Resin particles, toner, resin particle manufacturing method, toner manufacturing method, developer, toner storage unit, and image forming apparatus

Abstract

To provide a resin particle that has a large contribution to carbon neutral and can satisfy low temperature fixability and cleaning properties.SOLUTION: A resin particle includes at least a crystalline polyester resin, an amorphous polyester resin, a mold release agent, and a coloring agent. An acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms. The average major axis of domains of the crystalline polyester resin is 2.0 μm or less, and the average aspect ratio (major axis / minor axis) of the domains is 4.0 or more. The concentration of a radioactive carbon isotope 14C is 5.4 pMC or more.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to resin particles, toner, a method for producing resin particles, a method for producing toner, a developer, a toner storage unit, and an image forming apparatus. [Background technology]

[0002] Carbon neutrality is generally used to describe biomass materials composed of organic matter. When such biomass materials are burned, carbon dioxide is emitted, but the carbon contained in this carbon dioxide comes from carbon dioxide absorbed from the atmosphere by the biomass materials through photosynthesis during their growth. Therefore, even if biomass materials are used, it is thought that the amount of carbon dioxide in the atmosphere is not increased overall. This property is called carbon neutrality.

[0003] Conventionally, the constituent materials of toner, particularly binder resins, have been almost entirely dependent on fossil resources, and the carbon dioxide generated when toner and printed images are discarded is released into the atmosphere, contributing to global warming, etc. Furthermore, the conversion from finite fossil resources to renewable biomass resources can be seen as a sustainable conversion to renewable resources, as living organisms are generated from solar energy, water, and carbon dioxide, and is a technology that is highly desired.

[0004] Examples of constituent materials of toner obtained from such renewable resources include release agents such as carnauba wax and candelilla wax. These are blended into toner to impart release properties during fixing, and their blending amount is generally around a few percent by mass, so this alone is far from achieving carbon neutrality.

[0005] Meanwhile, the use of resins made from renewable resources such as polylactic acid (PLA) and rosin compounds as binder resins for toners has been investigated. For example, (1) toner containing PLA obtained by direct dehydration condensation (see Patent Document 1), (2) toner containing terminal-modified PLA (see Patent Document 2), and (3) toner containing polyester resin using methacrylic acid-modified rosin as a monomer (see Patent Document 3) have been proposed.

[0006] Furthermore, in order to function as a toner, basic properties such as low-temperature fixability and low adhesive force are required. Patent Document 4 describes that a toner with excellent low-temperature fixability can be provided by making the maximum major axis of the crystalline polyester large and sharply shaped from the surface of the toner toward the inside. Patent Document 5 states that toner with low adhesive force can be provided by forming the toner into a flat shape. Summary of the Invention [Problem to be solved by the invention]

[0007] However, it is currently difficult to use renewable resources, contribute to carbon neutrality, and simultaneously satisfy the low-temperature fixability and cleanability (low adhesive strength) required as toner properties.

[0008] An object of the present invention is to provide resin particles that contribute greatly to carbon neutrality and are satisfactory in low-temperature fixability and cleanability. [Means for solving the problem]

[0009] The present invention, which has been made to solve the above problems, relates to resin particles as described in (1) below. (1) Resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant, the acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms, the domains of the crystalline polyester resin have an average major axis of 2.0 μm or less, and an average aspect ratio (major axis / minor axis) of 4.0 or more; radioactive carbon isotopes 14 Resin particles characterized by having a C concentration of 5.4 pMC or more. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide resin particles that contribute greatly to carbon neutrality and are satisfactory in low-temperature fixability and cleanability. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 is a diagram illustrating the crystalline polyester resin inside the resin particle. [Figure 2] FIG. 2 is a schematic diagram showing an example of the configuration of an image forming apparatus according to an embodiment of the present invention. [Figure 3] FIG. 3 is a schematic diagram showing another example of the image forming apparatus according to the embodiment of the present invention. [Figure 4] FIG. 4 is a schematic diagram showing another example of the image forming apparatus according to the embodiment of the present invention. [Figure 5] FIG. 5 is a partially enlarged view of FIG. [Figure 6] FIG. 6 is a schematic diagram showing an example of a process cartridge. DETAILED DESCRIPTION OF THE INVENTION

[0012] The resin particles, toner, resin particle manufacturing method, toner manufacturing method, developer, toner storage unit, and image forming apparatus according to the present invention will be described below with reference to the drawings. Note that the present invention is not limited to the following embodiments, and other modifications, additions, corrections, deletions, and other changes can be made within the scope of those skilled in the art. Any embodiment is within the scope of the present invention as long as it achieves the functions and effects of the present invention.

[0013] The resin particles of the present invention are suitable for use as a toner, which can be obtained by adding an external additive to toner base particles made of resin particles. The toner using the resin particles of the present invention will be explained below, and the resin particles will be explained in the section "Toner Base Particles" below.

[0014] (toner) The toner contains a radioactive carbon isotope. 14 C concentration (hereinafter referred to as “ 14 The concentration of HCl (sometimes referred to as "HCl concentration") must be 5.4 pMC or higher, preferably 10.8 pMC or higher. pMC (percent modern carbon) is 14 It is one of the units that expresses the C concentration of the standard sample in 1950. 14 When the C concentration is 100%, the unknown sample 14 The C concentration is expressed as a ratio to that in %. The aforementioned 14 If the C concentration is less than 5.4 pMC, the biomass degree will be low and the object of the present invention may not be achieved. The aforementioned 14 The C concentration is expressed as the biomass degree by the following formula: Biomass ratio (%) = 14 C concentration (pMC)×0.935 The aforementioned 14 A carbon concentration of 5.4 pMC or more means that the biomass ratio is 5% or more, which is a concentration desired from the standpoint of carbon neutrality. 14 The C concentration is more preferably 20% or more, and even more preferably 40% or more.

[0015] The aforementioned 14 The carbon concentration defines the amount of carbon that is derived from plants in the carbon elemental components of petrochemical products that contain carbon. 14 The concentration of C can be measured, for example, according to ASTM-D6866, an ASTM standard of the American Society for Testing and Materials.

[0016] The aforementioned 14C exists in nature (in the atmosphere), and while plants are active, it is taken up by plants through photosynthesis and is absorbed into the atmosphere by the carbon dioxide 14 C concentration and carbon in the organic components of plants 14 The concentration is equilibrium with the C concentration (107.5 pMC). When plants cease to function, carbon absorption through photosynthesis ceases, 14 According to the half-life of C, 5730 years 14 The C concentration decreases. Fossil resources derived from living organisms are those that have been around for tens of thousands to hundreds of millions of years since life ceased. 14 C is barely detectable.

[0017] In the toner, the acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms, the major axis of the domain of the crystalline polyester resin is 2.0 μm or less, and the aspect ratio of the domain (major axis / minor axis) is 4.0 or more.

[0018] According to the present invention, it is possible to provide a toner that contributes greatly to carbon neutrality and is capable of achieving both low-temperature fixability and cleanability. Furthermore, according to a preferred embodiment of the present invention, it is possible to improve heat-resistant storage stability while contributing greatly to carbon neutrality and achieving both low-temperature fixability and cleanability.

[0019] The toner of the present invention comprises toner base particles made of resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant, and an external additive. Hereinafter, an example of the constitution of a toner according to an embodiment containing toner base particles and external additives will be described.

[0020] <Toner base particles (resin particles)> The toner base particles contain a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant, and may further contain other components as required.

[0021] <<Crystalline polyester resin>> The crystalline polyester resin (hereinafter, sometimes referred to as "crystalline polyester resin C") has high crystallinity and therefore exhibits heat melting characteristics in which the viscosity changes suddenly near the fixing start temperature.

[0022] By using the crystalline polyester resin C having such properties together with the amorphous polyester resin, a toner having both good heat-resistant storage stability and low-temperature fixability can be obtained. For example, by using the crystalline polyester resin C and the amorphous polyester resin together, the heat-resistant storage stability is good due to the crystallinity of the crystalline polyester resin C until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin C melts, causing a sudden decrease in viscosity (sharp melt property), which leads to compatibility with the amorphous polyester resin B described below, and the viscosity of both resins decreases rapidly, resulting in good fixability. Also, good results are shown for the release width (the difference between the minimum fixing temperature and the temperature at which high-temperature offset occurs).

[0023] The crystalline polyester resin C can be obtained by using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic acid anhydride, or a polycarboxylic acid ester.

[0024] In the present invention, the crystalline polyester resin C refers to a resin obtained by using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic acid anhydride, or a polycarboxylic acid ester, as described above. Modified polyester resins, such as prepolymers described below, and resins obtained by subjecting the prepolymers to a crosslinking and / or elongation reaction, do not fall under the category of crystalline polyester resin C.

[0025] -Polyhydric alcohol- The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diols and trihydric or higher alcohols. Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferred, linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferred, and linear saturated aliphatic diols having 2 to 8 carbon atoms are even more preferred. If the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin C may decrease, resulting in a lower melting point. Furthermore, if the carbon number of the saturated aliphatic diol exceeds 12, it becomes difficult to obtain a practical material. It is more preferred that the carbon number is 12 or less.

[0026] Examples of the saturated aliphatic diol include ethylene glycol, 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-eicosanedecanediol, etc. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred because they provide the crystalline polyester resin C with high crystallinity and excellent sharp melt properties.

[0027] Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used alone or in combination of two or more.

[0028] -Polycarboxylic Acids- Examples of the dicarboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, sebacic acid, and dodecanedioic acid; unsaturated aliphatic dicarboxylic acids such as fumaric acid and maleic acid; and aromatic dicarboxylic acids such as terephthalic acid. These may be used alone or in combination of two or more.

[0029] The dicarboxylic acid is preferably a plant-derived saturated aliphatic dicarboxylic acid having 12 or less carbon atoms. Being plant-derived can enhance carbon neutrality. Furthermore, if the carbon number exceeds 12, compatibility with the amorphous polyester resin deteriorates, the aspect ratio of the crystalline polyester resin decreases, and low-temperature fixability deteriorates for reasons described below. Furthermore, saturated aliphatic dicarboxylic acids have the effect of enhancing the recrystallization properties of the crystalline polyester resin, increasing the aspect ratio of the crystalline polyester resin and improving low-temperature fixability.

[0030] The melting point of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is 60° C. or higher, the crystalline polyester resin C can be prevented from melting at low temperatures, which would otherwise cause a decrease in the heat-resistant storage stability of the toner. When the melting point is 80° C. or lower, the melting of the crystalline polyester resin C due to heating during fixing can be improved, which would prevent a decrease in low-temperature fixability.

[0031] The molecular weight of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint that a resin having a sharp molecular weight distribution and a low molecular weight has excellent low-temperature fixability, and that a large amount of low-molecular-weight components reduces heat-resistant storage stability, the crystalline polyester resin C preferably has an orthodichlorobenzene-soluble component having a weight-average molecular weight (Mw) of 3,000 to 30,000, a number-average molecular weight (Mn) of 1,000 to 10,000, and an Mw / Mn of 1.0 to 10, as measured by GPC. It is further preferable that the weight average molecular weight (Mw) is 5,000 to 15,000, the number average molecular weight (Mn) is 2,000 to 10,000, and Mw / Mn is 1.0 to 5.0.

[0032] The acid value of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of affinity between paper and resin, in order to achieve the desired low-temperature fixability, the acid value is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more. On the other hand, in order to improve high-temperature offset resistance, the acid value is preferably 45 mgKOH / g or less.

[0033] The hydroxyl value of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose. In order to achieve the desired low-temperature fixability and good charging characteristics, the hydroxyl value is preferably 0 mgKOH / g or more and 50 mgKOH / g or less, and more preferably 5 mgKOH / g or more and 50 mgKOH / g or less.

[0034] The molecular structure of the crystalline polyester resin C can be confirmed by NMR measurement of a solution or a solid, as well as by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. -1 or 990±10cm -1 In this method, a resin having absorption based on δCH (out-of-plane bending vibration) of olefin is detected as the crystalline polyester resin C.

[0035] The content of the crystalline polyester resin C is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 to 20 parts by mass, and more preferably 5 to 15 parts by mass, relative to 100 parts by mass of the toner. When the content is 3 parts by mass or more, the sharp melting effect of the crystalline polyester resin C can be improved, and low-temperature fixability can be improved. When the content is 20 parts by mass or less, deterioration of heat-resistant storage stability can be suppressed, and the occurrence of image fogging can be suppressed. When the content is within the above more preferred range, it is advantageous in that both high image quality and low-temperature fixability are excellent.

[0036] <<<Amorphous polyester resin>>> The amorphous polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the amorphous polyester resin contains an amorphous polyester resin A and an amorphous polyester resin B described below.

[0037] -Amorphous polyester resin A- The amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but preferably has a glass transition temperature (Tg) of −60° C. or higher and 20° C. or lower, more preferably −40° C. or higher and 20° C. or lower. In addition, it is preferably obtained by reacting a non-linear reactive precursor with a curing agent.

[0038] In addition, from the viewpoint of superior adhesion to recording media such as paper, it is preferable that amorphous polyester resin A contains at least one of a urethane bond and a urea bond. When amorphous polyester resin A contains either a urethane bond or a urea bond, the urethane bond or the urea bond behaves like a pseudo-crosslinking point, the rubber-like properties of amorphous polyester resin A are strengthened, and the heat-resistant storage stability and high-temperature offset resistance of the toner are superior.

[0039] --Nonlinear reactive precursors-- The non-linear reactive precursor is not particularly limited as long as it is a polyester resin (hereinafter sometimes referred to as a "prepolymer") having a group capable of reacting with the curing agent, and can be appropriately selected depending on the purpose. Examples of the group in the prepolymer that can react with the curing agent include a group that can react with an active hydrogen group. Examples of the group that can react with the active hydrogen group include an isocyanate group, an epoxy group, a carboxylic acid, and an acid chloride group. Among these, an isocyanate group is preferred because it can introduce a urethane bond or a urea bond into the amorphous polyester resin.

[0040] The prepolymer is preferably non-linear, which means that it has a branched structure imparted by at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. The prepolymer is preferably a polyester resin containing an isocyanate group.

[0041] ---Polyester resin containing isocyanate groups--- The polyester resin containing an isocyanate group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a reaction product of a polyester resin having an active hydrogen group with a polyisocyanate. The polyester resin having an active hydrogen group can be obtained, for example, by polycondensation of a diol, a dicarboxylic acid, and at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. The trivalent or higher alcohol and the trivalent or higher carboxylic acid impart a branched structure to the polyester resin containing an isocyanate group.

[0042] ----Diol---- The diol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include aliphatic diols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene Examples of suitable diols include diols having an oxyalkylene group such as glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols to which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide have been added; bisphenols such as bisphenol A, bisphenol F, and bisphenol S; and alkylene oxide adducts of bisphenols, such as bisphenols to which alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide have been added. Among these, aliphatic diols having 4 to 12 carbon atoms are preferred. These diols may be used alone or in combination of two or more.

[0043] ----Dicarboxylic acid---- The dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aliphatic dicarboxylic acids, aromatic dicarboxylic acids, etc. Furthermore, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may also be used.

[0044] The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.

[0045] The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, but is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, succinic acid, sebacic acid, and dodecanedioic acid, which are saturated aliphatic acids derived from plants, are preferred. Being plant-derived can enhance carbon neutrality. Saturated aliphatic groups have the effect of enhancing the recrystallization properties of crystalline polyester resins, increasing the aspect ratio of the crystalline polyester resins and improving low-temperature fixability. These dicarboxylic acids may be used alone or in combination of two or more.

[0046] ----Trihydric or higher alcohol---- The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols.

[0047] Examples of the trivalent or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol. Examples of the trivalent or higher polyphenols include trisphenol PA, phenol novolac, and cresol novolac. Examples of the alkylene oxide adducts of trivalent or higher polyphenols include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to trivalent or higher polyphenols.

