Toner

Abstract

Toner comprising a toner particle comprising a binder resin and a crystalline polyester, wherein the binder resin contains a polyester with a structure represented by the following formula (1), wherein the content of the polyester with the structure of formula (1) in the binder resin is at least 50 wt%: In formula (1), the Rs each represent hydrogen, a methyl group or a phenyl group independently of one another; A represents a polyester segment; B represents a polyester segment or functional group selected from the group consisting of -R 1 EAR 1 COOH, and -R 1 NH2, where R 1 a single bond or a C 1-4 represents an alkylene group; and an average number of repetitions n is between 10 and 80, and wherein the content of the structure represented by the following formula (2) in the polyester with the structure represented by formula (1) is from 0.5 wt% to 5.0 wt%: In formula (2) the Rs each independently represent hydrogen, a methyl group or a phenyl group and n is the average value of the number of repeats of the siloxane unit and ranges from 10 to 80.

Description

[Technical field]

[0001] The present invention relates to a toner for the development of an electrostatic image, which is used, for example, in electrophotographic processes and electrostatic recording processes. [State of the art]

[0002] Electrophotography-based full-color copiers have become widespread in recent years and are now even used in the printer market. The printing market demands high speeds, high image quality, and high productivity, while simultaneously adapting to a wide range of media (paper types). For example, when switching from thick to thin paper, a consistent media speed is required so that the printing process can continue without having to adjust the process speed or the heating temperature set at the fuser unit to the paper type. To enable consistent media speed performance, the toner must be able to fuse over a wide range of fusing temperatures. - from low to high temperatures - in a suitable manner. To achieve thorough fixing over a wide fixing temperature range, various investigations were carried out to improve low-temperature fixing properties by adding a high-melting-point crystalline polyester to the toner, which acts as a plasticizer for the binder resin. Various investigations were also carried out to improve the associated problem of toner shelf life.

[0003] Patent document 1, for example, discloses a toner which has improved low-temperature fixability achieved by mixing a crystalline polyester resin with an amorphous polyester resin, and which has improved toner shelf life achieved by forming a shell on the toner surface.

[0004] On the other hand, the storability of the image on the printed material is also considered critical in the printer market. With an image produced using a toner that exhibits good low-temperature fixability, the printed material can stick to itself, even if the toner itself has good storability, due to the softening of the fixed image when exposed to high temperatures. When the sticky printed material flakes off, uneven gloss may occur, and the image may detach.

[0005] Patent document 2 discloses a toner in which the compatibility between a crystalline polyester and an amorphous polyester is controlled to improve both low-temperature fixability and image storability.

[0006] JP 2011 - 203 511 A relates to a toner for the development of electrostatic charge images, comprising toner particles that include a binder resin, a polysiloxane-modified resin and an organopolysiloxane resin. [Citation list][Patent document] [Patent Document 1] JP 2015 - 036 723 A [Patent Document 2] JP 2016 - 080 934 A [Summary of the invention][Technical problem]

[0007] Although the toner described in patent document 1 exhibits good toner storage properties, the image storage properties are unsatisfactory due to the softening of the image after fixing.

[0008] Due to a composition that suppresses compatibility between the amorphous and crystalline polyesters, the toner described in patent document 2 exhibits unsatisfactory low-temperature fixability when image storability is improved. Furthermore, while image storability is demonstrably good at a temperature of 30°C and a relative humidity of 60%, high temperatures above the ambient air temperature can occur during transport of printed materials, e.g., by vehicle or ship, depending on the loading location, thus further improving image storability.

[0009] The present invention provides a toner which exhibits excellent low-temperature fixability and excellent image storability. [Solution to the problem]

[0010] The present invention relates to a toner comprising a toner particle comprising a binder resin and a crystalline polyester, wherein the binder resin contains a polyester having the structure represented by the following formula (1), wherein the content of the polyester having the structure represented by formula (1) in the binder resin is at least 50 wt%, and wherein the content of the structure represented by the following formula (2) in the polyester having the structure represented by formula (1) is from 0.5 wt% to 5.0 wt%: in formula (2) the Rs each independently represent hydrogen, a methyl group or a phenyl group and n is the average value of the number of repetitions of the siloxane unit and is from 10 to 80.

[0011] In formula (1), the Rs each independently represent 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 EAR 1 COOH, and -R 1 NH2, where R 1 a single bond or a C 1-4 represents an alkylene group; and the average number of repetitions n is 10 to 80. [Advantageous effects of the invention]

[0012] The present invention can thus provide a toner that exhibits excellent low-temperature fixability and excellent image storability. [Description of the embodiments]

[0013] Unless explicitly stated otherwise, the expressions "from XX to YY" and "XX to YY", which indicate numeric ranges of values, refer to numeric ranges of values ​​that include the lower bound and the upper bound, which represent the endpoints.

[0014] In stepped numerical value ranges, the upper and lower limits of the individual numerical value ranges can be combined in any combination.

