toner

Abstract

A toner including toner particles including a binder resin and a crystalline polyester, characterized in that the binder resin includes a polyester having a structure represented by formula (1). In formula (1), each of R independently represents hydrogen, a methyl group, or a phenyl group; A represents a polyester segment; B represents a polyester segment or any functional group selected from the group consisting of -R 1 OH, -R 1 COOH, a group of formula (2), and -R 1 NH2, R 1 represents a single bond or an alkylene group having a carbon number of 1 to 4; and the average number of repetitions n is a number of 10 to 80.

Description

Technical Field

[0001] This invention relates to toners for electrostatic image development used, for example, in electrophotography and electrostatic recording methods. Background Technology

[0002] In recent years, full-color photocopiers based on electrophotography have become widely used and are even beginning to be applied in the printing market. The printing market demands high speed, high image quality, and high productivity, while also being adaptable to a wide range of media (paper types). For example, even when the paper type changes from thick to thin, uniform media speed performance is required to allow printing to continue without changing the processing speed or the heating temperature setting of the fixing unit based on the paper type.

[0003] To accommodate uniform media velocity performance, toners must support proper fixing over a wide range of fixing temperatures, from low to high. Various studies have been conducted to improve low-temperature fixing capabilities by adding rapidly meltable crystalline polyesters to toners to induce plasticizer action as a binder resin, thus achieving adequate fixing over a broad temperature range. Various studies have also been conducted to address related toner storage issues.

[0004] For example, Patent Document 1 discloses a toner that improves low-temperature fixing properties by dissolving a crystalline polyester resin in an amorphous polyester resin, and that improves toner storage properties by forming a shell on the surface of the toner.

[0005] On the other hand, in the printing market, the image retention properties of printed materials are also considered important. Even when an image is formed using a toner that exhibits good low-temperature fixing properties, the printed materials can still adhere to each other when kept in a high-temperature environment due to the softening of the fixed image. When the adhered printed materials are peeled off, uneven gloss occurs, and the image undergoes peeling.

[0006] Patent document 2 discloses a toner that controls the compatibility between crystalline polyester and amorphous polyester in order to improve both low-temperature fixing and image storage properties.

[0007] [Existing Technical Documents]

[0008] [Patent Literature]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 2015-036723

[0010] [Patent Document 2] Japanese Patent Application Publication No. 2016-080934 Summary of the Invention

[0011] The problem the invention aims to solve

[0012] The toner described in Patent Document 1 does indeed exhibit good toner retention; however, image retention is not satisfactory due to softening after image fixing.

[0013] The toner described in Patent Document 2 exhibits unsatisfactory low-temperature fixing properties due to its composition, in which the compatibility between amorphous and crystalline polyesters is suppressed, even when image retention is improved. Furthermore, although it shows good image retention at 30°C and 60% RH, high temperatures exceeding the outside air temperature may occur during the transport of printing materials, for example, by vehicle or ship, depending on the loading location, and therefore there is still room for improvement in image retention.

[0014] This invention provides a toner that exhibits excellent low-temperature fixing properties and excellent image storage properties.

[0015] Solution for solving the problem

[0016] The present invention relates to a toner comprising toner particles including a binder resin and a crystalline polyester, wherein the binder resin comprises a polyester having a structure represented by the following formula (1).

[0017]

[0018] In formula (1), R independently represents hydrogen, methyl, or phenyl; A represents a polyester segment; B represents a polyester segment or is selected from -R 1 OH, -R 1 COOH,

[0019]

[0020] and -R 1 Any functional group in the group consisting of NH2, where R 1 Indicates a single bond or C 1-4 Alkylene; and the average number of repeats n is 10 to 80.

[0021] The effects of the invention

[0022] This invention thus provides a toner that exhibits excellent low-temperature fixing and excellent image storage properties. Detailed Implementation

[0023] Unless otherwise specified, the expressions “from XX to YY” and “XX to YY” indicating a range of values ​​refer to a range of values ​​that includes the lower and upper limits as endpoints.

[0024] When setting numerical ranges in segments, the upper and lower limits of each numerical range can be combined in any way.

[0025] The inventors conducted in-depth research with the aim of further improving low-temperature fixing and image storage performance.

[0026] The results showed that excellent low-temperature fixing and excellent image storage properties were obtained by using a toner containing a binder resin comprising a crystalline polyester and a polyester having a structure represented by the following formula (1).

[0027]

[0028] In formula (1), R independently represents hydrogen, methyl, or phenyl; A represents a polyester segment; B represents a polyester segment or is selected from -R 1 OH, -R 1 COOH,

[0029]

[0030] and -R 1 Any functional group in the group consisting of NH2, where R 1 Indicates a single bond or C 1-4 Alkylene; and the average number of repeats n is 10 to 80.

[0031] The reason why the above effect occurs when this structure is used for toner is believed to be as follows.

[0032] In the structure given by equation (1), the structure other than A and B is also called an organosilicon structure.

[0033] Polyesters having the structure given by formula (1) are resins that have both highly polar polyester segments and low polar organosilicon structures within the same molecule.

[0034] Crystalline polyesters exhibit high compatibility with polyester segments having the structure of formula (1), and therefore exhibit plasticity during fixing, resulting in excellent low-temperature fixing properties. On the other hand, crystalline polyesters exhibit low compatibility with organosilicon structures, and it is believed that recrystallization of crystalline polyesters existing in a state surrounded by polyesters having the structure of formula (1) is promoted in the temperature region below the melting point.

[0035] The result is believed to be that softening of the fixed image can be suppressed, and recrystallized crystalline polyester will also exist on a portion of the surface of the fixed image.

[0036] Recrystallized crystalline polyester (crystalline portion) exhibits high heat resistance and improves image storage performance; in addition, the segments other than the crystalline polyester in the fixed image (amorphous portion) also possess low surface free energy due to their organosilicon structure. It is believed that both the crystalline and amorphous portions can suppress adhesion between the fixed images, further improving image storage performance.

[0037] Based on the foregoing, by using a toner comprising a crystalline polyester and a polyester having the structure given by formula (1), excellent low-temperature fixing properties and excellent image storage properties, which have not been achieved to date, were obtained.

[0038] The glass transition temperature of the toner during the second heating process, as measured by differential scanning calorimetry, is preferably 45°C to 60°C, and more preferably 50°C to 55°C. By keeping the glass transition temperature (hereinafter also referred to as Tg) of the toner within the above range, better low-temperature fixing and better image storage properties are provided.

[0039] The heat endothermic originating from the crystalline polyester during the first heating process, measured by differential scanning calorimetry using ΔH1 as a toner, and

[0040] The heat endothermic originating from the crystalline polyester during the second heating process, measured by differential scanning calorimetry using ΔH2 as a toner.

[0041] ΔH1 is preferably from 0.5 J / g to 15.0 J / g, more preferably from 1.0 J / g to 10.0 J / g, even more preferably from 2.0 J / g to 8.0 J / g, and particularly preferably from 3.0 J / g to 7.0 J / g.

[0042] ΔH2 is preferably from 0.2 J / g to 10.0 J / g, more preferably from 0.5 J / g to 10.0 J / g, even more preferably from 1.5 J / g to 8.0 J / g, and particularly preferably from 2.0 J / g to 5.3 J / g.

[0043] Furthermore, the ratio of ΔH2 to ΔH1 (ΔH2 / ΔH1) is preferably 0.50 to 1.00, more preferably 0.60 to 1.00, and even more preferably 0.70 to 1.00.

[0044] ΔH1 is a value representing the amount of crystalline polyester present in a crystalline state introduced into the colorant.

[0045] On the other hand, (ΔH2 / ΔH1) is an indicator representing the proportion of crystalline polyester that recrystallizes after fixing.

[0046] By keeping ΔH1 and (ΔH2 / ΔH1) within the above range, highly heat-resistant crystalline portions can be effectively obtained at the surface of the fixed image, thereby further improving image storage performance.