[0048] The amorphous polyester resin A preferably contains a trivalent or higher aliphatic alcohol as a constituent component. The amorphous polyester resin A contains a trivalent or higher aliphatic alcohol as a constituent, which gives the resin a branched structure in the molecular skeleton and a three-dimensional network structure of molecular chains, resulting in rubber-like properties that deform at low temperatures but do not flow, enabling the toner to maintain its heat-resistant storage stability and high-temperature offset resistance.

[0049] The amorphous polyester resin A can also use trivalent or higher carboxylic acids or epoxy as crosslinking components, but in the case of carboxylic acids, they are often aromatic compounds and the ester bond density at the crosslinked portions is high, which can prevent the gloss of the fixed image produced by heat-fixing the toner from being fully expressed. When a crosslinking agent such as epoxy is used, the crosslinking reaction must be carried out after polymerization of the polyester, making it difficult to control the distance between crosslinking points and preventing the desired viscoelasticity from being obtained. In addition, the crosslinked portion is likely to react with the oligomer during polyester production, resulting in high crosslink density, which can cause unevenness in the fixed image and result in poor gloss and image density.

[0050] ----Trivalent or higher carboxylic acids---- The trivalent or higher carboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include trivalent or higher aromatic carboxylic acids. Furthermore, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may also be used.

[0051] The trivalent or higher aromatic carboxylic acid is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. Examples of the trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms include trimellitic acid and pyromellitic acid.

[0052] ----Polyisocyanate---- The polyisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diisocyanates and tri- or higher valent isocyanates.

[0053] Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those obtained by blocking these with phenol derivatives, oximes, caprolactam, etc.

[0054] The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.

[0055] The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.

[0056] The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, and 4,4′-diisocyanato-diphenyl ether.

[0057] The aromatic aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include α,α,α',α'-tetramethylxylylene diisocyanate.

[0058] The isocyanurates are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate. These polyisocyanates may be used alone or in combination of two or more.

[0059] --Hardening agent-- The curing agent is not particularly limited as long as it can react with the non-linear reactive precursor to produce the amorphous polyester resin A, and can be appropriately selected depending on the purpose. For example, an active hydrogen group-containing compound can be used.

[0060] ---Compounds containing active hydrogen groups--- The active hydrogen group in the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, etc. These may be used alone or in combination of two or more. The active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, but amines are preferred because they are capable of forming a urea bond.

[0061] The amines are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, blocked amino groups of these, etc. These may be used alone or in combination of two or more. Among these, diamines and mixtures of diamines with small amounts of trivalent or higher amines are preferred.

[0062] The diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include aromatic diamines, alicyclic diamines, aliphatic diamines, etc. The aromatic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, etc.

[0063] The alicyclic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, isophoronediamine, etc. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.

[0064] The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diethylenetriamine and triethylenetetramine. The amino alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ethanolamine and hydroxyethylaniline. The amino mercaptan is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.

[0065] The amino acid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include aminopropionic acid and aminocaproic acid.

[0066] The compound in which the amino group is blocked is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ketimine compounds and oxazoline compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0067] In order to lower the Tg of the amorphous polyester resin A and easily impart the property of deformation at low temperatures, the amorphous polyester resin A preferably contains a diol component as a constituent component, and the diol component preferably contains 50% by mass or more of an aliphatic diol having from 4 to 12 carbon atoms.

[0068] The amorphous polyester resin A preferably contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms in all alcohol components. In this case, the Tg of the amorphous polyester resin A can be lowered, and the amorphous polyester resin A can be easily imparted with the property of deformation at low temperatures.

[0069] The amorphous polyester resin A preferably contains a dicarboxylic acid component as a constituent, and the dicarboxylic acid component preferably contains 50% by mass or more of an aliphatic dicarboxylic acid having from 4 to 12 carbon atoms. In this case, the Tg of the amorphous polyester resin A can be lowered, making it easier to impart the property of deformation at low temperatures.

[0070] The weight-average molecular weight of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10,000 to 1,000,000, more preferably 10,000 to 300,000, and particularly preferably 10,000 to 200,000, as measured by GPC (gel permeation chromatography). A weight-average molecular weight of 10,000 or more can prevent the toner from flowing at low temperatures and improve heat-resistant storage stability. Furthermore, a decrease in viscosity during melting can be prevented, and a decrease in high-temperature offset properties can be prevented.

[0071] The molecular structure of the amorphous polyester resin A can be confirmed by NMR measurement using a solution or a solid, as well as by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. -1 and 990±10cm -1One method is to detect amorphous polyester resins that do not have absorption due to olefin δCH (out-of-plane bending vibration).

[0072] The content of the amorphous polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 to 25 parts by mass, and more preferably 10 to 20 parts by mass, relative to 100 parts by mass of the toner. When the content is 5 parts by mass or more, deterioration of low-temperature fixability and high-temperature offset resistance can be suppressed. When the content is 25 parts by mass or less, deterioration of heat-resistant storage stability and reduction in gloss of the image obtained after fixing can be suppressed. When the content is within the above more preferred range, it is advantageous in that all of low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability are excellent.

[0073] -Amorphous polyester resin B- The amorphous polyester resin B is preferably a linear polyester resin, and more preferably an unmodified polyester resin. The unmodified polyester resin is a polyester resin obtained using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic acid anhydride, or a polycarboxylic acid ester, and is not modified with an isocyanate compound or the like. The amorphous polyester resin B preferably does not contain a urethane bond or a urea bond.

[0074] The amorphous polyester resin B preferably contains a dicarboxylic acid component as a constituent, and the dicarboxylic acid component preferably contains 50 mol % or more of terephthalic acid, which is advantageous in terms of heat-resistant storage stability.

[0075] Examples of the polyhydric alcohol include diols. Examples of the diol include alkylene (carbon number 2 to 3) oxide (average number of added moles 1 to 10) adducts of bisphenol A such as polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane; ethylene glycol, propylene glycol; hydrogenated bisphenol A, and alkylene (carbon number 2 to 3) oxide (average number of added moles 1 to 10) adducts of hydrogenated bisphenol A. These may be used alone or in combination of two or more.

[0076] Examples of the polycarboxylic acid include dicarboxylic acids. Examples of the dicarboxylic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid; and succinic acids substituted with an alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, such as dodecenylsuccinic acid and octylsuccinic acid. Among these, succinic acid, a saturated aliphatic acid derived from plants, is preferred. Being plant-derived can enhance carbon neutrality. Saturated aliphatic groups have the effect of enhancing the recrystallization properties of crystalline polyester resins, increasing the aspect ratio of the crystalline polyester resins and improving low-temperature fixability. These may be used alone or in combination of two or more.

[0077] Furthermore, for the purpose of adjusting the acid value and hydroxyl value, the amorphous polyester resin B may contain at least one of a trivalent or higher carboxylic acid and a trivalent or higher alcohol at the end of the resin chain. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, and acid anhydrides thereof. Examples of the trihydric or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

[0078] The molecular weight of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose. As measured by GPC (gel permeation chromatography), the weight average molecular weight (Mw) is preferably 3,000 to 10,000. The number average molecular weight (Mn) is preferably 1,000 to 4,000. The Mw / Mn ratio is preferably 1.0 to 4.0.

[0079] When the molecular weight is equal to or greater than the lower limit, it is possible to prevent the toner from having a deterioration in heat-resistant storage stability and durability against stress such as stirring in a developing machine, etc. When the molecular weight is equal to or less than the upper limit, it is possible to prevent the toner from having an increase in viscoelasticity when melted, and to prevent the toner from having a deterioration in low-temperature fixability.

[0080] The weight average molecular weight (Mw) is more preferably 4,000 to 7,000. The number average molecular weight (Mn) is more preferably 1,500 to 3,000. The Mw / Mn ratio is more preferably 1.0 to 3.5.

[0081] The acid value of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 1 mgKOH / g to 50 mgKOH / g, and more preferably 5 mgKOH / g to 30 mgKOH / g. When the acid value is 1 mgKOH / g or more, the toner tends to be negatively charged, and further, when fixed to paper, the affinity between the paper and the toner is improved, thereby improving low-temperature fixability. When the acid value is 50 mgKOH / g or less, it is possible to suppress a decrease in charging stability, particularly charging stability against environmental fluctuations.

[0082] The hydroxyl value of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 mgKOH / g or more.

[0083] The glass transition temperature (Tg) of the amorphous polyester resin B is preferably 40° C. or higher and 80° C. or lower, more preferably 50° C. or higher and 70° C. or lower. When the glass transition temperature is 40° C. or higher, the toner has sufficient heat-resistant storage stability and durability against stress such as stirring in a developing machine, and also has good filming resistance. When the glass transition temperature is 80° C. or lower, the toner is sufficiently resistant to deformation due to heat and pressure during fixing, and has good low-temperature fixability.

[0084] The molecular structure of the amorphous polyester resin B can be confirmed by NMR measurement using a solution or a solid, as well as by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. -1 and 990±10cm -1 One method is to detect amorphous polyester resins that do not have absorption due to olefin δCH (out-of-plane bending vibration).

[0085] The content of the amorphous polyester resin B is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 to 90 parts by weight, and more preferably 60 to 80 parts by weight, relative to 100 parts by weight of the toner. When the content is 50 parts by weight or more, the dispersibility of the pigment and release agent in the toner can be prevented from deteriorating, and the occurrence of image fogging and distortion can be suppressed. When the content is 90 parts by weight or less, the contents of the crystalline polyester resin C and amorphous polyester resin A can be prevented from decreasing, and a decrease in low-temperature fixability can be suppressed. When the content is within the above-mentioned more preferred range, it is advantageous in that both high image quality and low-temperature fixability are excellent.

[0086] To further improve low-temperature fixability, it is preferable to use the amorphous polyester resin A and the crystalline polyester resin C in combination. To achieve both low-temperature fixability and high-temperature, high-humidity storage stability, the amorphous polyester resin A preferably has an extremely low glass transition temperature. Because the glass transition temperature is extremely low, the resin has the property of deforming at low temperatures, deforming under heat and pressure during fixation, and has the property of easily adhering to recording media such as paper at lower temperatures. Furthermore, in one embodiment of the amorphous polyester resin A, the reactive precursor is nonlinear, so that the resin has a branched structure in the molecular skeleton and the molecular chain forms a three-dimensional network structure. This results in rubber-like properties of deforming at low temperatures but not flowing. This enables the toner to maintain its heat-resistant storage stability and high-temperature offset resistance.

[0087] When the amorphous polyester resin A has a urethane bond or urea bond with high cohesive energy, the resin has better adhesion to recording media such as paper. Furthermore, the urethane bond or urea bond behaves like a pseudo-crosslinking point, and therefore the rubber-like properties are stronger, resulting in better heat-resistant storage stability and high-temperature offset resistance of the toner.

[0088] That is, the toner of the present invention exhibits extremely excellent low-temperature fixability when the amorphous polyester resin A and the crystalline polyester resin C are used in combination, and if necessary, another amorphous polyester resin B. Furthermore, by using the amorphous polyester resin A having a glass transition temperature in the low temperature range, it becomes possible to maintain heat-resistant storage stability and high-temperature offset resistance even when the glass transition temperature of the toner is set lower than conventional toners, and the lower glass transition temperature of the toner results in excellent low-temperature fixability.

[0089] <<Coloring agent>> The colorant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the colorant include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, yellow ochre, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Balkan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, anthrazan yellow BGL, isoindolinone yellow, red iron oxide, red lead, vermilion, Cadmium Red, Cadmium Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Faise Red, Parachlor Orthonitroaniline Red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belcan Fast Rubin B, Brilliant Scarlet G, Lithol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet Red 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Couleur Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Prussian Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake,Examples include malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, and lithopone.

[0090] The content of the colorant is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the toner.

[0091] The colorant can also be used as a masterbatch combined with a resin. Examples of resins to be produced by the masterbatch or kneaded together with the masterbatch include, in addition to the amorphous polyester resin, polymers of styrene or its substitution products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, and styrene-α-chloromethyl methacrylate copolymer. styrene copolymers such as styrene-acrylonitrile copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resins, epoxy polyol resins, polyurethanes, polyamides, polyvinyl butyral, polyacrylic acid resins, rosin, modified rosin, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used alone or in combination of two or more.

[0092] The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant under high shear force. In this process, an organic solvent can be used to enhance the interaction between the colorant and the resin. A method known as the flushing method, in which an aqueous paste containing the colorant in water is mixed and kneaded with the resin and organic solvent, the colorant is transferred to the resin, and the water and organic solvent components are removed, is also preferably used because the wet cake of the colorant can be used as is, eliminating the need for drying. A high-shear dispersing device such as a three-roll mill is preferably used for mixing and kneading.

[0093] <<Release Agent>> The release agent is not particularly limited and can be appropriately selected from known ones. Examples of wax and wax release agents include natural waxes such as plant waxes such as carnauba wax, cotton wax, and wood wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cerusine; and petroleum waxes such as paraffin, microcrystalline, and petrolatum. In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers; and the like can also be used.

[0094] Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalimide anhydride, and chlorinated hydrocarbons; low-molecular-weight crystalline polymer resins, such as polyacrylate homopolymers or copolymers (e.g., n-stearyl acrylate-ethyl methacrylate copolymers); and crystalline polymers having long alkyl groups in their side chains.

[0095] Among these, plant-based waxes and ester waxes using plant-derived materials are preferred, as their plant-derived properties can enhance carbon neutrality.

[0096] The melting point of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. When the melting point is 60° C. or higher, the release agent can be prevented from melting at low temperatures, and a decrease in heat-resistant storage stability can be prevented. When the melting point is 80° C. or lower, when the resin melts and is in the fixing temperature range, the release agent can be prevented from melting sufficiently, which can prevent fixing offset and prevent image defects.

[0097] The content of the release agent is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 2 to 10 parts by mass, more preferably 3 to 8 parts by mass, relative to 100 parts by mass of the toner. When the content is 2 parts by mass or more, it is possible to prevent a decrease in high-temperature offset resistance and low-temperature fixability during fixing, and when it is 10 parts by mass or less, it is possible to prevent a decrease in heat-resistant storage stability and the occurrence of image fogging. When the content of the release agent is within the above-mentioned more preferred range, it is advantageous in terms of improving image quality and fixing stability.

[0098] <<Other ingredients>> Examples of the other components contained in the toner base particles include a charge control agent, a deforming agent, a flowability improver, a cleaning property improver, and a magnetic material.

[0099] <<<Charge control agent>>> The charge control agent is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compounds, tungsten simple substance or compounds, fluorine-based activators, salicylic acid metal salts, and salicylic acid derivative metal salts.

[0100] Specific examples include the nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, the salicylic acid metal complex E-84, and the phenolic condensate E-89 (all manufactured by Orient Chemical Industry Co., Ltd.), the quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.), LRA-901, the boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymeric compounds having functional groups such as sulfonic acid groups, carboxyl groups, and quaternary ammonium salts.

[0101] The content of the charge control agent is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, relative to 100 parts by mass of the toner. When the content is 10 parts by mass or less, the chargeability of the toner can be prevented from becoming too high, the effect of the main charge control agent can be maintained, the electrostatic attraction force with the developing roller can be prevented from increasing, and a decrease in the fluidity of the developer and a decrease in image density can be suppressed. These charge control agents can be melt-kneaded with a master batch and a resin and then dissolved and dispersed, or they can be added when directly dissolved and dispersed in an organic solvent, or they can be fixed on the surface of the toner after toner particles are produced.

[0102] <<<Deforming Agent>>> In this embodiment, the toner may contain a deforming agent for the purpose of deforming the shape of the color toner. The deforming agent may be appropriately selected depending on the purpose as long as it can achieve this purpose, but it is preferable that the toner contains a layered inorganic mineral in which at least a part of the interlayer ions of the layered inorganic mineral have been modified with organic ions.