[0015] The present inventors have carried out intensive investigations with the aim of achieving further improvements in low-temperature fixability and image storage capability.

[0016] As a result, it was discovered that excellent low-temperature fixability and excellent image storability are obtained by using toner containing a crystalline polyester and a binder resin containing polyester with the structure given by the following formula (1).

[0017] In formula (1), the Rs each independently represent 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 EAR 1 COOH, and -R 1 NH2, where R 1 a single bond or a C 1-4 represents an alkylene group; and the average number of repetitions n is 10 to 80.

[0018] The reasons for the occurrence of the above-mentioned effects when this design is used for the toner are presumably the following.

[0019] Within the framework of the structure specified by formula (1), the structure without A and B is also referred to as the silicone structure.

[0020] A polyester with the structure of formula (1) is a resin that has within the same molecule both a highly polar polyester segment and a low-polar silicone structure.

[0021] The crystalline polyester exhibits high compatibility with the polyester segment of the polyester with the structure of formula (1), resulting in a plasticizing effect during fixation and excellent low-temperature fixability. Conversely, the crystalline polyester exhibits low compatibility with the silicone structure, and it is assumed that this promotes the recrystallization of the crystalline polyester—which exists in a state where it is surrounded by the polyester with the structure of formula (1)—in the temperature range below its melting point.

[0022] It is assumed that this will suppress the softening of the fixed image and that recrystallized crystalline polyester will also be present on part of the surface of the fixed image.

[0023] The recrystallized crystalline polyester (crystalline component) has high heat resistance and improves image storability; furthermore, the segment (amorphous component), which differs from the crystalline polyester, has a low free surface energy in the fixed image due to its silicone structure. It is assumed that both the crystalline and amorphous components can suppress adhesion between the fixed images, further improving image storability.

[0024] Based on the foregoing, the use of toner containing crystalline polyester and polyester with the structure given by formula (1) achieves previously unavailable excellent low-temperature fixability and excellent image storability.

[0025] The glass transition temperature of the toner, measured by differential scanning calorimetry in a second heating step, is preferably between 45°C and 60°C, and more preferably between 50°C and 55°C. Improved low-temperature fixability and better image storage are achieved by ensuring that the glass transition temperature (hereinafter also referred to simply as Tg) of the toner lies within the specified range.

[0026] Using ΔH1 for the endothermic amount originating from the crystalline polyester in a first heating step, measured at the toner by differential scanning calorimetry, and using ΔH2 for the endothermic amount originating from the crystalline polyester in a second heating step, measured on the toner by differential scanning calorimetry, 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. 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.

[0027] Furthermore, the ratio of ΔH2 to ΔH1 (ΔH2 / ΔH1) is preferably from 0.50 to 1.00, more preferably from 0.60 to 1.00 and even more preferably from 0.70 to 1.00. ΔH1 is a value that indicates the amount of crystalline polyester integrated into the toner that is in the crystalline state. (ΔH2 / ΔH1), on the other hand, is an index that indicates the proportion of the crystalline polyester that is recrystallized after fixation.

[0028] By ensuring that ΔH1 and (ΔH2 / ΔH1) are within the specified ranges, the highly heat-resistant crystalline fraction on the surface of the fixed image can be effectively preserved, and the image storability is further improved.

[0029] The melting point of the crystalline polyester is preferably from 65°C to 85°C and more preferably from 70°C to 80°C.

[0030] Because the melting point of the crystalline polyester lies within the specified range, it exhibits a crystalline structure during image storage, further improving its storability. Conversely, during fixation, it mixes with the polyester segment present in the binder resin, resulting in a plasticizing effect. This further enhances low-temperature fixability.

[0031] The glass transition temperature (Tg) of the binder resin, the melting point of the crystalline polyester, the glass transition temperature (Tg) of the toner and the endothermic amounts ΔH1 and ΔH2 originating from the crystalline polyester are measured using the following procedure.

[0032] This means that the measurement is performed based on ASTM D 3418-82 under the following conditions and using an MDSC-2920 (TA Instruments) Differential Scanning Calorimeter (DSC).

[0033] First, approximately 3 mg of the sample are accurately weighed and placed in an aluminum dish; an empty aluminum dish serves as a reference.

[0034] The measurement temperature range used is from 30°C to 200°C; the temperature is increased from 30°C to 200°C at a rate of 10°C / min; subsequently, it is cooled from 200°C to 30°C at a rate of 10°C / min.

[0035] The temperature is then increased again from 30°C to 200°C at a rate of 10°C / min.

[0036] Using the curve for the change in specific heat (i.e., the DSC curve) obtained in this second heating step, the glass transition temperature (Tg) is determined as the temperature at the intersection between the curve segment for the step change at the glass transition and a straight line equidistant in the direction of the vertical axis to the straight lines extending the baseline before the change in specific heat and the baseline after the change in specific heat, respectively.

