Toner

Abstract

To provide a toner which is excellent in the low-temperature fixability and in the gloss of a printed material and can suppress transfer dropout in vertical fine line images.SOLUTION: In a toner having toner particles containing a binder resin, the binder resin contains polyester A by at least 50 mass% and the polyester A contains a unit Uiso derived from isophthalic acid by at least 60 mol% based on all units derived from acid components. The toner particles contain core shell particles including a core part and a shell part. The shell part contains a resin B having a monomer unit with a functional group selected from the group consisting of salicylic acid-based functional groups and sulfonic acid groups.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] Electrophotographic technology is a technology that forms an electrostatic latent image on a uniformly charged photoreceptor and visualizes the image information with charged toner, and is used in devices such as copiers and printers. In recent years, in order to cope with various usage methods of copiers and printers, it has been required to reduce power consumption, extend the service life, and obtain high-quality images regardless of the environment. In Patent Document 1, in order to obtain a toner with improved low-temperature fixability and excellent gloss of printed matter, a polycondensation resin component obtained by polycondensing an alkylene oxide adduct of bisphenol A, an isophthalic acid compound, and an aliphatic saturated carboxylic acid compound, and a toner containing an amorphous composite resin having a styrene-based resin component are disclosed. Compared with the case of using a terephthalic acid compound or the like as a raw material, since the entanglement of polymer chains is less, the melt viscosity during fixing is reduced, and the gloss of the printed matter can be improved. In Patent Document 2, when writing from the back surface of a recording medium on which a solid image is fixed, in order to suppress the occurrence of back transfer to another recording medium, the state of the release agent in the toner particles and the dynamic viscoelasticity of the toner particles are controlled, and further, a toner in which the ratio of isophthalic acid to the total polyvalent carboxylic acid of the polyester as the binder resin is defined is disclosed. By containing isophthalic acid, the compatibility between the binder resin and the release agent is improved, the growth of the diameter of the release agent domain is suppressed, and back transfer caused by cracking of the release agent can be improved.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, as a result of the inventors' study, although the toner described in Patent Document 1 is excellent in low-temperature fixability and can obtain a high gloss, in the case of a vertical thin line image where a large pressure is applied to the toner during transfer, transfer dropout may occur. In addition, although the toner described in Patent Document 2 can suppress back transfer due to its high affinity with the release agent of isophthalic acid, similar to the toner described in Patent Document 1, in the case of a vertical thin line image where a large pressure is applied to the toner during transfer, transfer dropout may occur. For the above reasons, there is a demand for a toner that is excellent in low-temperature fixability, the gloss of printed matter, and can suppress transfer dropout in vertical thin line images. The present disclosure provides a toner that is excellent in low-temperature fixability, the gloss of printed matter, and can suppress transfer dropout in vertical thin line images.

Means for Solving the Problems

[0005] The present disclosure relates to a toner having toner particles containing a binder resin, the binder resin contains 50% by mass or more of polyester A, and the polyester A contains 60 mol% or more of unit U derived from isophthalic acid based on all units derived from acid components, iso and the toner particles are core-shell particles composed of a core part and a shell part, and the shell part contains a resin B having a monomer unit having a functional group selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group.

Effects of the Invention

[0006] According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability, the gloss of printed matter, and can suppress transfer dropout.

Embodiments for Carrying Out the Invention

[0007] In the present disclosure, descriptions such as "XX or more and YY or less" and "XX to YY" representing numerical ranges mean numerical ranges including the lower limit and the upper limit which are endpoints, unless otherwise specified. When numerical ranges are described stepwise, the upper and lower limits of each numerical range can be arbitrarily combined. Also, a monomer unit refers to the reacted form of the monomer substance in a polymer.

[0008] 〔Features of the Present Disclosure〕 In electrophotography, the transfer process is a process of moving and adhering the toner image formed on the surface of the photoreceptor to the paper. In order to obtain a high-quality image, it is important to move the toner image on the photoreceptor obtained in the development process as it is to the paper without collapsing it. Also, it is known that the transfer process is greatly affected by the environment in which it is used and the image pattern, and various image defects occur.

[0009] Toner excellent in low-temperature fixability and gloss of the printed matter had a problem that transfer dropout, in which the central part was missing, was likely to occur in the transfer process of a vertical thin-line image. The reason why only the central part of the vertical thin-line image was not transferred was due to the fact that a vertical thin line with a small toner-bearing area with respect to the entire length was likely to receive strong pressure. Furthermore, while the toner can be displaced in the non-image part direction at the image end, it cannot be displaced at the central part, so the pressure further increases, and transfer dropout occurs due to an increase in the adhesion force between the toner and the drum and between the toner and the toner. In order to solve the above problems, the present inventor has studied toner in which the viscoelasticity and chargeability of the toner are controlled.

[0010] However, even when controlling the viscoelasticity and chargeability of the toner, it was not possible to sufficiently suppress transfer dropout while being excellent in low-temperature fixability and gloss of the printed matter. Through the studies of the present inventors, it has been found that the ease of plastic deformation of the toner is greatly involved in the increase in the adhesion force, and furthermore, the structure of the monomer unit of the resin contained in the toner affects the adhesion force of the resin. At the same time, attention was also paid to the fact that by adopting core-shell particles composed of a core part and a shell part as toner particles, a suitable resin component design can be expected for each.

[0011] Therefore, as a result of further intensive studies by the present inventors, it has been found that the above problems can be solved by combining a core portion containing a polyester having a unit derived from isophthalic acid with a shell portion containing a resin having a monomer unit having a functional group selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group.

[0012] First, the present inventors focused on isophthalic acid, which is a monomer unit of polyester. Isophthalic acid is an aromatic dicarboxylic acid having two carboxylic acids in the meta-position with respect to the benzene ring, and is more likely to adopt a zigzag polymer structure compared to terephthalic acid having two carboxylic acids in the para-position with respect to the benzene ring, and is more likely to adopt a flexible structure by suppressing the interaction between polymer chains. For this reason, it has excellent low-temperature fixing properties, and furthermore, due to the small entanglement of molecular chains, a high gloss can be obtained. On the other hand, when a high pressure is applied, plastic deformation is likely to occur, and an increase in adhesion accompanying an increase in the contact area occurs. In addition, isophthalic acid becomes a polyester by polycondensation, and has a wide polar surface due to the COO bonds of two ester groups being arranged in the same direction with respect to the central benzene ring, so the interaction between molecules works strongly, and the adhesion between the toner and the drum and between the toner and the toner increases. For the above reasons, it has been difficult to sufficiently suppress dropout during transfer in a toner having excellent low-temperature fixing properties and high gloss of printed matter.

[0013] In order to improve the transferability, the present inventors tried to increase the chargeability of the toner and raise the electrostatic force, but were unable to suppress the above increase in adhesion, and no sufficient effect was observed in suppressing dropout during transfer. The present inventors have intensively studied and found that it is effective to combine a core portion containing the above polyester with a shell portion containing a resin B having a monomer unit having a functional group selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group.

[0014] That is, the present disclosure is directed to a toner having toner particles containing a binder resin, The binder resin contains 50% by mass or more of polyester A, and the polyester A contains unit U derived from isophthalic acid at 60 mol% or more based on all units derived from acid components. iso and contains The toner particles are core-shell particles composed of a core part and a shell part, and the shell part contains a resin B having a monomer unit having a functional group selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group.

[0015] With the above configuration, it is possible to solve the problem of occurrence of dropout during transfer for vertical thin line images in a toner excellent in low-temperature fixability and gloss of printed matter. The reason is explained below. The resin contained in the shell part has a charge control ability by containing a monomer unit having a functional group selected from the group consisting of a salicylic acid functional group and a sulfonic acid group, and can maintain charging because it is a resin. By improving the chargeability of the toner, the electrostatic force, which is the driving force for transfer, can be increased. Further, while the core part has a flexible structure and is prone to plastic deformation, by covering it with the shell part, the flexible core part releases the pressure applied to the shell part from the outside, and by suppressing the increase in the contact area due to elastic deformation, it is possible to suppress the increase in the adhesion force between the toner and the drum and between the toner and the toner. Furthermore, by covering the strong intermolecular interaction due to the wide polar surface derived from the ester group of isophthalic acid in the core part with the shell part, it is possible to suppress the increase in the adhesion force between the toner and the drum and between the toner and the toner.

[0016] As a result, it was found that the dropout during transfer for vertical thin line images in a toner excellent in low-temperature fixability and gloss of printed matter was significantly improved.

[0017] Hereinafter, each component of the present disclosure will be described in detail.

[0018] The toner of the present disclosure has toner particles containing a binder resin.

[0019] The binding resin contains 50% by mass or more of polyester A, and the polyester A contains 60 mol% or more of unit U derived from isophthalic acid based on all units derived from acid components (U iso / total acid components × 100 is 60 mol% or more). Thereby, not only the fixing property becomes good, but also the gloss of the image after fixing becomes good. U iso / total acid components × 100 is preferably 90 mol% or more. iso The polyester A of the present disclosure contains unit U derived from an ethylene oxide adduct of bisphenol A

[0020] and unit U derived from a propylene oxide adduct of bisphenol A EO , and the total content ratio of the unit U PO and the unit U EO is preferably 90 mol% or more based on all units derived from alcohol components. The ethylene oxide adduct of bisphenol A and the propylene oxide adduct of bisphenol A have a benzene ring in the main chain, so the durability of the toner is improved, and the dropout during transfer to vertical thin line images can be suppressed over a long period. PO Also, U

[0021] / (U EO +U PO )×100 of the content ratio of the unit U EO is preferably 15 mol% or more and 40 mol% or less with respect to the total of the content ratio of the unit U EO and the content ratio of the unit U EO . U PO is a bisphenol A unit to which propylene oxide having a larger number of carbon atoms and a branched structure is added compared to U PO . When U EO / (U EO +U EO )×100 is 15 mol% or more, the durability is improved due to an increase in the density of benzene rings in the main chain, and U PO / (U EO +U EO +U PO)×100 is 40 mol% or less, the density of hydrocarbons in the main chain increases, resulting in good low-temperature fixability. For the above reasons, U EO / (U EO +U PO )×100 is preferably 15 mol% or more and 40 mol% or less.

[0022] When measuring the number-average molecular weight (Mn) and the weight-average molecular weight (Mw) of the tetrahydrofuran (THF) soluble fraction of the polyester A of the present invention using gel permeation chromatography (GPC), the number-average molecular weight (Mn) is preferably 3000 or more and 10000 or less, and (Mw / Mn) is preferably 2.5 or more.

[0023] When the number-average molecular weight (Mn) is 3,000 or more and 10,000 or less, the change in melt fluidity due to the pressure difference caused by the image pattern during fixing can be reduced, and the gloss unevenness after low-temperature fixing can be suppressed, which is preferable. More preferably, the number-average molecular weight (Mn) is 4000 or more and 8000 or less.

