wet manufacturing methods. Wet manufacturing methods are preferred from the viewpoint of uniform particle size, shape controllability, and ease of obtaining toner particles with a core-shell structure. The toner particles may have core particles containing a binder resin and a shell on the surface of the core particles. Examples of wet manufacturing methods include suspension polymerization, dissolution-suspension method, emulsion polymerization agglutination method, and emulsion agglutination method, and suspension polymerization is more preferred because it is easier to obtain toner particles that satisfy the preferred physical properties of the present invention.

[0083] In the suspension polymerization method, first, a polymerizable monomer composition is obtained by uniformly dispersing hydrocarbon wax, carbon black, and phthalocyanine compounds (and optionally ester compounds, polymerization initiators, crosslinking agents, charge regulators, and other additives) in a polymerizable monomer containing the unit monomer of formula (1). Then, the obtained polymerizable monomer composition is dispersed in a continuous layer (e.g., aqueous phase) containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is carried out using a polymerization initiator to obtain toner particles with the desired particle size.

[0084] When producing a polymerizable monomer composition, a pigment dispersion containing a portion of the polymerizable monomer, carbon black, and a phthalocyanine compound may be prepared in advance, and then the pigment dispersion may be mixed with the remaining polymerizable monomer to obtain the polymerizable monomer composition.

[0085] <Manufacturing method for black toner> Black toner particles (hereinafter sometimes simply referred to as "toner particles") may be used as black toner as is. To improve fluidity, electrostatic properties, cleaning properties, etc., so-called external additives such as fluidizers and cleaning aids may be added to the toner particles to obtain toner.

[0086] Examples of external additives include inorganic oxide nanoparticles such as silica nanoparticles, alumina nanoparticles, and titanium oxide nanoparticles; inorganic stearic acid compound nanoparticles such as aluminum stearate nanoparticles and zinc stearate nanoparticles; and inorganic titanate compound nanoparticles such as strontium titanate and zinc titanate. These can be used individually or in combination of two or more.

[0087] These inorganic fine particles are preferably treated with a gloss finish using silane coupling agents, titanium coupling agents, higher fatty acids, silicone oils, etc., to improve heat resistance and environmental stability. The BET specific surface area of ​​the external additive is 10 m². 2 / g or more 450m 2 It is preferable that the value be less than or equal to / g.

[0088] The BET specific surface area can be determined by a low-temperature gas adsorption method using a dynamic constant-pressure method, according to the BET method (preferably the BET multi-point method). For example, by using a specific surface area measuring device (product name: Gemini 2375 Ver. 5.0, manufactured by Shimadzu Corporation), nitrogen gas is adsorbed onto the sample surface, and the BET specific surface area (m²) is measured using the BET multi-point method. 2 It is possible to calculate ( / g).

[0089] The total amount of these various external additives added is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less, per 100 parts by mass of toner particles. Furthermore, various combinations of external additives may be used.

[0090] Toner can be used as a one-component developer, either magnetic or non-magnetic, or it may be mixed with a carrier to be used as a two-component developer. As the carrier, magnetic particles made of known materials such as metals like iron, ferrite, and magnetite, or alloys of these metals with metals like aluminum and lead, can be used, and among these, ferrite particles are preferred. Furthermore, as carriers, coated carriers in which the surface of magnetic particles is coated with a coating agent such as resin, or resin-dispersed carriers in which fine magnetic powder is dispersed in a binder resin may be used. Preferably, the carriers have a volume-average particle size of 15 μm or more and 100 μm or less, and more preferably 25 μm or more and 80 μm or less.

[0091] The following describes the methods for measuring the physical properties of toner and each material. <Method for separating binder resins, ester compounds, and hydrocarbon waxes, and for identifying their structure and content> (Separation method) The toner is dissolved in tetrahydrofuran (THF), and the solvent is removed from the resulting soluble fraction under reduced pressure to obtain the THF-soluble component of the toner. The obtained THF-soluble component of the toner is dissolved in chloroform to prepare a sample solution with a concentration of 25 mg / mL.

[0092] The obtained sample solution (3.5 mL) is poured into the apparatus described below, and under the conditions described below, samples with a number-average molecular weight (Mn) of less than 2000 are separated. Preparative GPC device: Preparative HPLC LC-980 model manufactured by Japan Analytical Industry Co., Ltd. Preparative columns: JAIGEL 3H, JAIGEL 5H (manufactured by Japan Analytical Industry Co., Ltd.) Eluent: Chloroform Flow rate: 3.5mL / min To calculate the molecular weight of the sample, a molecular weight calibration curve created using standard polystyrene resin (for example, "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation) is used.

