Toner and method for manufacturing the same, toner storage unit, image forming apparatus, image forming method, and method for manufacturing print

Abstract

To provide a toner that is excellent in low temperature fixability and can prevent filming even in a high temperature and high humidity environment.SOLUTION: A toner contains a polyester resin and a styrene resin. When the maximum peak height at 789 cm-1 to 852 cm-1 in the FT-IR spectrum of the toner measured by the ATR method is defined as W1, and the maximum peak height at 710 cm-1 to 690 cm-1 in the FT-IR spectrum of the toner measured by the ATR method is defined as R1, the peak ratio [R1 / W1] is 1.00 or more and 2.00 or less. When the maximum peak height at 789 cm-1 to 852 cm-1 in the FT-IR spectrum of the toner measured by the KBr method is defined as W2, and the maximum peak height at 710 cm-1 to 690 cm-1 in the FT-IR spectrum of the toner measured by the KBr method is defined as R2, the peak ratio [R2 / W2] is 0.80 or more and 1.20 or less.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Conventionally, in electrophotographic devices, electrostatic recording devices, and the like, an electric latent image or a magnetic latent image is visualized by a toner for developing an electrostatic latent image (also referred to as "toner" in the present invention). For example, in electrophotography, an electrostatic latent image is formed on a photoconductor, and then the electrostatic latent image is developed with a toner to form a toner image. The toner image is usually transferred onto a recording medium such as paper, and fixed by a method such as heating.

[0003] In recent years, there has been a demand for low-temperature fixing of toners in order to save energy by reducing the energy required for fixing. Furthermore, due to the demand for high-speed and high-image quality of image forming apparatuses, coupled with the diversification of the purposes of use of image forming apparatuses, there is an increasing demand for low-temperature fixing of toners. As a method for low-temperature fixing of toners, a technique of using an amorphous polyester resin and a crystalline polyester resin in combination is known.

[0004] For example, a pulverized toner has been disclosed that is manufactured by pulverizing and classifying a composition in which a styrene resin having a mass average molecular weight (Mw) of more than 3000 is internally added to a mixture of a binder resin and a colorant, with the aim of providing a toner that is excellent in pulverizability during production and excellent in fixing stability (see, for example, Patent Document 1). Also, a pulverized toner has been disclosed that specifies the maximum peak ratio of polyester resin and styrene resin by FT-IR with the aim of providing a pulverized toner that can achieve both low-temperature fixing property and heat-resistant storage stability (see, for example, Patent Document 2). Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a toner which is excellent in low-temperature fixing property and can suppress filming even in a high-temperature and high-humidity environment. [Means for solving the problem]

[0006] The toner of the present invention as a means for solving the above problems is A toner comprising a polyester resin and a styrene resin, 789 cm of the FT-IR spectrum of the toner measured by the ATR method -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the ATR method is defined as W1. -1 ~690cm -1 When the maximum peak height at is R1, The peak ratio [R1 / W1] is 1.00 or more and 2.00 or less, 789 cm of the FT-IR spectrum of the toner measured by the KBr method -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the KBr method is defined as W2. -1 ~690cm -1 When the maximum peak height at is R2, The peak ratio [R2 / W2] is characterized by being 0.80 or more and 1.20 or less. Effect of the Invention

[0007] According to the present invention, it is possible to provide a toner which has excellent low-temperature fixing properties and is capable of suppressing filming even in a high-temperature and high-humidity environment. [Brief description of the drawings]

[0008] [Figure 1] 1 is a schematic explanatory diagram for explaining an embodiment of an image forming apparatus of the present invention; [Diagram 2] FIG. 11 is a schematic explanatory diagram for explaining another embodiment of the image forming apparatus of the present invention. [Diagram 3] FIG. 11 is a schematic explanatory diagram for explaining still another embodiment of the image forming apparatus of the present invention. [Figure 4] FIG. 2 is a schematic explanatory diagram for explaining an image forming unit. [Diagram 5] FIG. 2 is a schematic diagram illustrating an example of a process cartridge according to an embodiment of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Conventional toners including those described in Patent Documents 1 and 2 above are concerned about problems such as image defects caused by filming, in which wax or polyester resin with low heat resistance exposed on the toner surface adheres to the photoreceptor. Such problems are particularly noticeable in high-temperature and high-humidity environments, and may cause similar image defects even when the printing area is small.

[0010] In contrast to the above-mentioned conventional techniques, the toner of the present invention contains a polyester resin and a styrene resin, and has a 789 cm -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the ATR method is defined as W1. -1 ~690cm -1 When the maximum peak height in the toner is R1, the peak ratio [R1 / W1] is 1.00 or more and 2.00 or less, and the 789 cm -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the KBr method is defined as W2. -1 ~690cm -1 When the maximum peak height in is R2, the peak ratio [R2 / W2] is 0.80 or more and 1.20 or less, thereby making it possible to eliminate the above-mentioned problems. More specifically, when the toner of the present invention has the above-mentioned specific peak ratio, it is possible to provide excellent low-temperature fixing property and suppress filming even in a high-temperature and high-humidity environment.

[0011] The present invention will now be described in detail.

[0012] (toner) The toner of the present invention contains a polyester resin and a styrene resin, and may contain a colorant, an external additive, and other components, as necessary. The toner of the present invention has a specific molecular weight of 789 cm in the FT-IR spectrum of the toner measured by the ATR method. -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the ATR method is defined as W1. -1 ~690cm -1 When the maximum peak height in the toner is R1, the peak ratio [R1 / W1] is 1.00 or more and 2.00 or less, and the maximum peak height in the toner measured by the KBr method is 789 cm -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the KBr method is defined as W2. -1 ~690cm -1 When the maximum peak height in is R2, the peak ratio [R2 / W2] is 0.80 or more and 1.20 or less. In this specification, the term "the 789 cm FT-IR spectrum of the toner measured by the ATR method" -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the ATR method is sometimes simply referred to as “W1”. -1 ~690cm -1 The maximum peak height at 789 cm in the FT-IR spectrum of the toner measured by the KBr method is sometimes simply referred to as “R1”. -1 ~852cm -1 The maximum peak height at 710 cm in the FT-IR spectrum of the toner measured by the KBr method is sometimes simply referred to as “W2”. -1 ~690cm -1"Maximum peak height at" is sometimes simply referred to as "R2". In addition, when multiple peaks exist in a particular FT-IR spectrum, the highest peak among them is taken as the maximum peak height.

[0013] In this specification, "FT-IR" means a Fourier transform infrared spectrometer. In this specification, the term "ATR method" refers to the attenuated total reflection method. In this specification, "KBr method" refers to the permeation method (KBr (potassium bromide) tablet method).

[0014] In the FT-IR spectrum, -1 ~852cm -1 The spectrum at 710 cm is derived from the polyester resin. -1 ~690cm -1 The spectrum at is a spectrum derived from styrene resin. The ATR method allows the qualitative and quantitative analysis of the substances present on the toner surface, while the KBr method allows the qualitative and quantitative analysis of the entire toner. That is, the peak ratio [R1 / W1] being 1.00 or more and 2.00 or less, and the peak ratio [R2 / W2] being 0.80 or more and 1.20 or less, means that the styrene resin is unevenly distributed on the toner surface. In such a toner, the styrene resin, which has excellent heat resistance and grindability, is exposed to the outermost surface of the toner, and a material with low heat resistance such as wax is encapsulated, so that the toner exhibits excellent low-temperature fixing property and heat-resistant storage stability.

[0015] The peak ratio [R1 / W1] is equal to or greater than 1.00 and equal to or less than 2.00, and preferably equal to or greater than 1.20 and equal to or less than 1.50. When the peak ratio [R1 / W1] is 1.00 or more, a sufficient amount of styrene resin is present on the toner surface, so that in a high temperature and high humidity environment, filming occurs in which the polyester resin adheres to the photoreceptor, and the occurrence of abnormal images such as black streak images can be suppressed. When the peak ratio [R1 / W1] is 2.00 or less, the amount of styrene resin present on the toner surface is appropriate, so that the toner is less likely to melt and the occurrence of problems such as poor fixing can be suppressed.

[0016] The peak ratio [R2 / W2] is not less than 0.80 and not more than 1.20, and preferably not less than 0.90 and not more than 1.10. When the peak ratio [R2 / W2] is 0.80 or more, when an image with a low image area ratio is printed, the amount of polyester resin having excellent low-temperature fixing properties present in the toner increases, and the toner melts due to frictional heat, which can prevent filming on the photoconductor. When the peak ratio [R2 / W2] is 1.20 or less, the toner has appropriate thermal properties, and the occurrence of problems such as poor fixing can be suppressed.