[0024] Also, (Mw / Mn) being 2.5 or more means that the molecular weight distribution of the polyester A is sufficiently wide, the change in melt fluidity due to the pressure difference caused by the image pattern during fixing can be reduced, and the gloss unevenness after low-temperature fixing can be suppressed, which is preferable.

[0025] The binder resin of the present disclosure further contains a crystalline polyester, which is preferable because it has excellent low-temperature fixability and can be a good toner for suppressing gloss unevenness after low-temperature fixing. The crystalline polyester is preferably contained in the binder resin in an amount of 3.0% by mass or more and 30.0% by mass or less. Preferred polyesters as the crystalline polyester will be described later.

[0026] The toner particles of the present disclosure preferably contain 0.015 mass% or more and 0.150 mass% or less of aluminum atoms, because this can more effectively suppress missing transfer during transfer to vertical thin line images in a low-temperature and low-humidity environment. When the amount of aluminum atoms is within the above range, aluminum in the toner particles forms a crosslinked structure, and by imparting elasticity in a low-temperature and low-humidity environment, plastic deformation under high pressure can be suppressed, and missing transfer during transfer to vertical thin line images in a low-temperature and low-humidity environment can be suppressed.

[0027] The toner particles of the present disclosure preferably have an average circularity of 0.950 or more and 0.980 or less, because this can more effectively suppress missing transfer during transfer to vertical thin line images. When within the above range, the toner can be appropriately displaced in the non-image part direction in the vertical thin line image, and pressure concentration can be alleviated, so missing transfer during transfer can be more effectively suppressed, which is preferable. More preferably, the average circularity of the toner particles is 0.955 or more and 0.975 or less.

[0028] On the other hand, the shell part of the present disclosure contains resin B, and the resin B has a monomer unit having a functional group selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group.

[0029] The monomer having a salicylic acid-based functional group is at least one or more monomers selected from the group consisting of 3-vinylsalicylic acid, 4-vinylsalicylic acid, 5-vinylsalicylic acid, 6-vinylsalicylic acid, 3-vinyl-5-isopropylsalicylic acid, 3-vinyl-5-t-butylsalicylic acid, 4-vinyl-6-t-butylsalicylic acid, etc., and is a monomer represented by the following formula (I), and particularly preferably a monomer represented by the following formula (I).

[0030]

Chemical formula

[0031] R 1 and R 2 Examples of the alkyl group in include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, an s-butyl group, a t-butyl group, etc., and examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, etc.

[0032] Examples of the monomer having a sulfonic acid group include resins derived from styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid (AMPS), vinyl sulfonic acid, methacrylic sulfonic acid, maleimide derivatives, or styrene derivatives, and maleic acid amide derivatives of the following formula (II). In particular, a monomer having a partial structure derived from 2-acrylamido-2-methylpropane sulfonic acid is preferred.

[0033] [Chemical formula]

[0034] The resin B is preferably a vinyl resin. By being a vinyl resin, the water content of the resin can be reduced, and by suppressing the increase in adhesion in a high-temperature and high-humidity environment, it is possible to suppress the dropout during transfer to a vertical thin line image in a high-temperature and high-humidity environment.

[0035] The content of the monomer unit having a functional group selected from the group consisting of a salicylic acid functional group and a sulfonic acid group in the resin B is preferably 0.3% by mass or more and 10% by mass or less.

[0036] In the toner particles of the present disclosure, in ATR-IR analysis, the peak P derived from the salicylic acid group-based functional group of the resin B S and the peak P derived from the carbonyl group of the polyester A A are detected. And the peak PS Let the intensity be I S and the intensity of peak P A be I A When this is the case, the ratio I S / I A is preferably in the range of 0.02 or more and 0.20 or less.

[0037] 〔Preferred embodiments of toner particles〕 Next, the preferred constituent components and embodiments of the toner particles of the present disclosure will be described.

[0038] <Binder resin> The toner particles of the present disclosure contain a binder resin. The content of the binder resin is preferably 50% by mass or more of the total amount of resin components in the toner particles.

[0039] As described above, as the binder resin, it is necessary to contain 50% by mass or more of polyester A, and 70% by mass or more is preferable because not only the fixability becomes good but also the gloss of the image after fixing becomes good.

[0040] In addition, the binder resin of the present disclosure may contain polyesters other than polyester A. For example, it may contain styrene acrylic resins, epoxy resins, polyesters, polyurethane resins, polyamides, cellulose resins, polyether resins, mixed resins and composite resins thereof, etc.

[0041] <Polyester A> As described above, the polyester A of the present disclosure needs to contain 60 mol% or more of the unit U derived from isophthalic acid, based on all units derived from acid components, and preferably contains 90 mol% or more. iso It is sufficient to use the unit derived from isophthalic acid as an essential component, and examples thereof include the following.

[0042] The polyester A used for the toner particles of the present disclosure is preferably an amorphous polyester.

[0043] It is sufficient to use the unit derived from isophthalic acid as an essential component, and examples thereof include the following.

[0044] The polyester is obtained by selecting and combining suitable ones from polycarboxylic acids, polyols, hydroxycarboxylic acids, etc., and synthesizing them using known methods such as the transesterification method or the polycondensation method. Preferably, the polyester contains a polycondensate of a dicarboxylic acid and a diol.

[0045] The polycarboxylic acid is a compound containing two or more carboxy groups in one molecule. Among these, the dicarboxylic acid is a compound containing two carboxy groups in one molecule and is preferably used. For example, 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-dicarboxylic acid, hexahydroterephthalic acid, malonic acid, pimelic acid, suberic 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, cyclohexanedicarboxylic acid, etc. can be mentioned.

[0046] In addition, examples of polycarboxylic acids other than the above dicarboxylic acids include trimellitic acid, trimesic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrenetricarboxylic acid, pyrenetetracarboxylic acid, itaconic acid, glutaconic acid, n-dodecylsuccinic acid, n-dodecenylsuccinic acid, isododecylsuccinic acid, isododecenylsuccinic acid, n-octylsuccinic acid, n-octenylsuccinic acid, etc. These may be used alone or in combination of two or more.

[0047] A polyol is a compound containing two or more hydroxyl groups in one molecule. Among these, a diol is a compound containing two hydroxyl groups in one molecule and is preferably used. Specifically, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 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, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,14-eicosandecanediol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-butenediol, neopentyl glycol, polytetramethylene glycol, hydrogenated bisphenol A, bisphenol A, bisphenol F, bisphenol S, alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols, etc. can be mentioned.

[0048] Among these, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols. Particularly preferred are alkylene oxide adducts of bisphenols and the combined use of these with alkylene glycols having 2 to 12 carbon atoms. Examples of the alkylene oxide adduct of bisphenol A include compounds represented by the following formula (A).

[0049]

Chemical formula

[0050] The alkylene oxide adduct of bisphenol A is preferably a propylene oxide adduct and / or an ethylene oxide adduct of bisphenol A. More preferably, it is a propylene oxide adduct. Further, the average value of x + y is preferably 1 or more and 5 or less.

[0051] Examples of the alcohol having a trivalent or higher valence include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, hexamethylolmelamine, hexaethylolemelamine, tetramethylolbenzoguanamine, tetraethylolebenzoguanamine, sorbitol, trisphenol PA, phenol novolak, cresol novolak, and alkylene oxide adducts of the above-mentioned polyphenols having a trivalent or higher valence. These may be used alone or in combination of two or more.

[0052] The acid value of the polyester A of the present disclosure is preferably 4.0 mgKOH / g or more and 10.0 mgKOH / g or less.

[0053] <Crystalline polyester> The toner particles of the present disclosure preferably contain a crystalline polyester. The crystalline polyester is preferably a polycondensate of monomers containing an aliphatic diol and / or an aliphatic dicarboxylic acid. Note that the crystalline polyester refers to a polyester having a distinct melting point as measured using a differential scanning calorimeter (DSC).

[0054] The crystalline polyester preferably contains monomer units derived from an aliphatic diol having 2 to 12 carbon atoms (more preferably 6 to 12 carbon atoms) and / or monomer units derived from an aliphatic dicarboxylic acid having 2 to 12 carbon atoms (more preferably 6 to 12 carbon atoms).

[0055] Such a crystalline polyester having such a structure provides good dispersibility of the crystalline polyester among toner particles, can suppress uneven wet spreading among toner particles during fixing, and is thus preferable because it provides good low-temperature fixability for halftone images and line images.

[0056] Examples of the aliphatic diol having 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.

[0057] Also, an aliphatic diol having a double bond can be used. Examples of the aliphatic diol having a double bond include the following compounds: 2-butene-1,4-diol, 3-hexene-1,6-diol, and 4-octene-1,8-diol.

[0058] Examples of the aliphatic dicarboxylic acid 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. Lower alkyl esters and acid anhydrides of these aliphatic dicarboxylic acids can also be used. Among these, sebacic acid, adipic acid, 1,10-decanedicarboxylic acid, and their lower alkyl esters and acid anhydrides are preferable. These can be used alone or in combination of two or more.

[0059] In addition, aromatic dicarboxylic acids can also be used. Examples of the 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 in terms of easy availability and its tendency to form polymers with low melting points.

[0060] Moreover, dicarboxylic acids having double bonds can also be used. Dicarboxylic acids having double bonds can be suitably used for suppressing hot offset during fixing in that they can crosslink the entire resin by utilizing their double bonds.

[0061] Examples of such dicarboxylic acids include fumaric acid, maleic acid, 3-hexenedioic acid, and 3-octenedioic acid. Also included are their lower alkyl esters and acid anhydrides. Among these, fumaric acid and maleic acid are more preferred.

[0062] The method for producing the crystalline polyester is not particularly limited, and it can be produced by a general polyester polymerization method in which a dicarboxylic acid component and a diol component are reacted. For example, it can be produced by using either the direct polycondensation method or the transesterification method, and appropriately selecting according to the type of monomer.

[0063] Note that the peak temperature of the maximum endothermic peak measured using a differential scanning calorimeter (DSC) of the crystalline polyester is preferably 50.0°C or higher and 100.0°C or lower, and more preferably 60.0°C or higher and 90.0°C or lower from the viewpoint of low-temperature fixability.

[0064] <Release agent> In the toner of the present disclosure, a release agent may be blended as necessary to improve fixability. All known release agents can be used as the release agent. Specifically, petroleum waxes such as paraffin wax, microcrystalline wax, and petrolatum and their derivatives, montan wax and its derivatives, hydrocarbon waxes and their derivatives by the Fischer-Tropsch method, polyolefin waxes represented by polyethylene and polypropylene and their derivatives, natural waxes such as carnauba wax and candelilla wax and their derivatives, ester waxes, etc. Here, derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products. Further, as the ester wax, monofunctional ester wax, bifunctional ester wax, and polyfunctional ester waxes such as tetrafunctional and hexafunctional can be used.

[0065] The melting point of the release agent is preferably 60°C or higher and 140°C or lower, more preferably 70°C or higher and 130°C or lower. When the melting point is 60°C or higher and 140°C or lower, the toner is easily plasticized during fixing, and the fixability is improved. Also, it is preferable because bleeding of the release agent is less likely to occur even after long-term storage.