[0103] Layered inorganic minerals that can be used as deforming agents, in which at least a portion of the interlayer ions of the layered inorganic mineral have been modified with organic ions, are not particularly limited and can be selected appropriately depending on the purpose. For example, those with a basic smectite crystal structure modified with organic cations are desirable. Metal anions can also be introduced by substituting a portion of the divalent metal of the layered inorganic mineral with a trivalent metal. However, because the introduction of metal anions increases hydrophilicity, layered inorganic compounds in which at least a portion of the metal anions have been modified with organic anions are desirable.

[0104] The organic cation modifier for a layered inorganic mineral in which at least a portion of the ions of the layered inorganic mineral are modified with organic ions is not particularly limited as long as it can be modified with organic ions in this manner, and examples thereof include quaternary alkyl ammonium salts, phosphonium salts, and imidazolium salts. Among these, quaternary alkyl ammonium salts are preferred. Examples of such quaternary alkyl ammonium salts include trimethylstearyl ammonium, dimethylstearyl benzyl ammonium, and oleyl bis(2-hydroxyethyl)methyl ammonium.

[0105] The organic anion modifier for a layered inorganic mineral in which at least a portion of the ions of the layered inorganic mineral have been modified with organic ions is not particularly limited as long as it can be modified with organic ions as described above, and examples thereof include sulfates, sulfonates, carboxylates, or phosphates having branched, unbranched, or cyclic alkyl (C1 to C44), alkenyl (C1 to C22), alkoxy (C8 to C32), hydroxyalkyl (C2 to C22), ethylene oxide, propylene oxide, etc. Carboxylic acids having an ethylene oxide skeleton are preferred.

[0106] By modifying at least a portion of the layered inorganic mineral with an organic ion, the layered inorganic mineral has a moderate hydrophobicity, the oil phase (described later) containing the toner composition has a non-Newtonian viscosity, and the toner can be deformed. In this case, the content of the layered inorganic mineral partially modified with an organic ion in the toner material is preferably 0.05% by mass to 10% by mass, and more preferably 0.05% by mass to 5% by mass.

[0107] Furthermore, a layered inorganic mineral partially modified with an organic ion can be appropriately selected, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferred because it does not affect the toner properties, allows easy viscosity adjustment, and allows the amount added to be small.

[0108] Commercially available layered inorganic minerals partially modified with organic cations include quaternium-18 bentonites such as Bentone 3, Bentone 38, and Bentone 38V (manufactured by Rheox Corporation), Thixogel VP (manufactured by United Catalyst), Kraton 34, Kraton 40, and Kraton XL (manufactured by Southern Clay Corporation); stearalkonium bentonites such as Bentone 27 (manufactured by Rheox Corporation), Thixogel LG (manufactured by United Catalyst), Kraton AF, and Kraton APA (manufactured by Southern Clay Corporation); and quaternium-18 / benzalkonium bentonites such as Kraton HT and Kraton PS (manufactured by Southern Clay Corporation). Kraton AF and Kraton APA are preferred.

[0109] Furthermore, as the layered inorganic mineral partially modified with an organic anion, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) modified with an organic anion represented by the following general formula (III) is more preferred. An example of the organic anion represented by the following general formula (III) is Hitenol 330T (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). R1(OR2) n OSO3M...General formula (III) [In the above formula, R1 represents an alkyl group having 13 carbon atoms, R2 represents an alkylene group having 2 to 6 carbon atoms, n represents an integer of 2 to 10, and M represents a monovalent metal element]

[0110] The content of the deforming agent is preferably from 0.05% to 10% by mass, and more preferably from 0.05% to 5% by mass, in the toner, similar to the content of the layered inorganic mineral.

[0111] <<<Flow improver>>> The flowability improver is not particularly limited, and can be appropriately selected according to the purpose, as long as it can be surface-treated to increase hydrophobicity and prevent deterioration of flowability and charging properties even under high humidity.For example, silane coupling agents, silylating agents, silane coupling agents having fluorinated alkyl groups, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, etc. can be mentioned.It is particularly preferable that the silica and titanium oxide are surface-treated with such flowability improvers and used as hydrophobic silica and hydrophobic titanium oxide.

[0112] <<<Cleaning improver>>> The cleaning property improver is not particularly limited as long as it is added to the toner to remove the developer remaining on the photoreceptor or primary transfer medium after transfer, and can be appropriately selected depending on the purpose. Examples include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, and polymer fine particles produced by soap-free emulsion polymerization, such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and are preferably those with a volume average particle size of 0.01 μm to 1 μm.

[0113] <<<Magnetic materials>>> The magnetic material is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include iron powder, magnetite, ferrite, etc. Among these, white materials are preferred in terms of color tone.

[0114] <External additives> In addition to oxide microparticles, inorganic microparticles or hydrophobized inorganic microparticles can be used in combination as the external additives. The average particle size of the hydrophobized primary particles is preferably 1 nm or more and 100 nm or less, and more preferably inorganic microparticles of 5 nm or more and 70 nm or less.

[0115] It is also preferable that the hydrophobic treated inorganic fine particles contain at least one type of inorganic fine particles having an average primary particle size of 20 nm or less, and at least one type of inorganic fine particles having an average primary particle size of 30 nm or more. 2 / g or more 500m 2 / g or less is preferable.

[0116] The external additive is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include silica fine particles, hydrophobic silica, fatty acid metal salts (e.g., zinc stearate, aluminum stearate, etc.), metal oxides (e.g., titania, alumina, tin oxide, antimony oxide, etc.), and fluoropolymers.

[0117] Suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Examples of titania microparticles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Kogyo Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation).

[0118] Examples of hydrophobized titanium oxide microparticles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-500T, TAF-1500T (all manufactured by Fuji Titanium Kogyo Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Corporation), and IT-S (manufactured by Ishihara Sangyo Kaisha, Ltd.).

[0119] Hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles can be obtained, for example, by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, etc. Silicone oil-treated oxide fine particles and inorganic fine particles, which are treated with silicone oil and heated if necessary, to form inorganic fine particles, are also suitable.

[0120] Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacrylic-modified silicone oil, and α-methylstyrene-modified silicone oil.

[0121] Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. Among these, silica and titanium dioxide are particularly preferred.

[0122] The content of the external additive is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the toner.

[0123] The average particle size of the primary particles of the inorganic fine particles is not particularly limited and can be appropriately selected depending on the purpose. It is preferably 100 nm or less, and more preferably 3 nm to 70 nm. If it is 3 nm or more, it is possible to prevent the inorganic fine particles from being buried in the toner and preventing their function from being effectively exerted. Furthermore, if it is 100 nm or less, it is possible to prevent uneven damage to the photoreceptor surface.

[0124] <Glass transition temperature> <<Tg1st(トナー)> > The glass transition temperature of the toner at the first temperature rise in differential scanning calorimetry (DSC) [Tg1st (toner)] is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of low-temperature fixability, it is preferably 20°C or higher and 50°C or lower, and more preferably 35°C or higher and 45°C or lower.

[0125] With conventional toners, when the Tg is around 50°C or lower, the toner tends to aggregate due to temperature changes during transportation and storage, such as in summer or tropical regions. As a result, the toner solidifies in the toner bottle and adheres to the developing unit. Furthermore, toner clogging in the toner bottle can lead to poor replenishment, and image defects can occur due to toner adhesion in the developing unit.

[0126] Even if the toner has a lower Tg than conventional toners, the toner can maintain heat-resistant storage stability if the amorphous polyester resin A, which is a low-Tg component in the toner, is non-linear. In particular, if the amorphous polyester resin A has a urethane bond or urea bond with high cohesive force, the effect of maintaining heat-resistant storage stability becomes more pronounced.

[0127] When the Tg1st (toner) is 20° C. or higher, it is possible to suppress a decrease in heat-resistant storage stability, blocking in a developing machine, and filming on a photoreceptor.When the Tg1st (toner) is 50° C. or lower, it is possible to suppress a decrease in low-temperature fixability of the toner.

[0128] <<[Tg2nd (Toner)]>> The glass transition temperature [Tg2nd (toner)] of the toner at the second temperature rise in differential scanning calorimetry (DSC) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0° C. or higher and 30° C. or lower, and more preferably 0° C. or higher and 15° C. or lower. When [Tg2nd (toner)] is 0° C. or higher, it is possible to prevent a decrease in the blocking resistance of the fixed image (printed matter), and when it is 30° C. or lower, it is possible to prevent a decrease in low-temperature fixability and glossiness. The value of the [Tg2nd (toner)] can be adjusted by, for example, the Tg of the crystalline polyester resin and the blending amount.

[0129] <<[[Tg1st (Toner)] - [Tg2nd (Toner)]]>> The difference [[Tg1st(toner)] - [Tg2nd(toner)]] between the glass transition temperature [Tg1st(toner)] at the first heating stage and the glass transition temperature [Tg2nd(toner)] at the second heating stage in differential scanning calorimetry (DSC) of the toner is not particularly limited and can be appropriately selected depending on the purpose, but is more preferably 10° C. or more. The upper limit of the difference is not particularly limited and can be appropriately selected depending on the purpose, but the difference [[Tg1st(toner)] - [Tg2nd(toner)]] is preferably 50° C. or less.

[0130] When the difference [Tg1st (toner) - Tg2nd (toner)] is 10 °C or more, it is advantageous in terms of better low-temperature fixing property. That the difference [Tg1st (toner) - Tg2nd (toner)] is 10 °C or more means that the crystalline polyester resin C, which existed in an incompatible state before heating (before the first temperature rise), and the amorphous polyester resin A and the amorphous polyester resin B become compatible after heating (after the first temperature rise). Note that the compatible state after heating does not necessarily have to be a complete compatible state.

[0131] <<Tg2nd (THF-insoluble fraction)>> There are no particular restrictions on the glass transition temperature [Tg2nd (THF-insoluble fraction)] in the second heating of the differential scanning calorimetry (DSC) of the tetrahydrofuran (THF) - insoluble fraction of the toner, and it can be appropriately selected according to the purpose. For example, it is preferably -40 °C or more and 30 °C or less, and more preferably 0 °C or more and 20 °C or less. When [Tg2nd (THF-insoluble fraction)] is -40 °C or more, the advantage of suppressing the decrease in blocking resistance of the fixed image (printed matter) can be obtained, and when it is 30 °C or less, the advantage of suppressing the decrease in low-temperature fixing property and glossiness can be obtained.

[0132] The [Tg2nd (THF-insoluble fraction)] can be adjusted, for example, by changing the number of carbon atoms of the diol and dicarboxylic acid of the amorphous polyester resin A.

[0133] <Storage elastic modulus> <<[G’(100) (THF-insoluble fraction)], and [G’(40) (THF-insoluble fraction)] / [G’(100) (THF-insoluble fraction)]>> There are no particular restrictions on the storage elastic modulus [G’(100) (THF-insoluble fraction)] at 100 °C of the tetrahydrofuran (THF) - insoluble fraction of the toner, and it can be appropriately selected according to the purpose, but 1.0×10 5 Pa to 1.0×10 7 Pa is preferable, and 5.0×105 Pa to 5.0×10 6 Pa is more preferable. When the storage elastic modulus [G’(100)(THF-insoluble content)] is within the more preferable range, it is advantageous in that the low-temperature fixing property is more excellent.

[0134] The ratio of the storage elastic modulus [G’(40)(THF-insoluble content)] at 40°C to the storage elastic modulus [G’(100)(THF-insoluble content)] at 100°C of the THF-insoluble content of the toner, [〔G’(40)(THF-insoluble content)〕 / 〔G’(100)(THF-insoluble content)〕], is not particularly limited and can be appropriately selected according to the purpose, but is preferably 3.5×10 or less. When the ratio [〔G’(40)(THF-insoluble content)〕 / 〔G’(100)(THF-insoluble content)〕] is 3.5×10 or less, it is possible to suppress the decrease in the low-temperature fixing property.

[0135] The toner has the [G’(100)(THF-insoluble content)] of 1.0×10 5 Pa to 1.0×10 7 Pa, and the ratio [〔G’(40)(THF-insoluble content)〕 / 〔G’(100)(THF-insoluble content)〕] is 3.5×10 or less, thereby promoting the compatibilization of the crystalline polyester resin and the amorphous polyester resin which is a high Tg component, lowering the 1 / 2 outflow temperature by a heat flow evaluation apparatus (flow tester), and improving the image gloss.

[0136] The [G’(100)(THF-insoluble content)] and the [G’(40)(THF-insoluble content)] can be adjusted in numerical value, for example, by the resin composition (a polyol having two or more functional groups, an acid component having two or more functional groups). Specifically, for example, it can be adjusted as follows. If G’ is to be increased, shorten the distance of the ester bond in the resin. Make the resin composition have an aromatic ring. If G’ is to be decreased, use a linear polyester resin. As a constituent component of the polyester resin, use a polyol having an alkyl group in the side chain.

[0137] <<THF-insoluble content>> The THF-insoluble matter of the toner can be obtained as follows. One part of toner is added to 100 parts of tetrahydrofuran (THF), and the mixture is refluxed for 6 hours. Then, the insoluble components are precipitated using a centrifuge, and the insoluble components are separated from the supernatant. The insoluble component is dried at 40° C. for 20 hours to obtain a THF-insoluble component.

[0138] <<Method for measuring storage modulus G'>> The storage modulus (G') under various conditions can be measured, for example, using a dynamic viscoelasticity measuring device (ARES, manufactured by TA Instruments) at a frequency of 1 Hz. Specifically, the measurement sample is molded into a pellet with a diameter of 8 mm and a thickness of 1 to 2 mm, and fixed to a parallel plate with a diameter of 8 mm. After stabilizing at 40°C, the temperature is increased to 200°C at a rate of 2.0°C / min at a frequency of 1 Hz (6.28 rad / s) and a strain of 0.1% (strain control mode), and the storage modulus is measured. In this specification, the storage modulus at 40°C may be represented as G'(40°C), and the storage modulus at 100°C may be represented as G'(100°C).

[0139] <Melting point> The melting point of the toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower.

[0140] <Volume average particle size> The volume average particle diameter of the toner is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 μm to 7 μm. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. It is also preferable that the toner contains 1% to 10% by number of components having a volume average particle diameter of 2 μm or less.

[0141] <Methods for calculating and analyzing various properties of toner and toner components> The Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the release agent may be measured for each of them. Alternatively, the Tg, molecular weight, melting point, and mass ratio of the constituent components may be calculated by separating the components from an actual toner by gel permeation chromatography (GPC) or the like and then applying the analytical techniques described below to each of the separated components.

[0142] Separation of each component by GPC can be carried out, for example, by the following method. In GPC measurement using THF (tetrahydrofuran) as the mobile phase, the eluate is fractionated using a fraction collector or the like, and fractions corresponding to the desired molecular weight portion of the full integral of the elution curve are collected.

[0143] The combined eluate is concentrated and dried using an evaporator or the like, and the solid content is then dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, 1 H-NMR measurement is carried out, and the ratio of constituent monomers of the polyester resin in the eluted components is calculated from the integral ratio of each element.

[0144] Another method involves concentrating the eluate, hydrolyzing it with sodium hydroxide or the like, and then qualitatively and quantitatively analyzing the decomposition products using high performance liquid chromatography (HPLC) or the like to calculate the proportion of constituent monomers.

[0145] In the case where the toner manufacturing method forms toner base particles while producing amorphous polyester resin A through an elongation reaction and / or crosslinking reaction between the non-linear reactive precursor and the curing agent, the amorphous polyester resin A may be separated from the actual toner by GPC or the like to determine the Tg and other properties of the amorphous polyester resin A. Alternatively, amorphous polyester resin A may be separately synthesized through an elongation reaction and / or crosslinking reaction between the non-linear reactive precursor and the curing agent, and the Tg and other properties of the synthesized amorphous polyester resin A may be measured.