[0017] There are no particular limitations on the method for controlling the peak ratio [R1 / W1] to be 1.00 or more and 2.00 or less, and the peak ratio [R2 / W2] to be 0.80 or more and 1.20 or less. For example, a method of appropriately adjusting the amount of styrene resin, which is easily pulverizable, added in the toner production process may be mentioned. The amount of the styrene resin added can be appropriately adjusted depending on the material of the toner. Although details will be described later, the amount of the styrene resin added in the production process of the toner base particles is preferably 5 parts by mass or more and 10 parts by mass or less when the total amount of the toner base particles is 100 parts by mass.

[0018] In the present invention, the method for measuring the "FT-IR spectrum" is not particularly limited and can be appropriately selected depending on the purpose, and can be measured, for example, using Thermo Nicolet NEXUS470 (manufactured by Thermo Scientific). An example of the measurement method is described below. [An example of how to measure FT-IR spectrum] Measurement equipment: Thermo Nicolet NEXUS470 (manufactured by Thermo SCIENTIFIC) ·Resolution: 4cm -1 -Sample integration count: 16Scans Background integration count: 16 scans ·Saved wavenumber range: 4000~400cm -1 From the FT-IR spectrum obtained under the above measurement conditions, -1 Perform baseline correction in the range of 800 to 600 cm to obtain the maximum peak value of polyester. -1 Baseline correction is performed within the range, and the maximum peak value of the styrene resin is obtained.

[0019] <Polyester resin> The polyester resin is not particularly limited and can be appropriately selected depending on the purpose. From the viewpoint of further improving thermal properties, it is preferable to use a mixture of a crystalline polyester resin and a non-crystalline polyester resin.

[0020] <<Crystalline polyester resin>> The crystalline polyester resin (hereinafter, sometimes referred to as "crystalline polyester resin C") has high crystallinity and exhibits a thermal melting property that shows a sudden change in viscosity near the fixing start temperature. When the crystalline polyester resin having such a property is used together with a non-crystalline polyester resin, the heat-resistant storage stability is good due to the crystallinity until just before the melting start temperature, and at the melting start temperature, a sudden viscosity drop (sharp melt property) occurs due to the melting of the crystalline polyester resin. Accordingly, the crystalline polyester resin is compatible with the non-crystalline polyester resin and is fixed by a sudden drop in viscosity, so that a toner having both good heat-resistant storage stability and low-temperature fixing property can be obtained. In addition, the release width (the difference between the minimum fixing temperature and the temperature at which high-temperature offset occurs) is also favorable.

[0021] The crystalline polyester resin can be obtained from a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic ester. In the present invention, the crystalline polyester resin refers to a resin obtained from a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic ester, as described above, and modified polyester resins (for example, prepolymers described below, and resins obtained by subjecting the prepolymers to a crosslinking and / or elongation reaction) do not belong to the crystalline polyester resin.

[0022] -Polyhydric alcohol- The polyhydric alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polyhydric alcohol include diols and trihydric or higher alcohols. Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diols include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferred from the viewpoint of preventing a decrease in melting point due to a decrease in crystallinity, and linear saturated aliphatic diols having a carbon number of 2 to 12 are more preferred from the viewpoint of availability.

[0023] 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 the crystalline polyester resin has high crystallinity and excellent sharp melt properties. These may be used alone or in combination of two or more.

[0024] Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, etc. These alcohols may be used alone or in combination of two or more.

[0025] -Polycarboxylic acids- The polycarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include dicarboxylic acids, tri- or higher carboxylic acids, etc. These polycarboxylic acids may be used alone or in combination of two or more.

[0026] Examples of the divalent carboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid; and aromatic dicarboxylic acids such as dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid. Furthermore, anhydrides of these acids and lower (carbon number 1 to 3) alkyl esters of these acids can also be used.

[0027] Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, etc. Furthermore, anhydrides of these acids and lower (carbon number 1 to 3) alkyl esters of these acids can also be used.

[0028] As the polyvalent carboxylic acid, in addition to saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, dicarboxylic acids having a sulfonic acid group and dicarboxylic acids having a double bond may be used.

[0029] The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. This is preferable in that the resin has high crystallinity and excellent sharp melting properties, and can therefore exhibit excellent low-temperature fixability.

[0030] The melting point of the crystalline polyester resin 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 of the crystalline polyester resin is 60° C. or higher, it is possible to suppress a decrease in the heat-resistant storage stability of the toner, which is caused by the crystalline polyester resin melting at a low temperature, and this is preferable. When the melting point of the crystalline polyester resin is 80° C. or less, it is possible to suppress a decrease in low-temperature fixability of the toner caused by insufficient melting of the crystalline polyester resin due to heating during fixation, which is preferable.

[0031] The molecular weight of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose. However, from the viewpoint that a resin having a sharp molecular weight distribution and a low molecular weight has excellent low-temperature fixability, and from the viewpoint that a large amount of low-molecular-weight components reduces heat-resistant storage stability, it is preferable that the ortho-dichlorobenzene-soluble portion of the crystalline polyester resin has a weight average molecular weight (Mw) of 3,000 or more and 30,000 or less, a number average molecular weight (Mn) of 1,000 or more and 10,000 or less, and an Mw / Mn ratio of 1.0 or more and 10 or less, as measured by gel permeation chromatography (GPC). Furthermore, it is more preferable that the orthodichlorobenzene soluble matter in the crystalline polyester resin has a weight average molecular weight (Mw) of 5,000 or more and 15,000 or less, a number average molecular weight (Mn) of 2,000 or more and 10,000 or less, and an Mw / Mn ratio of 1.0 or more and 5.0 or less, as measured by gel permeation chromatography (GPC).

[0032] The number average molecular weight (Mn) and the weight average molecular weight (Mw) can be measured by gel permeation chromatography (GPC) under the following conditions, for example. --Measurement conditions-- Equipment (example): "HLC-8120" (manufactured by Tosoh Corporation) Column (example): 2 "TSK GEL GMH6" (Tosoh Corporation) ·Measurement temperature: 40℃ Sample solution: 0.25% by weight tetrahydrofuran solution (undissolved matter was removed using a glass filter) ·Solution injection volume: 100μl Detector: Refractive index detector Reference material: 12 standard polystyrenes (TSKstandard POLYSTYRENE) (molecular weight: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) (manufactured by Tosoh Corporation)

[0033] The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of the affinity between the recording medium (paper, etc.) and the resin described later, 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, while in order to improve the high-temperature offset resistance, the acid value is preferably 45 mgKOH / g or less.

[0034] The hydroxyl value of the crystalline polyester resin 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.

[0035] The molecular structure of the crystalline polyester resin can be confirmed by NMR measurement of a solution or solid, as well as X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. -1 ±10cm -1 Or 990cm -1 ±10cm -1 One example is a method for detecting a crystalline polyester resin by detecting a material that has absorption due to the δCH (out-of-plane bending vibration) of olefin.

[0036] The content of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the toner. When the content of the crystalline polyester resin is 3 parts by mass or more with respect to 100 parts by mass of the toner, the crystalline polyester resin provides sharp melting and good low-temperature fixability, which is preferable. When the content of the crystalline polyester resin is 20 parts by mass or less with respect to 100 parts by mass of the toner, the heat-resistant storage stability is good, and high-quality images can be obtained, which is preferable.

[0037] -Non-crystalline polyester resin- The non-crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose. Examples of the non-crystalline polyester resin include non-crystalline polyester resin A having a glass transition temperature (Tg) of -40°C or more and 20°C or less, and non-crystalline polyester resin B having a glass transition temperature (Tg) of 40°C or more and 80°C or less.

[0038] --Non-crystalline polyester resin A-- The non-crystalline polyester resin A is not particularly limited as long as it has a glass transition temperature (Tg) of -40°C or more and 20°C or less, and can be appropriately selected depending on the purpose. The amorphous polyester resin A is preferably obtained by reacting a non-linear reactive precursor with a curing agent. In addition, the amorphous polyester resin A preferably has at least one of a urethane bond and a urea bond in order to provide better adhesion to recording media such as paper. When the amorphous polyester resin A has 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 the amorphous polyester resin A are enhanced, and the heat-resistant storage stability and high-temperature offset resistance of the toner are improved.

[0039] ---Nonlinear reactive precursors--- The non-linear reactive precursor is not particularly limited and can be appropriately selected according to the purpose as long as it is a polyester resin (hereinafter, sometimes referred to as "prepolymer") having a group capable of reacting with the curing agent. Here, "non-linear" means having a branched structure imparted by at least one of a trivalent or higher alcohol and a trivalent or higher carboxylic acid. When the reactive precursor in the non-crystalline polyester resin A is non-linear, it has a branched structure in the molecular skeleton, and the molecular chain has a three-dimensional network structure, which gives it rubber-like properties of being deformed but not flowing at low temperatures, making it possible to maintain the heat-resistant storage stability and high-temperature offset resistance of the toner.