[0047] The melting point of the crystalline polyester is preferably 65°C to 85°C, and more preferably 70°C to 80°C.

[0048] By keeping the melting point of the crystalline polyester within the aforementioned range, the crystalline polyester will possess a crystalline structure during image storage, thereby further improving image storage performance. On the other hand, during fixing, it becomes miscible with polyester segments present in the binder resin, exhibiting a plasticizing effect. As a result, low-temperature fixing performance is further improved.

[0049] The glass transition temperature (Tg) of the adhesive resin, the melting point of the crystalline polyester, the glass transition temperature (Tg) of the toner, and the heat endothermic ΔH1 and ΔH2 derived from the crystalline polyester are measured using the following methods.

[0050] That is, measurements were performed using the following conditions and an MDSC-2920 (TA Instruments) differential scanning calorimeter (DSC) based on ASTM D 3418-82.

[0051] First, accurately weigh approximately 3 mg of the measurement sample and transfer it into an aluminum pan; use an empty aluminum pan as a reference.

[0052] Use 30°C to 200°C as the measurement temperature range; heat from 30°C to 200°C at a heating rate of 10°C / min; and then cool from 200°C to 30°C at a cooling rate of 10°C / min.

[0053] Then, the temperature was increased again from 30°C to 200°C at a rate of 10°C / minute.

[0054] Using the specific heat change curve (i.e., DSC curve) obtained during the second heating process, the glass transition temperature (Tg) is taken as the temperature at the intersection of the curve of the step-like change at the glass transition point and the straight lines equidistant from the baseline before the specific heat change and the baseline after the specific heat change, in the vertical direction.

[0055] The melting point of the crystalline polyester was taken as the peak temperature of the maximum endothermic peak in the specific heat change curve obtained during the second heating process.

[0056] The heat absorption ΔH1 and ΔH2 derived from crystalline polyester were determined by calculating the peak area from the endothermic peak derived from crystalline polyester using the analysis software provided by the instrument.

[0057] When the endothermic peak originating from crystalline polyester does not overlap with the endothermic peak of other crystalline materials such as wax, the obtained heat of heat ΔH is treated as the heat of heat originating from crystalline polyester. On the other hand, when the endothermic peak of other crystalline materials such as wax overlaps with the endothermic peak of crystalline polyester, the heat of heat originating from crystalline materials other than crystalline polyester must be subtracted from the obtained heat of heat.

[0058] For example, the heat absorption from crystalline polyester can be obtained by subtracting the heat absorption from wax using the following method.

[0059] First, DSC measurements are performed on the wax itself to determine its endothermic properties. Then, the wax content in the toner is determined. There are no particular limitations on the measurement of the wax content in the toner; however, this measurement can be performed, for example, by peak separation in DSC measurements or by analysis of known structures.

[0060] The heat endothermic from the wax can then be calculated from the wax content in the toner, and this amount can be subtracted from the heat endothermic of the toner. When the wax is readily compatible with the resin component, the wax content can be multiplied by the compatibility ratio, followed by calculating and subtracting the heat endothermic from the wax. This compatibility ratio can be calculated as the heat endothermic determined by a predetermined mixture of the wax and resin components in a molten mixture, divided by the theoretical heat endothermic calculated from the initially determined heat endothermic of the molten mixture and the heat endothermic of the wax itself.

[0061] The content of crystalline polyester in the colorant is preferably 2.0 to 12.0 parts by weight, and more preferably 3.0 to 8.0 parts by weight, relative to 100 parts by weight of the binder resin.

[0062] By keeping the content of crystalline polyester within the above range, plasticizing effect can be effectively obtained during fixing, thereby improving low-temperature fixing performance; in addition, highly heat-resistant crystalline portions can be effectively obtained on the surface of the fixed image, thereby improving image storage performance.

[0063] The content of organosilicon structure in the polyester having the structure of formula (1) is preferably from 0.5% to 5.0% by mass, and more preferably from 2.0% to 4.0% by mass.

[0064] By keeping the content of the structure in formula (1) within the above range, the surface free energy of the amorphous portion of the fixed image is effectively reduced; in addition, the recrystallization of crystalline polyester can be effectively promoted. Furthermore, there is no hindrance to the plasticizing effect of crystalline polyester on polyester chain segments, and thus, image storage and low-temperature fixing properties are improved.

[0065] The adhesive resin shall contain a polyester having the structure given by formula (1), and may contain other resins.

[0066] Other resins may be exemplified as polyesters, vinyl copolymers, polyurethanes, epoxy resins, phenolic resins, and hybrid resins provided by chemical bonding between two or more of these resin structures, without having the structure given by formula (1).

[0067] The polyester segments in the polyester having the structure of formula (1) are preferably amorphous polyesters.

[0068] The content of polyester having the structure of formula (1) in the adhesive resin should be 50% by mass or more, and may be 60% by mass or more, 70% by mass or more, 80% by mass or more, 90% by mass or more, or 100% by mass. The upper limit is 100% by mass or less.

[0069] The above-mentioned interaction with crystalline polyester can be obtained more effectively by making the content of polyester having the structure of formula (1) in the adhesive resin 50% by mass or more.

[0070] The components constituting the polyester segments of a polyester having the structure of formula (1) will now be described. One or more of the following components may be used depending on the type and application.

[0071] Examples of dicarboxylic acids and their derivatives that constitute polyester segments include:

[0072] Examples include phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride, as well as their anhydrides and lower alkyl esters; alkyl dicarboxylic acids, such as succinic acid, adipic acid, sebacic acid, and azelaic acid, as well as their anhydrides and lower alkyl esters; alkenyl succinic acids and alkyl succinic acids with an average carbon number of 1 to 50, as well as their anhydrides and lower alkyl esters; and unsaturated dicarboxylic acids, such as fumaric acid, maleic acid, citracic acid, and itaconic acid, as well as their anhydrides and lower alkyl esters. Examples of alkyl groups in lower alkyl esters include methyl, ethyl, propyl, and isopropyl.

[0073] On the other hand, the diol components constituting the polyester segments can be exemplified as follows:

[0074] Ethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanediol (CHDM), hydrogenated bisphenol A, bisphenols and their derivatives given by formula (I-1), and diols given by formula (I-2).

[0075]

[0076] In formula (I-1), R represents ethylidene or propylidene, x and y are each integers greater than or equal to 0, and the average value of x+y is between 0 and 10.

[0077]

[0078] In equation (I-2), R' represents ethylidene or propylidene, x' and y' are each integers greater than or equal to 0, and the average value of x'+y' is between 0 and 10.

[0079] In addition to the aforementioned dicarboxylic acid compounds and diol compounds, the constituent components of the polyester chain segment may include tri- or more carboxylic acid compounds and tri- or more alcohol compounds as constituent components.

[0080] There are no particular restrictions on carboxylic acid compounds with three or more nucleotides, and examples include trimellitic acid, trimellitic anhydride, and pyromellitic acid. Examples of alcohol compounds with three or more nucleotides include trimethylolpropane, pentaerythritol, and glycerol.

[0081] In addition to the compounds mentioned above, the constituent components of the polyester segment may include monocarboxylic acid compounds and monohydric alcohol compounds. Specifically, examples of monocarboxylic acid compounds include palmitic acid, stearic acid, arachidic acid, and benzalkonium acid. Other examples include ceric acid, heptadecanic acid, linalic acid, beeswax acid, dodecanoic acid, tetracontanoic acid, and pentacontanoic acid.

[0082] Examples of monohydric alcohol compounds include benzyl alcohol, wax alcohol, beeswax alcohol, and tetracontanol.

[0083] The following describes the components constituting the structure (i.e., the organosilicon structure) provided by removing A and B from the structure given by formula (1) in a polyester having the structure given by formula (1). One or more of the following components may be used depending on the type and application. The organosilicon structure has the structure given by formula (2) below.