[0093] Components with a number-average molecular weight (Mn) of less than 2000 include the first ester compound, the second ester compound, and hydrocarbon waxes. Components with a number-average molecular weight (Mn) of 2000 or more include binder resins such as vinyl resins and acid group-containing resins having monomer units represented by formula (1). Furthermore, if necessary, the components are further fractionated by silica gel column chromatography (eluent: chloroform, toluene, hexane, methanol, etc.) or the solid is separated by recrystallization (solvent: acetone, hexane, etc.), after which the solvent is removed and the mixture is heated and dried under reduced pressure. The above procedure is repeated until approximately 100 mg of each component is obtained.

[0094] (Identification of structure and content) The structure of the separated components was determined by nuclear magnetic resonance spectroscopy. 1 H-NMR) [400MHz, CDCl3, Identify using room temperature (25°C). Measuring device: FT NMR device JNM-EX400 (manufactured by JEOL Ltd.) Measurement frequency: 400MHz Pulse condition: 5.0 μs Frequency range: 10500Hz Total number of times: 64 Furthermore, by performing NMR measurements of the toner using the method described above and comparing them with the isolated components, the content of the first ester compound, the second ester compound, hydrocarbon wax, and binder resin can be determined from the spectral intensity. This allows for the determination of the mass parts of each material, such as hydrocarbon wax, relative to 100 mass parts of binder resin. Furthermore, 1 Analysis using 1H-NMR can also be used to calculate the proportion of monomer units represented by formula (1) in the vinyl resin.

[0095] <Measurement of polyvalent metal element content by X-ray fluorescence analysis> The Axios wavelength-dispersive X-ray fluorescence analyzer (PANalytical) and its accompanying dedicated software, SuperQ ver.4.0F (PANalytical), for setting measurement conditions and analyzing measurement data will be used. Rh will be used as the anode for the X-ray tube, the measurement atmosphere will be vacuum, the measurement diameter (collimator mask diameter) will be 27 mm, and the measurement time will be 10 seconds. A proportional counter (PC) will be used for measuring light elements, and a scintillation counter (SC) will be used for measuring heavy elements.

[0096] For the measurement sample, 4g of toner particles were placed in a dedicated aluminum ring for pressing, leveled, and then compressed at 20MPa for 60 seconds using a tablet molding and compression machine "BRE-32" (manufactured by Maekawa Testing Machinery Co., Ltd.) to form pellets with a thickness of 2mm and a diameter of 39mm.

[0097] For quantification, add the polyvalent metal to be quantified to 100 parts by mass of a resin sample that does not contain metal elements, to a concentration of 5.0 ppm by mass, and mix thoroughly using a coffee grinder. Similarly, mix the resin sample with the polyvalent metal to be quantified to concentrations of 50.0 ppm, 500.0 ppm, and 5000.0 ppm, respectively, and use these as calibration curve samples.

[0098] For each sample, a pellet of the sample for calibration curve is prepared and measured using a tablet molding compressor as described above. The acceleration voltage and current values ​​of the X-ray generator are set to 24kV and 100mA, respectively. A linear calibration curve is obtained by plotting the obtained X-ray count rate on the vertical axis and the amount of polyvalent metal added to each calibration curve sample on the horizontal axis.

[0099] Next, the toner particles to be analyzed are measured as pellets using a tablet molding and compression machine as described above. Then, the polyvalent metal element content (mass concentration) in the black toner particles is determined from the calibration curve described above.

[0100] (Calculation of Net Strength) Furthermore, the net intensity is defined as the X-ray intensity obtained by subtracting the background intensity from the X-ray intensity at the peak angle indicating the presence of a metallic element, as obtained from the above measurement.

[0101] (Separation of external additives) If the surface of the toner particles has been treated with external additives, the external additives can be removed as needed by the following method to obtain the toner particles. Add 160g of sucrose (manufactured by Kishida Chemical) to 100mL of deionized water and dissolve it while heating in a water bath to prepare a concentrated sucrose solution. Put 31g of the above concentrated sucrose solution into a centrifugal tube (capacity 50mL) and Contaminon N (nonionic surfactant, anionic surfactant, iodine Prepare a dispersion by adding 6 mL of a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments (manufactured by Wako Pure Chemical Industries, Ltd.), which is made from machine builder. Add 1.0 g of toner to this dispersion and break up any clumps of toner with a spatula or similar tool.