[0037] The melting point of the crystalline polyester is the peak temperature of the maximum endothermic peak in the curve for the specific heat change obtained in the second heating step.

[0038] The endothermic amounts ΔH1 and ΔH2 originating from the crystalline polyester are determined by calculation using the analysis software supplied with the device from the peak areas of the endothermic peaks originating from the crystalline polyester.

[0039] If the endothermic peak originating from the crystalline polyester does not overlap with an endothermic peak for another crystalline material, e.g., wax, the resulting endothermic quantity ΔH is treated as originating from the crystalline polyester. However, if an endothermic peak for another crystalline material, e.g., wax, overlaps with the endothermic peak for the crystalline polyester, the endothermic quantity originating from the other crystalline material must be subtracted from the resulting endothermic quantity.

[0040] The endothermic quantity originating from the crystalline polyester can be determined, for example, by subtracting the endothermic quantity originating from the wax according to the following procedure.

[0041] The DSC measurement is first performed separately on the wax itself to determine its endothermic properties. Subsequently, the wax content in the toner is determined. There are no particular limitations for measuring the wax content in toner, but this measurement can be performed, for example, by peak separation during a DSC measurement or by a known structural analysis.

[0042] The endothermic amount derived from the wax can then be calculated based on the wax content in the toner, and this amount can be subtracted from the endothermic amount for the toner. If the wax is readily compatible with the resin component, the wax content can be multiplied by a compatibility ratio, and then the endothermic amount derived from the wax can be calculated and subtracted. This compatibility ratio can be calculated as the value obtained by dividing the endothermic amount determined for a mixture with a prescribed ratio of wax to a melt mixture of the resin component by the theoretical endothermic amount calculated from the previously determined endothermic amount for the melt mixture and the endothermic amount for the wax itself.

[0043] The content of crystalline polyester in the toner, per 100 parts by mass of the binder resin, is preferably from 2.0 parts by mass to 12.0 parts by mass and more preferably from 3.0 parts by mass to 8.0 parts by mass.

[0044] By keeping the crystalline polyester content within the specified range, an effective plasticizing effect can be achieved during fixing, which improves low-temperature fixability; furthermore, the highly heat-resistant crystalline component on the surface of the fixed image can be effectively preserved, which improves image storability.

[0045] The content of the silicone structure in the polyester with the structure of formula (1) is from 0.5 wt% to 5.0 wt% and preferably from 2.0 wt% to 4.0 wt%.

[0046] By ensuring that the content of the structure with formula (1) is within the specified range, the free surface energy of the amorphous portion of the fixed image is effectively reduced; furthermore, the recrystallization of the crystalline polyester can be effectively promoted. In addition, there is no inhibition of the plasticizing effect of the crystalline polyester on the polyester segment, thus improving image storability and low-temperature fixability.

[0047] The binder resin should contain polyester with the structure specified by formula (1) and may also contain other resins.

[0048] These other resins include, for example, polyesters that do not have the structure of formula (1), vinyl copolymer resins, polyurethane, epoxy resins, phenolic resins and hybrid resins produced by a chemical bond between two or more types of these resin structures.

[0049] The polyester segment in the polyester with the structure of formula (1) is preferably an amorphous polyester.

[0050] The polyester content of structure of formula (1) in the binder resin is at least 50% by mass and may be at least 60% by mass, at least 70% by mass, at least 80% by mass, at least 90% by mass or 100% by mass. The upper limit is equal to or less than 100% by mass.

[0051] The interaction with the crystalline polyester described above can be achieved more effectively if the content of the polyester with the structure of formula (1) in the binder resin is at least 50 wt%.

[0052] The following describes the components that form the polyester segment of the polyester with the structure of formula (1). Depending on the type and use, a single type or two or more types of the various components listed below may be used.

[0053] The dibasic acid component that constitutes the polyester segment can consist, for example, of the following dicarboxylic acids and their derivatives: Benzenedicarboxylic acids and their anhydrides and lower alkyl esters, e.g., phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride; alkyldicarboxylic acids, e.g., succinic acid, adipic acid, sebacic acid, and azelaic acid, and their anhydrides and lower alkyl esters; alkenyl succinic acids and alkyl succinic acids with an average carbon number of 1 to 50 and their anhydrides and lower alkyl esters; and unsaturated dicarboxylic acids, e.g., fumaric acid, maleic acid, citraconic acid, and itaconic acid, and their anhydrides and lower alkyl esters. The alkyl group in the lower alkyl esters can be, for example, a methyl group, ethyl group, propyl group, or isopropyl group.

[0054] The divalent alcohol component that constitutes the polyester segment, on the other hand, can be, for example, as follows: 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, neopentyl glycol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 1,4-cyclohexanedimethanol (CHDM), hydrogenated bisphenol A, bisphenols of formula (I-1) and their derivatives, and diols of formula (I-2).

[0055] In formula (I-1) R represents the ethylene group or the propylene group, x and y are each integers equal to or greater than 0, and the average value of x + y is from 0 to 10.