[0084]

[0085] In formula (2), R independently represents hydrogen, methyl, or phenyl, and n is 10 to 80. This n is the average number of repetitions of the siloxane unit, and is preferably 20 to 65.

[0086] By keeping the value of n within the above range, excellent diffusion properties in the adhesive resin are readily achieved. It is believed that, as a result, crystalline polyesters readily and effectively recrystallize and readily reduce surface free energy, thereby resulting in better image storage performance.

[0087] In preferred formula (1), all R are methyl groups.

[0088] This makes all Rs methyl-supported recrystallization of crystalline polyesters more readily available and provides greater improvement in image storage properties.

[0089] Silicone oils having functional groups that react with polyester at one or more ends of formula (2) can be used as components in polyesters having the structure of formula (1) to form the structure of formula (2). Examples of functional groups that react with polyester include hydroxyl, carboxyl, epoxy, and amino groups.

[0090] From the viewpoint of controlling the reactivity with polyester, it is preferable to use hydroxyl or carboxyl groups as terminal functional groups in silicone oil.

[0091] One, two, or more functional groups can be used at one or more ends of the silicone oil. To provide better image storage properties by controlling compatibility with crystalline polyesters through the introduction of organosilicon structures into the main framework of the polyester, silicone oils having functional groups at both ends are preferred. Specific examples are silicone oils with hydroxyl groups at both ends (KF-6000, KF-6001, and KF-6002, all from Shin-Etsu Chemical Co., Ltd.).

[0092] There are no particular restrictions on the production method of polyester with the structure of formula (1), and known methods can be used.

[0093] For example, a polyester having the structure of formula (1) can be produced by polymerizing the above-mentioned dicarboxylic acid compound, diol compound and silicone oil with terminal functional groups via esterification reaction or transesterification reaction and condensation reaction.

[0094] There are no particular restrictions on the polymerization temperature, but a range of 180°C to 290°C is preferred.

[0095] During polymerization, polymerization catalysts such as titanium catalysts, tin catalysts, zinc acetate, antimony trioxide, and germanium dioxide can be used to obtain polyesters.

[0096] The softening point (hereinafter also referred to as Tm) of the polyester having the structure of formula (1) is preferably 85°C to 150°C, and more preferably 100°C to 150°C.

[0097] By making the softening point of the polyester having the structure of formula (1) within the above range, the image storage performance of the fixed image is further improved, and in addition, the low-temperature fixing performance also becomes excellent.

[0098] The glass transition temperature (Tg) of the polyester having the structure of formula (1) during the second heating process, as measured by the differential scanning calorimeter as described above, is preferably 50°C to 65°C, and more preferably 53°C to 60°C.

[0099] The softening point (Tm) was measured as follows.

[0100] The softening point was measured using the Flowtester CFT-500D flow property evaluation instrument (Shimadzu Corporation), a constant load extrusion capillary rheometer, according to the instrument's instruction manual.

[0101] Using this instrument, a constant load is applied from the top of the sample via a piston, heating and melting the sample filled in the barrel, and then extruding the molten sample from a die at the bottom of the barrel; a flow curve showing the relationship between piston stroke and temperature can be obtained.

[0102] The "melting temperature of the 1 / 2 method" as described in the instruction manual provided with the "Flowtester CFT-500D Flow Property Evaluation Instrument" is used as the softening point in this disclosure.

[0103] The melting temperature of the 1 / 2 method is determined as follows.

[0104] First, determine half of the difference between the piston stroke Smax at the end of the outflow and the piston stroke Smin at the beginning of the outflow (denote this value as X, where X = (Smax - Smin) / 2).

[0105] The temperature in the flow profile is the melting temperature of the half-method when the piston stroke in the flow profile reaches the sum of X and Smin. The measurement samples used were prepared by compressing approximately 1.3 g of sample at 10 MPa for 60 seconds using a tablet compression molding machine (e.g., NT-100H, NPaSystem Co., Ltd.) at 25°C to provide a cylindrical shape with a diameter of approximately 8 mm. The measurement conditions for the CFT-500D are as follows.

[0106] Experimental mode: Heating method

[0107] Starting temperature: 50℃

[0108] Saturation temperature: 200℃

[0109] Measurement interval: 1.0℃

[0110] Heating rate: 4.0℃ / minute

[0111] Piston cross-sectional area: 1.000 cm² 2

[0112] Test load (piston load): 10.0 kgf / cm 2 (0.9807MPa)

[0113] Warm-up time: 300 seconds

[0114] Mold hole diameter: 1.0mm

[0115] Mold length: 1.0mm

[0116] The toner particles contain crystalline polyester.

[0117] In this disclosure, the crystalline polyester is a polyester in which an endothermic peak is observed during measurement by differential scanning calorimetry (DSC).

[0118] Because easy molecular movement is required to present a eutectic structure, crystalline polyesters are preferably crystalline polyesters that can present a layered structure, that is, a folded structure.

[0119] Examples of alcohol components used as starting monomers for crystalline polyesters are as follows.

[0120] Examples include, but are not limited to, 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, and 1,20-eicosenediol.

[0121] Of the aforementioned, from the viewpoints of low-temperature fixing and image storage, aliphatic diols having 6 to 18 carbons are preferred, and aliphatic diols having 8 to 14 carbons are more preferred.

[0122] From the viewpoint of achieving a significant improvement in the crystallinity of crystalline polyester, the content of aliphatic diols in the alcohol component is preferably 80 mol% to 100 mol%.

[0123] The alcohol component used to obtain crystalline polyester may include polyol components other than the aliphatic diols described above. Examples here include, for instance, aromatic diols such as bisphenol A epoxy alkane adducts comprising 2,2-bis(4-hydroxyphenyl)propane polyoxypropylene adducts and 2,2-bis(4-hydroxyphenyl)propane polyoxyethylene adducts, as well as ternary or higher alcohols such as glycerol, pentaerythritol, and trimethylolpropane.

[0124] On the other hand, the carboxylic acid component used as a starting monomer for crystalline polyesters can be exemplified as follows:

[0125] Examples include aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanodicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid. Other examples are the aforementioned acid anhydrides and the aforementioned lower alkyl esters. Examples of alkyl groups in lower alkyl esters include methyl, ethyl, propyl, and isopropyl.

[0126] Of the aforementioned, from the viewpoints of low-temperature fixing and image storage, it is preferable to use aliphatic dicarboxylic acid compounds having 6 to 18 carbons, and even more preferable are aliphatic dicarboxylic acid compounds having 6 to 12 carbons.

[0127] The preferred content of the aliphatic dicarboxylic acid compound is 80 mol% to 100 mol% in the carboxylic acid component.

[0128] The carboxylic acid component used to obtain crystalline polyesters may include carboxylic acid components other than the aforementioned aliphatic dicarboxylic acid compounds. Examples include aromatic dicarboxylic acid compounds and trivalent or higher aromatic polycarboxylic acid compounds, but are not limited to these.

[0129] Derivatives of aromatic dicarboxylic acids are also included in aromatic dicarboxylic acid compounds. Preferred specific examples of aromatic dicarboxylic acid compounds are, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalene-2,6-dicarboxylic acid, as well as the anhydrides of these acids and their alkyl (1 to 3 carbon) esters. Examples of alkyl groups in alkyl esters include methyl, ethyl, propyl, and isopropyl. Examples of polycarboxylic acid compounds with three or more alkyl groups include 1,2,4-benzenetricarboxylic acid (triphenyltricarboxylic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid and their derivatives such as anhydrides and alkyl (1 to 3 carbon) esters.

[0130] The crystalline polyester is preferably a condensation polymer of an aliphatic diol having 6 to 18 carbon atoms and an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms. A condensation polymer of an aliphatic diol having 8 to 14 carbon atoms and an aliphatic dicarboxylic acid compound having 6 to 12 carbon atoms is more preferred.