[0102] Shake the centrifugation tube in a shaker at 350 spm (strokes per min) for 20 minutes. After shaking, transfer the solution to a 50 mL glass tube for a swing rotor and separate it using a centrifuge (H-9R, manufactured by Kokusan Co., Ltd.) at 3500 rpm for 30 minutes. This procedure separates the toner particles from the detached external additives. Visually confirm that the toner and aqueous solution are sufficiently separated, and collect the toner particles separated at the top layer using a spatula or similar tool. Filter the collected toner particles using a vacuum filter, then dry them in a dryer for at least 1 hour to obtain toner particles. Repeat this procedure multiple times to obtain the required amount.

[0103] <Measurement of Acid Value> The acid value of the acid group-containing resin separated by the method described above can be measured by the following procedure. The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 gram of the sample. The acid value of resins is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure. (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%), add deionized water to make a total volume of 100 ml, and obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethyl alcohol (95 vol%) to make 1 L. Place the solution in an alkali-resistant container, taking care not to allow it to come into contact with carbon dioxide, etc., and leave it for 3 days. After that, filter the solution to obtain potassium hydroxide solution. Store the obtained potassium hydroxide solution in an alkali-resistant container. The factor of the potassium hydroxide solution is determined by taking 25 ml of 0.1 mol / L hydrochloric acid in an Erlenmeyer flask, adding a few drops of the phenolphthalein solution, titrating with the potassium hydroxide solution, and determining the amount of potassium hydroxide solution required for neutralization. The 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998.

[0104] (2) Operation (A) Main examination 2.0 g of the pulverized resin sample is accurately weighed into a 200 ml Erlenmeyer flask, and 100 ml of a toluene / ethanol (2:1) mixture is added. The mixture is dissolved over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and the mixture is titrated with the potassium hydroxide solution. The titration endpoint is reached when the indicator turns a pale pink color for approximately 30 seconds. (B) Blank test The titration procedure is the same as described above, except that no sample is used (i.e., only a mixed solution of toluene / ethanol (2:1) is used).

[0105] (3) Substitute the obtained results into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S Here, A: acid value (mgKOH / g), B: volume of potassium hydroxide solution added in the blank test (ml), C: volume of potassium hydroxide solution added in the main test (ml), f: factor of the potassium hydroxide solution, and S: mass of the sample (g).

[0106] <Method for measuring the weight-average particle size (D4) of toner> The weight-average particle size (D4) of the toner is calculated as follows. The measuring device used is the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter), a precision particle size distribution analyzer using the pore electrical resistance method equipped with a 100 μm aperture tube. Setting the measurement conditions and analyzing the measurement data are performed using the included dedicated software, "Beckman Coulter." The Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter) will be used. The measurement will be performed with an effective measurement channel count of 25,000. The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in deionized water to a concentration of 1% by mass; for example, "ISOTON II" (manufactured by Beckman Coulter) can be used. Before performing the measurements and analysis, the dedicated software was configured as follows. In the "Change Standard Measurement Method (SOMME)" screen of the dedicated software, set the total count in control mode to 50,000 particles, the number of measurements to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). Press the "Measure Threshold / Noise Level Button" to automatically set the threshold and noise level. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check "Flush aperture tube after measurement". In the "Pulse to Particle Size Conversion Settings" screen of the dedicated software mentioned above, set the bin spacing to logarithmic particle size, the particle size bins to 256 particle size bins, and the particle size range from 2 μm to 60 μm.

[0107] The specific measurement method is as follows: (1) Place 200 ml of the electrolytic solution into a 250 ml round-bottom glass beaker specifically designed for the Multisizer 3, set it on the sample stand, and stir the mixture with the stirrer rod at 24 revolutions per second in a counterclockwise direction. Then, use the "Aperture Tube Flash" function of the dedicated software to remove any dirt and air bubbles from inside the aperture tube. (2) Place 30 ml of the electrolytic aqueous solution into a 100 ml flat-bottomed glass beaker. Add 0.3 ml of a diluted solution of "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) diluted three times by mass with deionized water as a dispersant. (3) Prepare an ultrasonic dispersion system "Ultrasonic Dispersion System Tetra150" (manufactured by Nikko Bios Co., Ltd.) with an electrical output of 120W, which incorporates two oscillators with an oscillation frequency of 50kHz with a phase difference of 180 degrees. Add 3.3L of deionized water to the water tank of the ultrasonic dispersion system, and add 2ml of Contaminon N to this water tank. (4) Place the beaker from (2) into the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height of the beaker so that the resonance state of the liquid surface of the electrolytic aqueous solution inside the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker described in (4) with ultrasound, add 10 mg of toner to the electrolytic aqueous solution in small amounts and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During ultrasonic dispersion, adjust the water temperature in the tank to be between 10°C and 40°C as appropriate. (6) Using a pipette, the electrolytic aqueous solution (5) containing the dispersed toner is dropped into the round-bottom beaker (1) placed in the sample stand, and the concentration is adjusted to 5%. The measurement is then continued until the number of particles measured reaches 50,000. (7) The measurement data is analyzed using the dedicated software provided with the device to calculate the weight-average particle size (D4). Note that the "Average Diameter" on the "Analysis / Volume Statistics (Arithmetic Mean)" screen when the dedicated software is set to Graph / Volume % is the weight-average particle size (D4).