[0066] <Colorant> In the toner of the present disclosure, examples of the colorant include organic pigments, organic dyes, and inorganic pigments, etc., but it is not particularly limited, and conventionally known colorants can be used.

[0067] Examples of cyan-based colorants include copper phthalocyanine compounds and their derivatives, anthraquinone compounds, and basic dye lake compounds. Specifically, the following are included. C.I. Pigment Blue 1, C.I. Pigment Blue 7, C.I. Pigment Blue 15, C.I. Pigment Blue 15:1, C.I. Pigment Blue 15:2, C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 60, C.I. Pigment Blue 62, and C.I. Pigment Blue 66.

[0068] Examples of magenta colorants include the following: condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specific examples include the following: C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Violet 19, C.I. Pigment Red 23, C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red 48:4, C.I. Pigment Red 57:1, C.I. Pigment Red 81:1, C.I. Pigment Red 122, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 150, C.I. Pigment Red 166, C.I. Pigment Red 169, C.I. Pigment Red 177, C.I. Pigment Red 184, C.I. Pigment Red 185, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 220, C.I. Pigment Red 221, and C.I. Pigment Red 254.

[0069] Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following can be mentioned. C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 15, C.I. Pigment Yellow 17, C.I. Pigment Yellow 62, C.I. Pigment Yellow 74, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 95, C.I. Pigment Yellow 97, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 111, C.I. Pigment Yellow 120, C.I. Pigment Yellow 127, C.I. Pigment Yellow 128, C.I. Pigment Yellow 129, C.I. Pigment Yellow 147, C.I. Pigment Yellow 151, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 168, C.I. Pigment Yellow 174, C.I. Pigment Yellow 175, C.I. Pigment Yellow 176, C.I. Pigment Yellow 180, C.I. Pigment Yellow 181, C.I. Pigment Yellow 185, C.I. Pigment Yellow 191, and C.I. Pigment Yellow 194.

[0070] Examples of black colorants include carbon black, and those toned to black using the above yellow colorants, magenta colorants, cyan colorants, and magnetic materials.

[0071] These colorants can be used alone, mixed, or even in a solid solution state. The colorants used in the present disclosure are selected from the viewpoints of hue angle, chroma, lightness, lightfastness, OHP transparency, and dispersibility in toner particles.

[0072] When a magnetic material is used as a colorant in the toner of the present disclosure, the magnetic material mainly consists of magnetic iron oxides such as magnetite and γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. These magnetic materials have a BET specific surface area by the nitrogen adsorption method of 2 m 2 / g or more and 30 m 2 / g or less, preferably 3 m 2 / g or more and 28 m 2 / g or less. Also, those with a Mohs hardness of 5 or more and 7 or less are preferred. As the shape of the magnetic material, there are polyhedrons, octahedrons, hexahedrons, spherical shapes, needle shapes, flake shapes, etc. Among them, those with less anisotropy such as polyhedrons, octahedrons, hexahedrons, and spherical shapes are preferred for increasing the image density.

[0073] The addition amount of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer constituting the binder resin. When using magnetic powder, it is preferably 20 parts by mass or more and 200 parts by mass or less, more preferably 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the binder resin or the polymerizable monomer constituting the binder resin.

[0074] <External additive> For the toner of the present disclosure, an inorganic external additive or the like may be mixed with the toner particles and adhered to the surface of the toner particles. Examples of the inorganic external additive include silica, strontium titanate, fatty acid metal salts, alumina, and metal oxide fine particles (inorganic fine particles) such as titanium oxide, hydrotalcite compounds, zinc oxide fine particles, cerium oxide fine particles, and calcium carbonate fine particles.

[0075] Also, as the external additive, composite oxide fine particles using two or more metals can be used, or two or more selected from any combination of these fine particle groups can be used. Also, resin fine particles, and organic-inorganic composite fine particles of resin fine particles and inorganic fine particles can be used.

[0076] The external additive may be hydrophobically treated with a hydrophobizing agent. Examples of the hydrophobizing agent include chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, t-butyldimethylchlorosilane, vinyltrichlorosilane; alkoxysilanes such as tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, o-methylphenyltrimethoxysilane, p-methylphenyltrimethoxysilane, n-butyltrimethoxysilane, i-butyltrimethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, dodecyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, i-butyltriethoxysilane, decyltriethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane; silazanes such as hexaethyldisilazane, hexapropyldisilazane, hexabutyldisilazane, hexapentyldisilazane, hexaphenyldisilazane, hexacyclohexyldisilazane, hexaphenyldisilazane, divinyltetramethyldisilazane, dimethyltetravinyldisilazane; Silicone oils such as dimethyl silicone oil, methyl hydrogen silicone oil, methyl phenyl silicone oil, alkyl-modified silicone oil, chloroalkyl-modified silicone oil, chlorophenyl-modified silicone oil, fatty acid-modified silicone oil, polyether-modified silicone oil, alkoxy-modified silicone oil, carbinol-modified silicone oil, amino-modified silicone oil, fluorine-modified silicone oil, and terminal-reactive silicone oil; Siloxanes such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, hexamethyldisiloxane, and octamethyltrisiloxane; Examples of fatty acids and their metal salts include long-chain fatty acids such as undecylic acid, lauric acid, tridecylic acid, dodecylic acid, myristic acid, palmitic acid, pentadecylic acid, stearic acid, heptadecylic acid, arachidic acid, montanic acid, oleic acid, linoleic acid, and arachidonic acid, and salts of the above fatty acids with metals such as zinc, iron, magnesium, aluminum, calcium, sodium, and lithium.

[0077] Among these, alkoxysilanes, silazanes, and silicone oils are preferably used because they are easy to subject to hydrophobization treatment. These hydrophobizing agents may be used alone or in combination of two or more.

[0078] The content of the external additive is preferably 0.05 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the toner particles.

[0079] <Others> The glass transition temperature (Tg) of the toner of the present disclosure is preferably 40°C or higher and 70°C or lower. When the glass transition temperature of the toner is 40°C or higher and 70°C or lower, storage stability and durability can be improved while maintaining good fixability.

[0080] The weight average particle diameter (D4) of the toner is preferably 3.0 μm or more and 12.0 μm or less, more preferably 4.5 μm or more and 7.5 μm or less. When the weight average particle diameter (D4) is 3.0 μm or more and 12.0 μm or less, good fluidity can be obtained and the latent image can be developed faithfully.

[0081] [Method for manufacturing toner] The method for manufacturing the toner is not particularly limited, and known manufacturing methods can be adopted. Examples of the method for manufacturing the toner include a kneading and pulverizing method and a wet manufacturing method. From the viewpoint of easily obtaining a core-shell particle structure and uniformizing the particle diameter and controlling the shape, the wet manufacturing method is preferable. Examples of the wet manufacturing method include a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method, and the emulsion aggregation method is more preferable. That is, the method for manufacturing toner particles preferably has a step of aggregating fine particles of a binder resin to form aggregated particles and a step of fusing the aggregated particles to obtain toner particles. Further, the toner particles are preferably emulsion aggregation toner particles. This is because it is easy to produce core-shell particles by coating a desired shell portion on the core portion aggregated in an aqueous medium.

[0082] Hereinafter, the method for manufacturing toner particles by the emulsion aggregation method will be exemplified and described in detail.

[0083] (Dispersion preparation step) The binder resin particle dispersion is prepared, for example, as follows. When the binder resin is a homopolymer or copolymer (vinyl resin) of a vinyl monomer, vinyl resin particles are dispersed in an ionic surfactant by performing emulsion polymerization, seed polymerization, etc. of the vinyl monomer in the ionic surfactant to prepare a dispersion. When the binder resin is a resin other than a vinyl resin such as polyester, the resin is mixed with an aqueous medium in which an ionic surfactant or a polyelectrolyte is dissolved.

[0084] Thereafter, this solution is heated to a temperature equal to or higher than the melting point or softening point of the resin and dissolved, and a dispersion in which the binder resin particles are dispersed in an ionic surfactant is prepared using a powerful dispersing machine with a shearing force such as a homogenizer.

[0085] As the means of dispersion, there is no particular limitation. For example, known dispersion devices such as a rotary shear type homogenizer, a ball mill having media, a sand mill, and a dyno mill can be mentioned.

[0086] Also, a phase inversion emulsification method may be used as a method for preparing the dispersion liquid. The phase inversion emulsification method is a method in which a binder resin is dissolved in an organic solvent, a neutralizing agent and a dispersion stabilizer are added as necessary, an aqueous solvent is dropped under stirring to obtain emulsified particles, and then the organic solvent in the resin dispersion liquid is removed to obtain an emulsion. At this time, the charging order of the neutralizing agent and the dispersion stabilizer may be changed. The number average particle diameter of the binder resin particles is usually 1 μm or less, preferably 0.01 μm or more and 1.00 μm or less. When the number average particle diameter is 1.00 μm or less, the particle size distribution of the finally obtained toner is suitable, and the generation of free particles can be suppressed. Further, when the number average particle diameter is within the above range, the uneven distribution between toners is reduced, the dispersion in the toner is improved, and the variations in performance and reliability are reduced.

[0087] The number average particle diameter of the resin particles (resin B particles) containing a monomer unit selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group in the shell portion is preferably 0.01 μm or more and 0.50 μm or less, more preferably 0.02 μm or more and 0.50 μm or less. By being within the above range, it is easy to obtain core-shell particles coated with a thin film.

[0088] In the emulsion aggregation method, a colorant particle dispersion liquid can be used as necessary. The colorant particle dispersion liquid is obtained by dispersing at least colorant particles in a dispersant. The number average particle diameter of the colorant particles is preferably 0.5 μm or less, more preferably 0.2 μm or less. When the number average particle diameter is 0.5 μm or less, diffuse reflection of visible light can be prevented, and it is easy to aggregate the binder resin particles and the colorant particles in the aggregation step. When the number average particle diameter is within the above range, the uneven distribution between toners is reduced, the dispersion in the toner is improved, and the variations in performance and reliability are reduced.

[0089] In the emulsion aggregation method, a wax particle dispersion can be used as necessary. The wax particle dispersion is formed by dispersing at least wax particles in a dispersant. The number average particle diameter of the wax particles is preferably 2.0 μm or less, more preferably 1.0 μm or less. When the number average particle diameter is 2.0 μm or less, the variation in the wax content among toner particles is small, and the long-term image stability is good. When the number average particle diameter is within the above range, the uneven distribution among toners is reduced, the dispersion in the toner becomes good, and the variations in performance and reliability are small.

[0090] The combination of the colorant particles, binder resin particles, and wax particles is not particularly limited and can be appropriately and freely selected according to the purpose. In addition to the above dispersion, other particle dispersions formed by dispersing appropriately selected particles in a dispersant may be further mixed. The particles contained in the other particle dispersions are not particularly limited and can be appropriately selected according to the purpose, and examples include internal additive particles, charge control agent particles, inorganic particles, abrasive particles, and the like. These particles may be dispersed in the binder resin particle dispersion or the colorant particle dispersion.