[0131] The molar ratio (carboxylic acid component / alcohol component) between the alcohol component and the carboxylic acid component of the starting monomer for crystalline polyester is preferably 0.80 to 1.20.

[0132] The preferred weight-average molecular weight of the crystalline polyester is 1.0 × 10⁻⁶. 4 Up to 1.0×10 5 And more preferably 2.0×10 4 Up to 5.0×10 4 .

[0133] The weight-average molecular weight of crystalline polyesters was measured using gel permeation chromatography (GPC) as follows.

[0134] First, 50 mg of sample was introduced into 5 mL of chloroform; it was left at 25°C for several hours; then it was shaken thoroughly to achieve complete mixing with chloroform; and left to stand for another 24 hours or more until no aggregates of sample were found.

[0135] The resulting solution was filtered through a solvent-resistant membrane filter ("Pretreatment Box H-25-5") with a pore size of 0.5 μm to obtain a sample solution.

[0136] Use the sample solution and the following conditions for measurement.

[0137] Instrument: "Lab Solutions GPC" high-performance GPC instrument (Shimadzu Corporation)

[0138] Column: PLgel 5μm MIXED-C 300mm×7.5mm (Agilent Technologies, Inc.): 2; PLgel 5μm Guard 50mm×7.5mm (Agilent Technologies, Inc.): 1

[0139] Elution buffer: chloroform

[0140] Flow rate: 1.0 mL / min

[0141] Oven temperature: 45℃

[0142] Sample injection volume: 60 μL

[0143] Detector: RI (Refractive Index) Detector

[0144] The weight-average molecular weight (Mw) of the samples was determined using molecular weight calibration curves constructed using polystyrene resin standards (trade names "TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", Tosoh Corporation).

[0145] Toners can be used in the form of magnetic single-component toners, non-magnetic single-component toners, or non-magnetic two-component toners.

[0146] When using a toner in the form of a magnetic one-component toner, it is preferable to use a magnetic material as the colorant. Examples of magnetic materials included in a magnetic one-component toner include magnetic iron oxides such as magnetite, maghemite, and ferrite, as well as magnetic iron oxides containing other metal oxides. Examples include metals such as Fe, Co, and Ni, alloys of these metals with metals such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures thereof.

[0147] The magnetic content is preferably 30 to 150 parts by weight relative to 100 parts by weight of the adhesive resin.

[0148] The following provides examples of colorants used in the form of non-magnetic one-component toners or non-magnetic two-component toners.

[0149] Carbon blacks such as furnace black, channel black, acetylene black, thermal cracking black, and lampblack can be used as black pigments, as can magnetic materials such as magnetite and ferrite.

[0150] Pigments or dyes can be used as colorants suitable for yellow. Examples of pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183, and 191, as well as CI Vat Yellow 1, 3, and 20. Examples of dyes include CI Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, and 162. These can be used alone or in combination of two or more.

[0151] Pigments or dyes can be used as colorants suitable for cyan. Examples of pigments include CI Pigment Blue 1, 7, 15, 15:1, 15:2, 15:3, 15:4, 16, 17, 60, 62, and 66; CI Vat Blue 6; and CI Acid Blue 45. Examples of dyes include CI Solvent Blue 25, 36, 60, 70, 93, and 95. These can be used individually or in combination of two or more.

[0152] Pigments or dyes can be used as colorants suitable for magenta. Examples of pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57, 57:1, 58, 60, 63, 6 4, 68, 81, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, and 254; CI Pigment Violet 19; and CI Vat Red 1, 2, 10, 13, 15, 23, 29, and 35. Examples of magenta dyes include: for example, CI Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, and 122; CI Disperse Red 9; CI Solvent Violet 8, 13, 14, 21, and 27; and CI Disperse Violet 1, etc., oil-soluble dyes. Examples of magenta dyes include: for example, CI Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, and 40, and CI Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, and 28, etc. These can be used alone or in combination of two or more.

[0153] The colorant content is preferably 1 to 20 parts by weight relative to 100 parts by weight of adhesive resin.

[0154] The colorant particles may contain a release agent (wax) to provide release properties. Examples of such waxes are as follows.

[0155] Examples include aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, olefin copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxidized waxes of aliphatic hydrocarbon waxes such as polyethylene oxide wax; waxes in which the main component is fatty acid ester, such as carnauba wax, benzyl ester, and lignite ester wax; and waxes provided by partial or complete deacidification of fatty acid esters, such as deacidified carnauba wax. Other examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and linalic acid; unsaturated fatty acids such as brassinolic acid, tung oil acid, and octadecanoic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, betaine alcohol, carbamate alcohol, wax alcohol, and beeswax alcohol; polyols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauryl amide; saturated fatty acid diamides such as methylene bis-stearamide, ethylene bis-decanoic acid amide, ethylene bis-lauranamide, and hexamethylene bis-stearamide; and ethylene bis-oleic acid amide, hexamethylene bis-oleic acid amide, N, Unsaturated fatty acid amides such as N'-dioleoyl adipamide and N,N'-dioleoyl sebacate amide; aromatic diamides such as m-xylene bis-stearamide and N,N'-distearate isophthalamide; aliphatic metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes provided by grafting aliphatic hydrocarbon waxes with vinyl copolymer monomers such as styrene or acrylic acid; partial esterifications of fatty acids and polyols such as betaine monoglycerides; and hydroxyl-containing methyl ester compounds obtained by, for example, hydrogenation of vegetable oils.

[0156] Aliphatic hydrocarbon waxes are the preferred waxes among those described above. Examples include low molecular weight hydrocarbons obtained by high-pressure free radical polymerization of alkylene groups or by low-pressure polymerization of alkylene groups in the presence of Ziegler or metallocene catalysts; Fischer-Tropsch waxes synthesized from coal or natural gas; olefin polymers obtained by pyrolysis of high molecular weight olefin polymers; and synthetic hydrocarbon waxes obtained from the distillation residues of hydrocarbons obtained from syngas containing carbon monoxide and hydrogen via the Arge process, and synthetic hydrocarbon waxes obtained by hydrogenation of such synthetic hydrocarbon waxes.

[0157] Other examples are waxes obtained by fractionating hydrocarbon waxes using methods such as pressure sweating, solvent extraction, vacuum distillation, or fractional crystallization. Waxes synthesized by methods that do not involve alkylene polymerization are also particularly preferred in terms of their molecular weight distribution.

[0158] Regarding the timing of wax addition, waxes can be added during the production of the colorant or during the production of the binder resin. These waxes can be used alone or in combination of two or more. The wax content is preferably 1 to 20 parts by weight relative to 100 parts by weight of binder resin.

[0159] In the toner particles, known charge control agents can be used as charge control agents. Examples of known charge control agents include azo iron compounds, azo chromium compounds, azo manganese compounds, azo cobalt compounds, azo zirconium compounds, chromium compounds of carboxylic acid derivatives, zinc compounds of carboxylic acid derivatives, aluminum compounds of carboxylic acid derivatives, and zirconium compounds of carboxylic acid derivatives. Aromatic hydroxycarboxylic acids are preferred for carboxylic acid derivatives. Charge control resins can also be used. If necessary, two or more charge control agents can be used in combination. The content of charge control agent is preferably 0.1 to 10 parts by weight relative to 100 parts by weight of binder resin.

[0160] The toner can be used in the form of a two-component developer provided by mixing with a carrier. Common carriers, such as ferrite and magnetite, or resin-coated carriers can be used as carriers. Binder-type carriers in which the magnetic material is dispersed in resin can also be used.