[0108] <Method for measuring average circularity> The average circularity of toner particles is measured using the flow-type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions used during calibration. The specific measurement method is as follows: First, 20 ml of deionized water, from which impurities and other contaminants have been removed, is placed in a glass container. To this, "Contaminon N" (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments, consisting of a nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) is added as a dispersant and diluted three times with the deionized water. Add 0.2 ml of the diluted solution. Then add approximately 0.02 g of the sample to be measured and disperse it using an ultrasonic disperser for 2 minutes to obtain the dispersion for measurement. During this process, cool the dispersion as needed so that its temperature is between 10°C and 40°C. As the ultrasonic disperser, use a tabletop ultrasonic cleaner disperser with an oscillation frequency of 50 kHz and an electrical output of 150 W (for example, "VS-150" (manufactured by Velvo-Clear)). Add a predetermined amount of deionized water to the water tank and add 2 ml of the aforementioned Contaminon N to this water tank.

[0109] For the measurement, the aforementioned flow-type particle image analyzer equipped with "UPlanApro" (magnification 10x, numerical aperture 0.40) as the objective lens was used, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion liquid prepared according to the above procedure was introduced into the flow-type particle image analyzer, and 3000 toner particles were measured in HPF measurement mode and total count mode. Then, the binarization threshold for particle analysis was set to 85%, and the analyzed particle diameter was limited to a circular equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles was determined.

[0110] Before starting the measurement, autofocus adjustment should be performed using standard latex particles (for example, Duke Scientific's "RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" diluted with deionized water). Subsequently, it is preferable to perform focus adjustment every two hours from the start of the measurement.

[0111] In this embodiment, a flow-type particle image analyzer was used, which had been calibrated by Sysmex Corporation and for which a calibration certificate issued by Sysmex Corporation had been received. Except for limiting the analyzed particle size to an equivalent circle diameter of 1.985 μm or more and less than 39.69 μm, measurements were performed under the measurement and analysis conditions at the time the calibration certificate was received. [Examples]

[0112] The present disclosure will be further described below with reference to examples and comparative examples, but the disclosure is not limited thereto. Unless otherwise specified, the term "part" used in the examples refers to a mass-based unit.

[0113] The following describes examples of toner manufacturing. <Example of Pigment Dispersion 1 Production> • Styrene 30.0 parts • Carbon Black 8.0 parts (Product name: Nipex35, manufactured by Orion Engineered Carbons) • Copper phthalocyanine 0.8 parts (Product name: CIPigment Blue 15:3, manufactured by Dainichi Seika Co., Ltd.) • Aluminum distearate 0.07 parts The above materials were placed in an attritor (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.), and then dispersed using 1.7 mm diameter zirconia particles at 220 rpm for 5 hours to obtain pigment dispersion 1.

[0114] <Examples of manufacturing pigment dispersions 2-19> As shown in Table 1, pigment dispersions 2 to 19 were obtained in the same manner as in the production example of pigment dispersion 1, except that the type and amount of compound containing styrene, colorant, phthalocyanine complex, and polyvalent metal element were changed.

[0115] [Table 1]

[0116] <Example of Toner 1 manufacturing> • Styrene 47.0 parts n-butyl acrylate 17.0 parts • Formula (1) Unit monomer 6.0 parts • Hydrocarbon wax 5.0 parts (Product name: HNP-51, manufactured by Nippon Seiro Co., Ltd.) • 12.0 parts of the ester compound represented by formula (4) (R 5 =-C2H4-, R 6 =R 7 =-C 17 H 35 ) • 1.0 part of the ester compound represented by formula (8) (R 10 =-C8H 16 -, R 11 =R 12 =-C 22 H 45 ) • Hexanediol diacrylate (HDDA) 0.5 parts ·Acid group-containing resin 12.0 parts (Styrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, acid value 10 mg KOH / g, glass transition temperature (Tg) 80°C, weight-average molecular weight (Mw) 15,000) The above materials were mixed and added to a pigment dispersion in a ratio of 1:38.87 parts. The resulting mixture was kept warm at 60°C and stirred at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to uniformly dissolve and disperse, thereby preparing a polymerizable monomer composition.