[0056] In formula (I-2) R' represents the ethylene group or the propylene group, x' and y' are each integers equal to or greater than 0, and the average value of x' + y' is from 0 to 10.

[0057] In addition to the above-mentioned dibasic carboxylic acid compound and dihydric alcohol compound, the components of the polyester segment may contain at least a tribasic carboxylic acid compound and at least a trihydric alcohol compound as components.

[0058] The at least tribasic carboxylic acid compound is not particularly limited and can be, for example, trimellitic acid, trimellitic anhydride, and pyromellitic acid. The at least trihydric alcohol compounds can be, for example, trimethylolpropane, pentaerythritol, and glycerol.

[0059] In addition to the aforementioned compounds, the constituents of the polyester segment can include a monobasic carboxylic acid compound and a monohydric alcohol compound. Examples of monobasic carboxylic acids include palmitic acid, stearic acid, arachidic acid, and behenic acid. Further examples are cerotic acid, heptacosanoic acid, montanic acid, melissic acid, lacceric acid, tetracontanoic acid, and pentacontanoic acid.

[0060] Examples of monohydric alcohol compounds include behenyl alcohol, ceryl alcohol, melissyl alcohol, and tetracontanol.

[0061] The following describes the components that constitute the structure (i.e., a silicone structure) obtained by removing A and B from the structure given by formula (1) in the polyester with the structure given by formula (1). Depending on the type and intended use, a single species or two or more species of the various components below may be used. The silicone structure has the structure given by the following formula (2).

[0062] In formula (2), Rs each independently represent hydrogen, a methyl group, or a phenyl group, and n is from 10 to 80. This n is the average value of the number of repeats of the siloxane unit and is preferably from 20 to 65.

[0063] The occurrence of excellent diffusion capacity into the binder resin is facilitated by the fact that the value of n lies within the specified range. It is assumed that this facilitates effective recrystallization of the crystalline polyester and a reduction in the free surface energy, thereby improving image storage stability.

[0064] All R's in formula (1) are preferably the methyl group.

[0065] If all Rs are methyl groups, the recrystallization of the crystalline polyester is more strongly promoted and a greater improvement in image storability is provided.

[0066] Silicone oil, which has a functional group at one or more ends in formula (2) that chemically reacts with the polyester, can be used as a component that forms the structure of formula (2) in the polyester with the structure of formula (1). This functional group that reacts with the polyester can be, for example, a hydroxyl group, a carboxyl group, an epoxy group, or an amino group.

[0067] To control the reactivity with the polyester, the hydroxy group or carboxyl group is preferably used as a terminal functional group in the silicone oil.

[0068] The number of functional groups at the silicone oil end(s) can be 1, 2, 3, or more. To achieve better image storage by controlling compatibility with the crystalline polyester through the introduction of the silicone structure into the polyester's main backbone, the use of a silicone oil with a functional group at both ends is preferred. Specific examples are silicone oils with a hydroxyl group at both ends (KF-6000, KF-6001, and KF-6002, all from Shin-Etsu Chemical Co., Ltd.).

[0069] The process for producing the polyester with the structure of formula (1) is not particularly limited and a known process can be used.

[0070] The polyester with the structure of formula (1) can be produced, for example, by polymerization - via an esterification reaction or transesterification reaction and a condensation reaction - of the above-mentioned dibasic carboxylic acid compound, dihydric alcohol compound and silicone oil with functional end groups.

[0071] The polymerization temperature is not particularly limited, but the range of 180°C to 290°C is preferred.

[0072] For example, a polymerization catalyst, e.g., a titanium catalyst, tin catalyst, zinc acetate, antimony trioxide, germanium dioxide, etc., can be used during polymerization to obtain the polyester.

[0073] The softening point (hereinafter also referred to simply as Tm) of the polyester with the structure of formula (1) is preferably from 85°C to 150°C and more preferably from 100°C to 150°C.

[0074] Because the softening point of the polyester with the structure of formula (1) lies within the specified range, the storability of the fixed image is further improved, and in addition, the low-temperature fixability is also excellent.

[0075] The glass transition temperature (Tg) of the polyester with the structure of formula (1) in a second heating step when measured by differential scanning calorimetry as described above is preferably from 50°C to 65°C and more preferably from 53°C to 60°C.

[0076] The softening point (Tm) is measured as follows.

[0077] The softening point is measured using a “Flowtester CFT-500D Flow Property Evaluation Instrument” (Shimadzu Corporation), a constant-load extrusion type capillary rheometer, according to the manual supplied with the instrument.

[0078] In this device, the sample filled into a cylinder is heated and melted under a constant load applied from above by a piston, and the molten sample is extruded from a nozzle at the bottom of the cylinder; from this, a flow curve can be obtained that shows the relationship between piston stroke and temperature.

[0079] The “melting temperature by the 1 / 2 method”, as described in the manual of the “Flowtester CFT-500D Flow Property Evaluation Instrument”, is used in this disclosure as the softening point.