[0146] <<Means for separating toner components>> An example of a means for separating each component when analyzing the toner will be described in detail below. First, 1 g of toner is placed in 100 mL of THF and stirred for 30 minutes at 25°C to obtain a solution in which the soluble matter is dissolved. This is then filtered through a membrane filter with 0.2 μm openings to obtain the THF-soluble matter in the toner. Next, this is dissolved in THF to prepare a sample for GPC measurement, and the sample is injected into the GPC used to measure the molecular weight of each resin described above. Meanwhile, a fraction collector is placed at the eluate outlet of the GPC, and the eluate is fractionated at predetermined counts, and the eluate is obtained at 5% area ratios from the start of elution (the rising edge of the curve) of the elution curve. Next, for each elution, 30 mg of the sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a standard substance. The solution is filled into a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by 128 accumulations at a temperature of 23°C to 25°C using a nuclear magnetic resonance spectrometer (JNM-AL400 manufactured by JEOL Ltd.). The monomer compositions and constituent ratios of the amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and the like contained in the toner can be determined from the peak integral ratios of the obtained spectrum.

[0147] For example, the peaks are assigned as follows, and the component ratio of the constituent monomers is determined from the integral ratio of each peak. Peak assignments can be made, for example, as follows: Around 8.25 ppm: Derived from the benzene ring of trimellitic acid (one hydrogen) Around 8.07 ppm to 8.10 ppm: From the benzene ring of terephthalic acid (4 hydrogen atoms) Around 7.1 ppm to 7.25 ppm: Derived from the benzene ring of bisphenol A (4 hydrogen atoms) Around 6.8 ppm: from the benzene ring of bisphenol A (4 hydrogen atoms) and from the double bond of fumaric acid (2 hydrogen atoms) Around 5.2 ppm to 5.4 ppm: derived from methine of bisphenol A propylene oxide adduct (one hydrogen) Around 3.7 ppm to 4.7 ppm: Methylene-derived compounds of bisphenol A propylene oxide adducts (2 hydrogen atoms) and methylene-derived compounds of bisphenol A ethylene oxide adducts (4 hydrogen atoms) Around 1.6 ppm: This can be attributed to the methyl group of bisphenol A (6 hydrogen atoms).

[0148] From these results, for example, the extract recovered in the fraction in which the amorphous polyester resin A accounts for 90% or more can be treated as the amorphous polyester resin A. Similarly, the extract recovered in the fraction in which the amorphous polyester resin B accounts for 90% or more can be treated as the amorphous polyester resin B. The extract recovered in the fraction in which the crystalline polyester resin C accounts for 90% or more can be treated as the crystalline polyester resin C.

[0149] <<Method for measuring melting point and glass transition temperature (Tg)>> The melting point and glass transition temperature (Tg) in the present invention can be measured, for example, using a DSC system (differential scanning calorimeter) ("Q-200", manufactured by TA Instruments). Specifically, the melting point and glass transition temperature of the sample can be measured by the following procedure. First, approximately 5.0 mg of the target sample was placed in an aluminum sample container, which was then placed on a holder unit and placed in an electric furnace. Next, under a nitrogen atmosphere, the sample was heated from -80°C to 150°C at a heating rate of 10°C / min (first heating). The sample was then cooled from 150°C to -80°C at a cooling rate of 10°C / min, and further heated to 150°C at a heating rate of 10°C / min (second heating). During both the first and second heating, DSC curves were measured using a differential scanning calorimeter (TA Instruments, model Q-200).

[0150] From the DSC curves obtained, the analysis program in the Q-200 system can be used to select the DSC curve during the first heating cycle and determine the glass transition temperature of the sample during the first heating cycle. Similarly, the DSC curve during the second heating cycle can be selected and the glass transition temperature of the sample during the second heating cycle can be determined.

[0151] Furthermore, using the analysis program in the Q-200 system, the DSC curve during the first heating run can be selected from the obtained DSC curves, and the endothermic peak top temperature during the first heating run of the target sample can be determined as the melting point. Similarly, the DSC curve during the second heating run can be selected, and the endothermic peak top temperature during the second heating run of the target sample can be determined as the melting point.

[0152] In this specification, when toner is used as a target sample, the glass transition temperature at the first temperature rise is referred to as Tg1st, and the glass transition temperature at the second temperature rise is referred to as Tg2nd. Furthermore, in this specification, unless otherwise specified, the glass transition temperature and melting point of the amorphous polyester resin A, the amorphous polyester resin B, the crystalline polyester resin C, and other components such as the release agent are defined as the endothermic peak top temperature, Tg, during the second heating, which is the melting point, Tg, of each target sample.

[0153] <<Method for measuring particle size distribution>> The volume average particle diameter (D4), number average particle diameter (Dn), and the ratio (D4 / Dn) of the toner can be measured using, for example, a Coulter Counter TA-II or a Coulter Multisizer II (both manufactured by Coulter). In the present invention, a Coulter Multisizer II was used. The measurement method is described below.

[0154] First, 0.1 mL to 5 mL of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersant to 100 mL to 150 mL of electrolytic solution. Here, the electrolytic solution is a 1% by mass NaCl aqueous solution prepared using primary sodium chloride, such as ISOTON-II (manufactured by Coulter). 2 mg to 20 mg of a measurement sample is then added. The electrolytic solution with the suspended sample is subjected to a dispersion treatment using an ultrasonic disperser for approximately 1 to 3 minutes, and the volume and number of toner particles are measured using a 100 μm aperture on the measuring device, and the volume distribution and number distribution are calculated. The volume average particle size (D4) and number average particle size (Dn) of the toner can be determined from the distributions obtained.

[0155] Thirteen channels are used: 2.00 μm or more and less than 2.52 μm; 2.52 μm or more and less than 3.17 μm; 3.17 μm or more and less than 4.00 μm; 4.00 μm or more and less than 5.04 μm; 5.04 μm or more and less than 6.35 μm; 6.35 μm or more and less than 8.00 μm; 8.00 μm or more and less than 10.08 μm; 10.08 μm or more and less than 12.70 μm; 12.70 μm or more and less than 16.00 μm; 16.00 μm or more and less than 20.20 μm; 20.20 μm or more and less than 25.40 μm; 25.40 μm or more and less than 32.00 μm; and 32.00 μm or more and less than 40.30 μm, and the target particles are 2.00 μm or more and less than 40.30 μm in size.

[0156] <<Average particle size, average circularity>> In this embodiment, the average particle diameter and average circularity are measured using, for example, a flow particle image analyzer FPIA-3000 (manufactured by Sysmex Corporation).

[0157] Specifically, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of water from which solid impurities have been removed, and then approximately 0.1 to 0.5 g of the sample to be measured is added. The suspension containing the sample is subjected to a dispersion treatment in an ultrasonic disperser for approximately 1 to 3 minutes, and the dispersion concentration is adjusted to 3,000 to 10,000 particles / μl. The average particle size, average circularity, and standard deviation (SD) of the circularity are measured using the same device.

[0158] However, the particle diameter is the equivalent circle diameter, the average particle diameter is determined from the equivalent circle diameter (number basis), and the analysis conditions for the flow type particle image analyzer are as follows: Particle size limit: 0.5 μm≦circle equivalent diameter (number basis)≦200.0 μm Particle shape limit: 0.93<circularity≦1.00 In the present embodiment, the definition of the average circularity is as follows. (Average circularity) = (perimeter of a circle equal to the projected area) / (perimeter of the projected image)

[0159] <<Molecular weight measurement>> The molecular weight of each component of the toner can be measured, for example, by the following method. Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperHZM-H 15cm triple column (Tosoh Corporation) Temperature: 40℃ Solvent: THF Flow rate: 0.35mL / min Sample: 100 μL of 0.15% by mass sample injected Sample pretreatment: The toner is dissolved in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass, then filtered through a 0.2 μm filter, and the filtrate is used as the sample. 100 μL of the THF sample solution is injected and measured.

[0160] When measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithm of the calibration curve prepared using several monodisperse polystyrene standard samples and the count number. The standard polystyrene samples used to prepare the calibration curve are Showdex STANDARD (Showa Denko K.K.), Std. Nos. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, and S-0.580. An RI (refractive index) detector is used.

[0161] <<Long axis and aspect ratio of crystalline polyester resin>> The major axis and aspect ratio of the crystalline polyester resin of the toner can be measured, for example, by the following method. The toner was embedded in a visible light-curable embedding resin (D-800, Nissin EM Co., Ltd.), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, Leica), and then stained with Ru using a vacuum staining device (Filgen). Observation was then performed using a transmission electron microscope (H7500, Hitachi) at an accelerating voltage of 120 kV. 50 particles of toner within ±2.0 μm of the weight-average particle size were selected and photographed. In the configuration of the present invention, RuO4 staining resulted in a darker shade of the polyester resin C in the toner, and when wax was used, the wax was projected even darker. The average major axis and average aspect ratio of the domains composed of polyester resin C could be determined from the observed image, but the average aspect ratio could also be calculated using image processing software if necessary.

[0162] Image-Pro Plus 5.1J (Media Cybernetics) can be used for image processing. Cross-sectional images of toner particles captured using the method described above are used. First, to extract the toner particles to be analyzed, select the toner particle area to separate the toner particles from the background. Select "Measurement" - "Count / Size" in Image-Pro Plus 5.1J. From the "Count / Size" window, select "Measurement" - "Measurement Items." Select "Diameter (Minimum)" and "Diameter (Maximum)" from the measurement items. In "Brightness Range Selection," the brightness range must be adjusted so that only polyester resin A is selected. Depending on the RuO4 staining conditions, the brightness range may need to be changed each time, but polyester resin A can be easily identified by the aforementioned difference in shading. Select "Count" to display the measurement results. The aspect ratio (major diameter / minor diameter) can then be calculated by using the obtained "Diameter (Minimum)" as the minor diameter and the "Diameter (Maximum)" as the major diameter. From the aspect ratio data for one toner particle thus obtained, the average value of 10 points in descending order of diameter (maximum) is calculated, and this is repeated for 10 toner particles to obtain the average aspect ratio. The major axis of the crystalline polyester resin is preferably 2.0 μm or less, more preferably 1.0 μm or less. If the major axis is large, the crystalline polyester resin is more likely to be exposed on the toner surface, increasing the toner adhesion and deteriorating the cleaning ability. The aspect ratio is preferably 4.0 or more, and more preferably 10.0 or more. If the aspect ratio is small, the contact area with the amorphous polyester resin becomes small, which deteriorates the compatibility between the amorphous polyester resin and the crystalline polyester resin during fixing, thereby deteriorating the low-temperature fixing property.

[0163] <Measuring the particle size of wax in wax dispersion> The particle size of the wax dispersion in the present invention can be measured, for example, using a Nanotrac particle size distribution analyzer UPA-EX150 (Nikkiso Co., Ltd., dynamic light scattering method / laser Doppler method). Specifically, the measurement is performed by adjusting the dispersion in which the resin microparticles are dispersed to a measurement concentration range. At this time, a background measurement is performed in advance using only the dispersion solvent of the dispersion. This measurement method makes it possible to measure the volume average particle size range of the resin microparticles used in the present invention, from several tens of nanometers to several micrometers. The particle size of the wax in the present invention refers to the volume average particle size (volume average diameter). In the present invention, the dispersed particle size of the wax in the wax dispersion is preferably 50 nm or more and 600 nm or less, and more preferably 50 nm or more and 300 nm or less.

[0164] <Measurement of particle size of crystalline polyester resin in crystalline polyester resin dispersion> The particle size of the crystalline polyester resin dispersion liquid of the present invention can be measured, for example, using a Nanotrac particle size distribution analyzer UPA-EX150 (Nikkiso Co., Ltd., dynamic light scattering method / laser Doppler method). Specifically, the measurement is performed by adjusting the dispersion liquid containing dispersed resin microparticles to a measurement concentration range. At this time, background measurement is performed in advance using only the dispersion solvent of the dispersion liquid. This measurement method makes it possible to measure the volume average particle size range of the resin microparticles used in the present invention, from several tens of nanometers to several micrometers. The particle size of the crystalline polyester resin in the present invention refers to the volume average particle size (volume average diameter). In the present invention, the dispersed particle size of the crystalline polyester resin in the crystalline polyester resin dispersion is preferably 20 nm or more and 500 nm or less, and more preferably 50 nm or more and 300 nm or less.

[0165] <Toner manufacturing method> The method for producing the toner is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the method includes a mixing step of mixing the toner base particles with the external additive.

[0166] The toner base particles preferably contain the amorphous polyester resin A, the amorphous polyester resin B, and the crystalline polyester resin C, and are preferably granulated by further dispersing an oil phase containing the release agent, the colorant, and the like in an aqueous medium, as needed.

[0167] The toner base particles preferably contain the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and are preferably granulated by dispersing an oil phase containing the curing agent, the release agent, the colorant, etc., in an aqueous medium, as needed.

[0168] One example of a method for producing such toner base particles is a known emulsion aggregation method. As an example of a method for producing the toner base particles, the following method is described: forming toner base particles while elongating amorphous polyester resin A through an elongation reaction and / or crosslinking reaction between the prepolymer and the curing agent. In this method, a fine particle dispersion is obtained by preparing an aqueous medium, preparing an oil phase containing toner materials, emulsifying the toner materials by phase inversion, and removing the organic solvent. The fine particle dispersion is aggregated and fused to obtain toner base particles. The obtained toner base particles are then mixed with the external additive to obtain the toner.

[0169] <<Preparation of aqueous medium (aqueous phase)>> The aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Examples include water, a solvent miscible with water, and a mixture thereof. These may be used alone or in combination of two or more. Among these, water is preferred.

[0170] The water-miscible solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. The alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include methanol, isopropanol, and ethylene glycol. The lower ketones are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include acetone and methyl ethyl ketone.

[0171] <<Preparation of oil phase>> The oil phase containing the toner materials can be prepared by, for example, dissolving or dispersing the toner materials, which include the non-linear reactive precursor, the amorphous polyester resin B, and the crystalline polyester resin C, and further include the curing agent, the release agent, the colorant, etc., as required, in an organic solvent. The oil phase may also contain a profile-forming agent.

[0172] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but an organic solvent having a boiling point of less than 150° C. is preferred in terms of ease of removal. The organic solvent having a boiling point of less than 150° C. is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, etc. These may be used alone or in combination of two or more. Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, etc. are preferred, and ethyl acetate is more preferred.

[0173] <<Phase inversion emulsification>> The phase inversion emulsification of the toner materials can be performed by dispersing an oil phase containing the toner materials in the aqueous medium. During the emulsification or dispersion of the toner materials, the curing agent and the non-linear reactive precursor undergo an elongation reaction and / or a crosslinking reaction to produce the amorphous polyester resin A.

[0174] The amorphous polyester resin A can be produced, for example, by the following methods (1) to (3). (1) A method of producing the amorphous polyester resin A by emulsifying or dispersing an oil phase containing the non-linear reactive precursor and the curing agent in an aqueous medium, and causing an elongation reaction and / or a crosslinking reaction between the curing agent and the non-linear reactive precursor in the aqueous medium. (2) A method in which an oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium to which the curing agent has been added in advance, and the curing agent and the non-linear reactive precursor are subjected to an elongation reaction and / or a crosslinking reaction in the aqueous medium to produce the amorphous polyester resin A. (3) A method in which an oil phase containing the non-linear reactive precursor is emulsified or dispersed in an aqueous medium, and then the curing agent is added to the aqueous medium, and an elongation reaction and / or crosslinking reaction occurs between the curing agent and the non-linear reactive precursor at the particle interface in the aqueous medium, thereby producing the amorphous polyester resin A.

[0175] In addition, when the curing agent and the non-linear reactive precursor are subjected to an elongation reaction and / or a crosslinking reaction from the particle interface, the amorphous polyester resin A is preferentially formed on the surface of the toner produced, and a concentration gradient of the amorphous polyester resin A can be provided in the toner.

[0176] The reaction conditions (reaction time, reaction temperature) for producing the amorphous polyester resin A are not particularly limited and can be appropriately selected depending on the combination of the curing agent and the non-linear reactive precursor. The reaction time is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 10 minutes to 40 hours, more preferably from 2 hours to 24 hours. The reaction temperature is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0°C or higher and 150°C or lower, and more preferably 40°C or higher and 98°C or lower.