[0117] Meanwhile, 850.0 parts of a 0.10 mol / L Na3PO4 aqueous solution and 8.0 parts of 10% hydrochloric acid were added to a container equipped with a high-speed stirring device, Creamix (manufactured by M-Technique), the rotation speed was adjusted to 15,000 rpm, and the mixture was heated to 70°C. 68.0 parts of a 1.0 mol / L CaCl2 aqueous solution were then added to prepare an aqueous medium containing a calcium phosphate compound.

[0118] After adding the polymerizable monomer composition to the aqueous medium, 6.5 parts of t-butyl peroxypivalate, which is a polymerization initiator, are added, and the mixture is cultured for 10 minutes while maintaining a rotation speed of 15,000 rpm. The mixture was then granulated. After that, the agitator was changed from a high-speed agitator to a propeller-type agitator, and the mixture was reacted at 70°C for 5 hours under reflux, then the liquid temperature was raised to 85°C and the mixture was reacted for another 2 hours. After the polymerization reaction was complete, the resulting slurry was cooled, a portion was taken, and the particle size distribution was measured. Furthermore, hydrochloric acid was added to the slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. The slurry was then washed with three times its volume of water, filtered, and dried to obtain toner particles. The molecular weight distribution of these toner particles was measured, and the weight-average molecular weight (Mw) was calculated to be 30,000.

[0119] To 100.0 parts of the obtained toner particles 1, 2.0 parts of silica microparticles (number-average particle size of primary particles: 10 nm, BET specific surface area: 170 m2 / g) hydrophobized with dimethyl silicone oil (20% by mass) and 0.05 parts of zinc stearate particles (median diameter D50s by volume: 0.3 μm) were added as external additives, and the mixture was prepared using a Mitsui Henschel mixer (manufactured by Mitsui Miike Chemical Machinery Co., Ltd.) at 3000 rpm for 15 minutes to obtain toner 1.

[0120] <Manufacturing examples for toners 2-35> As shown in Table 2, toners 2 to 35 were obtained in the same manner as in the production example of toner 1, except that the type and amount of the pigment dispersion, styrene, n-butyl acrylate, phthalocyanines, and polyvalent metal elements were changed.

[0121] [Table 2] In the table, St represents styrene, and n-BA represents n-butyl acrylate. wax represents carbon This shows hydrogenated wax.

[0122] <Example of manufacturing magnetic material 1> Fe 2+50 liters of a ferrous sulfate aqueous solution containing 2.0 mol / L of ferrous sulfate was mixed with 55 L of a 4.0 mol / L sodium hydroxide aqueous solution and stirred to obtain a ferrous salt aqueous solution containing ferrous hydroxide colloid. This aqueous solution was maintained at 85°C, and an oxidation reaction was carried out while blowing air at 20 L / min to obtain a slurry containing core particles. The obtained slurry was filtered using a filter press, washed, and then the core particles were dispersed again in water to re-slurry. Sodium silicate was added to this re-slurry liquid at a silicon content of 0.2 mass% per 100.0 parts of core particles, the pH of the slurry liquid was adjusted to 6.0, and the mixture was stirred to obtain magnetic iron oxide particles with a silicon-rich surface.

[0123] The obtained slurry was filtered using a filter press, washed, and then re-slurred with deionized water. 500.0 parts (10.0% by mass relative to magnetic iron oxide) of ion exchange resin (product name: SK110, manufactured by Mitsubishi Chemical Corporation) were added to this re-slurry (solid content 50 g / L), and ion exchange was performed by stirring for 2 hours. After that, the ion exchange resin was removed by filtration with a mesh, filtered using a filter press, washed, dried, and crushed to obtain magnetic iron oxide with a number-average particle size of 0.23 μm.

[0124] Next, a surface treatment agent was prepared. 30.0 parts of iso-butyltrimethoxysilane were added dropwise to 70.0 parts of deionized water with stirring. Then, this aqueous solution was maintained at pH 5.5 and temperature 55°C, and hydrolysis was carried out by dispersing with a disperser blade at a peripheral speed of 0.46 m / s for 120 minutes. After that, the pH of the aqueous solution was adjusted to 7.0, and the hydrolysis reaction was stopped by cooling to 10°C. Thus, an aqueous solution containing a silane compound was obtained.

[0125] 100.0 parts of magnetic iron oxide were placed in a high-speed mixer (product name: LFS-2, manufactured by Fukae Pawtech Co., Ltd.), and 8.0 parts of an aqueous solution containing a silane compound were added dropwise over 2 minutes while stirring at a rotation speed of 2000 rpm. Mixing and stirring were then continued for 5 minutes. Next, to improve the adhesion of the silane compound, the mixture was dried at 40°C for 1 hour to reduce the moisture content, and then the mixture was dried at 110°C for 3 hours to allow the condensation reaction of the silane compound to proceed. After that, the mixture was crushed and passed through a sieve with a mesh size of 100 μm to obtain magnetic material 1.