[0080] The melting temperature according to the 1 / 2 method is determined as follows.

[0081] First, half the difference between the piston stroke Smax at the end of the outflow and the piston stroke Smin at the beginning of the outflow is determined (this value is called X, where X = (Smax - Smin) / 2).

[0082] The temperature in the flow curve when the piston stroke reaches the sum of X and Smin is the melting temperature according to the 1 / 2 method. The test sample is prepared by compressing approximately 1.3 g of the sample for 60 seconds at 10 MPa in a 25°C environment using a tablet former (e.g., NT-100H, NPa System Co., Ltd.) to obtain a cylindrical shape with a diameter of approximately 8 mm. The measurement conditions with the CFT-500D are as follows. Test mode: Ramp-up procedure Starting temperature: 50°C Saturation temperature: 200°C Measurement interval: 1.0°C Rate of increase: 4.0°C / min Cross-sectional area of ​​the piston: 1,000 cm² 2 Test force (piston load): 10.0 kgf / cm 2 (0.9807 MPa) Preheating time: 300 seconds Die opening diameter: 1.0 mm Die length: 1.0 mm

[0083] The toner particle contains crystalline polyester.

[0084] In the present disclosure, a crystalline polyester is a polyester in which an endothermic peak is observed during measurement by differential scanning calorimetry (DSC).

[0085] Due to the condition of simple molecular motion to assume a eutectic structure, the crystalline polyester is preferably a crystalline polyester that can assume a lamellar structure, i.e., a folded structure.

[0086] The alcohol component used as the starting monomer for the crystalline polyester can, for example, be as follows.

[0087] Examples 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 and 1,20-eicosanediol, although there is no restriction to these.

[0088] Of the aforementioned, aliphatic diols with 6 to 18 carbons are preferred from the point of view of low-temperature fixability and image storage capability, and aliphatic diols with 8 to 14 carbons are more preferred.

[0089] From the point of view of a greater increase in the crystallinity of the crystalline polyester, the content of aliphatic diol is preferably a content in the alcohol component of 80 mol% to 100 mol%.

[0090] The alcohol component used to obtain the crystalline polyester may contain a different polyhydric alcohol component than the aliphatic diol described above. Examples include aromatic diols, e.g., alkylene oxide adducts of bisphenol A, including polyoxypropylene adducts of 2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene adducts of 2,2-bis(4-hydroxyphenyl)propane, as well as at least trihydric alcohols such as glycerol, pentaerythritol, and trimethylolpropane.

[0091] On the other hand, the carboxylic acid component used as the starting monomer for the crystalline polyester can be, for example, as follows: Aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, cortic 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. Further examples include the anhydrides of the aforementioned acids and their lower alkyl esters. The alkyl group in the lower alkyl ester can be, for example, the methyl group, ethyl group, propyl group, or isopropyl group.

[0092] Among the above, and considering low-temperature fixability and image storage capability, the use of aliphatic dicarboxylic acid compounds with 6 to 18 carbons is preferred, and aliphatic dicarboxylic acid compounds with 6 to 12 carbons are more preferred.

[0093] The content of the aliphatic dicarboxylic acid compound is preferably a content in the carboxylic acid component of 80 to 100 mol%.

[0094] The carboxylic acid component for obtaining the crystalline polyester can contain a different carboxylic acid component than the aliphatic dicarboxylic acid compounds described above. Examples include aromatic dicarboxylic acid compounds and at least tribasic aromatic polybasic carboxylic acid compounds, but there are no particular restrictions on this.

[0095] Derivatives of aromatic dicarboxylic acids also fall under the category of aromatic dicarboxylic acid compounds. Preferred specific examples of aromatic dicarboxylic acid compounds are 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 esters (from 1 to 3 carbon atoms). The alkyl group in the alkyl esters can be, for example, the methyl group, ethyl group, propyl group, and isopropyl group. Examples of polybasic carboxylic acid compounds with at least three bases include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, and pyromellitic acid, and their derivatives such as the anhydrides and alkyl esters (1 to 3 carbon atoms).

[0096] The crystalline polyester is preferably a polycondensate of an aliphatic diol with 6 to 18 carbon atoms and an aliphatic dicarboxylic acid compound with 6 to 18 carbon atoms. A polycondensate of an aliphatic diol with 8 to 14 carbon atoms and an aliphatic dicarboxylic acid compound with 6 to 12 carbon atoms is more preferred.

[0097] The molar ratio between the alcohol component and the carboxylic acid component, which are the starting monomers for the crystalline polyester (carboxylic acid component / alcohol component), is preferably from 0.80 to 1.20.

[0098] The weight-averaged molecular weight of the crystalline polyester is preferably 1.0 × 10 4 up to 1.0 × 10 5 and is preferably 2.0 × 10 4 up to 5.0 × 10 4 .