[0177] The method for phase inversion emulsification of the dispersion containing the non-linear reactive precursor in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. For example, there is a method in which an oil phase is neutralized with a base or the like, and then an aqueous phase is added thereto, thereby obtaining a microparticle dispersion by phase inversion emulsification, in which the water-in-oil dispersion is inverted into an oil-in-water dispersion.

[0178] The base for neutralizing the oil phase is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include sodium hydroxide, potassium hydroxide, and aqueous ammonia.

[0179] The amount of the aqueous medium used when inverting and emulsifying the oil phase containing the toner materials is not particularly limited and can be appropriately selected depending on the purpose. The amount is preferably 50 parts by mass or more and 2,000 parts by mass or less, and more preferably 100 parts by mass or more and 1,000 parts by mass or less, relative to 100 parts by mass of the toner materials. When the amount of the aqueous medium used is 50 parts by mass or more, it is possible to prevent the dispersion state of the toner materials from becoming poor and to suppress the failure to obtain toner base particles having the predetermined particle size, and when the amount is 2,000 parts by mass or less, it is possible to suppress an increase in production costs.

[0180] When the oil phase containing the toner materials is subjected to phase inversion emulsification, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion of oil droplets and the like, forming them into a desired shape, and sharpening the particle size distribution. The dispersant is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, and polymeric protective colloids. These may be used alone or in combination of two or more. Among these, surfactants are preferred.

[0181] The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. can be used.

[0182] The anionic surfactant is not particularly limited and can be appropriately selected depending on the purpose. Examples include alkylbenzene sulfonates, α-olefin sulfonates, phosphates, etc. Among these, those having a fluoroalkyl group are preferred.

[0183] In the elongation reaction and / or crosslinking reaction when producing the amorphous polyester resin A, a catalyst can be used. The catalyst is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include dibutyltin laurate and dioctyltin laurate.

[0184] <<Removal of organic solvents>> The method for removing the organic solvent from the dispersion liquid such as the emulsified slurry is not particularly limited and can be appropriately selected depending on the purpose. For example, a method of gradually increasing the temperature of the entire reaction system to evaporate the organic solvent in the oil droplets, a method of spraying the dispersion liquid into a dry atmosphere to remove the organic solvent in the oil droplets, etc. can be mentioned. <<Aggregation, fusion>>

[0185] As the aggregation method, existing methods such as adding a flocculant or adjusting pH can be used. When adding the flocculant, it may be added directly, but it is preferable to add the flocculant in an aqueous solution, since this can avoid localized high concentrations. In addition, it is preferable to add the flocculant salt gradually while monitoring the particle size of the colored particles. The temperature of the dispersion during aggregation is preferably near the Tg of the amorphous polyester B. If the liquid temperature is too low, aggregation does not proceed very well, resulting in poor efficiency, whereas if the liquid temperature is too high, the aggregation rate increases, resulting in the generation of coarse particles and a deterioration in particle size distribution. When the target particle size is reached, aggregation is stopped by adding a salt having a lower ionic valence than the aggregating salt or a chelating agent, adjusting the pH, lowering the temperature of the dispersion, or adding a large amount of an aqueous medium to dilute the concentration. By the above method, a dispersion of colored aggregated particles can be obtained.

[0186] In the aggregation step, a release agent may be added, or for low-temperature fixability, crystalline polyester resin C may be added. In this case, a dispersion in which the release agent is dispersed in an aqueous medium or a dispersion of crystalline polyester resin C is prepared, and these are mixed with the colored particle dispersion and then aggregated, thereby obtaining aggregated particles in which the release agent and crystalline polyester resin are uniformly dispersed.

[0187] Next, the resulting aggregated particles are fused by heat treatment to reduce unevenness. Fusion can be achieved by heating the dispersion of colored aggregated particles while stirring. The temperature of the solution is preferably from Tg of the amorphous polyester B to Tg + 20°C, more preferably from Tg to Tg + 10°C. If the temperature exceeds Tg + 20°C, the compatibility between the amorphous polyester resin and the crystalline polyester resin will be too advanced, resulting in a large domain diameter during recrystallization of the crystalline polyester resin, which will be more likely to be exposed to the toner surface.

[0188] Thereafter, the toner base particles may be subjected to washing, drying, etc., and further to classification, etc. The classification may be performed by removing fine particle portions in a liquid using a cyclone, a decanter, centrifugal separation, etc., or the classification operation may be performed after drying.

[0189] <<Mixing process>> The obtained toner base particles are mixed with the external additive, and at this time, by applying a mechanical impact force, it is possible to prevent the external additive particles from being detached from the surfaces of the toner base particles.

[0190] The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method for applying an impact force to the mixture using blades rotating at high speed, and a method for introducing the mixture into a high-speed air stream and accelerating it to cause particles to collide with each other or with an appropriate collision plate.

[0191] The apparatus used in the method is not particularly limited and can be appropriately selected depending on the purpose. Examples include an Ang Mill (manufactured by Hosokawa Micron Corporation), an apparatus obtained by modifying an I-type Mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the pulverizing air pressure, a Hybridization System (manufactured by Nara Machinery Works), a Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

[0192] (developer) The developer of the present invention contains at least the toner, and optionally contains other components such as a carrier that are appropriately selected. Therefore, it is possible to stably form high-quality images with excellent transferability, charging property, etc. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer or the like that corresponds to the recent improvement in information processing speed, a two-component developer is preferred because of its improved lifespan.

[0193] When the developer is used as a one-component developer, even if the toner is balanced, there is little fluctuation in the particle size of the toner, there is little toner filming on the developing roller, and there is little toner fusion to components such as blades that thin the toner layer, and good and stable developability and images can be obtained even with long-term stirring in the developing device.

[0194] When the developer is used as a two-component developer, fluctuations in the particle size of the toner are small even when the toner is balanced over a long period of time, and good and stable developability and images can be obtained even when the developer is stirred for a long period of time in a developing device.

[0195] <Career> The carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably one having a core material and a resin layer covering the core material.

[0196] <<Core material>> The material for the core is not particularly limited and can be appropriately selected depending on the purpose. Examples include manganese-strontium-based materials with an emu / g to 90 emu / g and manganese-magnesium-based materials with an emu / g to 90 emu / g. To ensure image density, it is preferable to use high-magnetization materials such as iron powder with an emu / g or more and magnetite with an emu / g to 120 emu / g. It is also preferable to use low-magnetization materials such as copper-zinc-based materials with an emu / g to 80 emu / g, as this can reduce the impact of the developer in a standing state on the photoreceptor and is advantageous for achieving high image quality. These may be used alone or in combination of two or more.

[0197] The volume average particle diameter of the core material is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 10 μm to 150 μm, and more preferably 40 μm to 100 μm. When the volume average particle diameter is 10 μm or more, it is possible to prevent the carrier from containing a large amount of fine powder, thereby reducing the magnetization per particle and preventing carrier scattering. When the volume average particle diameter is 150 μm or less, it is possible to prevent a decrease in specific surface area, preventing toner scattering, and preventing poor reproduction of solid areas, especially in full-color printers with many solid areas.

[0198] When the toner is used in a two-component developer, it may be mixed with the carrier. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 90 parts by mass or more and 98 parts by mass or less, and more preferably 93 parts by mass or more and 97 parts by mass or less, relative to 100 parts by mass of the two-component developer.

[0199] The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

[0200] (Image forming apparatus and image forming method) The image forming apparatus of the present invention has at least an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and may further have other means as required. The image forming method according to the present invention includes at least an electrostatic latent image forming step and a development step, and may further include other steps as required. The image forming method can be suitably performed by the image forming apparatus, the electrostatic latent image forming step can be suitably performed by the electrostatic latent image forming means, the developing step can be suitably performed by the developing means, and the other steps can be suitably performed by the other means.

[0201] <Electrostatic latent image carrier> The material, structure, and size of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known materials. Examples of the material include inorganic photoconductors such as amorphous silicon and selenium, and organic photoconductors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferred in terms of long life.

[0202] The amorphous silicon photoreceptor may be, for example, a photoreceptor having a photoconductive layer made of a-Si formed on a support by heating the support to 50° C. to 400° C. and depositing the photoconductive layer on the support by a film-forming method such as vacuum deposition, sputtering, ion plating, thermal CVD (chemical vapor deposition), photo-CVD, or plasma CVD. Among these, plasma CVD, i.e., a method in which a source gas is decomposed by direct current, high frequency, or microwave glow discharge to form an a-Si deposited film on the support, is preferred.

[0203] The shape of the electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably cylindrical. The outer diameter of the cylindrical electrostatic latent image carrier is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 mm to 100 mm, more preferably 5 mm to 50 mm, and particularly preferably 10 mm to 30 mm.

[0204] <Electrostatic latent image forming means and electrostatic latent image forming process> The electrostatic latent image forming unit is not particularly limited as long as it is a unit that forms an electrostatic latent image on the electrostatic latent image bearing member, and can be appropriately selected depending on the purpose. For example, it may be a unit that has at least a charging member that charges the surface of the electrostatic latent image bearing member and an exposing member that imagewise exposes the surface of the electrostatic latent image bearing member. The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image bearing member, and can be appropriately selected depending on the purpose. For example, it can be performed by charging the surface of the electrostatic latent image bearing member and then exposing it to light in an imagewise manner, and can be performed using the electrostatic latent image forming unit.

[0205] <<Charging materials and charging>> The charging member is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a known contact charger equipped with a conductive or semiconductive roller, brush, film, rubber blade, etc., and a non-contact charger utilizing corona discharge such as a corotron or scorotron. The charging can be carried out, for example, by applying a voltage to the surface of the electrostatic latent image bearing member using the charging member.

[0206] The shape of the charging member may be a roller, a magnetic brush, a fur brush, or any other shape, and can be selected according to the specifications and shape of the image forming apparatus. The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because it allows an image forming apparatus in which the amount of ozone generated from the charging member is reduced.

[0207] <<Exposure member and exposure>> The exposing member is not particularly limited and can be appropriately selected depending on the purpose as long as it can expose the surface of the electrostatic latent image bearing member charged by the charging member in the form of an image to be formed, and examples thereof include various exposing members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. The light source used in the exposure member is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include general light-emitting materials such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), and electroluminescence (EL).

[0208] In order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used. The exposure can be carried out, for example, by exposing the surface of the electrostatic latent image bearing member imagewise using the exposure member. In the present invention, a backlight system may be employed in which exposure is performed imagewise from the back side of the electrostatic latent image bearing member.

[0209] <Developing means and developing process> The developing unit is not particularly limited as long as it is a developing unit that has a toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, and can be appropriately selected depending on the purpose. The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a visible image, and can be appropriately selected depending on the purpose. For example, the developing step can be performed by the developing unit.

[0210] The developing means may be of a dry developing type or a wet developing type, and may be a single-color developing means or a multi-color developing means. The developing means is preferably a developing device having an agitator that frictionally agitates the toner to charge it, a magnetic field generating means fixed inside, and a rotatable developer carrier that carries a developer containing the toner on its surface. In the developing unit, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction during this process and held in a standing state on the surface of a rotating magnet roller, forming a magnetic brush. The magnet roller is disposed near the electrostatic latent image carrier. Therefore, a portion of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by electrical attraction. As a result, the electrostatic latent image is developed with the toner, and a visible toner image is formed on the surface of the electrostatic latent image carrier.

[0211] <Other means and other steps> Examples of the other means include a transfer means, a fixing means, a cleaning means, a discharging means, a recycling means, and a control means. Examples of the other steps include a transfer step, a fixing step, a cleaning step, a discharging step, a recycling step, and a control step.

[0212] <<Transfer means and transfer process>> The transfer means is not particularly limited as long as it is a means for transferring a visible image onto a recording medium, and can be appropriately selected depending on the purpose. Among them, an embodiment having a primary transfer means for transferring a visible image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium is preferred. The transfer step is not particularly limited as long as it is a step of transferring a visible image onto a recording medium, and can be appropriately selected depending on the purpose. Among them, an embodiment in which an intermediate transfer member is used, a visible image is primarily transferred onto the intermediate transfer member, and then the visible image is secondarily transferred onto the recording medium is preferred.

[0213] The transfer step can be carried out by, for example, charging the visible image on the photosensitive member using a transfer charger, and can be carried out by the transfer unit. Here, when the image to be secondarily transferred onto the recording medium is a color image made up of toners of multiple colors, the transfer means can be configured to sequentially overlay toners of each color on the intermediate transfer body to form an image on the intermediate transfer body, and the intermediate transfer means can secondarily transfer the image on the intermediate transfer body onto the recording medium all at once. The intermediate transfer body is not particularly limited and can be appropriately selected from known transfer bodies depending on the purpose, and a suitable example is a transfer belt.

[0214] The transfer means (the primary transfer means and the secondary transfer means) preferably includes at least a transfer device that peels and charges the visible image formed on the photosensitive member onto the recording medium. Examples of the transfer device include a corona transfer device that uses corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium is typically plain paper, but is not particularly limited as long as it can be used to transfer the unfixed image after development, and can be selected appropriately depending on the purpose. PET base for overhead projectors can also be used.

[0215] <<Fixing means and fixing process>> The fixing unit is not particularly limited as long as it can fix the transferred image on the recording medium, and can be appropriately selected depending on the purpose, but a known heating and pressing unit is preferred. Examples of the heating and pressing unit include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt. The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected depending on the purpose. For example, the fixing step may be performed for each color toner transferred to the recording medium, or may be performed simultaneously for each color toner in a stacked state.

[0216] The fixing step can be carried out by the fixing means. The heating temperature in the heating and pressing member is preferably 80° C. or higher and 200° C. or lower. In the present invention, depending on the purpose, a known optical fixing device may be used together with or in place of the fixing means. The surface pressure in the fixing step is not particularly limited and can be appropriately selected depending on the purpose. 2 More than 80N / cm 2 It is preferable that:

[0217] <<Cleaning means and cleaning process>> The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose, such as a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, or a web cleaner. The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose. For example, the cleaning step can be performed by the cleaning unit.

[0218] <<Static Charge Elimination Means and Static Charge Elimination Process>> The charge eliminating means is not particularly limited as long as it is a means for eliminating charges by applying a charge eliminating bias to the photosensitive member, and can be appropriately selected depending on the purpose. For example, a charge eliminating lamp can be used. The charge-eliminating step is not particularly limited as long as it is a step of applying a charge-eliminating bias to the photosensitive member to eliminate charges, and can be appropriately selected depending on the purpose. For example, it can be performed by the charge-eliminating unit.

[0219] <<Recycling methods and processes>> The recycling means is not particularly limited as long as it is a means for recycling the toner removed by the cleaning step into the developing device, and can be appropriately selected depending on the purpose. For example, known conveying means can be used. The recycling step is not particularly limited as long as it is a step of recycling the toner removed by the cleaning step into the developing device, and can be appropriately selected depending on the purpose. For example, it can be performed by the recycling means.

[0220] <<Control means and control process>> The control means is not particularly limited as long as it is a means capable of controlling the movement of each of the means, and can be appropriately selected depending on the purpose. Examples thereof include devices such as a sequencer and a computer. The control step is not particularly limited as long as it is a step that can control the movement of each step, and can be appropriately selected depending on the purpose, and can be performed, for example, by the control means.

[0221] Next, one embodiment of a method for forming an image using the image forming apparatus of the present invention will be described with reference to Fig. 2. The color image forming apparatus 100A shown in Fig. 2 includes a photosensitive drum 10 (hereinafter sometimes referred to as "photosensitive member 10") as the electrostatic latent image carrier, a charging roller 20 as the charging means, an exposure device 30 as the exposure means, a developing unit 40 as the developing means, an intermediate transfer body 50, a cleaning device 60 as the cleaning means having a cleaning blade, and a discharging lamp 70 as the discharging means.