[0161] The resin-coated carrier consists of carrier core particles and a coating material, which is the surface of the resin on the carrier core particles. Examples of resins used for the coating material include, for example, styrene-acrylate resins such as styrene-acrylate copolymers and styrene-methyl methacrylate copolymers; acrylic resins such as acrylate copolymers and methacrylate copolymers; fluoropolymers such as polytetrafluoroethylene, polychlorotrifluoroethylene polymers, and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; and amino acrylate resins. Ionomer resins and polyphenylene sulfide resins are other examples. These resins can be used alone or in combination.

[0162] Toners may have external additives, such as fine silica particles, added to the toner particles to improve their electrical stability, developability, flowability, and durability.

[0163] The preferred specific surface area of ​​the fine silica particles based on nitrogen adsorption using the BET method is 30 m². 2 / g to 500m 2 / g, and more preferably 50m 2 / g to 400m 2 / g.

[0164] The content of fine silica particles is preferably from 0.01 to 8.00 parts by weight, and more preferably from 0.10 to 5.00 parts by weight, relative to 100 parts by weight of toner particles.

[0165] The BET specific surface area of ​​fine silica particles can be determined using, for example, an Autosorb 1 specific surface area analyzer (Yuasa Ionics Co., Ltd.), a Gemini 2360 / 2375 (Micromeritics Instrument Corporation), or a TriStar 3000 (Micromeritics Instrument Corporation) via the BET multi-point method, by adsorbing nitrogen on the surface of the fine silica particles.

[0166] To improve hydrophobicity and control triboelectricity, if necessary, fine silica particles can be treated with agents such as unmodified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane coupling agents, silane compounds with functional groups, and other silicone compounds, and several different agents can be used in combination.

[0167] The toner may optionally contain external additives other than silica fine particles. Examples of external additives include inorganic and resin fine particles used as, for example, charge aids, conductivity imparting agents, flowability imparting agents, anti-caking agents, release agents during hot roller fixing, lubricants, or abrasives. Examples of charge aids include metal oxide fine particles such as titanium dioxide fine particles, zinc oxide fine particles, and alumina fine particles. Examples of lubricants include polyvinyl fluoride powder, zinc stearate powder, and polyvinylidene fluoride powder. Examples of abrasives include cerium oxide powder, silicon carbide powder, and strontium titanate powder.

[0168] There are no particular restrictions on the production method of colorant particles, and known methods can be used. Examples include pulverization, emulsification aggregation, suspension polymerization, and dissolution suspension.

[0169] Toner granules produced by pulverization can be manufactured in the following ways:

[0170] Crystalline polyester, including a binder resin of polyester having the structure of formula (1), and optional colorants, waxes, and other additives are thoroughly mixed using a mixer such as a Henschel mixer or a ball mill.

[0171] The resulting mixture is melt-blended using a heated mixer such as a twin-screw compounding extruder, heated rollers, a mixer, or an extruder. The resulting melt-blended material is cooled and solidified, and then pulverized and graded to obtain toner particles. During this process, the average sphericity of the toner particles can also be controlled by adjusting the exhaust temperature during fine pulverization. If necessary, the toner can be obtained by mixing the toner particles with external additives using a mixer such as a Henschel mixer.

[0172] Examples of mixers include: Henschel mixers (Mitsui Mining Co., Ltd.); super mixers (Kawata Mfg.Co., Ltd.); Ribocon (Okawara Corporation); Nauta mixers, Turbulizers, and Cyclomixes (Hosokawa Micron Corporation); screw-pin mixers (Pacific Machinery & Engineering Co., Ltd.); and Loedige mixers (Matsubo Corporation).

[0173] Examples of mixing mills include: KRC mixing mill (Kurimoto, Ltd.); Buss Ko- mixing mill (BussCorp.); TEM mixing mill (Toshiba Machine Co., Ltd.); TEX twin-screw mixing mill (The Japan SteelWorks, Ltd.); PCM mixing mill (Ikegai Ironworks Corporation); three-roll mill, mixing roll mill, and mixing mill (Inoue Manufacturing Co., Ltd.); Kneadex (Mitsui Mining Co., Ltd.); Model MS pressure mixing mill and Kneader-Ruder (Moriyama Mfg.Co., Ltd.); and Banbury internal mixer (Kobe Steel, Ltd.).

[0174] Examples of pulverizers include: convection jet mills, Micron jet mills, and Inomizer (Hosokawa Micron Corporation); IDS mills and PJM air jet mills (Nippon Pneumatic Mfg. Co., Ltd.); cross-flow mills (Kurimoto, Ltd.); Ulmax (Nisso Engineering Co., Ltd.); SK Jet-O-Mill (Seishin Enterprise Co., Ltd.); Kryptron (Kawasaki Heavy Industries, Ltd.); turbo mills (TurboKogyo Co., Ltd.); and super rotors (Nisshin Engineering Inc.).

[0175] If necessary, after pulverization, the average sphericity of the toner particles is controlled by surface treatment using a hybrid system (Nara Machinery Co., Ltd.), Nobilta (Hosokawa Micron Corporation), Mechanofusion system (Hosokawa Micron Corporation), Faculty (Hosokawa Micron Corporation), Inomizer (Hosokawa Micron Corporation), Theta Composer (Tokuju Corporation), Mechanomill (Okada Seiko Co., Ltd.), or MeteoRainbow MR Type (Nippon Pneumatic Mfg.Co., Ltd.).

[0176] Examples of classifiers include: Classiel, Micron classifiers, and Spedic classifiers (Seishin Enterprise Co., Ltd.); turbine classifiers (Nisshin Engineering Inc.); Micron separators, Turboplex (ATP), and TSP separators (Hosokawa Micron Corporation); curved-tube injectors (Nittetsu Mining Co., Ltd.); dispersion separators (Nippon Pneumatic Mfg. Co., Ltd.); and YM Microcut (Yasukawa Shoji Co., Ltd.).

[0177] Examples of screening devices that can be used to screen coarse particles include: Ultrasonic (Koei Sangyo Co., Ltd.), Rezona Sieve and Gyro-Sifter (Tokuju Corporation), Vibrasonic Systems (Dalton Co., Ltd.), Sonilean (Sintokogio, Ltd.), Turbo Screen (Turbo Kogyo Co., Ltd.), Microsifter (Makino Mfg. Co., Ltd.), and circular vibrating screens.

[0178] The following describes various measurement methods.

[0179] <Method for measuring weight-average particle size (D4)>

[0180] The weight-average particle size (D4) of the toner or toner particles (hereinafter also referred to as, for example, toner) is determined as follows.

[0181] The measuring instrument used was a "Coulter Counter Multisizer 3" (registered trademark, Beckman Coulter, Inc.), a precision particle size distribution measuring instrument based on pore resistance and equipped with a 100 μm orifice.

[0182] Use the included dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter, Inc.), to set the measurement conditions and analyze the measurement data. Measurements were performed using 25,000 effective measurement channels.

[0183] The electrolyte aqueous solution used for measurement is prepared by dissolving super-grade sodium chloride in deionized water to provide a concentration of 1.0%, and can be, for example, "ISOTON II" (Beckman Coulter, Inc.).

[0184] Configure the dedicated software as follows before measurement and analysis.

[0185] In the "Change Standard Operating Method (SOM)" screen of the dedicated software, set the total count in the control mode to 50,000 particles; the number of measurements to 1; and the Kd value to the value obtained using "Standard Particle 10.0 μm" (Beckman-Coulter, Inc.). Automatically set the threshold and noise level by pressing the "Threshold / Noise Level Measurement Button". Additionally, set the current to 1600 μA; the gain to 2; the electrolyte solution to ISOTON II; and check "Flush the measuring tube after measurement".

[0186] In the "Set Pulse to Particle Size Conversion" screen of the dedicated software, set the element spacing to logarithmic particle size; set the particle size element to 256 particle size elements; and set the particle size range to 2μm to 60μm.

[0187] The specific measurement steps are as follows.