[0099] The weight-averaged molecular weight of the crystalline polyester is measured by gel permeation chromatography (GPC) as follows.

[0100] First, 50 mg of the sample is added to 5 mL of chloroform; the sample is left to stand at 25°C for several hours; then it is shaken thoroughly to ensure good mixing with the chloroform; and it is left to stand for at least another 24 hours until no aggregates of the sample remain.

[0101] The resulting solution is filtered through a solvent-resistant membrane filter “Pretreatment Cartridge H-25-5” with a pore diameter of 0.5 µm to obtain a sample solution.

[0102] The measurement is performed with this sample solution and under the following conditions.

[0103] Instrument: “Lab Solutions GPC” high-performance GPC instrument (Shimadzu Corporation) Column: PLgel 5 µm MIXED-C 300 mm × 7.5 mm (Agilent Technologies, Inc.): 2; PLgel 5 µm Guard 50 mm × 7.5 mm (Agilent Technologies, Inc.): 1 Eluent: Chloroform Flow rate: 1.0 mL / min Oven temperature: 45°C Sample injection volume: 60 µL Detector: RI detector (refractive index)

[0104] The weight-averaged molecular weight (Mw) of the sample is determined using a molecular weight calibration curve created using polystyrene resin standards (product name “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).

[0105] The toner can be used in the form of a magnetic single-component toner, a non-magnetic single-component toner, or a non-magnetic two-component toner.

[0106] When the toner is used in the form of a magnetic single-component toner, a magnetic body is preferably used as the colorant. The magnetic body contained in the magnetic single-component toner can be, for example, magnetic iron oxides such as magnetite, maghemite, ferrite, and magnetic iron oxides containing another metal oxide, as well as metals such as Fe, Co, and Ni, alloys of these metals with a metal such as Al, Co, Cu, Pb, Mg, Ni, Sn, Zn, Sb, Be, Bi, Cd, Ca, Mn, Se, Ti, W, and V, and mixtures of the aforementioned.

[0107] The magnetic body content is preferably from 30 parts by mass to 150 parts by mass per 100 parts by mass of the binder resin.

[0108] Examples of the colorant are listed below for use in the form of a non-magnetic single-component toner or a non-magnetic two-component toner.

[0109] Soot, e.g. furnace black, canal black, acetylene black, thermal soot and lamp black, can be used as a black pigment, as can magnetic substances such as magnetite and ferrite.

[0110] A pigment or dye can be used as a colorant suitable for the color 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, and CI Vat Yellow 1, 3 and 20. The dyes can be, for example, CI Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, and 162. A single one of these substances can be used alone, or two or more can be used in combination.

[0111] A pigment or dye can be used as a colorant suitable for the color 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. A single one of these substances can be used alone, or two or more can be used in combination.

[0112] A pigment or dye can be used as a colorant suitable for the color magenta. The pigments can be, for example, 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, 64, 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. Magenta dyes may include, for example, oil-soluble dyes such as 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, and basic dyes such as 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 CIBasic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27 and 28. A single one of these fabrics can be used alone, or two or more can be used in combination.

[0113] The dye content is preferably from 1 part by mass to 20 parts by mass per 100 parts by mass of the binder resin.

[0114] The toner particle may contain a release agent (wax) to enable separation. This wax could be, for example, the following.

[0115] 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 derived from aliphatic hydrocarbon waxes, e.g., oxidized polyethylene wax; waxes whose main component is a fatty acid ester, e.g., carnauba wax, behenyl behenate, and montanic acid ester wax; and waxes formed by partial or complete deacidification of a fatty acid ester, e.g., deacidified carnauba wax. Further examples include saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and parinaric acid; saturated alcohols such as stearyl alcohol, aralkyl alcohols, behenyl alcohol, carnaubyl alcohol, ceryl alcohol, and melissyl alcohol; and polyhydric alcohols such as sorbitol. Fatty acid amides such as linoleamide, oleamide and lauramide;Saturated fatty acid bisamides such as methylenebisstearamide, ethylenebiscapramide, ethylenebislauramide, and hexamethylenebisstearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N,N'-dioleyladipamide, and N,N'-dioleylsebacamide; aromatic bisamides such as m-xylenebisstearamide and N,N'-distearylisophthalamide; aliphatic metal salts (commonly known as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes produced by grafting an aliphatic hydrocarbon wax using a vinyl copolymer monomer such as styrene or acrylic acid; partial esters between a fatty acid and a polyhydric alcohol, such as behenyl monoglyceride; and hydroxy-containing methyl ester compounds obtained, for example, by the hydrogenation of vegetable oils.

[0116] Aliphatic hydrocarbon waxes are waxes preferred for use among those mentioned above. Examples include low molecular weight hydrocarbons prepared by high-pressure radical polymerization of alkylenes or by low-pressure polymerization of alkylenes in the presence of a Ziegler or metallocene catalyst; 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 residue of hydrocarbons produced by the Arge method from synthesis gas containing carbon monoxide and hydrogen, as well as synthetic hydrocarbon waxes obtained by hydrogenation of such synthetic hydrocarbon waxes.