[0040] 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 non-crystalline polyester resin.

[0041] The prepolymer is preferably a polyester resin containing an isocyanate group. The polyester resin containing an isocyanate group is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include a reaction product of a polyester resin having an active hydrogen group and a polyisocyanate. The polyester resin having an active hydrogen group can be obtained, for example, by polycondensing 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] The diol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the diol 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 glycol. Examples of the diols include diols having an oxyalkylene group such as lycol, 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] 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. In addition, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may be used.

[0044] The aliphatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid. 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, aliphatic dicarboxylic acids having 4 to 12 carbon atoms are preferred. These dicarboxylic acids may be used alone or in combination of two or more.

[0045] The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the trihydric or higher alcohol include aliphatic trihydric or higher alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. 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.

[0046] The non-crystalline polyester resin A preferably contains a tri- or higher hydric aliphatic alcohol as a constituent component. The amorphous polyester resin A contains a trivalent or higher aliphatic alcohol as a constituent, and thus has a branched structure in the molecular skeleton, and the molecular chain has a three-dimensional network structure, so that the resin has rubber-like properties of being deformed at low temperatures but not flowing, and therefore the toner can maintain its heat-resistant storage stability and high-temperature offset resistance.

[0047] 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 of the crosslinked portion is high, so the gloss of the fixed image created by heating and fixing the toner may not be fully expressed. When a crosslinking agent such as epoxy is used, a crosslinking reaction must be carried out after polymerization of the polyester, making it difficult to control the distance between crosslinking points, making it impossible to obtain the desired viscoelasticity, and they are prone to reacting with oligomers during polyester production to produce portions with high crosslinking density, which may cause unevenness in the fixed image and poor gloss and image density.

[0048] 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. In addition, anhydrides, lower (1 to 3 carbon atoms) alkyl esters, or halides of these may be used. 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.

[0049] The polyisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the polyisocyanate include diisocyanates and tri- or higher valent isocyanates.

[0050] Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactams, and the like.

[0051] The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.

[0052] The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate.

[0053] The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aromatic diisocyanate 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.

[0054] The aromatic aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the purpose. For example, α,α,α',α'-tetramethylxylylene diisocyanate is exemplified.

[0055] The isocyanurates are not particularly limited and can be appropriately selected depending on the purpose. Examples of the isocyanurates include tris(isocyanatoalkyl)isocyanurate and tris(isocyanatocycloalkyl)isocyanurate. These polyisocyanates may be used alone or in combination of two or more kinds.

[0056] ---Hardening agent--- The curing agent is not particularly limited as long as it is a curing agent that can react with the non-linear reactive precursor to produce the non-crystalline polyester resin A, and can be appropriately selected depending on the purpose. For example, an active hydrogen group-containing compound can be used.

[0057] 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.

[0058] 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. Among these, diamines and mixtures of diamines and small amounts of trivalent or higher amines are preferred. These may be used alone or in combination of two or more.

[0059] The diamine is not particularly limited and can be appropriately selected depending on the purpose. Examples of the diamine include aromatic diamines, alicyclic diamines, and aliphatic diamines. The aromatic diamine is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane. The alicyclic diamine is not particularly limited and can be appropriately selected depending on the purpose. Examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, and isophoronediamine. The aliphatic diamine is not particularly limited and can be appropriately selected depending on the purpose. Examples of the aliphatic diamine include ethylenediamine, tetramethylenediamine, and hexamethylenediamine.

[0060] The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

[0061] The amino alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino alcohol include ethanolamine and hydroxyethylaniline.

[0062] The amino mercaptan is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino mercaptan include aminoethyl mercaptan and aminopropyl mercaptan.

[0063] The amino acid is not particularly limited and can be appropriately selected depending on the purpose. Examples of the amino acid include aminopropionic acid and aminocaproic acid.

[0064] The blocked amino group is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ketimine compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and oxazoline compounds.

[0065] The non-crystalline polyester resin A 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. Such a non-crystalline polyester resin A is preferable because it can lower the glass transition temperature (Tg) and impart the property of deformation at low temperatures to the toner.

[0066] The non-crystalline polyester resin A preferably contains 50% by mass or more of an aliphatic diol having 4 to 12 carbon atoms in the total alcohol components. Such a non-crystalline polyester resin A is preferable because it can lower the glass transition temperature (Tg) and impart the property of deformation at low temperatures to the toner.

[0067] The non-crystalline 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. Such a non-crystalline polyester resin A is preferable because it can lower the glass transition temperature (Tg) and impart the property of deformation at low temperatures to the toner.

[0068] The weight average molecular weight of the non-crystalline polyester resin A is not particularly limited and can be appropriately selected depending on the purpose. However, the weight average molecular weight is preferably 20,000 to 1,000,000, more preferably 50,000 to 300,000, and particularly preferably 100,000 to 200,000, as measured by GPC (gel permeation chromatography). When the weight average molecular weight of the non-crystalline polyester resin A is 20,000 or more, it is possible to solve problems such as the toner becoming easily fluid at low temperatures, resulting in poor heat-resistant storage stability, and problems such as a decrease in viscosity during melting, resulting in poor high-temperature offset properties, which are favorable.

[0069] The molecular structure of the amorphous polyester resin A can be confirmed by NMR measurement of a solution or solid, as well as X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. -1 and 990±10cm -1 In one example, a material that does not have absorption due to δCH (out-of-plane bending vibration) of olefin is detected as amorphous polyester resin A.

[0070] The content of the non-crystalline polyester resin A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 parts by mass or more and 25 parts by mass or less, and more preferably 10 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the toner. When the content of the non-crystalline polyester resin A is 5 parts by mass or more with respect to 100 parts by mass of the toner, low-temperature fixability and high-temperature offset resistance are favorable. When the content of the non-crystalline polyester resin A is 25 parts by mass or less with respect to 100 parts by mass of the toner, the heat-resistant storage stability and the glossiness of the image obtained after fixing are favorable, which is preferable. That is, when the content of the non-crystalline polyester resin A is within the above-mentioned preferred range, it is advantageous in that all of the low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability are excellent.

[0071] --Non-crystalline polyester resin B-- The non-crystalline polyester resin B is not particularly limited as long as it has a glass transition temperature (Tg) of 40° C. or more and 80° C. or less, and can be appropriately selected depending on the purpose.

[0072] The non-crystalline polyester resin B is preferably a linear polyester resin. The non-crystalline polyester resin B preferably does not contain a urethane bond or a urea bond.

[0073] The non-crystalline polyester resin B is preferably an unmodified polyester resin. The unmodified polyester resin is a polyester resin obtained by using a polyhydric alcohol and a polycarboxylic acid or a derivative thereof, such as a polycarboxylic acid, a polycarboxylic anhydride, or a polycarboxylic ester, and is not modified by an isocyanate compound or the like.

[0074] 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.

[0075] 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. These may be used alone or in combination of two or more.

[0076] 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. Such an amorphous polyester resin is advantageous in terms of heat resistance storage stability.

[0077] The non-crystalline 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 for the purpose of adjusting the acid value and the hydroxyl value. 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 non-crystalline polyester resin B is not particularly limited and can be appropriately selected depending on the purpose. However, in the measurement by GPC (gel permeation chromatography), the weight average molecular weight (Mw) is preferably from 3,000 to 10,000, and more preferably from 4,000 to 7,000, the number average molecular weight (Mn) is preferably from 1,000 to 4,000, and more preferably from 1,500 to 3,000, and the Mw / Mn is preferably from 1.0 to 4.0, and more preferably from 1.0 to 3.5. If the molecular weight of the non-crystalline polyester resin B is too low, the toner may have poor heat-resistant storage stability and poor durability against stress such as stirring in a developing machine, and if the molecular weight is too high, the toner may have high viscoelasticity when melted, resulting in poor low-temperature fixability. The above-mentioned problems can be eliminated if the molecular weight is within the above-mentioned preferred numerical range, which is suitable.

[0079] The acid value of the non-crystalline polyester resin B is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 1 mgKOH / g to 50 mgKOH / g, more preferably from 5 mgKOH / g to 30 mgKOH / g. When the acid value of the non-crystalline polyester resin B is 1 mgKOH / g or more, the toner is likely to be negatively charged, and further, when fixed to a recording medium such as paper, the affinity between the recording medium and the toner is good, thereby improving low-temperature fixability. When the acid value of the non-crystalline polyester resin B is 50 mgKOH / g or less, the charge stability, particularly the charge stability against environmental changes, becomes good.

[0080] The hydroxyl value of the non-crystalline polyester resin B is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 5 mgKOH / g or more.