[0126] <Example of Toner 36 manufacturing> 720 parts of deionized water were mixed with 450 parts of a 0.1 mol / L NaPO4 aqueous solution and heated to 60°C. Then, 67.7 parts of a 1.0 mol / L CaCl2 aqueous solution were added to obtain an aqueous medium containing a dispersion stabilizer. Next, we prepared the following materials. • Styrene: 81.0 parts n-butyl acrylate: 13.0 parts n-Lauryl acrylate: 6.0 parts · Hexanediol diacrylate (HDDA): 1.5 parts ·Magnetic material 1: 65.0 parts • Polar resin (polyester resin, acid value: 8.0 mg KOH / g, glass transition temperature: 69°C) , weight average molecular weight: 9500): 4.0 parts

[0127] These materials were uniformly dispersed and mixed using an attritor (manufactured by Nippon Coke Industries Co., Ltd.). The resulting monomer composition was heated to 60°C, and the following materials were mixed and dissolved therein to obtain a polymerizable monomer composition. • 15.0 parts of the ester compound represented by formula (4) (R 5 =-C2H4-, R 6 =R 7 =-C 17 H 35 ) • Hydrocarbon wax 5.0 parts (Product name: HNP-51, manufactured by Nippon Seiro Co., Ltd.) • Polymerization initiator (t-butyl peroxypivalate) 9.0 parts

[0128] The polymerizable monomer composition was added to the aqueous medium obtained above, and a granulation process was carried out for 10 minutes at a temperature of 60°C and under a nitrogen atmosphere using a Creamix (manufactured by M-Technique Co., Ltd.) while maintaining a rotation speed of 15,000 rpm. Subsequently, the mixture was stirred with a paddle agitator, and the polymerization reaction was carried out at a reaction temperature of 70°C for 300 minutes. After the reaction was complete, the suspension was heated to 100°C and held there for 2 hours. Then, as a cooling step, 0°C water was added to the suspension, and the suspension was cooled from 98°C to 30°C at a rate of 60°C / min. After that, hydrochloric acid was added to the suspension and thoroughly washed to dissolve the dispersion stabilizer, and the mixture was filtered and dried to obtain toner particles. The obtained toner particles were subjected to an external additive treatment in the same manner as in the manufacturing example of toner 1 to obtain toner 36.

[0129] Table 3 shows the content of monomer units represented by formula (1) in the vinyl resin of various toners, the content of carbon black, phthalocyanine complex and hydrocarbon wax per 100 parts by mass of resin binder resin; a / b, which is the ratio of the carbon black content a (mass%) based on the mass of black toner particles to the total content b (mass%) of copper phthalocyanine and zinc phthalocyanine; and the mass concentration of polyvalent metal elements in the toner particles.

[0130] [Table 3] The ratio of formula (1) in vinyl resin indicates the content (mass%) of the monomer unit represented by formula (1) in the vinyl resin.

[0131] The following evaluations were performed using the obtained toner. <Image Evaluation> Image evaluation was performed using a commercially available color laser printer (HP LaserJet Enter). The test was conducted using a modified HP Color M555dn printer. The modification allowed the printer to operate even with only one process cartridge installed. The toner was removed from the black cartridge and replaced with 100g of the toner to be evaluated, and the evaluation was performed.

[0132] [Evaluation Method for Cold Offset] Cold offset was evaluated in a normal temperature and humidity environment (temperature 25.0°C, relative humidity 50%). The fixing temperature of the fuser in the evaluation electrophotographic apparatus was modified to be arbitrarily set. In this apparatus, the fuser temperature was controlled in 5°C increments within the range of 140°C to 180°C, using GF-C081 (manufactured by Canon Marketing Japan, basis weight 81.4 g / cm²), a smooth paper, as the media. 2 A4 size was used. The toner load was 0.40 mg / cm². 2 Three solid black images were output. At this time, the presence or absence of cold offset was visually evaluated in the third solid black image, and the lowest temperature at which no cold offset occurred was used for evaluation according to the following criteria. A: Below 150℃ B: 150℃ or higher but less than 160℃ C: 160℃ or higher, less than 170℃ D: 170℃ or higher, but less than 180℃ E: Above 180℃

[0133] [How to rate white dots] The evaluation of the white dots was based on using Vitality paper (manufactured by Xerox, basis weight 75g / cm²) as the media. 2 The format was changed to letter, and the image was output under the same conditions as the cold offset evaluation method. At this time, the presence or absence of white areas where toner was missing in the third solid image was visually evaluated, and the lowest temperature at which no white spots occurred was used for evaluation according to the following criteria. A: Below 150℃ B: 150℃ or higher but less than 160℃ C: 160℃ or higher, less than 170℃ D: 170℃ or higher, but less than 180℃ E: Above 180℃