[0222] The intermediate transfer body 50 is an endless belt that is designed to move in the direction of the arrow by three rollers 51 arranged inside and tensioning it. Some of the three rollers 51 also function as transfer bias rollers that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer body 50. A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer body 50. Also, a transfer roller 80 serving as the transfer means that can apply a transfer bias for transferring (secondary transfer) the developed image (toner image) to transfer paper 95 as a recording medium is arranged near the intermediate transfer body 50, facing the intermediate transfer body 50. A corona charger 58 for applying an electric charge to the toner image on the intermediate transfer body 50 is arranged around the intermediate transfer body 50, between the contact point between the photoreceptor 10 and the intermediate transfer body 50 and the contact point between the intermediate transfer body 50 and the transfer paper 95, in the direction of rotation of the intermediate transfer body 50.

[0223] The developing device 40 is composed of a developing belt 41 as the developer carrier, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C arranged around the developing belt 41. The black developing unit 45K includes a developer container 42K, a developer supply roller 43K, and a developing roller 44K. The yellow developing unit 45Y includes a developer container 42Y, a developer supply roller 43Y, and a developing roller 44Y. The magenta developing unit 45M includes a developer container 42M, a developer supply roller 43M, and a developing roller 44M. The cyan developing unit 45C includes a developer container 42C, a developer supply roller 43C, and a developing roller 44C. The developing belt 41 is an endless belt that is rotatably stretched around multiple belt rollers, and a portion of the belt is in contact with the electrostatic latent image carrier 10.

[0224] In the color image forming apparatus 100A shown in FIG. 2, for example, a charging roller 20 uniformly charges the photosensitive drum 10. An exposure device 30 exposes the photosensitive drum 10 to light in an imagewise manner to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 10 is developed by supplying toner from a developing device 40 to form a toner image. The toner image is transferred (primary transfer) onto an intermediate transfer body 50 by a voltage applied from a roller 51, and is further transferred (secondary transfer) onto a transfer paper 95. As a result, a transfer image is formed on the transfer paper 95. Any remaining toner on the photosensitive drum 10 is removed by a cleaning device 60, and the charge on the photosensitive drum 10 is temporarily removed by a discharging lamp 70.

[0225] Another example of the image forming apparatus of the present invention is shown in Figure 3. Image forming apparatus 100B has the same configuration as image forming apparatus 100A shown in Figure 2, except that it does not have developing belt 41 and has black developing unit 45K, yellow developing unit 45Y, magenta developing unit 45M, and cyan developing unit 45C arranged directly opposite each other around photosensitive drum 10.

[0226] Another example of the image forming apparatus of the present invention is shown in Fig. 4. The image forming apparatus 100C shown in Fig. 4 includes a copying machine main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400. An endless belt-like intermediate transfer member 50 is provided in the center of the copying machine main body 150. The intermediate transfer body 50 is stretched around support rollers 14, 15, and 16 and is rotatable clockwise in FIG. 4 . An intermediate transfer body cleaning device 17 for removing residual toner from the intermediate transfer body 50 is located near the support roller 15. A tandem developing device 120 is located around the intermediate transfer body 50, stretched around the support rollers 14 and 15, along the transport direction of the intermediate transfer body 50. Four image forming units 18 for yellow, cyan, magenta, and black are arranged side by side, facing each other. An exposure device 21, which serves as the exposure member, is located near the tandem developing device 120. A secondary transfer device 22 is located on the side of the intermediate transfer body 50 opposite the side where the tandem developing device 120 is located. In the secondary transfer device 22, an endless secondary transfer belt 24 is stretched around a pair of rollers 23, allowing the intermediate transfer body 50 and the transfer paper transported on the secondary transfer belt 24 to come into contact with each other. The fixing device 25, which is the fixing means, is disposed near the secondary transfer device 22. The fixing device 25 includes a fixing belt 26, which is an endless belt, and a pressure roller 27 that is disposed so as to be pressed against the fixing belt 26. In the tandem image forming apparatus, a sheet reversing device 28 is disposed near the secondary transfer device 22 and the fixing device 25 for reversing the transfer paper in order to form images on both sides of the transfer paper.

[0227] Next, we will explain how to form a full-color image (color copy) using the tandem developing device 120. That is, first, an original is set on the platen 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and the original is set on the contact glass 32 of the scanner 300, and then the automatic document feeder 400 is closed.

[0228] When the start switch is pressed, the scanner 300 is driven after the document is transported and moved onto the contact glass 32 when the document is set on the automatic document feeder 400, or immediately when the document is set on the contact glass 32. Then, the first travelling body 33 and the second travelling body 34 travel. At this time, light from a light source is irradiated by the first travelling body 33, and the light reflected from the document surface is reflected by a mirror on the second travelling body 34 and received by the reading sensor 36 through the imaging lens 35, and the color document (color image) is read, and image information of black, yellow, magenta, and cyan is generated.

[0229] The image information for black, yellow, magenta, and cyan is then transmitted to the image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120. Then, the toner images for black, yellow, magenta, and cyan are formed in the image forming means.

[0230] That is, as shown in FIG. 5, each image forming means 18 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing device 120 includes an electrostatic latent image carrier 10 (black electrostatic latent image carrier 10K, yellow electrostatic latent image carrier 10Y, magenta electrostatic latent image carrier 10M, and cyan electrostatic latent image carrier 10C), a charging device 160 which is the charging means for uniformly charging the electrostatic latent image carrier 10, and a charging unit 160 which is a charging unit for charging the electrostatic latent image carrier 10 based on each color image information. The device is equipped with an exposure device that exposes the electrostatic latent image carrier to light (L in FIG. 5) in the form of an image corresponding to each color image, thereby forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, a developing device 61 that is the developing means that develops the electrostatic latent image using each color toner (black toner, yellow toner, magenta toner, and cyan toner) to form a toner image using each color toner, a transfer charger 62 that transfers the toner image onto the intermediate transfer body 50, a cleaning device 63, and a static eliminator 64.

[0231] Each image forming unit 18 can form a single-color image (black image, yellow image, magenta image, and cyan image) based on the image information of the corresponding color. The black, yellow, magenta, and cyan images thus formed are sequentially transferred (primary transfer) onto an intermediate transfer body 50, which is rotated by support rollers 14, 15, and 16: the black image formed on the black electrostatic latent image carrier 10K, the yellow image formed on the yellow electrostatic latent image carrier 10Y, the magenta image formed on the magenta electrostatic latent image carrier 10M, and the cyan image formed on the cyan electrostatic latent image carrier 10C. The black, yellow, magenta, and cyan images are then superimposed on the intermediate transfer body 50 to form a composite color image (color transfer image).

[0232] Meanwhile, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in a paper bank 143. The sheets are separated one by one by a separation roller 145 and sent out to a paper feed path 146, then transported by a transport roller 147 and guided to a paper feed path 148 inside the copier main body 150, where they are stopped by striking against a registration roller 49. Alternatively, the paper feed roller 142 is rotated to feed out sheets (recording paper) from a manual feed tray 54, and the sheets are separated one by one by a separation roller 52 and placed in a manual feed path 53, where they are also stopped by striking against a registration roller 49. Note that the registration roller 49 is generally grounded when used, but may be used with a bias applied to remove paper dust from the sheets.

[0233] Then, the registration rollers 49 are rotated in time with the composite color image (color transfer image) formed on the intermediate transfer body 50, and a sheet (recording paper) is sent between the intermediate transfer body 50 and the secondary transfer device 22, and the composite color image (color transfer image) is transferred (secondary transfer) onto the sheet (recording paper) by the secondary transfer device 22. In this way, a color image is transferred and formed on the sheet (recording paper). After the image transfer, any remaining toner on the intermediate transfer body 50 is cleaned by the intermediate transfer body cleaning device 17.

[0234] The sheet (recording paper) onto which the color image has been transferred is transported by secondary transfer device 22 and sent to fixing device 25, where the composite color image (color transfer image) is fixed onto the sheet (recording paper) by heat and pressure. Thereafter, the sheet (recording paper) is switched by switching claw 55, discharged by discharge rollers 56, and stacked on paper output tray 57. Alternatively, the sheet can be switched by switching claw 55, inverted by sheet inverting device 28, and guided to the transfer position again, where an image is also recorded on the back side, and then discharged by discharge rollers 56 and stacked on paper output tray 57.

[0235] (Toner storage unit) The toner storage unit in the present invention refers to a unit having a function of storing toner and storing the toner. Examples of the toner storage unit include a toner storage container, a developing unit, and a process cartridge. The toner container refers to a container that stores toner. The developing device is a device that contains toner and has means for developing. The process cartridge is a device that integrates at least an image carrier and a developing means, contains toner, and is detachably mountable to an image forming apparatus. The process cartridge may further include at least one selected from a charging means, an exposure means, and a cleaning means.

[0236] By mounting the toner storage unit of the present invention in an image forming apparatus and forming an image using the toner of the present invention, both cleaning properties and low-temperature fixability can be achieved.

[0237] The toner container is not particularly limited and can be appropriately selected from known containers, such as those having a container body and a cap.

[0238] Furthermore, the size, shape, structure, material, etc. of the container body are not particularly limited and can be changed as appropriate. The shape is preferably cylindrical or the like, and spiral irregularities are formed on the inner circumferential surface, so that by rotating the container, the developer contained therein can be transferred to the outlet side. It is particularly preferable that part or all of the spiral irregularities have a bellows function.

[0239] Furthermore, the material is not particularly limited, but is preferably one with good dimensional accuracy, such as polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, etc.

[0240] The toner storage container is easy to store, transport, and handle, and can be detachably attached to a process cartridge, an image forming apparatus, or the like, and used to replenish toner.

[0241] An example of a process cartridge according to the present invention is molded so as to be detachably mountable to various image forming apparatuses, and includes at least an electrostatic latent image carrier that carries an electrostatic latent image, and developing means that develops the electrostatic latent image carried on the electrostatic latent image carrier with the developer of the present invention to form a toner image. The process cartridge of the present invention may further include other means, if necessary.

[0242] The developing means includes at least a developer container for containing the developer of the present invention and a developer carrier for carrying and transporting the developer contained in the developer container. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

[0243] An example of a process cartridge according to the present invention is shown in Figure 6. The process cartridge 110 includes the photosensitive drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90. [Example]

[0244] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. "Parts" means "parts by mass" unless otherwise specified. "%" means "% by mass" unless otherwise specified.

[0245] The measurements in the following examples were carried out by the methods described in the present specification. The Tg and molecular weight of amorphous polyester resin A, amorphous polyester resin B, crystalline polyester resin C, etc. were measured using the resins obtained in the production examples.

[0246] (Production Example 1) <Ketimine synthesis> A reaction vessel equipped with a stirrer and a thermometer was charged with 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone, and the mixture was reacted at 50°C for 5 hours to obtain [Ketimine Compound 1]. The amine value of [Ketimine Compound 1] was 418 mgKOH / g.

[0247] (Manufacturing example A-1) <Synthesis of amorphous polyester resin A-1> -Synthesis of Prepolymer A-1- 3-methyl-1,5-pentanediol, isophthalic acid, and plant-derived sebacic acid were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, along with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the hydroxyl to carboxyl molar ratio (OH / COOH) was 1.1, the diol component was 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component was 66 mol% isophthalic acid and 34 mol% sebacic acid, and the amount of trimethylolpropane in the total monomers was 1.5 mol%. The mixture was then heated to 200°C over approximately 4 hours, then to 230°C over 2 hours, and the reaction was continued until no water was discharged. The mixture was then further reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester A-1].

[0248] Next, the obtained [Intermediate Polyester A-1] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [Prepolymer A-1].

[0249] -Synthesis of amorphous polyester resin A-1- The resulting [Prepolymer A-1] was stirred in a reaction vessel equipped with a heater, stirrer, and nitrogen inlet tube. Further, [Ketimine Compound 1] was added dropwise to the reaction vessel in an amount such that the amine content of [Ketimine Compound 1] was equimolar to the amount of isocyanate in [Prepolymer A-1]. After stirring at 45°C for 10 hours, the prepolymer elongation product was removed. The resulting prepolymer elongation product was dried under reduced pressure at 50°C until the residual ethyl acetate content was 100 ppm or less, yielding [Amorphous Polyester Resin A-1]. The physical properties of this resin are listed in Table 1.

[0250] (Manufacturing example A-2) <Synthesis of amorphous polyester resin A-2> -Synthesis of prepolymer A-2- 3-methyl-1,5-pentanediol, isophthalic acid, and plant-derived sebacic acid were added to a reaction vessel equipped with a condenser, stirrer, and nitrogen inlet tube, along with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the hydroxyl to carboxyl molar ratio (OH / COOH) was 1.1, the diol component was 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component was 83 mol% isophthalic acid and 17 mol% sebacic acid, and the amount of trimethylolpropane in the total monomers was 1.5 mol%. The mixture was then heated to 200°C over approximately 4 hours, then to 230°C over 2 hours, and the reaction was continued until no water was discharged. The mixture was then further reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester A-2].

[0251] Next, the obtained [Intermediate Polyester A-2] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [Prepolymer A-2].

[0252] -Synthesis of amorphous polyester resin A-2- The resulting [Prepolymer A-2] was stirred in a reaction vessel equipped with a heater, stirrer, and nitrogen inlet tube. Further, [Ketimine Compound 1] was added dropwise to the reaction vessel in an amount such that the amine content of [Ketimine Compound 1] was equimolar to the amount of isocyanate in [Prepolymer A-2]. After stirring at 45°C for 10 hours, the prepolymer elongation product was removed. The resulting prepolymer elongation product was dried under reduced pressure at 50°C until the residual ethyl acetate content was 100 ppm or less, yielding [Amorphous Polyester Resin A-2]. The physical properties of this resin are listed in Table 1.

[0253] (Manufacturing example A-3) <Synthesis of amorphous polyester resin A-3> -Synthesis of prepolymer A-3- 3-methyl-1,5-pentanediol, isophthalic acid, and adipic acid were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, along with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the hydroxyl to carboxyl molar ratio (OH / COOH) was 1.1, the diol component was 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component was 50 mol% isophthalic acid and 50 mol% adipic acid, and the amount of trimethylolpropane in the total monomers was 1.5 mol%. The mixture was then heated to 200°C over approximately 4 hours, then to 230°C over 2 hours, and the reaction was continued until no water was discharged. The mixture was then further reacted for 5 hours under a reduced pressure of 10 to 15 mmHg to obtain [Intermediate Polyester A-3].

[0254] Next, the obtained [Intermediate Polyester A-3] and isophorone diisocyanate (IPDI) were added to a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube in a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0, diluted with ethyl acetate to make a 50% ethyl acetate solution, and reacted at 100°C for 5 hours to obtain [Prepolymer A-3].

[0255] -Synthesis of amorphous polyester resin A-3- The resulting [Prepolymer A-3] was stirred in a reaction vessel equipped with a heater, stirrer, and nitrogen inlet tube. Further, [Ketimine Compound 1] was added dropwise to the reaction vessel in an amount such that the amine content of [Ketimine Compound 1] was equimolar to the amount of isocyanate in [Prepolymer A-3]. After stirring at 45°C for 10 hours, the prepolymer elongation product was removed. The resulting prepolymer elongation product was dried under reduced pressure at 50°C until the residual ethyl acetate content was 100 ppm or less, yielding [Amorphous Polyester Resin A-3]. The physical properties of this resin are listed in Table 1.

[0256] [Table 1]

[0257] (Manufacturing example B-1) <Synthesis of amorphous polyester resin B-1> A four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple was charged with plant-derived propylene glycol, terephthalic acid, and plant-derived succinic acid in a molar ratio (terephthalic acid / succinic acid) of 86 / 14 and a molar ratio (OH / COOH) of 1.3 between hydroxyl and carboxyl groups. The mixture was then reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at atmospheric pressure and 230°C for 8 hours. After further reaction at a reduced pressure of 10-15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% relative to the total resin components, and the reaction was continued at 180°C, atmospheric pressure, and 3 hours to obtain [Amorphous Polyester Resin B-1]. The physical properties of this resin are listed in Table 2.