[0081] The glass transition temperature (Tg) of the non-crystalline polyester resin B is 40° C. or more and 80° C. or less, and more preferably 50° C. or more and 70° C. or less. The glass transition temperature of the non-crystalline polyester resin B is preferably 40° C. or higher, since this provides the toner with sufficient heat-resistant storage stability and durability against stress such as stirring in a developing machine, and also provides good filming resistance. When the glass transition temperature of the non-crystalline polyester resin B is 80° C. or less, deformation due to heating and pressure during toner fixing becomes sufficient, and low-temperature fixing properties become favorable, which is preferable.

[0082] The method for measuring the glass transition temperature (Tg) of the non-crystalline polyester resin A and the non-crystalline polyester resin B is not particularly limited and may be appropriately selected depending on the purpose, and may be measured, for example, using a differential scanning calorimeter (Q-200, manufactured by TA Instruments). An example of a specific measurement method is as follows. [An example of how to measure glass transition temperature (Tg)] Approximately 5.0 mg of the target sample is placed in an aluminum sample container, which is then placed on a holder unit and set in an electric furnace. The sample is then heated from -80°C to 150°C at a rate of 10°C / min in a nitrogen atmosphere, and the glass transition temperature (Tg) of the target sample is determined from the obtained DSC curve using the analysis program in the differential scanning calorimeter.

[0083] The molecular structure of the amorphous polyester resin B can be confirmed by NMR measurement of a solution or a solid, as well as X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. -1 and 990±10cm -1 For example, a method is used to detect a resin that does not have absorption due to the δCH (out-of-plane bending vibration) of olefin as a non-crystalline polyester resin.

[0084] The content of the non-crystalline polyester resin B is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 parts by mass or more and 90 parts by mass or less, and more preferably 60 parts by mass or more and 80 parts by mass or less, relative to 100 parts by mass of the toner. When the content of the non-crystalline polyester resin B is 50 parts by mass or more relative to 100 parts by mass of the toner, the dispersibility of the pigment and the release agent in the toner is good, and the occurrence of image fogging and distortion can be suppressed, which is preferable. When the content of the non-crystalline polyester resin B is 90 parts by mass or more relative to 100 parts by mass of the toner, the contents of the crystalline polyester resin C and the non-crystalline polyester resin A become appropriate, and low-temperature fixing properties are favorable, which is preferable. When the content of the non-crystalline polyester resin B is 60 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the toner, it is advantageous in that both high image quality and low-temperature fixability are excellent.

[0085] From the viewpoint of further improving the low-temperature fixability, it is preferable to use the non-crystalline polyester resin A and the crystalline polyester resin C in combination. From the viewpoint of achieving both low-temperature fixability and high-temperature / high-humidity storage stability, it is preferable that the amorphous polyester resin A has a low glass transition temperature. If the amorphous polyester resin A has a low glass transition temperature, it is preferable because it deforms due to heating or pressure during fixation and is easily adhered to a recording medium such as paper at a lower temperature.

[0086] <Styrene resin> The styrene resin used in the present invention is not particularly limited and can be appropriately selected depending on the purpose. Examples of the styrene resin include polymers of styrene and its substitutes such as polystyrene, poly-p-styrene, and polyvinyl toluene, styrene-α-methylstyrene copolymers, styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, styrene-vinyl toluene copolymers, styrene-methyl acrylate copolymers, styrene-ethyl acrylate copolymers, styrene-butyl acrylate copolymers, styrene-methyl methacrylate copolymers, styrene-ethyl methacrylate copolymers, styrene-butyl methacrylate copolymers, styrene-α-chloromethyl methacrylate copolymers, styrene-acrylonitrile copolymers, styrene-vinyl methyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers.

[0087] From the viewpoint of improving heat-resistant storage stability, the glass transition temperature (Tg) of the styrene resin is preferably 60° C. or higher, more preferably 80° C. or higher and 90° C. or lower, and even more preferably 83° C. or higher and 87° C. or lower. It is preferable that the glass transition temperature (Tg) of the styrene resin is 83° C. or higher, since the filming resistance is good. It is preferable that the glass transition temperature (Tg) of the styrene resin is 87° C. or lower, since low-temperature fixability is excellent.

[0088] The method for measuring the glass transition temperature (Tg) is not particularly limited and can be appropriately selected depending on the purpose, and can be measured, for example, using a differential scanning calorimeter (Q-200, manufactured by TA Instruments). An example of a specific measurement method is as follows. [An example of how to measure glass transition temperature (Tg)] Approximately 5.0 mg of the target sample is placed in an aluminum sample container, which is then placed on a holder unit and set in an electric furnace. The sample is then heated from -80°C to 150°C at a rate of 10°C / min in a nitrogen atmosphere, and the glass transition temperature (Tg) of the target sample is determined from the obtained DSC curve using the analysis program in the differential scanning calorimeter.

[0089] The content of the styrene resin is preferably from 2 to 10 parts by mass, and more preferably from 3 to 6 parts by mass, relative to 100 parts by mass of the toner, from the viewpoint of improving the thermal properties of the toner.

[0090] <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 ocher, 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, and anthrazan yellow BG. L, Isoindolinone Yellow, Bengala, Red Lead, Cinnabar, Cadmium Red, Cadmium Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Phaysee Red, Parachlor Orthonitroaniline Red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Lithol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 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, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, 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. These may be used alone or in combination of two or more.

[0091] The content of the colorant is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 part by mass to 15 parts by mass, more preferably 3 parts by mass to 10 parts by mass, relative to 100 parts by mass of the toner.

[0092] <External additives> The external additive is not particularly limited and can be appropriately selected depending on the purpose. Examples of the external additive include metal oxides, silicon compounds, and other fine particles. Examples of the metal oxide include aluminum oxide, zinc oxide, cerium oxide, zirconium oxide, etc. These may be used alone or in combination of two or more. Examples of the silicon compound include silicon oxide (silica), silicon carbide, silicon nitride, silicon tetrachloride, etc. Among these, silicon oxide (silica) is preferable. These may be used alone or in combination of two or more. Examples of such other fine particles include metal salts of fatty acids (eg, zinc stearate, aluminum stearate, etc.), fluoropolymers, and the like.

[0093] <Other ingredients> The other components are not particularly limited and may be appropriately selected depending on the purpose. Examples of the other components include a release agent, a charge control agent, a flowability improver, a cleaning property improver, and a magnetic material.

[0094] -Release agent- The release agent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the waxes include vegetable waxes such as carnauba wax, cotton wax, and wood wax rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cerusin; and natural waxes such as 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. Further, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalimide anhydride, and chlorinated hydrocarbons; homopolymers or copolymers of polyacrylates such as poly-n-stearyl methacrylate and poly-n-lauryl methacrylate, which are low molecular weight crystalline polymer resins (for example, copolymers of n-stearyl acrylate and ethyl methacrylate); and crystalline polymers having long alkyl groups in their side chains can also be used. Among these, from the viewpoint of suppressing the occurrence of filming, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferred.

[0095] 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. It is preferable for the melting point of the release agent to be 60° C. or higher, since this provides good heat-resistant storage stability. It is preferable that the melting point of the release agent is 80° C. or less, since a high quality image can be obtained.

[0096] The content of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 2 parts by mass or more and 10 parts by mass or less, and more preferably 3 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the toner.

[0097] -Charge control agent- The charge control agent is not particularly limited and can be appropriately selected depending on the purpose. Examples of the charge control agent include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compounds, tungsten simple substance or compounds, fluorine-based activators, metal salicylate, and metal salts of salicylic acid derivatives. 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 phenol 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.

[0098] The content of the charge control agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the toner.

[0099] -Flow improver- The flow improver is not particularly limited and can be appropriately selected according to the purpose as long as it can increase hydrophobicity by surface treatment and prevent deterioration of flowability and electrostatic chargeability even under high humidity, and examples thereof include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils, etc. It is preferable that the silica and titanium oxide as the external additives are surface-treated with such flow improvers and used as hydrophobic silica and hydrophobic titanium oxide.

[0100] -Cleaning improver- The cleaning property improver is not particularly limited and may be appropriately selected depending on the purpose as long as it is added to the toner in order to remove the developer remaining on the photoconductor or primary transfer medium after transfer, and examples thereof include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, 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 ones having a volume average particle size of 0.01 μm to 1 μm.

[0101] -Magnetic materials- The magnetic material is not particularly limited and may be appropriately selected depending on the purpose, and examples thereof include iron powder, magnetite, ferrite, etc. Among these, those that are white in color are preferred.

[0102] <Developer> The toner of the present invention can be used as a developer. The developer may be either a one-component developer or a two-component developer. When the developer is a two-component developer, it contains the toner of the present invention and a carrier.

[0103] 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.