[0188] (1) Pour 200 mL of electrolyte solution into a 250 mL round-bottom glass beaker for Multisizer 3 and place it on the sample stage. Stir counterclockwise with a stir bar at 24 revolutions per second. Use the "Venere rinse" function of the dedicated software to initially remove dirt and air bubbles from the ureter.

[0189] (2) Introduce approximately 30 mL of electrolyte aqueous solution into a 100 mL flat-bottomed glass beaker and add 0.3 mL of a diluent prepared by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral pH 7 detergent for cleaning precision measuring instruments, including nonionic surfactants, anionic surfactants, and organic detergent builders, from WakoPure Chemical Industries, Ltd.) with three times (by mass) of ion-exchanged water as a dispersant.

[0190] (3) Prepare an "Ultrasonic Dispersion System Tetora 150" (Nikkaki Bios Co., Ltd.); it is an ultrasonic disperser with a power output of 120W and equipped with two phase-shifted oscillators (oscillation frequency = 50kHz) configured with a phase offset of 180°. Add 3.3L of deionized water to the water tank of the ultrasonic disperser and add 2mL of Contaminon N to the water tank.

[0191] (4) Position the beaker described in (2) in the beaker fixing hole of the ultrasonic disperser and start the ultrasonic disperser. Adjust the vertical position of the beaker in such a way that the surface resonance state of the electrolyte aqueous solution in the beaker is maximized.

[0192] (5) While irradiating the electrolyte solution in the beaker prepared according to (4) with ultrasound, add 10 mg of, for example, a colorant in small equal parts to the electrolyte solution and disperse it. Continue the ultrasonic dispersion treatment for another 60 seconds. During the ultrasonic dispersion, keep the water temperature in the tank appropriately controlled between 10°C and 40°C.

[0193] (6) Using a pipette, add dropwise the aqueous electrolyte solution prepared in (5), in which an electrolyte, for example a toner, is dispersed, into a round-bottom beaker set in the sample stage as described in (1), wherein the solution is adjusted to provide a measurement concentration of approximately 5%. Then perform measurements until the number of particles measured reaches 50,000.

[0194] (7) Analyze the measurement data using the dedicated software provided by the instrument and calculate the weight-average particle size (D4). When the dedicated software is set to graph / volume %, the "average diameter" on the analysis / volume statistics (arithmetic mean) screen is the weight-average particle size (D4).

[0195] <Identification method for polyesters with a structure represented by equation (1)>

[0196] The structure represented by equation (1) is identified using the following method.

[0197] The hydrocarbon group and organosilicon structure represented by R in formula (1) are used13 C-NMR and solid-state 29 Identification was performed using Si-NMR.

[0198] ( 13 C-NMR measurement conditions)

[0199] Instruments: JNM-ECX500II, JEOL RESONANCE

[0200] Sample tube: 3.2mm Φ

[0201] Sample: Deuterated chloroform-soluble substances in the sample used for NMR measurements

[0202] Temperature measured: room temperature

[0203] Pulse mode: CP / MAS

[0204] Measured nuclear frequency: 123.25MHz 13 C)

[0205] Reference substance: adamantane (external standard: 29.5 ppm)

[0206] Sample rotation speed: 20kHz

[0207] Contact time: 2ms

[0208] Delay time: 2s

[0209] Number of scans: 1024

[0210] In this method, the hydrocarbon group represented by R in formula (1) is identified by the presence or absence of a signal originating from, for example, silicon atom-bonded methyl (Si-CH3) or phenyl (Si-C6H5).

[0211] solid state 29 The specific measurement conditions for Si-NMR are as follows.

[0212] Instrument: JNM-ECX5002 (JEOL RESONANCE)

[0213] Temperature: Room temperature

[0214] Measurement method: DD / MAS method 29 Si, 45°

[0215] Sample tube: Zirconia 3.2mm Φ

[0216] Sample: Filled into the sample tube as powder

[0217] Sample rotation speed: 10kHz

[0218] Relaxation time: 180s

[0219] Scan: 2000

[0220] <Methods for measuring the content of crystalline polyester and the content of the structure represented by formula (2)>

[0221] The content of crystalline polyester and the content of the structure represented by equation (2) were determined using the aforementioned instrument. 1 To determine by H-NMR.

[0222] ( 1 H-NMR measurement conditions)

[0223] Sample: Deuterated chloroform-soluble substance

[0224] Pulse condition: 5.0 μs

[0225] Frequency range: 10,500Hz

[0226] Number of scans: 64

[0227] Example

[0228] The present disclosure is described in detail below based on production examples, embodiments, and comparative examples. However, the present disclosure is by no means limited to or restricted by these. Unless otherwise specifically stated, "parts" and "%" in all production examples, embodiments, and comparative examples are based on mass.

[0229] <Production Example of Adhesive Resin 1>

[0230] Bisphenol A / ethylene oxide (2.2 mol adduct): 50.0 mol parts

[0231] Bisphenol A / propylene oxide (2.2 mol adduct): 50.0 mol parts

[0232] ·Terephthalic acid: 90.0 mol

[0233] Trimeric triglyceride: 10.0 mol

[0234] 97.0 parts of the monomer for forming the polyester segment and 3.0 parts of silicone oil (KF-6000, Shin-Etsu Chemical Co., Ltd.) with hydroxyl groups at both ends were introduced into a 5L autoclave and mixed together with 500 ppm of tetrabutoxytitanium.

[0235] Then, a reflux condenser, a moisture separator, an N2 gas inlet pipe, a thermometer, and a stirrer are installed on the autoclave, and a polycondensation reaction is carried out at 230°C while N2 gas is introduced into the autoclave.

[0236] The reaction time was adjusted to give the desired softening point; after the reaction was complete, the product was removed from the container, cooled, and crushed to obtain polyester 1 having the structure represented by formula (1). The softening point (Tm) of polyester 1 is 130°C and the glass transition temperature (Tg) is 55°C. Polyester 1 is designated as binder resin 1.

[0237] The polyester having the structure of formula (1) contains 3.0% by mass of the structure of formula (2); all R in formula (1) are methyl; and n is 26.

[0238] <Production Example of Adhesive Resin 2>

[0239] Except for replacing the silicone oil with hydroxyl groups at both ends with 4.0 parts of silicone oil (KF-6002, Shin-Etsu Chemical Co., Ltd.), polyester 2 is obtained according to the production example of adhesive resin 1. Polyester 2 is designated as adhesive resin 2. The polyester having the structure of formula (1) contains 4.0% by mass of the structure of formula (2); all R in formula (1) are methyl; and n is 63.

[0240] <Production Examples of Adhesive Resins 3 to 10>

[0241] Except for changing the silicone oil with hydroxyl groups at both ends to silicone oil (KF-6001, Shin-Etsu Chemical Co., Ltd.), changing the amount of silicone oil added as shown in Table 1, and adjusting the softening point (Tm) and glass transition temperature (Tg) by adjusting the reaction time, polyesters 3 to 10 were obtained according to the production example of adhesive resin 1. These polyesters 3 to 10 are designated as adhesive resins 3 to 10. In formula (1), all R are methyl and n is 38.

[0242] [Table 1]

[0243] Table 1

[0244] Adhesive resin No. Polyester No. Amount of silicone oil added (parts by weight) Content (mass%) of the structure in formula (2) Tm (°C) Tg (°C) 1 1 3.0 3.0 130 55 2 2 4.0 4.0 128 53 3 3 2.0 2.0 136 56 4 4 0.5 0.5 135 58 5 5 5.0 5.0 143 58 6 6 6.0 6.0 140 56 7 7 0.3 0.3 135 60 8 8 0.3 0.3 125 52 9 9 0.3 0.3 150 65 10 10 0.3 0.3 135 59

[0245] <Production Example of Adhesive Resin 11>

[0246] Except for adjusting the amount of silicone oil added to 0 and adjusting the softening point (Tm) and glass transition temperature (Tg) by adjusting the reaction time, an unmodified polyester 11 was obtained according to the production example of adhesive resin 1. The unmodified polyester 11 has a softening point (Tm) of 113°C and a glass transition temperature (Tg) of 44°C. This unmodified polyester 11 is designated as adhesive resin 11.