[0258] (Manufacturing example B-2) <Synthesis of amorphous polyester resin B-2> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, propylene glycol, bisphenol A propylene oxide 2-mol adduct, terephthalic acid, and plant-derived succinic acid were added in a molar ratio of 60 / 40 (propylene glycol / bisphenol A ethylene oxide 2-mol adduct) and 60 / 40 (terephthalic acid / succinic acid). The mixture was charged with titanium tetraisopropoxide (500 ppm based on the resin components) at atmospheric pressure and 230°C for 8 hours, and then reacted at a reduced pressure of 10-15 mmHg for 4 hours. After that, trimellitic anhydride was added to the reaction vessel at 1 mol% based on the total resin components, and the reaction was continued at 180°C, atmospheric pressure, and for 3 hours, yielding [Amorphous Polyester Resin B-2]. The physical properties of this resin are listed in Table 2.

[0259] (Manufacturing example B-3) <Synthesis of amorphous polyester resin B-3> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide 2-mol adduct, bisphenol A propylene oxide 2-mol adduct, terephthalic acid, and adipic acid were added to form a mixture in which the molar ratio of bisphenol A propylene oxide 2-mol adduct to bisphenol A ethylene oxide 2-mol adduct (bisphenol A propylene oxide 2-mol adduct / bisphenol A ethylene oxide 2-mol adduct) was 60 / 40, and the molar ratio of terephthalic acid to adipic acid was 60 / 40. The mixture was charged with adipic acid in a molar ratio (terephthalic acid / adipic acid) of 97 / 3, with a hydroxyl to carboxyl group molar ratio of OH / COOH of 1.3, and reacted with titanium tetraisopropoxide (500 ppm based on the resin components) at normal pressure and 230°C for 8 hours. After further reaction at a reduced pressure of 10-15 mmHg for 4 hours, trimellitic anhydride was added to the reaction vessel in an amount of 1 mol% based on the total resin components, and the reaction was continued at 180°C, normal pressure, and for 3 hours to obtain [Amorphous Polyester Resin B-3]. The physical properties of this resin are listed in Table 2.

[0260] [Table 2]

[0261] (Manufacturing example C-1) <Synthesis of crystalline polyester resin C-1> A 5L four-neck flask equipped with a nitrogen inlet, dehydration tube, stirrer, and thermocouple was charged with plant-derived sebacic acid and 1,6-hexanediol at a molar ratio of 0.9 (OH / COOH). The mixture was then reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at 180°C for 10 hours, then heated to 200°C for 3 hours, and then further reacted at 8.3 kPa for 2 hours to obtain [Crystalline Polyester Resin C-1]. The physical properties of this resin are listed in Table 3.

[0262] (Manufacturing example C2) <Synthesis of crystalline polyester resin C-2> Crystalline polyester resin C-2 was obtained in the same manner as in the synthesis of crystalline polyester resin C-1, except that the dicarboxylic acid was replaced with plant-derived dodecanedioic acid. The physical properties are shown in Table 3.

[0263] (Manufacturing example C-3) <Synthesis of crystalline polyester resin C-3> Crystalline polyester resin C-3 was obtained in the same manner as in the synthesis of crystalline polyester resin C-1, except that the diol was replaced with plant-derived ethylene glycol. The physical properties are shown in Table 3.

[0264] (Manufacturing example C-4) <Synthesis of crystalline polyester resin C-4> Crystalline polyester resin C-4 was obtained in the same manner as in the synthesis of Crystalline polyester resin C-1, except that the dicarboxylic acid was replaced with adipic acid. The physical properties are shown in Table 3.

[0265] (Manufacturing example C-5) <Synthesis of crystalline polyester resin C-5> Crystalline polyester resin C-5 was obtained in the same manner as in the synthesis of crystalline polyester resin C-1, except that the diol was replaced with 1,8-octanediol and the dicarboxylic acid was replaced with plant-derived tetradecanoic acid. The physical properties are shown in Table 3.

[0266] [Table 3]

[0267] <Preparation of Masterbatch (MB)> 1,200 parts of water, 500 parts of carbon black (Printex 35, manufactured by Dexa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], and 500 parts of [amorphous polyester resin B-1] were added and mixed in a Henschel mixer (manufactured by Nippon Coke and Engineering Co., Ltd.). The mixture was kneaded using two rolls at 150°C for 30 minutes, then rolled to cool and pulverized in a pulverizer to obtain [Masterbatch 1].

[0268] <Preparation of WAX Dispersion 1> In a container equipped with a stirring rod and a thermometer, 42 parts of carnauba wax (manufactured by Noda Ceramica, RN-5, plant-based wax, melting point 82°C) as [Release Agent 1] and 420 parts of ethyl acetate were charged. The temperature was raised to 80°C under stirring and held at 80°C for 5 hours, then cooled to 30°C over 1 hour. Using a bead mill (Ultraviscomill, manufactured by Imex Co., Ltd.), dispersion was carried out under the conditions of a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% volume filling with zirconia beads with a diameter of 0.5 mm, and 3 passes to obtain [WAX Dispersion 1]. The volume average particle size of the obtained wax particles was 420 nm, and the solid content concentration of the resin particles was 10%.

[0269] <Preparation of WAX Dispersion 2> To 720 parts of ion-exchanged water, 180 parts of ester wax (manufactured by NOF Corporation, WE-11, synthetic wax from plant-derived monomers, melting point 67°C) as [Release Agent 1] and 17 parts of an anionic surfactant (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Neogen SC, sodium dodecylbenzenesulfonate) as a surfactant were added. This was dispersed using a homogenizer while heating to 90°C to obtain [WAX Dispersion 2]. The volume average particle size of the obtained wax particles was 250 nm, and the solid content concentration of the resin particles was 25%.

[0270] <Preparation of WAX Dispersion 3> In a container equipped with a stirring rod and a thermometer, 50 parts of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-9, hydrocarbon-based wax, melting point 75°C, SP value 8.8) as [Release Agent 1] and 450 parts of ethyl acetate were charged. The temperature was raised to 80°C under stirring and held at 80°C for 5 hours, then cooled to 30°C over 1 hour. Using a bead mill (Ultraviscomill, manufactured by Imex Co., Ltd.), dispersion was carried out under the conditions of a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% volume filling with zirconia beads with a diameter of 0.5 mm, and 3 passes to obtain [WAX Dispersion 3]. The volume average particle size of the obtained wax particles was 350 nm, and the solid content concentration of the resin particles was 25%. The compositions and physical properties of WAX Dispersions 1 to 3 are shown in Table 4.

[0271] [Table 4]

[0272] <Preparation of Crystalline Polyester Resin Dispersion 1> A vessel equipped with a stirrer and thermometer was charged with 45 parts of [Crystalline Polyester Resin C-1] and 450 parts of ethyl acetate. The mixture was heated to 80°C with stirring, held at 80°C for 5 hours, then cooled to 30°C over 1 hour. The mixture was dispersed in a bead mill (Ultraviscomill, manufactured by Imex) at a feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% volumetric loading of 0.5 mm diameter zirconia beads, with three passes to obtain [Crystalline Polyester Resin Dispersion 1]. The volume average particle size of the resulting crystalline polyester resin particles was 350 nm, and the solids concentration of the resin particles was 10%.

[0273] <Preparation of Crystalline Polyester Resin Dispersion 2> A vessel equipped with a stirrer and thermometer was charged with 45 parts of [Crystalline Polyester Resin C-2] and 450 parts of ethyl acetate. The mixture was heated to 80°C with stirring, held at 80°C for 5 hours, then cooled to 30°C over 1 hour. The mixture was dispersed in a bead mill (Ultraviscomill, manufactured by Imex) at a feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% volumetric loading of 0.5 mm diameter zirconia beads, with three passes to obtain [Crystalline Polyester Resin Dispersion 2]. The volume average particle size of the resulting crystalline polyester resin particles was 350 nm, and the solids concentration of the resin particles was 10%.

[0274] <Preparation of Crystalline Polyester Resin Dispersion 3> A vessel equipped with a stirrer and thermometer was charged with 45 parts of [Crystalline Polyester Resin C-3] and 450 parts of ethyl acetate. The mixture was heated to 80°C with stirring, held at 80°C for 5 hours, then cooled to 30°C over 1 hour. The mixture was dispersed in a bead mill (Ultraviscomill, manufactured by Imex) at a feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% volumetric loading of 0.5 mm diameter zirconia beads, with three passes to obtain [Crystalline Polyester Resin Dispersion 3]. The volume average particle size of the resulting crystalline polyester resin particles was 360 nm, and the solids concentration of the resin particles was 10%.

[0275] <Preparation of Crystalline Polyester Resin Dispersion 4> 350 parts of [Crystalline Polyester Resin C-1], 210 parts of methyl ethyl ketone, and 61.8 parts of isopropyl alcohol were placed in a separable flask and thoroughly mixed and dissolved at 40°C. After this, 16.24 parts of 10% aqueous ammonia solution was added dropwise. The heating temperature was lowered to 65°C, and ion-exchanged water was added dropwise using a liquid pump at a rate of 8 g / min while stirring. After the liquid became uniformly cloudy, the rate was increased to 12 g / min. When the total liquid volume reached 1,400 parts, the addition of ion-exchanged water was stopped. The solvent was then removed under reduced pressure to obtain [Crystalline Polyester Resin Dispersion 4]. The volume average particle size of the resulting crystalline polyester resin particles was 160 nm, and the solids concentration of the resin particles was 30%.

[0276] <Preparation of Crystalline Polyester Resin Dispersion 5> A vessel equipped with a stirrer and thermometer was charged with 45 parts of [Crystalline Polyester Resin C-4] and 450 parts of ethyl acetate. The mixture was heated to 80°C with stirring, held at 80°C for 5 hours, then cooled to 30°C over 1 hour. The mixture was dispersed in a bead mill (Ultraviscomill, manufactured by Imex) at a feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% volumetric loading of 0.5 mm diameter zirconia beads, with three passes to obtain [Crystalline Polyester Resin Dispersion 5]. The volume average particle size of the resulting crystalline polyester resin particles was 340 nm, and the solids concentration of the resin particles was 10%.

[0277] <Preparation of Crystalline Polyester Resin Dispersion 6> A vessel equipped with a stirrer and thermometer was charged with 45 parts of [Crystalline Polyester Resin C-5] and 450 parts of ethyl acetate. The mixture was heated to 80°C with stirring, held at 80°C for 5 hours, then cooled to 30°C over 1 hour. The mixture was dispersed in a bead mill (Ultraviscomill, manufactured by Imex) at a feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% volumetric loading of 0.5 mm diameter zirconia beads, with three passes to obtain [Crystalline Polyester Resin Dispersion 6]. The volume average particle size of the resulting crystalline polyester resin particles was 340 nm, and the solids concentration of the resin particles was 10%.

[0278] Example 1 <Preparation of oil phase> 50 parts of [WAX Dispersion 1], 150 parts of [Amorphous Polyester Resin A-1], 50 parts of [Crystalline Polyester Resin Dispersion 1], 750 parts of [Amorphous Polyester Resin B-1], and 50 parts of [Masterbatch 1] (pigment) were placed in a container and mixed at 5,000 rpm for 60 minutes using a TK Homomixer (manufactured by Primix Corporation) to obtain [Oil Phase 1]. The above blending amounts indicate the blending amounts of solid content in each raw material.

[0279] <Preparation of aqueous phase> 990 parts of water, 20 parts of sodium dodecyl sulfate, and 90 parts of ethyl acetate were mixed and stirred to obtain a milky white liquid, which was designated as [aqueous phase 1].

[0280] <Emulsification> 700 parts of [Oil Phase 1] were stirred at 8,000 rpm using a TK Homomixer, and 20 parts of 28% aqueous ammonia were added. After mixing for 10 minutes, 1,200 parts of [Aqueous Phase 1] were gradually added dropwise to obtain [Emulsified Slurry 1].

[0281] <Solvent removal> [Emulsified slurry 1] was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed at 30° C. for 180 minutes, yielding [solvent-removed slurry 1].

[0282] <Agglutination> 100 parts of a 3% magnesium chloride solution was added dropwise to [Desolvated Slurry 1] and stirred for another 5 minutes, and then the temperature was raised to 60°C. When the particle size reached 5.0 μm, 50 parts of sodium chloride was added to terminate the aggregation process, and [Aggregated Slurry 1] was obtained.

[0283] <Fusion> [Agglomerated Slurry 1] was heated to 70° C. while stirring, and cooled when the desired average circularity of 0.957 was reached, to obtain [Dispersed Slurry 1].

[0284] <Washing and drying> After 100 parts of [Dispersion Slurry 1] was filtered under reduced pressure, (1) 100 parts of ion-exchanged water was added to the filter cake, and the mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered. (2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), and the mixture was mixed in a TK homomixer (at 12,000 rpm for 30 minutes), followed by filtration under reduced pressure. (3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), and the mixture was mixed in a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered. (4): 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. The above steps (1) to (4) were repeated twice to obtain [filter cake 1]. The filtered cake 1 was dried in a circulating air dryer at 45° C. for 48 hours and sieved through a mesh with 75 μm openings to obtain toner base particles 1.

[0285] <External additive processing process> 100 parts of [toner base particles 1] and 2.0 parts of hydrophobic silica (HDK-2000, manufactured by Clariant Co., Ltd.) as an external additive were mixed in a Henschel mixer, and the mixture was passed through a 500 mesh sieve to obtain [toner 1].

[0286] Example 2 [Toner 2] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was replaced with [Amorphous polyester resin A-2], the amount of [Amorphous polyester resin B-1] was changed to 800 parts, and [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 2].

[0287] Example 3 [Toner 3] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to 0 parts, [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-2], [Crystalline polyester resin dispersion 1] was changed to [Crystalline polyester resin dispersion 3], and [WAX dispersion 1] was changed to 0 parts, and in <Aggregation>, 40 parts of [WAX dispersion 2] was added initially.

[0288] Example 4 [Toner 4] was obtained in the same manner as in Example 1, except that in the <Preparation of Oil Phase> of Example 1, [Amorphous Polyester Resin A-1] was replaced with [Amorphous Polyester Resin A-3].

[0289] Example 5 [Toner 5] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], [Crystalline polyester resin dispersion 1] was replaced with 0 parts, and [WAX dispersion 1] was replaced with 0 parts, and in <Aggregation>, 50 parts of [Crystalline polyester resin dispersion 4] and 50 parts of [WAX dispersion 2] were added initially.

[0290] Example 6 [Toner 6] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], [Crystalline polyester resin dispersion 1] was changed to 100 parts, and [WAX dispersion 1] was replaced with [WAX dispersion 3].

[0291] Example 7 [Toner 7] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was replaced with [Amorphous polyester resin A-3], [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], and [WAX dispersion 1] was changed to 0 parts, and in <Aggregation>, 50 parts of [WAX dispersion 2] was added initially.

[0292] Example 8 [Toner 8] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was replaced with [Amorphous polyester resin A-3], [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], [Crystalline polyester resin dispersion 1] was changed to 130 parts, and [WAX dispersion 1] was replaced with [WAX dispersion 3].

[0293] Example 9 [Toner 9] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was changed to 300 parts, [Amorphous polyester resin B-1] was changed to [Amorphous polyester resin B-2], [Crystalline polyester resin dispersion 1] was changed to 100 parts of [Crystalline polyester resin dispersion 3], and [WAX dispersion 1] was changed to 0 parts, and in <Aggregation>, 40 parts of [WAX dispersion 2] was added initially.

[0294] Example 10 [Toner 10] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was replaced with [Amorphous polyester resin A-3] and [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-2].