[0091] Examples of the dispersant contained in the binder resin particle dispersion, colorant particle dispersion, wax fine dispersion, other particle dispersions, etc. include an aqueous medium containing a polar surfactant. Examples of the aqueous medium include water such as distilled water and ion-exchanged water, and alcohols. These may be used alone or in combination of two or more. The content of the polar surfactant cannot be generally defined and can be appropriately selected according to the purpose.

[0092] Examples of polar surfactants include anionic surfactants such as sulfate ester salts, sulfonates, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts. Specific examples of anionic surfactants include sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate, sodium dodecyl sulfate, sodium alkylnaphthalenesulfonate, and sodium dialkylsulfosuccinate. Specific examples of cationic surfactants include alkylbenzyldimethylammonium chloride, alkyltrimethylammonium chloride, and distearylammonium chloride. These may be used alone or in combination of two or more.

[0093] As the polar surfactant, it is preferable to use sodium alkylbenzenesulfonate having an alkyl group with 12 to 14 carbon atoms because it can suppress dropout during transfer to vertical thin-line images in a high-temperature and high-humidity environment. More preferably, sodium dodecylbenzenesulfonate is used.

[0094] These polar surfactants can also be used in combination with nonpolar surfactants. Examples of nonpolar surfactants include nonionic surfactants such as polyethylene glycol-based, alkylphenol ethylene oxide adduct-based, and polyhydric alcohol-based surfactants.

[0095] The content of the colorant particles is preferably 0.1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the binder resin in the aggregated particle dispersion when the aggregated particles are formed.

[0096] The content of the wax particles is preferably 0.5 part by mass or more and 25 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin in the aggregated particle dispersion when the aggregated particles are formed.

[0097] Furthermore, in order to more precisely control the chargeability of the resulting toner, the charge control particles and the binder resin particles may be added after the aggregated particles are formed.

[0098] The particle size of particles such as binder resin particles and colorant particles is measured using a laser diffraction / scattering particle size distribution measuring device LA-960V2 manufactured by Horiba, Ltd.

[0099] (Aggregation step) The aggregation step of forming aggregated particles is a step of forming aggregated particles containing binder resin particles and, if necessary, colorant particles, wax particles, etc. in an aqueous medium containing binder resin particles and, if necessary, added colorant particles and wax particles.

[0100] Aggregated particles can be formed in the aqueous medium, for example, by adding a flocculant, a pH adjuster, and a stabilizer to the aqueous medium, mixing them, and appropriately applying temperature, mechanical power, etc.

[0101] Examples of the flocculant include monovalent metal salts such as sodium and potassium; divalent metal salts such as calcium and magnesium; trivalent metal salts such as iron and aluminum; and alcohols such as methanol, ethanol, and propanol. Preferably, it is a flocculant containing a divalent or higher metal element with high flocculation power that can cause flocculation with a small amount of addition.

[0102] Specifically, divalent inorganic metal salts such as calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, and zinc chloride can be mentioned. Also, trivalent metal salts such as iron(III) chloride, iron(III) sulfate, aluminum sulfate, and aluminum chloride can be mentioned. Also, inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, ferric polysulfate, and calcium polysulfide can be mentioned, but are not limited thereto. These may be used alone or in combination of two or more. Aluminum metal salts are preferred in terms of controlling the amount of aluminum element in the toner particles.

[0103] Examples of pH adjusters include alkalis such as ammonia and sodium hydroxide, and acids such as nitric acid and citric acid.

[0104] Examples of stabilizers mainly include the polar surfactant itself or an aqueous medium containing the same. For example, when the polar surfactant contained in each particle dispersion is anionic, a cationic one can be selected as the stabilizer.

[0105] The flocculant etc. may be added in either the form of a dry powder or an aqueous solution dissolved in an aqueous medium, but in order to cause uniform flocculation, it is preferably added in the form of an aqueous solution.

[0106] The addition and mixing of the flocculant etc. are preferably carried out at a temperature equal to or lower than the glass transition temperature of the resin contained in the aqueous medium. When mixing is carried out under this temperature condition, flocculation proceeds in a stable state. Mixing can be carried out using, for example, a mixing device, a homogenizer, a mixer, etc. that are well-known per se.

[0107] Also, in the flocculation step, by attaching a dispersion containing polyester to the surface of the flocculated particles to form a shell portion, toner particles having a core-shell structure with a shell portion formed on the surface of the core portion can be obtained. Note that the flocculation step may be repeatedly carried out in multiple stages step by step.

[0108] (Fusion step) The fusion step is a step of heating and fusing the obtained flocculated particles. Before entering the fusion step, in order to prevent fusion between the toner particles, a pH adjuster, a polar surfactant, a non-polar surfactant, etc. can be appropriately added. The heating temperature may be the glass transition temperature of the resin contained in the flocculated particles (when there are two or more types of resins, the glass transition temperature of the resin having the highest glass transition temperature) to the decomposition temperature of the resin. Therefore, the heating temperature varies depending on the type of resin of the binder resin particles and cannot be generally defined, but generally it is 140°C or lower and equal to or higher than the glass transition temperature of the resin contained in the flocculated particles. Note that heating can be carried out using a heating device or instrument that is well-known per se.

[0109] As for the fusing time, a shorter time is sufficient if the heating temperature is high, and a longer time is required if the heating temperature is low. That is, since the fusing time depends on the heating temperature, it cannot be generally specified, but it is generally 30 minutes or more and 10 hours or less.

[0110] The toner particles obtained through the above steps can be separated by solid-liquid separation according to a known method, the toner particles can be recovered, and then they can be washed, dried, etc. under appropriate conditions.

[0111] (External addition step) The obtained toner particles can be added with an external additive such as an inorganic external additive to obtain a toner. From the viewpoint of the dispersibility of the external additive, the mixing time in the external addition step is preferably adjusted to a range of 0.5 minutes or more and 10.0 minutes or less, and more preferably adjusted to a range of 1.0 minutes or more and 5.0 minutes or less.

[0112] [Measurement methods for each physical property] Next, the measurement methods for each physical property will be described.

[0113] [Isolation method of toner particles] 0.50 g of Triton-X100 (manufactured by Kishida Chemical Co., Ltd.) is added to 100 g of ion-exchanged water to prepare a dispersion medium. (1) Weigh 1.00 g of toner accurately into a vial, add the above dispersion medium to make it 10.00 g, and then prepare a sample solution that is allowed to stand for 24 hours. (2) The sample solution is subjected to ultrasonic homogenizer treatment to release the external additive from the toner and disperse it in the dispersion medium. Ultrasonic treatment device: Ultrasonic homogenizer VP-050 (manufactured by Taitec Corporation) Microchip: Step-type microchip, tip diameter φ2 mm Tip position of the microchip: Center of the glass vial and 5 mm height from the bottom of the vial Ultrasonic conditions: Intensity 30%, 180 minutes. At this time, ultrasonic waves are applied while cooling the vial with ice water so that the dispersion liquid does not heat up. (3) Separate the toner particles in the sample solution and the dispersion medium in which the external additives are dispersed (filtrate) by suction filtration (10 μm membrane filter). (4) Recover the toner particles after filtration, add the dispersion medium again to make it 10.00 g, then recover the toner particles obtained by repeating the above (2) and (3) a total of 10 times, and dry them sufficiently at 45 °C for 24 hours to isolate the toner particles.

[0114] <Method for Isolating Binder Resin from Toner Particles> Dissolve 100 mg of toner particles in 3 mL of chloroform. Then, remove the insoluble matter by suction filtration with a syringe equipped with a sample treatment filter (pore size 0.2 μm or more and 0.5 μm or less, for example, using Micron Disc H-25-2 (manufactured by Tosoh Corporation)). Introduce the soluble matter into preparative HPLC (apparatus: LC-9130 NEXT preparative column [60 cm] manufactured by Nippon Analytical Industry Co., Ltd., exclusion limit: 20000, 70000, two columns connected in series) and send the chloroform eluent. When a peak can be confirmed by the display of the obtained chromatograph, collect the retention time with a molecular weight of 2000 or more using a monodisperse polystyrene standard sample. Dry and solidify the solution of the obtained fraction to separate and collect the binder resin from the release agent.

[0115] <Composition Analysis of Binder Resin Composed of Multiple Components> Use the chloroform-soluble matter of the collected binder resin as a sample. The sample is adjusted with chloroform so that the concentration of toner particles is 0.1% by mass, and the solution filtered through a 0.45 μm PTFE filter is used for measurement. The gradient polymer LC measurement conditions are shown below.

[0116] Apparatus: UlTIMATE3000 (manufactured by Thermo Fisher Scientific) Mobile phase: A Chloroform (HPLC), B Acetonitrile (HPLC) Gradient: 2 min (A / B = 0 / 100) → 25 min (A / B = 100 / 0) (Note that the gradient of the change in the mobile phase was made linear.) Flow rate: 1.0 mL / min Injection: 0.1 mass% × 20 μL Column: Tosoh TSKgel ODS (4.6 mm φ × 150 mm × 5 μm) Column temperature: 40 °C Detector: Corona charged particle detector (Corona-CAD) (manufactured by Thermo Fisher Scientific)

[0117] Regarding the time-intensity graph obtained by measurement, a peak corresponding to a highly polar component, i.e., resin A, and a peak corresponding to a low-polarity component, i.e., resin B, are confirmed. Also, when resins other than resin A and resin B are contained, peaks corresponding to their polarities are observed. Then, by performing the above measurement again and fractionating at the time of the valley of each peak, it is possible to separate resin A, resin B, and other resins.

[0118] In addition, when the toner contains a release agent, it is necessary to separate the release agent from the toner. The separation of the release agent is performed by recycling HPLC to separate components with a molecular weight of 2000 or less as the release agent. The measurement method is shown below. First, a chloroform solution of the toner is prepared by the method described above. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Microlidisk" (manufactured by Tosoh Corporation) with a pore size of 0.2 μm to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in chloroform is 1.0 mass%. Using this sample solution, measurement is performed under the following conditions. · Apparatus: LC-Sakura NEXT (manufactured by Japan Analytical Industry Co., Ltd.) · Column: JAIGEL2H, 4H (manufactured by Japan Analytical Industry Co., Ltd.) · Eluent: Chloroform · Flow rate: 10.0 mL / min · Oven temperature: 40.0 °C · Sample injection volume: 1.0 mL

[0119] In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a standard polystyrene resin (e.g., trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500”, manufactured by Tosoh Corporation) is used. From the molecular weight curve thus obtained, components with a molecular weight of 2000 or less are fractionated repeatedly to remove the release agent from the toner. In the fractionation, the required amount of each chloroform / acetonitrile solution is collected, dried and concentrated, and then used as samples of polyester A (resin A) and crystalline polyester (resin D).