[0104] The material of the core material is not particularly limited and can be appropriately selected depending on the purpose, and for example, manganese-strontium (Mn-Sr)-based materials and manganese-magnesium (Mn-Mg)-based materials having a density of 50 emu / g or more and 90 emu / g or less are preferable, and from the viewpoint of ensuring image density, highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 emu / g or more and 120 emu / g or less) are preferable. Furthermore, weakly magnetized materials such as copper-zinc (Cu-Zn)-based materials (30 emu / g or more and 80 emu / g or less) are preferable because they can weaken the contact of the toner with the photoconductor in a standing state and are advantageous for improving image quality. These may be used alone or in combination of two or more.

[0105] The volume average particle diameter of the core material is preferably 25 μm or more and 200 μm or less.

[0106] The material for the resin layer is not particularly limited and can be appropriately selected depending on the purpose. Examples of the material include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene resins, copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and vinyl fluoride, fluoro terpolymers such as terpolymers of tetrafluoroethylene, vinylidene fluoride and a non-fluorinated monomer, and silicone resins. These may be used alone or in combination of two or more.

[0107] When the developer is a two-component developer, the mixture ratio of the toner and the carrier (mass ratio of the toner to the carrier) is preferably 2.0% by mass to 12.0% by mass, more preferably 2.5% by mass to 10.0% by mass.

[0108] (Toner manufacturing method) The method for producing the toner of the present invention includes a step of producing toner base particles containing a polyester resin and a styrene resin, and may include other steps as necessary. The amount of the styrene resin added in the production process of the toner base particles is preferably 5 parts by mass or more and 10 parts by mass or less when the total amount of the toner base particles is 100 parts by mass.

[0109] <Toner base particle manufacturing process> The toner base particles can be produced, for example, by mixing, kneading, pulverizing, and classifying the above-mentioned toner materials to obtain toner base particles (colored particles) having a desired particle size. If necessary, the toner base particles can be mixed with inorganic fine particles or the like as other components (other steps). Specifically, first, the above components are thoroughly mixed with a mixer such as a Henschel mixer, and then the constituent materials are thoroughly kneaded using a continuous twin-screw extruder (for example, a KTK type twin-screw extruder manufactured by Kobe Steel, Ltd., a TEM type twin-screw extruder manufactured by Toshiba Machine Co., Ltd., a PCM type twin-screw extruder manufactured by Ikegai Iron Works Co., Ltd., and a KEX type twin-screw extruder manufactured by Kurimoto Iron Works Co., Ltd.) or a continuous single-screw kneader (for example, a hot kneader such as a Buss Co., Ltd. Co-kneader or a KCK kneader). At this time, as a method for increasing the specific energy, a method for reducing the kneading processing amount or a method for lowering the kneader set temperature and kneading the kneaded material in a high viscosity state can be used. Next, after cooling the kneaded material, it is coarsely pulverized using a hammer mill or the like, and further pulverized with a fine pulverizer using a jet stream or a mechanical pulverizer, and classified into a predetermined particle size using a classifier using a swirling air stream or a classifier using the Coanda effect. The classification can be performed by removing fine particle portions using, for example, a cyclone, a decanter, a centrifuge, etc. After the pulverization and classification are completed, the pulverized material is classified in an air current by centrifugal force or the like to produce a toner having a predetermined particle size.

[0110] The weight average particle size of the toner obtained by the toner production method is not particularly limited and can be appropriately selected depending on the purpose, but is preferably from 4 μm to 10 μm, and more preferably from 5 μm to 8 μm. The method for measuring the weight-average particle diameter is not particularly limited and can be appropriately selected depending on the purpose, and can be measured, for example, by using a measuring device for measuring the particle size distribution of toner particles by the Coulter Counter method. Examples of the measuring device include Coulter Counter TA-II (manufactured by Coulter), Coulter Multisizer II (manufactured by Coulter), etc.

[0111] (Toner storage unit) The toner storage unit of the present invention stores the toner of the present invention. 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, an image having excellent low-temperature fixability and heat-resistant storage stability can be obtained.

[0112] The toner storage unit of the present invention refers to a unit having a function of storing the toner of the present invention, in which the toner of the present invention is stored. Examples of the toner storage unit include a toner storage container, a developing unit, and a process cartridge. The toner storage container refers to a container that stores toner. The developing device has a means for storing toner and developing the toner.

[0113] The process cartridge has at least an electrostatic latent image carrier that carries an electrostatic latent image, and a developing means that develops the electrostatic latent image carried on the electrostatic latent image carrier with a toner to form a visible image, and may further have other means, such as a charging means, an exposure means, a developing means, a transfer means, a cleaning means, and a discharging means, appropriately selected as necessary. The developing means includes at least a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container, and may further include a layer thickness regulating member for regulating the thickness of the toner layer to be carried. The process cartridge can be detachably installed in various electrophotographic devices, facsimiles, and printers, and is preferably detachably installed in the image forming apparatus of the present invention described below.

[0114] (Image forming method and image forming apparatus) The image forming apparatus of the present invention includes an electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, a developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a toner image, a transfer means for transferring the toner image formed on the electrostatic latent image carrier to the surface of a recording medium, and a fixing means for fixing the toner image transferred to the surface of the recording medium, and may further include other means such as a static eliminating means, a cleaning means, a recycling means, and a control means, as necessary. The image forming method of the present invention includes an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier, a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier using the toner of the present invention to form a toner image, a transfer step of transferring the toner image formed on the electrostatic latent image carrier to a surface of a recording medium, and a fixing step of fixing the toner image transferred to the surface of the recording medium, and may further include other steps such as a static eliminating step, a cleaning step, a recycling step, and a control step, as necessary.

[0115] -Electrostatic latent image forming process and electrostatic latent image forming means- The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image bearing member. The electrostatic latent image forming unit is a unit for forming an electrostatic latent image on an electrostatic latent image carrier. The electrostatic latent image forming step can be suitably carried out by the electrostatic latent image forming means.

[0116] The latent image carrier (hereinafter sometimes referred to as "electrophotographic photoreceptor" or "photoreceptor") is not particularly limited in terms of its material, shape, structure, size, etc., and can be appropriately selected from known ones. A preferred shape is a drum shape, and examples of its material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Examples of the organic photoreceptor include a laminated type photoreceptor having a laminated structure in which a layer (charge generation layer) in which a charge generation material such as metal-free phthalocyanine or titanyl phthalocyanine is dispersed in a binder resin and a layer (charge transport layer) in which a charge transport material is dispersed in a binder resin are stacked on a support such as an aluminum drum, and a single-layer type photoreceptor having a single-layer structure photosensitive layer in which both a charge generation material and a charge transport material are dispersed in a binder resin on a support. In the single-layer type photoreceptor, a hole transport material and an electron transport material can also be added to the photosensitive layer as charge transport materials. An undercoat layer may be provided between the support and the multi-layer charge generating layer or the single-layer photosensitive layer.

[0117] The electrostatic latent image can be formed, for example, by uniformly charging the surface of the electrostatic latent image bearing member and then exposing it to light in an imagewise manner.

[0118] It is preferable that the electrostatic latent image forming means has at least a charging means (charger) that uniformly charges the surface of the electrostatic latent image carrier, and an exposure means (exposure device) that imagewise exposes the surface of the electrostatic latent image carrier.

[0119] The charging can be carried out, for example, by applying a voltage to the surface of the electrostatic latent image bearing member using the charger. The charger is not particularly limited and can be appropriately selected depending on the purpose. Examples of the charger include a contact charger known per se having a conductive or semiconductive roll, brush, film, rubber blade, or the like, and a non-contact charger utilizing corona discharge such as a corotron or scorotron. The charger is preferably one that is arranged in contact or non-contact with the electrostatic latent image carrier and charges the surface of the electrostatic latent image carrier by applying superimposed DC and AC voltages to the electrostatic latent image carrier, and is preferably a charging roller that is arranged in close proximity to the electrostatic latent image carrier in a non-contact manner via a gap tape and charges the surface of the electrostatic latent image carrier by applying superimposed DC and AC voltages to the charging roller.

[0120] The exposure can be carried out, for example, by exposing the surface of the electrostatic latent image bearing member imagewise using the exposure unit. The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger in the form of an image to be formed, and can be appropriately selected depending on the purpose. Examples of the exposure device include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system. In the present invention, a light back system may be adopted in which exposure is performed imagewise from the back side of the electrostatic latent image bearing member.

[0121] -Developing process and developing means- The developing step is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner to form a toner image. The developing unit is a unit that develops the electrostatic latent image formed on the electrostatic latent image carrier with the toner to form a toner image. The developing step can be suitably carried out by the developing means.

[0122] The toner image can be formed, for example, by developing the electrostatic latent image with the toner. The developing means preferably has at least a developing unit that contains the toner and can apply the toner to the electrostatic latent image in a contact or non-contact manner, and more preferably has a developing unit equipped with a toner container. The developing device may be a single-color developing device or a multi-color developing device, and a suitable example is one having an agitator that charges the toner by frictional agitation, and a rotatable magnetic roller.