[0134] [Image density (coloring power)] Image density was evaluated using print images at the lowest fixing temperature in the fixing test described above. A Macbeth RD918 reflectance densitometer (Macbeth Corporation) was used to measure the relative density of the printout image relative to the white background area with a document density of 0.00. Three points were measured at the left, center, and right sides of the output image, and the average value was used to evaluate the image density. A: Image density is 1.40 or higher B: Image density is between 1.30 and less than 1.40 C: Image density is between 1.20 and less than 1.30 D: Image density is less than 1.20

[0135] [Image gloss stability] In the low-temperature fixing test described above, the printed image at the lowest fixing temperature was left to stand for one day in a normal temperature and humidity environment (temperature 23°C, relative humidity 60%), and the image gloss of the fixed image was measured. A handheld gloss meter PG-1 (manufactured by Nippon Denshoku Industries Co., Ltd.) was used to measure the image gloss. The measurement conditions were set to a light projection angle and light reception angle of 75° each, and five different points on the fixed image were measured, with the average value taken as the initial gloss value after fixing. Furthermore, the images with measured gloss were left standing for two weeks in an environment of 50°C and 30% relative humidity, and then left standing for one day in a normal temperature and humidity environment (temperature 23°C, relative humidity 60%). After that, the image gloss was... Measurements were taken and compared with the initial gloss values ​​after fixation. Image gloss stability was evaluated according to the following criteria. A: Image gloss change range (Δgloss) is 3 or less. B: Image gloss change range is greater than 3 and less than or equal to 6. C: Image gloss change range is greater than 6 and less than or equal to 10. D: Image gloss change range is greater than 10 and less than or equal to 15 E: Image gloss change range is greater than 15

[0136] [Examples 1-31] In Examples 1 to 31, the above evaluation was performed using toners 1 to 31, respectively. The evaluation results are shown in Table 4.

[0137] [Table 4]

[0138] [Comparative Examples 1-5] In Comparative Examples 1-5, the above evaluation was performed using toners 32-36, respectively. The evaluation results are shown in Table 4.

[0139] This disclosure relates to the following configuration. (Composition 1) Black toner particles having a binder resin, hydrocarbon wax, and carbon black. It is a colored toner, The black toner particles further contain at least one selected from the group consisting of copper phthalocyanine and zinc phthalocyanine. A black toner characterized in that the binder resin contains a vinyl resin having monomer units represented by the following formula (1). TIFF2026054644000010.tif48168 (In formula (1), R 1 R represents a hydrogen atom or a methyl group. 2 (This represents a linear alkyl group with 8 to 22 carbon atoms.) (Configuration 2) The black toner according to configuration 1, wherein the vinyl resin contains 1.0 to 15.0% by mass of monomer units represented by formula (1). (Composition 3) The black toner according to configuration 1 or 2, wherein the carbon black content is 5.0 to 25.0 parts by mass per 100 parts by mass of the binder resin. (Composition 4) The black toner according to any one of configurations 1 to 3, wherein the total content of the copper phthalocyanine and the zinc phthalocyanine is 0.10 to 8.00 parts by mass per 100 parts by mass of the binder resin. (Composition 5) A black toner according to any of configurations 1 to 4, wherein when the carbon black content based on the mass of the black toner particles is a (mass%), and the total content of copper phthalocyanine and zinc phthalocyanine based on the mass of the black toner particles is b (mass%), a and b satisfy the following formula (2). 2.0 ≤ a / b ≤ 30.0 ···(2) (Composition 6) The black toner according to any one of configurations 1 to 5, wherein the content of the hydrocarbon wax is 1.5 to 15.0 parts by mass per 100 parts by mass of the binder resin. (Composition 7) The aforementioned black toner particles A first ester compound which is at least one ester compound selected from the group consisting of the ester compound represented by the following formula (3), the ester compound represented by the following formula (4), and the ester compound represented by the following formula (5), and A black toner according to any one of configurations 1 to 6, comprising a second ester compound which is at least one ester compound selected from the group consisting of an ester compound represented by the following formula (6), an ester compound represented by the following formula (7), and an ester compound represented by the following formula (8). TIFF2026054644000011.tif122168 (In formula (3), R 3 and R 4 Each is independently a linear alkyl group having 16 to 22 carbon atoms (however, R 3 When the carbon number is 18-22, R 4 This represents the case where the carbon number is between 19 and 22. In formula (4), R 5 R represents a linear alkylene group with 1 to 6 carbon atoms. 6 and R 7 Each of these independently represents a linear alkyl group with 14 to 22 carbon atoms. In formula (5), R 5 R represents a linear alkylene group with 1 to 6 carbon atoms. 6 and R 7 Each of these independently represents a linear alkyl group with 14 to 22 carbon atoms. In formula (6), R 8 R represents a linear alkyl group with 21 carbon atoms. 9 This represents a linear alkyl group with 22 carbon atoms. In formula (7), R 10 R represents a linear alkylene group with 8 to 12 carbon atoms. 11 and R 12 Each of these independently represents a linear alkyl group with 18 to 22 carbon atoms. In formula (8), R 10 R represents a linear alkylene group with 8 to 12 carbon atoms. 11 and R 12 Each of these independently represents a linear alkyl group with 18 to 22 carbon atoms. (Composition 8) The aforementioned black toner particles contain polyvalent metal elements, The polyvalent metal element contains at least one selected from the group consisting of aluminum and magnesium. The black toner according to any one of configurations 1 to 7, wherein the mass concentration of the polyvalent metal element in the black toner particles is 5 to 500 ppm. (Composition 9) The black toner according to any one of configurations 1 to 8, wherein the black toner particles contain aluminum distearate.