[0120] Using the samples of resin A component and resin D component, the composition ratio and mass ratio by nuclear magnetic resonance spectroscopy (NMR) are measured as follows.

[0121] To 20 mg of the samples of resin A component and resin D component, 1 mL of deuterated chloroform is added and the proton NMR spectrum of the dissolved resin is measured. From the obtained NMR spectrum, the molar ratio and mass ratio of each monomer can be calculated, and the content ratio of each monomer unit can be determined. For example, in the case of a styrene-acrylic copolymer, the composition ratio and mass ratio can be calculated based on the peak around 6.5 ppm derived from the styrene monomer and the peak around 3.5 - 4.0 ppm derived from the acrylic monomer.

[0122] For nuclear magnetic resonance spectroscopy (NMR), the following apparatus and measurement conditions can be used. NMR apparatus: RESONANCE ECX500 manufactured by JEOL Ltd. Observed nucleus: Proton Measurement mode: Single pulse

[0123] <Quantification method of U, U, U in polyester A by NMR measurement iso 、U EO 、U PO > The component identification of polyester A and the measurement of molar ratio and mass ratio by nuclear magnetic resonance spectroscopy (NMR) are as follows.

[0124] Add 1 mL of deuterated chloroform to 20 mg of the obtained polyester A, and measure the proton NMR spectrum of the dissolved polyester A. Regarding the smallest unit sandwiched by ester bonds as the structure derived from monomers, the molar ratio and mass ratio of each monomer were calculated from the obtained NMR spectrum.

[0125] For example, the composition ratio and mass ratio can be calculated based on the following peaks (chemical shift value, number of protons).

[0126] Unit derived from isophthalic acid: 7.5 ppm (1), 8.2 ppm (2), 8.7 ppm (1) Unit derived from terephthalic acid: 8.1 ppm (4) Unit derived from ethylene oxide adduct of bisphenol A: 1.6 ppm (6), 4.3 ppm (4), 4.7 ppm (4), 6.8 ppm (4), 7.1 ppm (4) Unit derived from propylene oxide adduct of bisphenol A: 1.5 ppm (6), 1.6 ppm (6), 4.1 ppm (4), 5.5 ppm (2), 6.8 ppm (4), 7.1 ppm (4) Unit derived from ethylene glycol: 4.3 ppm (4) NMR apparatus: JEOL RESONANCE ECX500 Observed nucleus: proton Measurement mode: single pulse Reference peak: TMS

[0127] By this NMR analysis, the content (mol%) of the unit U derived from isophthalic acid was determined based on all units derived from acid components. iso Also, the total content ratio (mol%) of U EO and U PO was determined based on all units derived from alcohol components. And, with respect to the total of the content ratio of U EO and the content ratio of U PO the content ratio of U EOThe content ratio (mol%) was determined.

[0128] <Identification of monomer units of resin by pyrolysis gas chromatography-mass spectrometry (pyrolysis GC / MS)> For the identification of monomer units of the resin contained in the toner particles, pyrolysis gas chromatography-mass spectrometry (pyrolysis GC / MS) is used. Pyrolysis device: TPS-700 manufactured by JEOL Ltd. Pyrolysis temperature: appropriate value at 400°C to 600°C, 590°C in this case GC / MS device: ISQ manufactured by Thermo Fisher Scientific K.K. Column: "HP5-MS" (Agilent / 19091S-433), length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm GC / MS conditions Inlet conditions: InletTemp: 250°C, SplitFlow: 50 ml / min GC temperature rising conditions: 40°C (5 min) → 10°C / min (300°C) → 300°C (20 min) Mass range: m / z = 10 to 550 Peaks specific to the monomer units having salicylic acid-based functional groups and sulfonic acid groups contained in Resin B are selected as follows.

[0129] In the case of Resin B-1 in the examples, peaks at m / z = 153 (corresponding to the site containing salicylic acid) and 253 (corresponding to the monomer unit containing salicylic acid) are selected.

[0130] In the case of Resin B-2 in the examples, a peak at m / z = 163 (corresponding to the monomer unit containing salicylic acid) is selected.

[0131] In the case of Resin B-3 in the examples, peaks at m / z = 80 (corresponding to SO3 - and 206 (corresponding to the monomer unit containing sulfonic acid) are selected.

[0132] Also, select the peaks of m / z = 76, 120, 121 (corresponding to isophthalic acid and terephthalic acid sites) and 211 (corresponding to bisphenol A site) derived from the dicarboxylic acid or diol of the polyester contained in Resin A.

[0133] <Identification of Monomer Units of Resin Contained in Shell of Toner Particles> The identification and mapping of the monomer units of the resin contained in the shell of the toner particles are analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS). For the measurement of the ion amount (peak intensity) using TOF-SIMS, nanoTOFII manufactured by ULVAC-PHI, Inc. is used. The analysis conditions are as follows. Sample preparation: Attach the toner particles separated from the toner by the method described above to an indium sheet. Sample pretreatment: None Primary ion: Bi3 ++ Ion Acceleration voltage: 30 kV Charge neutralization mode: On Measurement mode: Negative Raster: 300 × 300 μm 2 Mass range: m / z = 0.5 ~ 1850 Measurement time: 30 s

[0134] Also in TOF-SIMS, select the peaks specific to the monomer units selected by pyrolysis GC / MS and perform mapping to analyze the presence or absence of the shell and the monomer units having a salicylic acid-based functional group or a sulfonic acid group contained in the shell.

[0135] <Method for Measuring Weight-Average Molecular Weight Mw and Number-Average Molecular Weight Mn> The molecular weights of samples such as Polyester A, crystalline polyester, and styrene acrylic are measured by gel permeation chromatography (GPC) as follows.

[0136] First, dissolve the sample in tetrahydrofuran (THF). In the case of polyester A or styrene acrylic, dissolve it in THF at room temperature over 24 hours. In the case of crystalline polyester, warm THF to 40 °C to dissolve it and then leave it standing for 24 hours.

[0137] For each solution in which the sample is dissolved, filter it through a solvent-resistant membrane filter "Microlidisk" with a pore size of 0.2 μm (manufactured by Tosoh Corporation) to obtain a sample solution. Note that the sample solution is adjusted so that the concentration of the components soluble in THF is 0.8% by mass. Using this sample solution, measurements are made under the following conditions. Apparatus: HLC8120GPC (Detector: RI) (manufactured by Tosoh Corporation) · Column: Seven columns of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK) Eluent: Tetrahydrofuran (THF) · Flow rate: 1.0 mL / min · Oven temperature: 40.0 °C · Sample injection volume: 0.10 ml

[0138] When calculating the molecular weight of the sample, use the molecular weight calibration curve prepared using a standard polystyrene resin (for example, trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", manufactured by Tosoh Corporation).

[0139] <Quantification Method of Aluminum Element in Toner Particles> The measurement of the fluorescent X-ray of the aluminum element conforms to JIS K 0119-1969, and specifically is as follows.

[0140] As the measuring device, a wavelength-dispersive X-ray fluorescence analyzer "Axios" (manufactured by PANalytical) and dedicated software "SuperQ ver.4.0F" (manufactured by PANalytical) attached for setting measurement conditions and analyzing measurement data are used. In addition, Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Also, a proportional counter (PC) is used for detection.

[0141] As the measurement sample, about 4 g of toner particles are placed in a dedicated aluminum ring for pressing and flattened, and a pellet molded to a thickness of about 2 mm and a diameter of about 39 mm by using a tablet molding compression machine "BRE-32" (manufactured by Maehara Testing Machine Co., Ltd.) at 20 MPa for 60 seconds is used.

[0142] The acceleration voltage and current value of the X-ray generator are measured at 24 kV and 160 mA respectively. Elements are identified based on the peak position of the obtained X-rays, and the concentration is calculated from the counting rate (unit: cps), which is the number of X-ray photons per unit time.

[0143] <Measurement of toner FT-IR spectrum (I S and I A calculation)> The FT-IR spectrum of the toner is measured by the ATR method using a Fourier transform infrared spectroscopic analyzer (product name: Spectrum One, manufactured by PerkinElmer) equipped with a universal ATR measurement accessory (UniversalATR Sampling Accessory). The specific measurement procedure and the calculation method of I S and I A are as follows.

[0144] The incident angle of the infrared light (λ = 5 μm) is set to 45°. As the ATR crystal, a germanium ATR crystal (refractive index = 4.0) is used. Other conditions are as follows. Range Start: 4000 cm -1 End: 600 cm -1(Ge ATR crystal) 400 cm -1 (Diamond ATR crystal) Duration Scan number: 16 Resolution: 4.00 cm -1 Advanced: With CO2 / H2O correction (1) Attach a Ge ATR crystal (refractive index = 4.0) to the apparatus. (2) Set the Scan type to Background and the Units to EGY, and measure the background. (3) Set the Scan type to Sample and the Units to A. (4) Weigh 0.01 g of toner precisely onto the ATR crystal. (5) Press the sample with the pressure arm (Force Gauge is 100). (6) Measure the sample. (7) Perform baseline correction on the obtained FT-IR spectrum using Automatic Correction. (8) From the corrected spectrum, for the range of 1658 cm -1 and above to 1678 cm -1 and below, calculate the peak intensity “I S ” of the maximum absorption peak P S and for the range of 1714 cm -1 and above to 1734 cm -1 and below, calculate the peak intensity “I A ” of the maximum absorption peak P A ”.

[0145] <Melting point measurement method> The melting points of materials such as crystalline polyester, mold release agent, and plasticizer are measured using a differential scanning calorimeter (DSC) Q2000 (manufactured by TA Instruments) under the following conditions. Heating rate: 10 °C / min Measurement start temperature: 20 °C Measurement end temperature: 180 °C

[0146] The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. Specifically, about 5 mg of the sample is precisely weighed, placed in an aluminum pan, and one measurement is performed. An empty aluminum pan is used as the reference. The peak temperature of the maximum endothermic peak at that time is taken as the melting point.

[0147] <Measurement of Glass Transition Temperature Tg> The glass transition temperature Tg is measured in accordance with ASTM D3418-82 using a differential scanning calorimeter "Q2000" (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. Specifically, about 2 mg of the sample is precisely weighed, placed in an aluminum pan, an empty aluminum pan is used as the reference, and the measurement is performed at a heating rate of 10 °C / min within the measurement temperature range of -10 to 200 °C. In the measurement, the temperature is first raised to 200 °C, then cooled to -10 °C, and then heated again. The specific heat change can be obtained in the temperature range of 30 °C to 100 °C during the second heating process. The intersection of the line at the midpoint between the baseline before and after the specific heat change appears and the differential thermal curve is defined as the glass transition temperature Tg.

[0148] <Measurement of Acid Value> The acid value is the number of milligrams of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value in the present disclosure is measured in accordance with JIS K 0070-1992. Specifically, the measurement is performed according to the following procedure.