[0123] -Transfer process and transfer means- The transfer step is a step of transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium. The transfer unit is a unit for transferring the toner image formed on the electrostatic latent image carrier onto the surface of a recording medium. The transfer step can be suitably carried out by the transfer means.

[0124] The transfer step is preferably carried out using an intermediate transfer body, and then a toner image is primarily transferred onto the intermediate transfer body, and then the toner image is secondarily transferred onto the recording medium. It is more preferable that the transfer step includes a primary transfer step in which the toner image is transferred onto the intermediate transfer body to form a composite transfer image using two or more colors, preferably a full-color toner, as the toner, and a secondary transfer step in which the composite transfer image is transferred onto the recording medium. The transfer means (primary transfer means and secondary transfer means) preferably includes at least a transfer device that peels and charges the toner image formed on the electrostatic latent image carrier (photoconductor) onto the recording medium. The number of transfer devices may be one or more. 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.

[0125] The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

[0126] -Fixing process and fixing means- The fixing step is a step of fixing the toner image transferred onto the surface of the recording medium. The fixing unit is a unit for fixing the toner image transferred onto the surface of the recording medium. The fixing step can be suitably carried out by the fixing means.

[0127] The fixing step may be carried out each time the developer of each color is transferred to the recording medium, or may be carried out simultaneously at one time with the developers of each color stacked. The fixing device as the fixing means is not particularly limited and can be appropriately selected depending on the purpose, but a known heating and pressurizing means is suitable. Examples of the heating and pressurizing means include a combination of a heating roller and a pressure roller, and a combination of a heating roller, a pressure roller and an endless belt.

[0128] -Static charge removal process and static charge removal means- The charge removing step is a step of removing electricity by applying a charge removing bias to the electrostatic latent image bearing member. The charge removing unit is a unit that applies a charge removing bias to the electrostatic latent image bearing member to remove electricity. The charge removing step can be suitably carried out by the charge removing means.

[0129] The charge removing means is not particularly limited as long as it can apply a charge removing bias to the electrostatic latent image bearing member, and can be appropriately selected from among known charge removers, such as a charge removing lamp.

[0130] -Cleaning process and cleaning means- The cleaning step is a step of removing the toner remaining on the electrostatic latent image bearing member. The cleaning means is a means for removing the toner remaining on the electrostatic latent image bearing member. The cleaning step can be suitably carried out by the cleaning means.

[0131] The cleaning means is not particularly limited as long as it can remove the toner remaining on the electrostatic latent image carrier, and can be appropriately selected from among known cleaners. Examples of the cleaning means include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.

[0132] -Recycling process and methods- The recycling step is a step of recycling the toner removed in the cleaning step to the developing means. The recycling unit is a unit for recycling the toner removed by the cleaning unit to the developing unit. The recycling unit is not particularly limited, and examples thereof include known transport units. The recycling step can be suitably carried out by the recycling means.

[0133] -Control process and control means- The control step is a step of controlling each of the steps. The control means is a means for controlling each of the means. The control step can be suitably carried out by the control means. The control means is not particularly limited as long as it can control the movement of each of the means, and can be appropriately selected depending on the purpose. Examples of the control means include devices such as a sequencer and a computer.

[0134] (Manufacturing method of printed matter) The method for producing a printed matter of the present invention forms a printed matter on a recording medium using an image forming apparatus including an electrostatic latent image carrier, an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image carrier, a developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner to form a toner image, a transfer means for transferring the toner image formed on the electrostatic latent image carrier to a surface of a recording medium, and a fixing means for fixing the toner image transferred to the surface of the recording medium. If necessary, the method may include other steps. The printed matter has an image formed on the recording medium using the toner of the present invention. Each step in the method for producing a printed matter can be the same as that in the image forming method, and therefore a duplicated description will be omitted.

[0135] Here, an embodiment of an image forming apparatus according to the present invention will be described with reference to the drawings, although the present invention is not limited to this embodiment. In addition, in each drawing, the same components are denoted by the same reference numerals, and duplicated explanations may be omitted. Furthermore, the number, position, shape, etc. of the following components are not limited to the present embodiment, and may be any number, position, shape, etc. that is preferable for implementing the present invention.

[0136] FIG. 1 is a schematic diagram for explaining an embodiment of an image forming apparatus of the present invention. The image forming apparatus 100A includes a photoconductor drum 10, a charging roller 20, an exposure device, a developing device 40, an intermediate transfer belt 50, a cleaning device 60 having a cleaning blade, and a discharging lamp . The intermediate transfer belt 50 is an endless belt stretched around three rollers 51 arranged on the inside, and can move in the direction of the arrow in Fig. 1. Some of the three rollers 51 also function as transfer bias rollers capable of applying a transfer bias (primary transfer bias) to the intermediate transfer belt 50. A cleaning device 90 having a cleaning blade is arranged near the intermediate transfer belt 50. Furthermore, a transfer roller 80 capable of applying a transfer bias (secondary transfer bias) for transferring a toner image to a transfer paper 95 is arranged facing the intermediate transfer belt 50. In addition, a corona charging device 58 for applying an electric charge to the toner image transferred to the intermediate transfer belt 50 is disposed around the intermediate transfer belt 50, between the contact point between the photosensitive drum 10 and the intermediate transfer belt 50 and the contact point between the intermediate transfer belt 50 and the transfer paper 95, in the direction of rotation of the intermediate transfer belt 50.

[0137] The developing device 40 is composed of a developing belt 41, 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. Each developing unit 45 of each color includes a developer container 42, a developer supply roller 43, and a developing roller (developer carrier) 44. The developing belt 41 is an endless belt stretched by a plurality of belt rollers, and can move in the direction of the arrow in FIG. 1. A part of the developing belt 41 contacts the photoconductor drum 10.

[0138] Next, a method of forming an image using image forming apparatus 100A will be described. First, the surface of the photoconductor drum 10 is uniformly charged using the charging roller 20, and then the photoconductor drum 10 is exposed to exposure light L using an exposure device (not shown) to form an electrostatic latent image. Next, the electrostatic latent image formed on the photoconductor drum 10 is developed with toner supplied from the developing device 40 to form a toner image. Furthermore, the toner image formed on the photoconductor drum 10 is transferred (primary transfer) onto the intermediate transfer belt 50 by a transfer bias applied from the roller 51, and then transferred (secondary transfer) onto the transfer paper 95 by a transfer bias applied from the transfer roller 80. Meanwhile, the photoconductor drum 10 from which the toner image has been transferred onto the intermediate transfer belt 50 is discharged by the discharge lamp 70 after the toner remaining on the surface has been removed by the cleaning device 60.

[0139] FIG. 2 is a schematic explanatory diagram for explaining another embodiment of the image forming apparatus of the present invention. Image forming device 100B has the same configuration as image forming device 100A, except that it does not have a developing belt 41 and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are arranged directly opposite each other around the photosensitive drum 10.

[0140] FIG. 3 is a schematic explanatory diagram for explaining still another embodiment of the image forming apparatus of the present invention. The image forming apparatus 100C is a tandem type color image forming apparatus, and includes a copying machine main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

[0141] Intermediate transfer belt 50, provided in the center of copying machine main body 150, is an endless belt stretched around three rollers 14, 15, and 16, and can move in the direction of the arrow in Fig. 3. Near roller 15, a cleaning device 17 having a cleaning blade for removing toner remaining on intermediate transfer belt 50 after a toner image has been transferred to recording paper is disposed. Facing intermediate transfer belt 50 stretched around rollers 14 and 15, yellow, cyan, magenta, and black image forming units 120 are arranged side by side along the transport direction.

[0142] An exposure device 21 is disposed near the image forming unit 120. A secondary transfer belt 24 is disposed on the side of the intermediate transfer belt 50 opposite to the side where the image forming unit 120 is disposed. The secondary transfer belt 24 is an endless belt stretched over a pair of rollers 23, and the recording paper transported on the secondary transfer belt 24 and the intermediate transfer belt 50 can come into contact with each other between the roller 16 and the roller 23.

[0143] Further, disposed near the secondary transfer belt 24 is a fixing device 25 including a fixing belt 26, which is an endless belt stretched over a pair of rollers, and a pressure roller 27 disposed so as to be pressed against the fixing belt 26. Further, disposed near the secondary transfer belt 24 and the fixing device 25 is a sheet inverting device 28 for inverting the recording paper when images are formed on both sides of the recording paper.