[0247] <Production Example of Adhesive Resin 12>

[0248] Except for adjusting the softening point (Tm) and glass transition temperature (Tg) by adjusting the reaction time, an unmodified polyester 12 was obtained according to the production example of adhesive resin 11. The unmodified polyester 12 has a softening point (Tm) of 150°C and a glass transition temperature (Tg) of 65°C. This unmodified polyester 12 is designated as adhesive resin 12.

[0249] <Production Example of Crystalline Polyester 1>

[0250] 100.0 mol of 1,10-decanoic acid as a carboxylic acid monomer and 100.0 mol of 1,9-nonanediol as an alcohol monomer were introduced into a reactor equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple. The temperature was raised to 140°C while stirring, and the reaction was carried out for eight hours under a nitrogen atmosphere and at atmospheric pressure, while the water was distilled off at 140°C.

[0251] Then, 0.57 parts of tin dioctanoate were added relative to 100 parts of the total carboxylic acid monomer and alcohol monomer, and the reaction was carried out while heating to 200°C at 10°C / hour. After reacting for two hours after reaching 200°C, the pressure in the reactor was reduced to below 5 kPa, and the reaction was carried out at 200°C while monitoring the molecular weight to obtain crystalline polyester 1. Crystalline polyester 1 has a melting point of 75°C and a weight-average molecular weight of 2.5 × 10⁻⁶. 4 .

[0252] <Production Example of Crystalline Polyester 2>

[0253] Besides adjusting the reaction time to change the weight-average molecular weight, crystalline polyester 2 can be obtained as in the production example of crystalline polyester 1. Crystalline polyester 2 has a melting point of 75°C and a weight-average molecular weight of 1.5 × 10⁻⁶. 4 .

[0254] <Production Example of Crystalline Polyester 3>

[0255] Except for changing the carboxylic acid monomer to sebacic acid and the alcohol monomer to 1,4-butanediol, crystalline polyester 3 is obtained as in the production example of crystalline polyester 1. Crystalline polyester 3 has a melting point of 65°C and a weight-average molecular weight of 1.5 × 10⁻⁶. 4 .

[0256] <Production Example of Toner 1>

[0257]

[0258] The materials listed above are initially mixed using a Henschel mixer, and then melt-mixed at 160°C using a twin-screw compounding extruder.

[0259] The resulting compound was cooled and coarsely crushed using a hammer mill, and then finely crushed using a turbine mill.

[0260] The finely pulverized material was classified using a multi-stage classifier based on the Coanda effect to obtain toner particles 1 with negative triboelectric charge and a weight-average particle size (D4) of 6.0 μm.

[0261] 2.0 parts of hydrophobic silica fine particles (specific surface area of ​​140 m²) 2 The toner (ΔH1, measured by the BET method using nitrogen adsorption) was externally added to 100 parts of toner particles 1 and mixed with them, and then sieved through a sieve with a pore size of 150 μm to obtain toner 1. The ΔH1 of toner 1 is 4.9 J / g and the ΔH2 is 3.5 J / g. The glass transition temperature (Tg) of toner 1 during the second heating process, measured by differential scanning calorimetry, is 53 °C.

[0262] <Example of production of magnetic nuclei used as carriers>

[0263]

[0264] Weigh out the materials listed above according to the above composition ratio as ferrite starting materials.

[0265] The mixture was then mixed and pulverized for five hours using a dry vibratory mill with 1 / 8-inch diameter stainless steel beads. The resulting pulverized material was then processed into granules of approximately 1 mm square using a roller press.

[0266] Coarse powder was removed from these granules using a vibrating screen with a 3 mm aperture; fine powder was then removed using a vibrating screen with a 0.5 mm aperture; and subsequently, the granules were calcined in a burner-type furnace at 1000°C for four hours under a nitrogen atmosphere (oxygen concentration 0.01 vol%) to produce pre-calcined ferrite. The composition of the obtained pre-calcined ferrite is as follows.

[0267] (MnO) a (MgO) b (SrO) c (Fe2O3) d

[0268] In the formula, a = 0.257, b = 0.117, c = 0.007, and d = 0.393.

[0269] The obtained pre-calcined ferrite was pulverized to approximately 0.3 mm using a pulverizer. Then, 30 parts water (relative to 100 parts pre-calcined ferrite) were added, and the mixture was further pulverized for one hour using a wet ball mill with 1 / 8-inch diameter zirconia beads. The resulting slurry was then pulverized for four hours using a wet ball mill with 1 / 16-inch diameter alumina beads to obtain a ferrite slurry (a finely pulverized version of the pre-calcined ferrite).

[0270] 1.0 part of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added to the ferrite slurry relative to 100 parts of pre-calcined ferrite, and then granulated into spherical particles using a spray dryer (manufacturer: Ohkawara Kakohki Co., Ltd.). The particle size of the obtained particles was adjusted, and then heated in a rotary kiln at 650°C for two hours to remove organic components such as dispersants and binders.

[0271] To control the firing atmosphere, an electric furnace was used to raise the temperature from room temperature to 1300°C over two hours in a nitrogen atmosphere (oxygen concentration 1.00 vol%), and then fired at 1150°C for four hours. Subsequently, the temperature was lowered to 60°C over four hours to return from the nitrogen atmosphere to the atmosphere, and the furnace was removed at a temperature below 40°C.

[0272] The aggregated particles are crushed; then a magnetic classifier is used to remove low magnetic products; and coarse particles are removed by sieving through a 250 μm sieve to obtain magnetic core particles with a 50% particle size (D50) of 37.0 μm by volume.

[0273] <Example of the production of coating resin for carrier>

[0274] ·Cyclohexyl methacrylate monomer 26.8%

[0275] ·Methyl methacrylate monomer 0.2%

[0276] ·Methyl methacrylate macromonomer 8.4%

[0277] (A macromonomer with a methacryloyl group at one end and a weight-average molecular weight of 5,000)

[0278] Toluene 31.3%

[0279] ·Methyl ethyl ketone 31.3%

[0280] • Azobisisobutyronitrile 2.0%

[0281] Among these materials, cyclohexyl methacrylate monomer, methyl methacrylate monomer, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were introduced into a four-necked separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirrer. Nitrogen was introduced into the separable flask to fully establish a nitrogen atmosphere, and then heated to 80°C, azobisisobutyronitrile (AIBN) was added, and polymerization was carried out under reflux for five hours.

[0282] Hexane is poured into the resulting reaction product to precipitate the copolymer.

[0283] The resulting precipitate is separated by filtration and vacuum drying to obtain resin.

[0284] Dissolve 30 parts of the resin in a mixed solvent of 40 parts toluene and 30 parts methyl ethyl ketone to obtain a resin solution (solid concentration = 30%).

[0285] <Preparation of Coating Resin Solution>

[0286] • Resin solution (30% solids concentration) 33.3%

[0287] Toluene 66.4%

[0288] • Carbon black (Regal 330, Cabot Corporation) 0.3%

[0289] (Number-average primary particle size: 25 nm, nitrogen adsorption specific surface area: 94 m²) 2 / g, DBP oil absorption: 75mL / 100g)

[0290] The materials listed above were introduced into a paint mixer and dispersed for one hour using 0.5 mm diameter zirconia beads. The resulting dispersion was then filtered through a 5.0 μm membrane filter to obtain the coating resin solution.

[0291] <Example of magnetic carrier production>

[0292] The coated resin solution and magnetic core particles (the amount of coated resin solution introduced as a resin component is 2.5 parts per 100 parts of magnetic core particles) are introduced into a vacuum degassing mixer maintained at room temperature.