[0149] Titration is carried out using a 0.1 mol / L potassium hydroxide ethyl alcohol solution (manufactured by Kishida Chemical Co., Ltd.). The factor of the above potassium hydroxide ethyl alcohol solution can be determined using a potentiometric titration apparatus (Potentiometric Titration Measuring Apparatus AT-510 manufactured by Kyoto Electronics Industry Co., Ltd.). Take 100 mL of 0.100 mol / L hydrochloric acid in a 250 mL tall beaker, titrate it with the above potassium hydroxide ethyl alcohol solution, and determine it from the amount of the above potassium hydroxide ethyl alcohol solution required for neutralization. The above 0.100 mol / L hydrochloric acid uses the one prepared according to JIS K 8001-1998.

[0150] The measurement conditions for acid value measurement are shown below. Titration apparatus: Potentiometric titration apparatus AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.) Electrode: Composite glass electrode double junction type (manufactured by Kyoto Electronics Industry Co., Ltd.) Control software for titration apparatus: AT-WIN Titration analysis software: Tview The titration parameters and control parameters during titration are carried out as follows. Titration parameters Titration mode: Blank titration Titration style: Total volume titration Maximum titration volume: 20 ml Waiting time before titration: 30 seconds Titration direction: Automatic Control parameters Endpoint judgment potential: 30 dE Endpoint judgment potential value: 50 dE / dmL Endpoint detection judgment: Not set Control speed mode: Standard Gain: 1 Data acquisition potential: 4 mV Data acquisition titration volume: 0.1 ml

[0151] In this test; accurately weigh 0.100 g of the measurement sample into a 250 mL tall beaker, add 150 ml of a toluene / ethanol (3:1) mixed solution, and dissolve it over 1 hour. Using the above potentiometric titration apparatus, titrate it with the above potassium hydroxide ethyl alcohol solution. Blank test; Except when no sample is used (i.e., only using the mixed solution of toluene / ethanol (3:1)), perform titration in the same manner as the above operation. Substitute the obtained result into the following formula to calculate the acid value. A = [(C - B) × f × 5.611] / S (In the formula, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide ethyl alcohol solution in the blank test (mL), C: addition amount of potassium hydroxide ethyl alcohol solution in this test (mL), f: factor of potassium hydroxide solution, S: sample (g).)

[0152] <Method for Measuring Average Circularity of Toner (Particles)> For measuring the average circularity of toner or toner particles, use the "FPIA - 3000 type" (manufactured by Sysmex Corporation), a flow - type particle image analyzer, and measure under the measurement and analysis conditions during the calibration operation.

[0153] To 20 mL of ion - exchanged water, add an appropriate amount of a surfactant, alkylbenzene sulfonate as a dispersant, and then add 0.02 g of the measurement sample. Use a table - top ultrasonic cleaner disperser (product name: VS - 150, manufactured by Verwo Clear Co., Ltd.) with an oscillation frequency of 50 kHz and an electrical output of 150 watts to perform a dispersion treatment for 2 minutes to obtain a dispersion liquid for measurement. At that time, appropriately cool so that the temperature of the dispersion liquid is 10°C or higher and 40°C or lower.

[0154] For measurement, use the above - mentioned flow - type particle image analyzer equipped with a standard objective lens (10 - fold), and use particle sheath "PSE - 900A" (manufactured by Sysmex Corporation) as the sheath liquid. Introduce the dispersion liquid adjusted according to the above procedure into the flow - type particle image analyzer, and in the HPF measurement mode, measure 3000 toner (particles) in the total count mode. Set the binarization threshold value during particle analysis to 85%, limit the analysis particle diameter to a circle - equivalent diameter of 1.98 μm or more and 19.92 μm or less, and obtain the average circularity of the toner (particles).

[0155] Prior to measurement, auto focus adjustment is performed using standard latex particles (e.g., 5100A (trade name) manufactured by Duke Scientific, diluted with ion-exchanged water). Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

[0156] <Measurement of Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner (Particles)> The weight average particle size (D4) and number average particle size (D1) of the toner (particles) are measured with a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter) using a pore electrical resistance method with a 100 μm aperture tube, and the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data. The measurement is carried out with an effective number of measurement channels of 25,000 channels, and the measurement data is analyzed and calculated.

[0157] The electrolytic aqueous solution used for measurement is prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass. For example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

[0158] Before performing measurement and analysis, the settings of the dedicated software are made as follows.

[0159] On the "Change Screen of Standard Measurement Method (SOM)" of the dedicated software, set the total count number in the control mode to 50,000 particles, the number of measurements to 1 time, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by Beckman Coulter). By pressing the measurement button for threshold / noise level, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, the electrolyte to ISOTON II, and check the flash of the aperture tube after measurement.

[0160] On the "Conversion Setting Screen from Pulse to Particle Size" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

[0161] The specific measurement method is as follows. (1) Pour about 200 mL of the electrolytic aqueous solution into a 250 mL round-bottom glass beaker dedicated to Multisizer 3, set it on the sample stand, and stir with a stirrer rod counterclockwise at 24 revolutions per second. Then, use the "Aperture Flash" function of the dedicated software to remove dirt and bubbles in the aperture tube. (2) Pour about 30 mL of the electrolytic aqueous solution into a 100 mL flat-bottom glass beaker, and add about 0.3 mL of a dilution obtained by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for precision measuring instrument cleaning with pH 7 composed of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) 3 times by mass with ion-exchanged water as a dispersant. (3) Put a predetermined amount of ion-exchanged water into the water tank of an ultrasonic disperser "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkei Kikai Bios Co., Ltd.) with an electrical output of 120 W, which incorporates two oscillators with an oscillation frequency of 50 kHz and a phase shift of 180 degrees, and add about 2 mL of the Contaminon N to this water tank. (4) Set the beaker in (2) in the beaker fixing hole of the ultrasonic disperser and operate the ultrasonic disperser. Then, adjust the height position of the beaker so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized. (5) While irradiating the electrolytic aqueous solution in the beaker in (4) with ultrasonic waves, add about 10 mg of toner (particles) little by little to the electrolytic aqueous solution and disperse it. Then, continue the ultrasonic dispersion treatment for another 60 seconds. Note that during ultrasonic dispersion, appropriately adjust the water temperature in the water tank to be 10 °C or more and 40 °C or less. (6) Using a pipette, drop the electrolytic aqueous solution of (5) in which toner (particles) is dispersed into the round-bottom beaker of (1) installed in the sample stand, and adjust so that the measurement concentration becomes about 5%. Then, perform the measurement until the number of measured particles reaches 50,000. (7) Analyze the measurement data using the dedicated software attached to the device, and calculate the weight average particle diameter (D4). When set to graph / volume% in the dedicated software, the "average diameter" on the "analysis / volume statistical value (arithmetic mean)" screen is the weight average particle diameter (D4), and when set to graph / number% in the dedicated software, the "average diameter" on the "analysis / number statistical value (arithmetic mean)" screen is the number average particle diameter (D1).

[0162] [Configuration included in the embodiment of the present disclosure] The disclosure of this embodiment includes the following configurations. (Configuration 1) In a toner having toner particles containing a binder resin, The binder resin contains 50% by mass or more of polyester A, and the polyester A contains 60 mol% or more of unit U derived from isophthalic acid based on all units derived from acid components. iso And, The toner particles are core-shell particles composed of a core part and a shell part, and the shell part contains a resin B having a monomer unit having a functional group selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group. (Configuration 2) The toner according to Configuration 1, wherein the unit U iso is contained in an amount of 90 mol% or more. (Configuration 3) The polyester A contains unit U derived from an ethylene oxide adduct of bisphenol A EO and unit U derived from a propylene oxide adduct of bisphenol A PO and the total content ratio of the unit U EO and the unit U PO is 90 mol% or more based on all units derived from alcohol components. (Configuration 4) The content ratio of the unit U EO and the unit UPO The ratio of the unit U to the total in terms of the content ratio EO is 15 mol% or more and 40 mol% or less, and the toner according to Configuration 3. (Configuration 5) When the tetrahydrofuran (THF) soluble content of the polyester A is measured for the number average molecular weight (Mn) and the weight average molecular weight (Mw) using gel permeation chromatography (GPC), the number average molecular weight (Mn) is 3000 or more and 10000 or less, and the ratio (Mw / Mn) is 2.5 or more, and the toner according to any one of Configurations 1 to 4. (Configuration 6) The toner particles contain 0.015 mass% or more and 0.150 mass% or less of aluminum atoms, and the toner according to any one of Configurations 1 to 5. (Configuration 7) The binder resin contains a crystalline polyester, and the toner according to any one of Configurations 1 to 6. (Configuration 8) The average circularity of the toner particles is 0.950 or more and 0.980 or less, and the toner according to any one of Configurations 1 to 7. (Configuration 9) The resin B is a vinyl resin, and the toner according to any one of Configurations 1 to 8. (Configuration 10) In the ATR-IR analysis, the toner particles have a peak intensity I derived from the salicylic acid group-based functional group of the resin B S and a peak intensity I derived from the carbonyl group of the polyester A A is detected, and the ratio I S / I A is in the range of 0.02 or more and 0.20 or less, and the toner according to any one of Configurations 1 to 9.

Examples

[0163] Hereinafter, it will be described more specifically by production examples and examples, but these do not limit the invention according to the present case in any way. In addition, all parts in the following formulations indicate parts by mass.

[0164] <Production Example 1 of Polyester A> · 25 mol parts of bisphenol A ethylene oxide 2 mol adduct · 75 mol parts of bisphenol A propylene oxide 2 mol adduct · 100 mol parts of isophthalic acid The above monomers were charged into a flask equipped with a stirring device, a nitrogen inlet tube, a temperature sensor, and a rectification column, heated to 190°C in 1 hour, and it was confirmed that the reaction system was uniformly stirred. 1.0 part of tin distearate was added to 100 parts of these monomers. Further, while distilling off the generated water, the temperature was raised from 190°C to 250°C over 5 hours, and a dehydration condensation reaction was carried out at 250°C for another 2 hours.

[0165] As a result, polyester A-1 with a glass transition temperature of 60.4°C, an acid value of 11 mgKOH / g, a hydroxyl value of 24 mgKOH / g, Mn of 8000, and Mw / Mn of 3.5 was obtained.

[0166] <Production Examples 2 to 14 of Polyester A> In Production Example 1 of polyester A, except that the monomers used were changed as described in Table 1 and the reaction temperature and dehydration condensation time were changed so that Mn and Mw / Mn of the obtained polyester A would be desired values, polyesters A-2 to A-14 were obtained in the same manner as in Production Example 1 of polyester A. The results are shown in Table 1.