[0144] Next, a method of forming a full-color image using image forming apparatus 100C will be described. First, a color original is placed on the platen 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a color original is placed on the contact glass 32 of the scanner 300, and the automatic document feeder 400 is closed. When the start switch is pressed, if an original is set on the automatic original feeder 400, the original is transported and moved onto the contact glass 32, whereas if an original is set on the contact glass 32, the scanner 300 is driven and the first travelling body 33 equipped with a light source and the second travelling body 34 equipped with a mirror travel immediately. At this time, the light irradiated from the first travelling body 33 is reflected from the original surface by the second travelling body 34, and then received by the reading sensor 36 via the imaging lens 35, whereby the original is read and image information of black, yellow, magenta and cyan is obtained.

[0145] The image information for each color is transmitted to the image forming means 18 in the image forming unit 120 for each color, and a toner image for each color is formed. As shown in Fig. 4, each image forming unit 120 for each color includes a photoconductor drum 10, a charging roller 160 for uniformly charging the photoconductor drum 10, an exposure device for exposing the photoconductor drum 10 to exposure light L based on the image information for each color to form an electrostatic latent image for each color, a developing device 61 for developing the electrostatic latent image with a developer for each color to form a toner image for each color, a transfer roller 62 for transferring the toner image onto the intermediate transfer belt 50, a cleaning device 63 having a cleaning blade, and a static elimination lamp 64. The toner images of each color formed by the image forming units 120 of each color are transferred sequentially (primary transfer) onto the intermediate transfer belt 50, which is stretched around rollers 14, 15, and 16, and are superimposed to form a composite toner image.

[0146] Meanwhile, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed recording paper from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143, which is separated one by one by the separation roller 145 and sent to the paper feed path 146, transported by the transport roller 147 and guided to the paper feed path 148 in the copying machine main body 150, where it is stopped by hitting the registration roller 49. Alternatively, the paper feed roller is rotated to feed recording paper on the manual feed tray 54, which is separated one by one by the separation roller 52 and guided to the manual feed path 53, where it is stopped by hitting the registration roller 49. The registration roller 49 is generally used while being grounded, but may be used with a bias applied thereto in order to remove paper dust from the recording paper.

[0147] Next, the registration roller 49 is rotated in synchronization with the composite toner image formed on the intermediate transfer belt 50, thereby feeding the recording paper between the intermediate transfer belt 50 and the secondary transfer belt 24, and the composite toner image is transferred (secondary transfer) onto the recording paper. Any toner remaining on the intermediate transfer belt 50 after the composite toner image has been transferred is removed by the cleaning device 17.

[0148] The recording paper onto which the composite toner image has been transferred is transported by secondary transfer belt 24, and then the composite toner image is fixed by fixing device 25. Next, the transport path of the recording paper is switched by switching claw 55, and the recording paper is discharged onto paper discharge tray 57 by discharge rollers 56. Alternatively, the transport path of the recording paper is switched by switching claw 55, the sheet is inverted by sheet inverting device 28, an image is formed on the back side in the same manner, and then the recording paper is discharged onto paper discharge tray 57 by discharge rollers 56.

[0149] Fig. 5 is a schematic diagram showing an example of a process cartridge according to the present embodiment. As shown in Fig. 5, a process cartridge 500 has a photosensitive drum 10, a corona charger 29 as a charging unit, a developing device 40, a cleaning device 60, and a transfer roller 62. In Fig. 5, P indicates a transfer paper, and L indicates an exposure light.

[0150] According to the image forming apparatus and image forming method of the present invention, the toner of the present invention is used, which can achieve both excellent low-temperature fixing property and heat-resistant storage stability, and can maintain good image quality even in a high-temperature and high-humidity environment, so that high-quality images can be provided for a long period of time. EXAMPLES

[0151] The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following examples and comparative examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0152] Example 1 [Preparation of toner developer 1] <Preparation of amorphous polyester resin> The monomer species and tetrabutoxy titanate as a condensation catalyst shown in Table 1 below were placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, and reacted at 230°C for 6 hours under a nitrogen stream while distilling off the water produced. Next, the reaction was carried out for 1 hour under a reduced pressure of 5 mmHg to 20 mmHg to obtain a non-crystalline polyester resin. In Table 1, the "25 mol%" shown for bisphenol A (2,2) propylene oxide indicates the proportion in the alcohol component when the acid component is 50 mol% and the alcohol component is 50 mol%.

[0153] [Table 1]

[0154] <Preparation of crystalline polyester resin> Fumaric acid and 1,6-hexanediol were charged into a 5L four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple so that the OH / COOH ratio was 0.9, and reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours. A crystalline polyester resin was obtained by further reacting for 2 hours at a pressure of 8.3 kPa.

[0155] <Preparation of toner base particles> The following materials were premixed using a Henschel mixer (FM20B, manufactured by Mitsui Miike Chemical Engineering Co., Ltd.), and then melted and kneaded at a temperature of 120° C. in a twin-screw kneader (PCM-30, manufactured by Ikegai Iron Works Co., Ltd.). Amorphous polyester resin: 91.0 parts Crystalline polyester resin: 4.0 parts Styrene-α-methylstyrene copolymer (SA140, Kraton, Tg value 87°C): 7.5 parts Hydrocarbon wax (FNP-0090, manufactured by Nippon Seiro): 2.5 parts Carbon black (#44, manufactured by Mitsubishi Chemical Corporation): 13 parts The obtained kneaded material was rolled to a thickness of 2.7 mm using a roller, cooled to room temperature using a belt cooler, and coarsely pulverized to 200 μm to 300 μm using a hammer mill. Next, it was finely pulverized using a supersonic jet pulverizer Labojet (manufactured by Nippon Pneumatic Mfg. Co., Ltd.), and then classified using an air classifier (MDS-I, manufactured by Nippon Pneumatic Mfg. Co., Ltd.) while appropriately adjusting the louver opening so that the weight average particle size was 6.8±0.2 μm, to obtain toner base particles. Although the catalog value of the Tg value of styrene-α-methylstyrene copolymer (SA140, manufactured by Kraton) is 87°C, there is a variation of about ±5°C depending on the production rod, so the Tg value was measured in advance by the following measurement method. The same applies to the following examples and comparative examples. [Method of measuring Tg value] Approximately 5.0 mg of the target sample was placed in an aluminum sample container, which was then placed on a holder unit and set in an electric furnace. The sample was then heated from -80°C to 150°C at a rate of 10°C / min in a nitrogen atmosphere, and the glass transition temperature (Tg) of the target sample was determined from the obtained DSC curve using an analysis program in the differential scanning calorimeter.

[0156] <Preparation of toner developer> 100 parts by mass of the obtained toner base particles were mixed with 1 part by mass of HDK-2000 (Clariant KK) as metal oxide fine particles by stirring in a Henschel mixer to prepare an external additive-treated toner. 5% by mass of the obtained external additive-treated toner and 95% by mass of the coated ferrite carrier were uniformly mixed at 48 rpm for 5 minutes using a Turbula mixer (manufactured by Willy & Bachofen (WAB)) to prepare a toner developer.

[0157] [Peak ratio measurement] Each peak ratio of the obtained external additive treated toner was measured by the following method. Measurement equipment: Thermo Nicolet NEXUS470 (manufactured by Thermo SCIENTIFIC) ·Resolution: 4cm -1 -Sample integration count: 16Scans Background integration count: 16 scans ·Saved wavenumber range: 4000~400cm -1 From the FT-IR spectrum obtained under the above measurement conditions, -1 Baseline correction was performed in the range of 829 cm -1 Similarly, the values ​​for 800 to 600 cm -1 Baseline correction was performed in the range of 100 nm to 150 nm, and the maximum peak of styrene-α-methylstyrene copolymer (694 cm -1 From these values, the peak ratio (R1 / W1) and the peak ratio (R2 / W2) were calculated. The results are shown in Table 2.

[0158] [Evaluation of low-temperature fixability] The obtained toner developer was placed in a copier (RICOH IM C5510) manufactured by Ricoh Co., Ltd., and an image was output. The amount of adhesion was 0.4 mg / cm 2A solid image of the above was output on paper (Ricoh Co., Ltd., Type 6200) through an exposure process, a development process, and a transfer process. The fixing linear speed was 256 mm / sec. The fixing temperature was output in succession at 2°C increments, and the lowest temperature at which cold offset did not occur (lowest fixing temperature: low-temperature fixability) was measured. The low-temperature fixability was evaluated based on the following evaluation criteria, and the results are shown in Table 2. A rating of "△" or higher was deemed sufficient for practical use. -Evaluation criteria for low temperature fixability- ◎: Less than 120℃ ○: 120℃ or higher but less than 125℃ △: 125℃ or higher but lower than 130℃ ×: 130℃ or higher

[0159] [Filming Evaluation] The obtained toner developer was placed in a Ricoh Co., Ltd. copying machine (RICOH IM C6010) and run for 100,000 sheets in a high temperature and high humidity environment (30°C, 90%) with an image area ratio of 1.3%, after which the filming state on the photoconductor was visually observed. Filming was evaluated based on the following evaluation criteria, and the results are shown in Table 2. A rating of "△" or better was deemed sufficient for practical use. -Filming evaluation criteria- ⊚: No toner deposits were found on the photoconductor. ◯: Small toner particles are found on some parts of the photoconductor, but there is no effect on the image. Δ: A large amount of toner deposits can be seen on the photoconductor, but there is no effect on the image. ×: A large amount of toner deposits was observed on the photoconductor, and an abnormality occurred in the image.