[0293] After introduction, the mixture is stirred at 30 rpm for 15 minutes, and at least a predetermined amount (80% by mass) of the solvent is evaporated. Then, the mixture is heated to 80°C while being mixed under reduced pressure, and the toluene is distilled off over two hours and then cooled.

[0294] The low-magnetic-force products were separated from the resulting magnetic carriers using a magnetic classifier, and then the magnetic carriers were passed through a sieve with a pore size of 70 μm and classified using an air classifier to obtain magnetic carriers with a 50% particle size (D50) of 38.2 μm by volume.

[0295] <Production Example of Developer 1>

[0296] By using a V-type mixer (Model V-10, Tokuju Seisakusho Co., Ltd.) and 0.5s -1 Under the condition of a rotation time of five minutes, and using toner 1 at a ratio of 10 parts to 90 parts magnetic carrier, toner 1 and magnetic carrier were mixed to prepare developer 1. The obtained developer 1 was evaluated as follows.

[0297] <Example 1>

[0298] <Evaluation of Low-Temperature Fixing Performance>

[0299] The image forming apparatus was a Canon, Inc. imageruner advance C5051 commercial digital printer for printing; it was modified to allow for free setting of fixing temperature and processing speed. Developer 1 was introduced into the developing unit at the cyan position of the modified machine; the DC voltage VDC of the electrostatic latent image carrier or developer carrier, the charging voltage VD of the electrostatic latent image carrier, and the laser power were adjusted to provide the desired toner load on the paper; and the following evaluation was performed.

[0300] • Paper: CS-680 (A4, 68.0g / m³) 2 )

[0301] (Sold by Canon Marketing Japan Inc.)

[0302] • Toner carrying capacity on paper: 0.90 mg / cm³ 2

[0303] • Image evaluation: Position the image 10cm in the center of an A4 sheet of paper. 2 Image

[0304] Fixing test environment: Low temperature and low humidity environment: temperature 15℃ / humidity 10%RH (hereinafter referred to as "L / L")

[0305] Set the processing speed to 450 mm / second; adjust the fixing temperature; output the fixed image; and visually evaluate the state of the fixed image.

[0306] (Evaluation Criteria)

[0307] A: Fixing can be performed in a temperature range below 115℃.

[0308] B: Fixing can be performed within a temperature range of 115℃ to 120℃.

[0309] C: Fixing can be performed within a temperature range of 120℃ to 125℃.

[0310] D: Fixing can be performed within a temperature range of 125℃ to 130℃.

[0311] E: Fixing is only possible in temperatures above 130°C.

[0312] <Evaluation of Image Storage Capabilities>

[0313] A reliable fixing temperature is set at a temperature 20°C higher than the lower limit of the fixing temperature, and plain paper GF-C104 (A4, 104g / cm³) for color copiers and printers is used. 2 (Sold by Canon Marketing Japan Inc.), forms two toner loading points on one side of A4 paper with a loading of 0.90 mg / cm². 2 A solid image (5cm × 5cm) is formed. Recording papers with the solid images formed on them are stacked face-to-face, so that the solid images are in contact with each other, and a 100g / cm² pressure is applied. 2 Under vertical load, the images were left to stand for one day at a temperature of 65°C and a relative humidity of 40% RH. The images on the two printed materials were then separated, and defects (presence or absence of gloss unevenness) caused by image adhesion on the image surfaces were evaluated. The percentage of area showing gloss fluctuations (i.e., the percentage of area with gloss unevenness) was determined by binarization during image processing.

[0314] (Evaluation Criteria)

[0315] A: There are no image defects.

[0316] B: Uneven gloss is present in the image. (The percentage of area showing gloss fluctuations is less than 2%).

[0317] C: Uneven gloss appears in the image. (The percentage of area showing gloss fluctuations is greater than 2% but less than 5%).

[0318] D: Uneven gloss appears in the image. (The percentage of area showing gloss fluctuations is greater than 5% but less than 10%).

[0319] E: The image undergoes stripping.

[0320] For all the evaluation items mentioned above, developer 1 received an A score.

[0321] <Examples 2 to 10>

[0322] (Production examples of colorants 2 to 10)

[0323] In addition to changing the type and amount of binder resin and crystalline polyester as shown in Table 2, toners 2 to 10 can be obtained as in the production example of toner 1.

[0324] [Table 2]

[0325] Table 2

[0326]

[0327] The content (parts by mass) of crystalline polyester in the table is a value relative to 100 parts by mass of adhesive resin.

[0328] (Production examples of developer 2 to 10)

[0329] Except for the toner changes shown in Table 3, developers 2 to 10 were obtained as in the production example of developer 1. The same evaluation was performed as in Example 1. The evaluation results are given in Table 3.

[0330] [Table 3]

[0331] Table 3

[0332]

[0333] <Comparative Examples 1 to 4>

[0334] (Production examples of toners 11 to 14)

[0335] In addition to changing the type and amount of binder resin and crystalline polyester as shown in Table 4, toners 11 to 14 are obtained as in the production example of toner 1.

[0336] [Table 4]

[0337] Table 4

[0338]

[0339] The content (parts by mass) of crystalline polyester in the table is a value relative to 100 parts by mass of adhesive resin.

[0340] (Production examples of developers 11 to 14)

[0341] Except for the toner changes shown in Table 5, developers 11 to 14 were obtained as in the production example of developer 1. The same evaluation was performed as in Example 1. The evaluation results are given in Table 5.

[0342] [Table 5]

[0343] Table 5

[0344]

[0345] This invention is not limited to or not restricted by the foregoing embodiments, and various modifications and alterations can be made without departing from the spirit or scope of the invention. Therefore, the claims are appended to disclose the scope of the invention.

[0346] This application claims priority based on Japanese Patent Application No. 2019-184657, filed on October 7, 2019, the entire contents of which are incorporated herein by reference.

Claims

1. A toner comprising toner particles including a binder resin and a crystalline polyester, wherein... The adhesive resin comprises a polyester having a structure represented by the following formula (1): In formula (1), R independently represents hydrogen, methyl, or phenyl; A represents a polyester segment; B indicates a polyester segment or is selected from -R 1 OH, -R 1 COOH, and -R 1 Any functional group in the group consisting of NH2, where R 1 Indicates a single bond or C 1-4 alkylene groups; and The average number of repetitions n is between 10 and 80, and In a polyester having a structure represented by formula (1), the content of the structure represented by formula (2) is from 0.5% by mass to 5.0% by mass: In equation (2), R independently represents hydrogen, methyl, or phenyl, and n is the average number of repetitions of the siloxane unit, ranging from 10 to 80. In the adhesive resin, the content of polyester having the structure of formula (1) is 70% by mass or more.

2. The toner according to claim 1, wherein the glass transition temperature of the toner, as measured by differential scanning calorimetry, during the second heating process is 45°C to 60°C.

3. The toner according to claim 1 or 2, wherein... The heat endothermic originating from the crystalline polyester during the first heating process, measured by differential scanning calorimetry using ΔH1 as the toner, and The heat endothermic originating from the crystalline polyester during the second heating process, measured by differential scanning calorimetry using ΔH2 as the toner. ΔH1 ranges from 1.0 J / g to 10.0 J / g, and The ratio of ΔH2 to ΔH1, i.e., ΔH2 / ΔH1, is between 0.50 and 1.

00.

4. The toner according to claim 1 or 2, wherein the content of the crystalline polyester in the toner is from 2.0 parts by weight to 12.0 parts by weight relative to 100 parts by weight of the binder resin.

5. The toner according to claim 1 or 2, wherein each of R is methyl.

6. The colorant according to claim 1 or 2, wherein the crystalline polyester is a condensation polymer of an aliphatic diol having 6 to 18 carbon atoms and an aliphatic dicarboxylic acid compound having 6 to 18 carbon atoms.

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