[0167]

Table 1

[0168] <Production Example of Resin B-1> 18 parts of 2,4-dihydroxybenzoic acid was dissolved in 150 parts of methanol, 36.9 parts of potassium carbonate was added, and the mixture was heated to 65°C. A mixed solution of 18.7 parts of 4-(chloromethyl)styrene and 100 parts of methanol was added dropwise to this reaction solution, and the reaction was carried out at 65°C for 3 hours. After cooling the reaction solution, it was filtered, and the filtrate was concentrated to obtain a crude product. The crude product was dispersed in 1500 parts of water with pH 2, ethyl acetate was added for extraction. Then, it was washed with water, dried over magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain a precipitate. The precipitate was washed with hexane and purified by recrystallization from toluene and ethyl acetate to obtain a vinyl monomer represented by the following formula (1).

[0169] [Chemical formula]

[0170] Next, 13.1 parts of the vinyl monomer shown in formula (1) and 81.9 parts of styrene were dissolved in 42.0 parts of toluene, stirred for 1 hour, and then heated to 110°C. To this reaction solution, a mixed solution of 3.0 parts of tert-butyl peroxyisopropyl monocarbonate (manufactured by NOF Corporation, trade name: Perbutyl I) and 42 parts of toluene was added dropwise. The reaction was further carried out at 110°C for 4 hours. Then, it was cooled and added dropwise to 1000 parts of methanol to obtain a precipitate. The obtained precipitate was dissolved in 120 parts of THF, then added dropwise to 1800 parts of methanol to precipitate a white precipitate, which was filtered and dried under reduced pressure at 90°C to obtain Resin B-1, which is a copolymer of styrene and the vinyl monomer shown in formula (1). The physical properties are shown in Table 2.

[0171] [Production Example of Resin B-2] In the production example of Resin B-1, the monomer used was changed to 7.9 parts of 4-vinylsalicylic acid, and by adjusting the polymerization temperature and polymerization time to control the molecular weight, Resin B-2 was obtained. The physical properties are shown in Table 2.

[0172] [Production Example of Resin B-3] 1000 parts of pure water and 4 parts of sodium dodecyl sulfate as an emulsifier were charged into a 3L flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen inlet tube, and nitrogen substitution was carried out for 30 minutes. 2 parts of potassium peroxydisulfate (KPS) was charged and stirred until dissolved. The contents were heated to 80°C under nitrogen introduction. When 80°C was reached, a mixed monomer of 300 parts of styrene and 60 parts of 2-ethylhexyl acrylate (2-EHA) and an aqueous solution in which 40 parts of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) was dissolved in 600 parts of pure water were separately added dropwise over 2 hours. Then, polymerization was carried out at 80°C for 8 hours to obtain an emulsion solution. The emulsion solution was dried in a vacuum dryer at 50°C until the water content was 1% or less to obtain Resin B-3, which is a styrene / 2-EHA / AMPS copolymer. The physical properties are shown in Table 2.

[0173]

Table 2

[0174] <Production Example of Styrene-Acrylate Resin C> · 77 parts of styrene · 23 parts of butyl acrylate · 1.0 part of di-t-butyl peroxide After heating xylene (200 parts) to 200°C, each of the above components was dropped into xylene over 4 hours, and then maintained for 1 hour under reflux of xylene to complete the polymerization.

[0175] As a result, styrene-acrylate resin C with Mn of 12,000 and Mw / Mn of 5.9 was obtained.

[0176] <Production Example D-1 of Crystalline Polyester> Into a reaction vessel equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer, and a thermocouple, · 100 mol parts of 1,10-decanedicarboxylic acid · 100 mol parts of 1,9-nonanediol · 0.8 part of tin dioctylate as a catalyst based on the total mass of the acid and alcohol The above materials were placed in a two-necked flask that had been heated and dried, nitrogen gas was introduced into the container to maintain an inert atmosphere, and the temperature was raised while stirring. Thereafter, stirring was carried out at 170°C for 6 hours. Then, while continuing stirring, the temperature was gradually raised to 230°C under reduced pressure and further maintained for 3 hours. When it became viscous, it was air-cooled and the reaction was stopped to produce crystalline polyester D-1. The physical properties obtained are shown in Table 3.

[0177] <Production Examples D-2 and D-3 of Crystalline Polyester> Crystalline polyesters D-2 and D-3 were obtained in the same manner as in Production Example D-1 of crystalline polyester, except that the alcohol monomer and acid monomer used were changed as shown in Table 3. The physical properties of crystalline polyesters D-2 and D-3 are shown in Table 3.

[0178]

Table 3

[0179] <Preparation of Resin Particle Dispersion of Polyester A-1> · 100 parts of Polyester A-1 · 50 parts of Methyl Ethyl Ketone · 20 parts of Isopropyl Alcohol The above-mentioned methyl ethyl ketone and isopropyl alcohol were put into a container. Then, the above-mentioned Polyester A-1 was gradually added and stirred until completely dissolved to obtain a Polyester A-1 solution. The container containing this Polyester A-1 solution was set at 65°C, and while stirring, a total of 5 parts of 10% aqueous ammonia solution was gradually added dropwise, and further 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min for phase inversion emulsification. Further, the solvent was removed under reduced pressure with an evaporator to obtain a resin particle dispersion of Polyester A-1. The volume average particle diameter of the resin particles contained in this resin particle dispersion was 130 nm. Also, the resin particle solid content was adjusted to 20% with ion-exchanged water.

[0180] <Preparation of Resin Particle Dispersion of Resin B-1> · 100 parts of Resin B-1 · 50 parts of Methyl Ethyl Ketone · 20 parts of Isopropyl Alcohol The above-mentioned methyl ethyl ketone and isopropyl alcohol were put into a container. Then, the above-mentioned Resin B-1 was gradually added and stirred until completely dissolved to obtain a Resin B-1 solution. The container containing this Resin B-1 solution was set at 65°C, and while stirring, a total of 5 parts of 10% aqueous ammonia solution was gradually added dropwise, and further 230 parts of ion-exchanged water was gradually added dropwise at a rate of 30 ml / min for phase inversion emulsification. Further, the solvent was removed under reduced pressure with an evaporator to obtain a resin particle dispersion of Resin B-1. The volume average particle diameter of the resin particles contained in this resin particle dispersion was 40 nm. Also, the resin particle solid content was adjusted to 20% with ion-exchanged water.

[0181] <Preparation of Resin Particle Dispersion of Styrene-Acrylic Resin C> · 100 parts of styrene-acrylic resin C · 50 parts of methyl ethyl ketone · 20 parts of isopropyl alcohol The above-mentioned methyl ethyl ketone and isopropyl alcohol were put into a container. Then, the above-mentioned styrene-acrylic resin C was gradually added, and stirring was carried out to completely dissolve it to obtain a styrene-acrylic resin C solution. The container containing this styrene-acrylic resin C solution was set at 65 °C, and while stirring, a total of 5 parts of 10% aqueous ammonia solution was gradually added dropwise, and further 230 parts of ion-exchanged water was gradually added dropwise at a rate of 30 ml / min to carry out phase inversion emulsification. Furthermore, the solvent was removed under reduced pressure with an evaporator to obtain a resin particle dispersion of styrene-acrylic resin C. The volume average particle diameter of the resin particles contained in this resin particle dispersion was 110 nm. Also, the resin particle solid content was adjusted to 20% with ion-exchanged water.

[0182] <Preparation of Resin Particle Dispersion of Crystalline Polyester D-1> · 100 parts of crystalline polyester D-1 · 50 parts of methyl ethyl ketone · 20 parts of isopropyl alcohol The above-mentioned methyl ethyl ketone and isopropyl alcohol were put into a container. Then, the above-mentioned crystalline polyester D-1 was gradually added, and stirring was carried out to completely dissolve it to obtain a crystalline polyester D-1 solution. The container containing this crystalline polyester D-1 solution was set at 40 °C, and while stirring, a total of 3.5 parts of 10% aqueous ammonia solution was gradually added dropwise, and further 230 parts of ion-exchanged water was gradually added dropwise at a rate of 10 ml / min to carry out phase inversion emulsification. Furthermore, the solvent was removed under reduced pressure to obtain a resin particle dispersion of crystalline polyester D-1. The volume average particle diameter of the resin particles of this resin particle dispersion was 150 nm. Also, the resin particle solid content was adjusted to 20% with ion-exchanged water.

[0183] <Preparation of Colorant Particle Dispersion 1> · 45 parts of copper phthalocyanine (Pigment Blue 15:3) · 5 parts of sodium dodecylbenzenesulfonate · 190 parts of ion-exchanged water The above components were mixed and dispersed for 10 minutes using a homogenizer (Ultra Turrax manufactured by IKA), and then subjected to a dispersion treatment at a pressure of 250 MPa for 20 minutes using an Altimizer (a counter-collision type wet grinder: manufactured by Sugino Machine Co., Ltd.) to obtain a colorant particle dispersion liquid 1 with a volume average particle diameter of 120 nm and a solid content of 20%.

[0184] <Preparation of Colorant Particle Dispersion Liquid 2> In the preparation of the colorant particle dispersion liquid 1, sodium dodecylbenzenesulfonate was changed to sodium tetradecylbenzenesulfonate, and it was prepared in the same manner. A colorant particle dispersion liquid 2 with a volume average particle diameter of 100 nm and a solid content of 20% was obtained.

[0185] <Preparation of Release Agent Particle Dispersion Liquid 1> · 15 parts of a release agent (hydrocarbon wax, melting point: 79 °C) · 2 parts of sodium dodecylbenzenesulfonate · 240 parts of ion-exchanged water The above was heated to 100 °C, sufficiently dispersed using an Ultra Turrax T50 manufactured by IKA, and then heated to 115 °C using a pressure discharge type Gorin homogenizer and subjected to a dispersion treatment for 1 hour to obtain a release agent particle dispersion liquid 1 with a volume average particle diameter of 160 nm and a solid content of 20%.

[0186] <Preparation of Release Agent Particle Dispersion Liquid 2> In the preparation of the release agent particle dispersion liquid 1, sodium dodecylbenzenesulfonate was changed to sodium tetradecylbenzenesulfonate, and it was prepared in the same manner. A release agent particle dispersion liquid 2 with a volume average particle diameter of 160 nm and a solid content of 20% was obtained.

[0187] <Manufacture of Toner Particles 1> · 880 parts of a resin particle dispersion liquid of polyester A-1 · 100 parts of a resin particle dispersion liquid of crystalline polyester D-1 · 50 parts of the colorant particle dispersion liquid 1 · 80 parts of the mold release agent particle dispersion liquid 1 First, each of the above materials was put into a round stainless steel flask and mixed. Subsequently, using a homogenizer Ultra Turrax T50 (manufactured by IKA), it was dispersed at 5000 r / min for 10 minutes. After adding a 1 mol / L aqueous sodium hydroxide solution to adjust the pH to 8.0, as a flocculant, an aqueous solution prepared by dissolving 0.50 part of aluminum chloride in 20 parts of ion-exchanged water was added dropwise over 10 minutes under stirring at 30°C. After leaving it standing for 3 minutes, the temperature was raised, and the temperature was raised to 50°C to form core particles.