[0160] Example 2 A toner developer was prepared and evaluated in the same manner as in Example 1, except that the amount of styrene-α-methylstyrene copolymer (SA140, manufactured by Kraton, Tg value 87° C.) was changed from 7.5 parts to 5 parts.

[0161] Example 3 A toner developer was prepared and evaluated in the same manner as in Example 1, except that the amount of styrene-α-methylstyrene copolymer (SA140, manufactured by Kraton, Tg value 87° C.) was changed from 7.5 parts to 10 parts.

[0162] Example 4 A toner developer was prepared and evaluated in the same manner as in Example 1, except that the wax type was changed from a hydrocarbon wax (FNP-0090, manufactured by Nippon Seiro Co., Ltd.) to a rice wax (TOWAX-3F16, manufactured by Toa Kasei Co., Ltd.).

[0163] Example 5 A toner developer was prepared and evaluated in the same manner as in Example 1, except that a styrene-α-methylstyrene copolymer (SA140, manufactured by Kraton) with an upper Tg limit (Tg: 90°C) was obtained and used.

[0164] Example 6 A toner developer was prepared and evaluated in the same manner as in Example 1, except that a styrene-α-methylstyrene copolymer (SA140, manufactured by Kraton) with a Tg lower limit (Tg: 81°C) was obtained and used.

[0165] Comparative Example 1 A toner developer was prepared and evaluated in the same manner as in Example 1, except that the amount of styrene-α-methylstyrene copolymer (SA140, manufactured by Kraton) was changed from 7.5 parts to 4.5 parts.

[0166] Comparative Example 2 A toner developer was prepared and evaluated in the same manner as in Example 1, except that the amount of styrene-α-methylstyrene copolymer (SA140, manufactured by Kraton) was changed from 7.5 parts to 10.5 parts.

[0167] [Table 2]

[0168] Examples of aspects of the present invention include the following. <1> A toner comprising a polyester resin and a styrene resin, 789 cm of the FT-IR spectrum of the toner measured by the ATR method -1 ~852cm -1 The maximum peak height at is W1, The toner has a diameter of 710 cm in the FT-IR spectrum measured by the ATR method. -1 ~690cm -1 When the maximum peak height at is R1, The peak ratio [R1 / W1] is 1.00 or more and 2.00 or less, 789 cm of the FT-IR spectrum of the toner measured by the KBr method -1 ~852cm -1 The maximum peak height at is W2, 710 cm of the FT-IR spectrum of the toner measured by the KBr method -1 ~690cm -1 When the maximum peak height at is R2, The toner is characterized in that the peak ratio [R2 / W2] is 0.80 or more and 1.20 or less. <2> The toner contains a hydrocarbon wax. <1> The toner is as described above. <3> The glass transition temperature (Tg) of the styrene resin is 60° C. or higher. <1> From the above <2> The toner according to any one of claims 1 to 5, <4> The above <1> From the above <3> 13. A toner storage unit comprising the toner according to claim 12. <5> An electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image bearing member; The electrostatic latent image formed on the electrostatic latent image carrier is <1> From the above <3> a developing unit which develops the toner image by using the toner according to any one of the preceding claims, a transfer means for transferring the toner image formed on the electrostatic latent image carrier onto a surface of a recording medium; and a fixing unit for fixing the toner image transferred onto the surface of the recording medium. <6> an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; The electrostatic latent image formed on the electrostatic latent image carrier is <1> From the above <3> a developing step of developing the toner image by using the toner according to any one of the above items to form a toner image; a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto a surface of a recording medium; and a fixing step of fixing the toner image transferred onto the surface of the recording medium. <7> An electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image bearing member; The electrostatic latent image formed on the electrostatic latent image carrier is <1> From the above <3> a developing unit which develops the toner image by using the toner according to any one of the preceding claims, a transfer means for transferring the toner image formed on the electrostatic latent image carrier onto a surface of a recording medium; and a fixing unit that fixes the toner image transferred to the surface of the recording medium. <8> The above <1> From the above <3> A method for producing the toner according to any one of the preceding claims, comprising the steps of: The method includes a process for producing toner base particles containing a polyester resin and a styrene resin, The toner production method is characterized in that the amount of the styrene resin added in the production process of the toner base particles is 5 parts by mass or more and 10 parts by mass or less when the total amount of the toner base particles is 100 parts by mass.

[0169] The above <1> from <3> The toner according to any one of the preceding claims. <4> The toner storage unit according to <5> The image forming apparatus according to the <6> The image forming method according to the <7> The method for producing the printed matter described in <8> The toner production method described above can solve the above-mentioned problems in the prior art and achieve the object of the present invention. [Explanation of symbols]

[0170] 10 Electrostatic latent image carrier (photoconductor drum) 14. Lola 15. Lola 16. Lola 17 Cleaning equipment 18 Image forming means 20 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 reversing device 29 Corona charger 32 Contact Glass 33 First Running Body 34 Second Running Body 35 Imaging Lens 36 Reading sensor 40 Developing device 41 Developing belt 42K Developer compartment 42Y Developer storage unit 42M Developer compartment 42C Developer container 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 belt 51 Lola 52 Separation roller 53 Manual feed path 54 Manual feed tray 55 Switching claw 56 Discharge roller 57 Output Tray 58 Corona charging device 60 Cleaning Equipment 61 Developing device 62 Transfer roller 63 Photoconductor cleaning device 64 Static electricity removal lamp 70 Static electricity removal lamp 80 Transfer roller 90 Cleaning Equipment 95 Transfer paper 100A Image forming device 100B Image forming device 100C image forming device 120 Image forming unit 130 Manuscript stand 142 Paper feed roller 143 Paper Bank 144 Paper feed cassette 145 Separation roller 146 Paper feed path 147 Transport roller 148 Paper feed path 150 Copying device body 200 Paper feed table 300 Scanner 400 Automatic Document Feeder (ADF) 500 Process Cartridge [Prior art documents] [Patent documents]

[0171] [Patent Document 1] JP 2005-62599 A [Patent Document 2] Patent Publication No. 2021-144186

Claims

1. A toner comprising a polyester resin and a styrene resin, 789 cm of the FT-IR spectrum of the toner measured by the ATR method －１ ~852cm －１ The maximum peak height at is W1, 710 cm of the FT-IR spectrum of the toner measured by the ATR method －１ ~690cm －１ When the maximum peak height in is R1, The peak ratio [R1 / W1] is 1.00 or more and 2.00 or less, 789 cm of the FT-IR spectrum of the toner measured by the KBr method －１ ~852cm －１ The maximum peak height at is W2, 710 cm of the FT-IR spectrum of the toner measured by the KBr method －１ ~690cm －１ When the maximum peak height in is R2, A toner having a peak ratio [R2 / W2] of 0.80 or more and 1.20 or less.

2. The toner of claim 1 , wherein the toner comprises a hydrocarbon-based wax.

3. 2. The toner according to claim 1, wherein the styrene resin has a glass transition temperature (Tg) of 80° C. or more and 90° C. or less.

4. A toner storage unit, comprising the toner according to claim 1 .

5. An electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image bearing member; a developing unit for developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to any one of claims 1 to 3 to form a toner image; a transfer means for transferring the toner image formed on the electrostatic latent image carrier onto a surface of a recording medium; and a fixing unit for fixing the toner image transferred onto the surface of the recording medium.

6. an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to claim 1 to form a toner image; a transfer step of transferring the toner image formed on the electrostatic latent image carrier onto a surface of a recording medium; a fixing step of fixing the toner image transferred onto the surface of the recording medium.

7. An electrostatic latent image carrier; an electrostatic latent image forming means for forming an electrostatic latent image on the electrostatic latent image bearing member; a developing unit for developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner according to any one of claims 1 to 3 to form a toner image; a transfer means for transferring the toner image formed on the electrostatic latent image carrier onto a surface of a recording medium; and a fixing unit that fixes the toner image transferred onto the surface of the recording medium.

8. A method for producing the toner according to any one of claims 1 to 3, comprising the steps of: The method includes a process for producing toner base particles containing a polyester resin and a styrene resin, a toner production method comprising the steps of: adding the styrene resin in a production process of the toner base particles in an amount of 5 parts by mass or more and 10 parts by mass or less when a total amount of the toner base particles is taken as 100 parts by mass;

Images