Claims

1. A black toner having black toner particles having a binder resin, hydrocarbon wax, and carbon black, The black toner particles further contain at least one selected from the group consisting of copper phthalocyanine and zinc phthalocyanine. A black toner characterized in that the binder resin contains a vinyl resin having monomer units represented by the following formula (1). (In formula (1), R １ R represents a hydrogen atom or a methyl group. ２ (This represents a linear alkyl group with 8 to 22 carbon atoms.)

2. The black toner according to claim 1, wherein the vinyl resin has 1.0 to 15.0% by mass of the monomer unit represented by formula (1).

3. The black toner according to claim 1 or 2, wherein the carbon black content is 5.0 to 25.0 parts by mass per 100 parts by mass of the binder resin.

4. The black toner according to claim 1 or 2, wherein the total content of the copper phthalocyanine and the zinc phthalocyanine is 0.10 to 8.00 parts by mass per 100 parts by mass of the binder resin.

5. The black toner according to claim 1 or 2, wherein when the carbon black content based on the mass of the black toner particles is a (mass%), and the total content of copper phthalocyanine and zinc phthalocyanine based on the mass of the black toner particles is b (mass%), a and b satisfy the following formula (2). 2.0 ≤ a / b ≤ 30.0 ... (2)

6. The black toner according to claim 1 or 2, wherein the content of the hydrocarbon wax is 1.5 to 15.0 parts by mass per 100 parts by mass of the binder resin.

7. The aforementioned black toner particles A first ester compound which is at least one ester compound selected from the group consisting of the ester compound represented by the following formula (3), the ester compound represented by the following formula (4), and the ester compound represented by the following formula (5), and The black toner according to claim 1 or 2, comprising a second ester compound which is at least one ester compound selected from the group consisting of an ester compound represented by the following formula (6), an ester compound represented by the following formula (7), and an ester compound represented by the following formula (8). (In formula (3), R ３ and R ４ Each is independently a linear alkyl group having 16 to 22 carbon atoms (where R ３ When the carbon number is 18 to 22, R ４ This represents the case where the carbon number is between 19 and 22. In formula (4), R ５ represents a linear alkylene group having 1 to 6 carbon atoms, and R ６ and R ７ each independently represent a linear alkyl group having 14 to 22 carbon atoms. In formula (5), R ５ R represents a linear alkylene group with 1 to 6 carbon atoms. ６ and R ７ Each of these independently represents a linear alkyl group having 14 to 22 carbon atoms. In formula (6), R ８ R represents a linear alkyl group with 21 carbon atoms. ９ This represents a linear alkyl group with 22 carbon atoms. In formula (7), R １０ R represents a linear alkylene group with 8 to 12 carbon atoms. １１ and R １２ Each of these independently represents a linear alkyl group having 18 to 22 carbon atoms. In formula (8), R １０ R represents a linear alkylene group with 8 to 12 carbon atoms. １１ and R １２ Each of these independently represents a linear alkyl group with 18 to 22 carbon atoms.

8. The aforementioned black toner particles contain polyvalent metal elements, The polyvalent metal element contains at least one selected from the group consisting of aluminum and magnesium. The black toner according to claim 1 or 2, wherein the mass concentration of the polyvalent metal element in the black toner particles is 5 to 500 ppm.

9. The black toner according to claim 1 or 2, wherein the black toner particles contain aluminum distearate.

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