[0295] (Comparative Example 1) [Toner 11] was obtained in the same manner as in Example 1, except that in the <Preparation of Oil Phase> of Example 1, [Crystalline Polyester Resin Dispersion 1] was replaced with [Crystalline Polyester Resin Dispersion 6].

[0296] (Comparative Example 2) [Toner 12] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was replaced with [Amorphous polyester resin A-3], [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], and [Crystalline polyester resin dispersion 1] was replaced with 20 parts of [Crystalline polyester resin dispersion 6].

[0297] (Comparative Example 3) [Toner 13] was obtained in the same manner as in Example 1, except that in the <Preparation of Oil Phase> of Example 1, [Crystalline Polyester Resin Dispersion 1] was replaced with [Crystalline Polyester Resin Dispersion 6] and [WAX Dispersion 1] was replaced with [WAX Dispersion 3].

[0298] Comparative Example 4 [Toner 14] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-2] and the amount was increased to 700 parts, and [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 5].

[0299] (Comparative Example 5) [Toner 15] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Crystalline polyester resin dispersion 1] was replaced with 5 parts of [Crystalline polyester resin dispersion 5], and in <Fusion>, the temperature was changed from 70°C to 60°C.

[0300] (Comparative Example 6) [Toner 16] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was replaced with [Amorphous polyester resin A-3], [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 5], and [WAX dispersion 1] was replaced with [WAX dispersion 3].

[0301] (Comparative Example 7) [Toner 17] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], [Crystalline polyester resin dispersion 1] was replaced with [Crystalline polyester resin dispersion 6], and [WAX dispersion 1] was replaced with [WAX dispersion 2].

[0302] (Comparative Example 8) [Toner 18] was obtained in the same manner as in Example 1, except that in <Preparation of oil phase> of Example 1, [Amorphous polyester resin A-1] was replaced with [Amorphous polyester resin A-3], [Amorphous polyester resin B-1] was replaced with [Amorphous polyester resin B-3], [Crystalline polyester resin dispersion 1] was replaced with 1 part, [WAX dispersion 1] was replaced with [WAX dispersion 3], and in <Fusion>, the temperature was changed from 70°C to 25°C.

[0303] Comparative Example 9 Instead of the <emulsification> step of Example 1, 1,200 parts of [Aqueous Phase 1] was added to a container containing [Oil Phase 1], and mixed with a TK Homomixer at 8,000 rpm for 20 minutes to obtain [Emulsified Slurry 2]. Instead of the <solvent removal> step, [Emulsified Slurry 2] was placed in a container equipped with a stirrer and a thermometer, and the solvent was removed at 30°C for 8 hours, followed by aging at 45°C for 4 hours to obtain [Dispersed Slurry 2]. No <aggregation> or <fusion> processes. <Washing and Drying> The subsequent steps were the same as in Example 1 to obtain [Toner 19].

[0304] Table 5 shows the composition of the oil phase components and the characteristics of the aggregation, emulsification, and desolvation processes in the examples and comparative examples.

[0305] [Table 5]

[0306] Crystalline polyester major axis, aspect ratio, and radioisotope for each toner 14 The combinations of C concentrations are shown in Table 6.

[0307] [Table 6]

[0308] <Method for measuring the average long diameter and average aspect ratio of crystalline polyester> The average major axis and average aspect ratio of the crystalline polyester of the toner were measured according to the following method. The toner was embedded in a visible light-curable embedding resin (D-800, Nissin EM Co., Ltd.), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, Leica), and then stained with Ru using a vacuum staining device (Filgen). Observation was then performed using a transmission electron microscope (H7500, Hitachi Co., Ltd.) at an accelerating voltage of 120 kV. 50 toner particles within ±2.0 μm of the weight-average particle size were selected for observation and photographed. In the configuration of the present invention, RuO4 staining resulted in a darker shade of the polyester resin C in the toner, and when wax was used, the wax was projected even darker. The average long diameter and average aspect ratio of the domains composed of polyester resin C can be determined from the observed image, but the average aspect ratio can be calculated using image processing software if necessary.

[0309] Image-Pro Plus 5.1J (Media Cybernetics) was used as the image processing software. Cross-sectional images of toner particles captured using the method described above were used. First, to extract the toner particles to be analyzed, the toner particle area was selected to separate the toner particles from the background. In Image-Pro Plus 5.1J, select "Measurement" - "Count / Size." From the "Count / Size" window, select "Measurement" - "Measurement Items." From the measurement items, select "Diameter (Minimum)" and "Diameter (Maximum)." In "Brightness Range Selection," the brightness range must be adjusted so that only polyester resin A is selected. Depending on the RuO4 staining conditions, the brightness range may need to be changed each time, but polyester resin A can be easily identified by the aforementioned difference in shading. Select "Count" to display the measurement results. The aspect ratio (major diameter / minor diameter) can then be calculated by using the obtained "Diameter (Minimum)" as the minor axis and the "Diameter (Maximum)" as the major axis. From the aspect ratio data for one toner particle thus obtained, the average value of 10 points in descending order of diameter (maximum) was calculated, and this was repeated for 10 toner particles to obtain the average aspect ratio.

[0310] <Radioisotope 14 C concentration measurement method> Radiocarbon isotopes in toner 14 The C concentration was measured by radiocarbon dating. The toner was burned, and the CO2 (carbon dioxide) was reduced to obtain C (graphite). 14 The C concentration was measured using AMS (Accelerator Mass Spectroscopy, Beta Analytic).

[0311] <Evaluation> The obtained toner was evaluated as follows, and the results are shown in Table 7.

[0312] <<Carbon neutrality>> Radioactive isotopes in toner 14 Carbon neutrality was evaluated based on the C concentration.

[0313] [Evaluation criteria] ◎: 40.0pMC or more ○: 20.0 pMC or more and less than 40.0 pMC △: 5.4pMC or more and less than 20.0pMC ×: Less than 5.4 pMC

[0314] <<Low temperature fixability>> The carrier used in imagio MP C5503 (manufactured by Ricoh Co., Ltd.) and the toner obtained above were mixed so that the toner concentration was 5% by mass, thereby obtaining [Developer 1]. After adding [Developer 1] to the unit of the imagio MP C5503 (manufactured by Ricoh Co., Ltd.), a 2cm x 15cm rectangular solid image was printed on PPC paper type 6000<70W>A4 T (manufactured by Ricoh Co., Ltd.) with a toner adhesion of 0.40mg / cm 2 At this time, the surface temperature of the fixing roller was changed, and it was observed whether cold offset, in which a residual image of a solid image is fixed in a location other than the desired location, occurred, and the low-temperature fixability was evaluated.

[0315] [Evaluation criteria] ◎: Less than 110℃ ○: 110℃ or higher but lower than 120℃ △: 120℃ or higher but lower than 130℃ ×: 130℃ or higher

[0316] <Cleaning performance evaluation> The carrier used in the imagio MP C5503 (manufactured by Ricoh Co., Ltd.) was mixed with the toner obtained above to give a toner concentration of 5% by mass to obtain a developer. After the developer was loaded into the unit of the imagio MP C5503 (manufactured by Ricoh Co., Ltd.), an image with an image area ratio of 30% was developed and transferred to transfer paper. After that, the copier was stopped while the residual toner remaining on the photoreceptor was being cleaned with a cleaning blade. The residual toner on the photoreceptor that had passed the cleaning process was transferred to white paper with Scotch tape (manufactured by Sumitomo 3M Limited). Ten points on this were measured using a Macbeth reflection densitometer RD514. The difference between the average value and the measurement result when simply applying tape to white paper was determined and evaluated according to the following criteria. The cleaning blade used had been used after cleaning 20,000 sheets.

[0317] [Evaluation criteria] ◎: Difference is 0.010 or less ○: Difference is more than 0.010 and less than 0.012 △: Difference is more than 0.012 and less than 0.015 ×: Difference exceeds 0.015

[0318] The evaluation results are shown in Table 7.

[0319] [Table 7]

[0320] The present invention relates to the toner described in (1) below, but also includes the following (2) to (15) as embodiments. (1) Resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant, the acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms, the domains of the crystalline polyester resin have an average major axis of 2.0 μm or less, and an average aspect ratio (major axis / minor axis) of 4.0 or more; radioactive carbon isotopes 14Resin particles characterized by having a C concentration of 5.4 pMC or more. (2) Radiocarbon isotopes 14 The resin particles according to (1) above, having a C concentration of 20.0 pMC or more. (3) Radiocarbon isotopes 14 The resin particles according to (1) or (2) above, wherein the C concentration is 40.0 pMC or more. (4) Resin particles according to any one of (1) to (3) above, wherein the acid component of the amorphous polyester resin contains either succinic acid or sebacic acid, which are derived from plants. (5) Resin particles according to any one of (1) to (4) above, wherein the alcohol component of the crystalline polyester resin is a diol having 8 or less carbon atoms. (6) Resin particles according to any one of (1) to (5) above, wherein the alcohol component of the crystalline polyester resin contains any one of 1,6-hexanediol, 1,8-octanediol, and plant-derived ethylene glycol. (7) Resin particles according to any one of (1) to (6) above, wherein the release agent for the amorphous polyester resin is a plant-based wax or an ester wax made from a plant-derived material. (8) Resin particles for toner, characterized by containing the resin particles according to any one of (1) to (7) above. (9) A toner characterized by containing the resin particles for toner described in (8) above. (10) The toner according to (9) above, wherein an external additive is further added to the toner resin particles. (11) a) A step of preparing an oil phase by dissolving or dispersing at least a crystalline polyester resin, an amorphous polyester resin, and a colorant in an organic solvent. b) adding water to the oil phase to invert the water-in-oil dispersion into an oil-in-water dispersion c) aggregating the particles of the oil-in-water dispersion Including, The method for producing resin particles according to any one of (1) to (8) above, wherein a release agent is added in the step a) or the step c). (12) a) A step of preparing an oil phase by dissolving or dispersing at least an amorphous polyester resin and a colorant in an organic solvent. b) adding water to the oil phase to invert the water-in-oil dispersion into an oil-in-water dispersion c) adding a crystalline polyester resin to the oil-in-water dispersion to aggregate the particles; Including, The method for producing resin particles according to any one of (1) to (8) above, wherein a release agent is added in the step a) or the step c). (13) A method for producing a toner, comprising adding an external additive to the resin particles obtained by the method for producing resin particles according to (11) or (12) above. (14) A developer containing the toner described in (9) or (10) above. (15) A toner storage unit containing the toner according to (9) or (10) above. (16) An electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, and a developing means having a toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image, An image forming apparatus, wherein the toner is the toner described in (9) or (10) above. [Explanation of symbols]

[0321] 10 Photoconductor, photoconductor drum, electrostatic latent image carrier 10K black electrostatic latent image carrier 10Y Yellow electrostatic latent image carrier 10M Magenta electrostatic latent image carrier 10C Cyan electrostatic latent image carrier 14 Support roller 15 Support roller 16 Support roller 17 Intermediate transfer body cleaning device 18 Image forming means 20 Charging device (charging roller) 21 Exposure equipment 22 Secondary transfer device 23 Laura 24 Secondary transfer belt 25 Fixing device 26 Fixing belt 27 Pressure roller 28 Sheet inverting device 30 Exposure equipment 32 Contact Glass 33 First running body 34 Second running body 35 Imaging lens 36 reading sensor 40 Developer 41 Developing belt 42K Developer compartment 42Y Developer storage unit 42M Developer compartment 42C Developer storage unit 43K Developer supply roller 43Y Developer supply roller 43M Developer supply roller 43C Developer supply roller 44K developing roller 44Y developing roller 44M developing roller 44C Developing roller 45K Black Development Unit 45Y Yellow Development Unit 45M Magenta Development Unit 45C Cyan Development Unit 49 Registration roller 50 Intermediate transfer body 51 Laura 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Paper output tray 58 Corona charger 60 Cleaning Device 61 Developing device 62 Transfer charger 63 Photoconductor cleaning device 64 Static eliminator 70 Static elimination lamp 80 Transfer roller 90 Cleaning Device 95 Transfer paper 100A, 100B, 100C image forming device 110 Process cartridge 120 Tandem developing unit 130 manuscript table 142 Paper feed roller 143 Paper Bank 144 Paper cassette 145 Separation roller 146 Paper feed path 147 Conveyor roller 148 Paper feed path 150 Copying device body 160 Charging device 200 Paper feed table 300 scanner 400 Automatic Document Feeder (ADF) L exposure [Prior art documents] [Patent documents]

[0322] [Patent Document 1] Patent No. 3343635 [Patent Document 2] Patent No. 2909873 [Patent Document 3] Patent No. 5473252 [Patent Document 4] Patent No. 5984528 [Patent Document 5] Japanese Patent Application Publication No. 2018-072454

Claims

1. Resin particles containing at least a crystalline polyester resin, an amorphous polyester resin, a release agent, and a colorant, the acid component of the crystalline polyester resin is a plant-derived dicarboxylic acid having 12 or less carbon atoms, The amorphous polyester resin contains trimethylolpropane as a constituent component, the acid component of the amorphous polyester resin contains either succinic acid or sebacic acid, which are derived from plants; the domains of the crystalline polyester resin have an average major axis of 2.0 μm or less and an average aspect ratio (major axis / minor axis) of 4.0 or more; radioactive carbon isotopes １４ Resin particles characterized in that the C concentration is 5.4 pMC or more.

2. radioactive carbon isotopes １４ 2. The resin particles according to claim 1, wherein the C concentration is 20.0 pMC or more.

3. The resin particles according to claim 1 or 2, wherein the glass transition temperature [Tg2nd (THF insolubles)] of the tetrahydrofuran (THF) insolubles of the resin particles at the second temperature rise in differential scanning calorimetry (DSC) is -40°C or higher and 30°C or lower.

4. 4. The resin particles according to claim 1, wherein the alcohol component of the crystalline polyester resin is a diol having 8 or less carbon atoms.

5. 5. The resin particles according to claim 1, wherein the alcohol component of the crystalline polyester resin contains any one of 1,6-hexanediol, 1,8-octanediol, and plant-derived ethylene glycol.

6. 6. The resin particles according to claim 1, wherein the release agent for the amorphous polyester resin is a plant-based wax or an ester wax made from a plant-derived material.

7. A resin particle for a toner, comprising the resin particle according to claim 1 .

8. A toner comprising the resin particles for toner according to claim 7.

9. The toner according to claim 8 , wherein an external additive is further added to the toner resin particles.

10. a) a step of preparing an oil phase in which at least a crystalline polyester resin containing a plant-derived dicarboxylic acid having 12 or less carbon atoms as an acid component, an amorphous polyester resin containing either a plant-derived succinic acid or a plant-derived sebacic acid as an acid component, and a colorant are dissolved or dispersed in an organic solvent; b) adding water to the oil phase to invert the water-in-oil dispersion into an oil-in-water dispersion c) agglomerating the particles of the oil-in-water dispersion Including, The method for producing resin particles according to claim 1 , wherein a release agent is added in the step a) or the step c).

11. a) a step of preparing an oil phase in which at least an amorphous polyester resin containing either succinic acid or sebacic acid, which is derived from a plant, as an acid component and a colorant are dissolved or dispersed in an organic solvent; b) adding water to the oil phase to invert the water-in-oil dispersion into an oil-in-water dispersion c) adding a crystalline polyester resin containing a plant-derived dicarboxylic acid having 12 or less carbon atoms as an acid component to the oil-in-water dispersion, and aggregating the particles; Including, The method for producing resin particles according to claim 1 , wherein a release agent is added in the step a) or the step c).

12. A method for producing a toner, comprising adding an external additive to the resin particles obtained by the method for producing resin particles according to claim 10 or 11.

13. A developer comprising the toner according to claim 8 or 9.

14. A toner storage unit containing the toner according to claim 8 or 9.

15. an electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier; and a developing means having a toner for developing the electrostatic latent image formed on the electrostatic latent image carrier to form a visible image; 10. An image forming apparatus, wherein the toner is the toner according to claim 8.

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