[0188] The volume average particle diameter of the formed aggregated particles was appropriately confirmed using a Coulter Multisizer III. When aggregated particles with a volume average particle diameter of 6.0 μm were formed, for the formation of the shell part, 20 parts of a resin particle dispersion liquid of resin B-1 having a monomer unit was further added, heated to 60°C, held for 30 minutes, and 2.0 parts of sodium chloride was added to complete the aggregation process.

[0189] Thereafter, as a spheroidization process, a 1 mol / L aqueous sodium hydroxide solution was added to adjust the pH to 9.0, and while continuing stirring, it was heated to 92°C.

[0190] When the desired surface shape was obtained, the heating was stopped. As a cooling process, ice was quickly added so that the cooling rate was 10°C / second or more, and it was cooled to 40°C. Further, as an annealing process, an annealing treatment was performed at 55°C for 3 hours.

[0191] Thereafter, it was cooled to 25°C, filtered and solid-liquid separated, and then washed with ion-exchanged water. After the washing was completed, it was dried using a vacuum dryer to obtain toner particles 1 having a weight average particle diameter (D4) of 7.1 μm. The physical properties of toner particles 1 are shown in Table 4.

[0192] <Manufacturing examples of toner particles 2 to 5, 7 to 26, 29, and 30> Toner particles 2 to 5, 7 to 26, 29, and 30 were obtained in the same manner as in the production example of toner particle 1, except that the compounding of the materials and the production conditions were changed so as to achieve the formulation and physical properties shown in Table 4. The physical properties of the obtained toner particles 2 to 5, 7 to 26, 29, and 30 are shown in Tables 4-1 to 4-3.

[0193] <Production Example of Toner Particles 6 and 28> In the generation of the core particles in the production example of toner particle 1, toner particles 6 and 28 were obtained by using the resin particle dispersion of styrene acrylic resin C and changing to the formulation shown in Table 4. The physical properties of toner particles 6 and 28 are shown in Tables 4-1 and 4-2.

[0194] <Production Example of Toner Particle 27> In the formation of the shell part in the production example of toner particle 1, toner particle 27 was obtained by using the resin particle dispersion of styrene acrylic resin C instead of the resin particle dispersion of resin B-1 having a monomer unit and changing to the formulation shown in Table 4. The physical properties of toner particle 27 are shown in Table 4-3.

[0195] <Production Example of Toner Particle 31> The following materials were thoroughly mixed with an FM mixer (manufactured by Nippon Coke & Engineering Co., Ltd.), and then melt-kneaded with a twin-screw kneader (manufactured by Ikegai Iron Works Co., Ltd.) set at a temperature of 100°C. · 95.0 parts of polyester A-1 · 2.0 parts of resin B-1 having a monomer unit · 3.0 parts of crystalline polyester D-1 · 8.0 parts of hydrocarbon wax (melting point: 79°C) · 5.0 parts of C.I. Pigment Blue15:3

[0196] The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely pulverized product.

[0197] Next, the obtained coarsely pulverized product was finely pulverized to about 6.5 μm using a turbo mill manufactured by Turbo Industries Co., and then the fine coarse powder was cut using a multi-stage classifier utilizing the Coanda effect to obtain toner particle 31.

[0198] The weight average particle diameter (D4) of the toner particles 31 was 7.4 μm, the Tg was 59.2°C, and the average circularity was 0.934. The physical properties are shown in Table 4-3.

[0199] <Production Example of Toner 1> External addition was performed on the above toner particles 1. Using an FM mixer (FM10 manufactured by Nippon Coke & Engineering Co., Ltd.), 20.0 g of hydrophobic silica fine particles (number average particle diameter of primary particles: 7 nm) surface-treated with dimethyl silicone oil was added to 2.0 kg of toner particles 1, and then external addition was carried out by mixing at 3000 rpm for 5 minutes. At this time, by diverting and controlling the temperature of the cold water flowing through the cooling jacket, the temperature in the tank after 5 minutes of mixing was adjusted to 35°C.

[0200] Thereafter, the toner was sieved with a mesh having an opening of 75 μm to obtain Toner 1. The physical properties of Toner 1 are shown in Table 4. In Table 4, "PES A" means polyester A, "St-Ac resin C" means styrene-acrylic resin C, and "C-PES D" means crystalline polyester D.

[0201] <Production Examples of Toners 2 to 31> In the production example of Toner 1, except that the type of toner particles was changed, Toners 2 to 31 were obtained in the same manner as in the production example of Toner 1. The physical properties of the obtained Toners 2 to 31 are shown in Table 4.

[0202]

Table 4-1

[0203]

Table 4-2

[0204]

Table 4-3

[0205] 〔Examples 1 to 26, Comparative Examples 1 to 5〕 Using the obtained toner, the following evaluations were conducted. The methods for the evaluations performed on each of Toners 1 to 31 are described below. The evaluation results are shown in Table 5.

[0206] The evaluation methods and criteria are as follows.

[0207] As the image forming apparatus, a modified machine obtained by modifying a commercially available laser printer "LBP-9660Ci (manufactured by Canon)" so that the process speed becomes 325 mm / sec was used. Also, a commercially available toner cartridge (cyan) (manufactured by Canon), which is a process cartridge, was used.

[0208] The product toner was removed from inside the cartridge, and after cleaning by air blowing, each toner to be evaluated was filled to 270 g. In addition, the product toner was removed from each of the yellow, magenta, and black stations, and evaluation was performed by inserting yellow, magenta, and black cartridges in which the toner remaining amount detection mechanism was invalidated.

[0209] (1) Low-temperature fixing property evaluation The above process cartridge, the modified machine of the above laser printer, and Business 4200 paper of LETTER size (manufactured by XEROX, basis weight: 75 g / m 2 ) were left standing in a low-temperature and low-humidity environment (15°C / 10%RH) for 24 hours.

[0210] An image with a toner loading amount of 0.40 mg / cm 2 and an area of 2 cm × 2 cm was output onto the above evaluation paper. While changing the fixing temperature adjustment, the fixing temperature at the time when offset occurred was confirmed and evaluated at the rear end in the paper passing direction of the evaluation paper when passing through the fixing unit.

[0211] The evaluation criteria were determined as follows. A: No offset at 130°C B: Offset occurs at 130°C C: Offset occurs at 140°C D: Offset occurs at 150°C E: Offset occurs at 160°C

[0212] (2) Gloss evaluation The above process cartridge, the modified machine of the above laser printer, and Canon Marketing Japan Inc.'s color laser copy gloss paper NS-701 (recording medium gloss: 70.3%, basis weight: 150 g / m 2 , were left standing in a normal temperature and humidity environment (23°C / 50%RH) for 24 hours. After outputting 1000 images with a printing ratio of 1.0%, a solid image with a toner loading of 0.40 mg / cm 2 was output, and the image gloss (%) was measured.

[0213] The gloss was measured using a handy gloss meter PG-1M (manufactured by Nippon Denshoku Industries Co., Ltd.). For the measurement, the projection angle and the light receiving angle were adjusted to 60° each. The gloss was measured at 20 points on the output image, and the average value was taken as the gloss (%).

[0214] Note that the evaluation criteria were determined as follows. A: Difference from the recording medium gloss is less than 3% B: Difference from the recording medium gloss is 3% or more and less than 7% C: Difference from the recording medium gloss is 7% or more and less than 11% D: Difference from the recording medium gloss is 11% or more and less than 15% E: Difference from the recording medium gloss is 15% or more

[0215] (3) Evaluation of missing transfer during printing in vertical thin line images The above process cartridge, the modified machine of the above laser printer, and LETTER size Business4200 paper (manufactured by XEROX, basis weight: 75 g / m 2 ) were left standing in a normal temperature and humidity environment (23°C / 50%RH), a low temperature and low humidity environment (15°C / 10%RH), and a high temperature and high humidity environment (30°C / 80%RH) for 24 hours each.

[0216] After outputting 1000 images with a printing ratio of 1.0% under each environment, a toner loading of 0.40 mg / cm 2It was adjusted to be as follows. Evaluation images were printed with two vertical lines each of 2, 4, 6, 8, and 10 dots, and the non-image area width between each line was about 10 mm. Further, after outputting 20,000 images with a printing ratio of 1.0%, evaluation images were similarly printed with two vertical lines each of 2, 4, 6, 8, and 10 dots, and the non-image area width between each line was about 10 mm.

[0217] The printed evaluation images were observed visually and with a 20x magnifying glass and evaluated based on the following criteria. A: In the 2-dot line, almost no missing dots can be confirmed even by magnified observation. B: In the 2-dot line, some missing dots are confirmed by magnified observation, and in the 4-dot line, almost no missing dots can be confirmed by magnified observation. C: In the 4-dot line, some missing dots are confirmed by magnified observation, and they cannot be confirmed visually in the 2-dot line. D: In the 2-dot line, missing dots can be confirmed visually, and in the 4-dot line, missing dots cannot be confirmed visually. E: In the 4-dot line, missing dots can be confirmed visually.

[0218]

Table 5

Claims

1. In a toner having toner particles containing a binder resin, The adhesive resin contains 50% by mass or more of polyester A, and the polyester A contains 60 mol% or more of unit U derived from isophthalic acid based on all units derived from acid components. iso ​ the toner particles are core-shell particles composed of a core part and a shell part, and the shell part contains a resin B having a monomer unit having a functional group selected from the group consisting of a salicylic acid-based functional group and a sulfonic acid group. The toner is characterized by this.

2. the unit U iso The toner according to claim 1, containing 90 mol% or more thereof.

3. The polyester A contains a unit U derived from an ethylene oxide adduct of bisphenol A EO and a unit U derived from a propylene oxide adduct of bisphenol A PO and the total content ratio of the unit U EO and the unit U PO is 90 mol% or more based on all the units derived from the alcohol component. The toner according to claim 1 or 2

4. Said unit U EO and the content ratio of said unit U PO such that the content ratio of said unit U EO is 15 mol% or more and 40 mol% or less with respect to the total of the content ratio of said unit U

5. When the tetrahydrofuran (THF) soluble content of the polyester A is measured for the number average molecular weight (Mn) and the weight average molecular weight (Mw) using gel permeation chromatography (GPC), the number average molecular weight (Mn) is 3000 or more and 10000 or less, and the ratio (Mw / Mn) is 2.5 or more. The toner according to Claim 1 or 2.

6. The toner according to Claim 1 or 2, wherein the toner particles contain 0.015 mass% or more and 0.150 mass% or less of aluminum atoms.

7. The toner according to Claim 1 or 2, wherein the binder resin contains a crystalline polyester.

8. The toner according to Claim 1 or 2, wherein the average circularity of the toner particles is 0.950 or more and 0.980 or less.

9. The toner according to Claim 1 or 2, wherein the resin B is a vinyl-based resin.

10. In the ATR-IR analysis, the toner particles have a peak intensity I derived from the salicylic acid group-based functional group of the resin B S and a peak intensity I derived from the carbonyl group of the polyester A A are detected, and the ratio I S / I A is in the range of 0.02 or more and 0.20 or less. The toner according to claim 1 or 2

Images