[0117] Other examples include waxes obtained by fractionating hydrocarbon waxes using a sweat pressing process, a solvent process, vacuum distillation, or a fractional crystallization method. Waxes synthesized by a process without alkylene polymerization are also particularly preferred with regard to their molecular weight distribution.

[0118] Regarding the timing of the wax addition, the wax can be added during the production of the toner or during the production of the binder resin. A single type of wax can be used alone, or a combination of two or more types of wax. The wax content is preferably between 1 part by mass and 20 parts by mass per 100 parts by mass of the binder resin.

[0119] A previously known charge-controlling agent can be used as a charge-controlling agent in the toner particle. Examples of known charge-controlling 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 among the carboxylic acid derivatives. Charge-controlling resins can also be used. Depending on requirements, two or more charge-controlling agents can be used in combination. The charge-controlling agent content is preferably from 0.1 parts by mass to 10 parts by mass per 100 parts by mass of the binder resin.

[0120] The toner can be used in the form of a two-component developer, which is prepared by mixing it with a carrier. The carrier can be a conventional substrate, such as ferrite, magnetite, etc., or a resin-coated substrate. Binder-like carriers, in which a magnetic body is dispersed in a resin, are also suitable.

[0121] The resin-coated substrate consists of a substrate particle and a coating material, which is a resin that coats the surface of the substrate particle. The resin used for the coating material can be, for example, styrene-acrylic resins, such as styrene-acrylate ester copolymers and styrene-methacrylate ester copolymers; acrylic resins such as acrylate ester copolymers and methacrylate ester copolymers; fluorocarbon resins such as polytetrafluoroethylene, monochlorotrifluoroethylene polymer, and polyvinylidene fluoride; silicone resins; polyester resins; polyamide resins; polyvinyl butyral; and aminoacrylate resins. Ionomer resins and polyphenylene sulfide resins are further examples. A single one of these resins or a variety of resins can be used.

[0122] An external additive, e.g., silicon dioxide particles, can be added to the toner to improve charge stability, development performance, flowability, and durability.

[0123] The silicon dioxide particles preferably have a specific surface area of ​​30 m² according to the BET process based on nitrogen adsorption. 2 / g up to 500 m 2 / g and more strongly preferred from 50 m 2 / g up to 400 m 2 / G.

[0124] The content of silicon dioxide fine particles per 100 parts by mass of the toner particle is preferably from 0.01 parts by mass to 8.00 parts by mass and more preferably from 0.10 parts by mass to 5.00 parts by mass.

[0125] The specific BET surface area of ​​the silicon dioxide particles can be determined using the BET multi-point method by adsorbing nitrogen gas onto the surface of the silicon dioxide particles, e.g. with an Autosorb 1 specific surface area analyzer (Yuasa Ionics Co., Ltd.), Gemini 2360 / 2375 (Micromeritics Instrument Corporation) or TriStar 3000 (Micromeritics Instrument Corporation).

[0126] To increase hydrophobicity and control triboelectric charge, the silicon dioxide particles can be treated as required with a treatment agent such as an unmodified silicone lacquer, differently modified silicone lacquers, unmodified silicone oil, differently modified silicone oils, silane coupling agents, functional group-bearing silane compounds and other organosilicon compounds, whereby several different treatment agents can also be used in combination.

[0127] The toner may optionally contain an external additive that differs from the silicon dioxide particles. This external additive could be, for example, inorganic particles and resin particles that serve as charge carriers, conductivity enhancers, flow carriers, anti-caking agents, release agents during hot roller curing, lubricants, or abrasives. The charge carrier could be, for example, metal oxide particles such as titanium oxide, zinc oxide, and aluminum oxide. The lubricant could be, for example, polyfluoroethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. The abrasive could be, for example, cerium oxide powder, silicon carbide powder, and strontium titanate powder.

[0128] The process for producing the toner particle is not particularly limited, and a known method can be used. Examples include the pulverization process, the emulsion aggregation process, the suspension polymerization process, and the solution suspension process.

[0129] A toner particle produced by the pulverization process can, for example, be manufactured as follows.

[0130] The crystalline polyester, the binder resin containing the polyester with the structure of formula (1), and optionally colorants, wax, other additives, etc., are thoroughly mixed using a mixer such as a Henschel mixer or a ball mixer.

[0131] The resulting mixture is melt-kneaded using a heated kneader such as a twin-screw extruder, a hot roller, a kneader, or an extruder. The resulting melt-kneaded material is cooled and solidified, then pulverized and classified to obtain a toner particle. During this process, the average roundness of the toner particle can also be controlled by adjusting the exhaust gas temperature during fine pulverization. If required, a toner can be obtained by mixing the toner particle with an external additive using a mixer, such as a Henschel mixer.

[0132] Examples of mixers include: Henschel mixer (Mitsui Mining Co., Ltd.); Supermixer (Kawata Mfg. Co., Ltd.); Ribocone (Okawara Corporation); Nauta mixer, Turbulizer and Cyclomix (Hosokawa Micron Corporation); Spiral Pin Mixer (Pacific Machinery & Engineering Co., Ltd.); and Loedige mixer (Matsubo Corporation).

[0133] Examples of kneaders include: KRC kneader (Kurimoto, Ltd.); Buss Ko kneader (Buss Corp.); TEM extruder (Toshiba Machine Co., Ltd.); TEX twin-screw kneader (The Japan Steel Works, Ltd.); PCM kneader (Ikegai Ironworks Corporation); three-roll mills, mixing roll mills and kneaders (Inoue Manufacturing Co., Ltd.); Kneadex (Mitsui Mining Co., Ltd.); pressure kneader model MS and kneader rudder (Moriyama Mfg. Co., Ltd.); and Banbury mixer (Kobe Steel, Ltd.).

[0134] Examples of pulverizers include: Counter Jet Mill, Micron Jet and Inomizer (Hosokawa Micron Corporation); IDS Mill and PJM Jet Mill (Nippon Pneumatic Mfg. Co., Ltd.); Cross Jet Mill (Kurimoto, Ltd.); Ulmax (Nisso Engineering Co., Ltd.); SK Jet-O-Mill (Seishin Enterprise Co., Ltd.); Kryptron (Kawasaki Heavy Industries, Ltd.); Turbo Mill (Turbo Kogyo Co., Ltd.); and Super Rotor (Nisshin Engineering Inc.).

[0135] If necessary, the control of the average roundness of the toner particle can follow pulverization by surface treatment of the toner particle with a hybridization 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 Meteo Rainbow MR Type (Nippon Pneumatic Mfg. Co., Ltd.).

[0136] Examples of classifiers include: Classiel, Micron Classifier and Spedic Classifier (Seishin Enterprise Co., Ltd.); Turbo Classifier (Nisshin Engineering Inc.); Micron Separator, Turboplex (ATP) and TSP Separator (Hosokawa Micron Corporation); Elbow Jet (Nittetsu Mining Co., Ltd.); Dispersion Separator (Nippon Pneumatic Mfg. Co., Ltd.); and YM Microcut (Yasukawa Shoji Co., Ltd.).

[0137] For example, the following sieving devices can be used to remove coarse particles: Ultrasonic (Koei Sangyo Co., Ltd.), Rezona Sieve and Gyro-Sifter (Tokuju Corporation), Vibrasonic System (Dalton Co., Ltd.), Soniclean (Sintokogio, Ltd.), Turbo Screener (Turbo Kogyo Co., Ltd.), Microsifter (Makino Mfg. Co., Ltd.) and circular vibrating screens.

[0138] The different measurement methods are described below. Method for measuring the weight-averaged particle diameter (D4)

[0139] The weight-averaged particle diameter (D4) of the toner or toner particle (hereinafter also referred to as toner, e.g.) is determined as follows.

[0140] The measuring instrument used is a “Coulter Counter Multisizer 3” (registered trademark, Beckman Coulter, Inc.), a precision instrument for measuring particle size distribution, which operates according to the method of electrical pore resistance and is equipped with a 100 µm aperture tube.

[0141] The measurement conditions are set and the measurement data is evaluated using the associated software "Beckman Coulter Multisizer 3 Version 3.51" (Beckman Coulter, Inc.). Measurements are performed in 25,000 channels, representing the number of effective measurement channels.

[0142] The aqueous electrolyte solution used for the measurements is prepared by dissolving sodium chloride of a special quality in deionized water to a concentration of 1.0%, for example using “ISOTON II” (Beckman Coulter, Inc.).

[0143] The special software is configured as follows before measurement and analysis.

[0144] On the "modify the standard operating method (SOM)" screen in the accompanying software, the total number of particles in control mode is set to 50,000, the number of measurements to 1, and the Kd value to the value obtained using "standard particle 10.0 µm" (Beckman Coulter, Inc.). The threshold and noise level are automatically set by pressing the "threshold value / noise level measurement button." Additionally, the current is set to 1600 µA, the gain to 2, the electrolyte solution to ISOTON II, and the "post-measurement aperture tube flush" checkbox is selected.

[0145] In the "setting conversion from pulses to particle diameter" screen of the associated software, the bin interval is set to the logarithmic particle diameter, the particle diameter bin is set to 256 particle diameter bins, and the particle diameter range is set to 2 µm to 60 µm.

[0146] The specific measurement procedure is as follows. (1) 200 ml of the aqueous electrolyte solution are placed in a 250 mL round-bottomed beaker intended for the Multisizer 3, which is placed in the sample rack and stirred counterclockwise at 24 revolutions per second using the stirring rod. Impurities and air bubbles in the aperture tube are removed beforehand using the "aperture tube flush" function of the associated software. (2) Approximately 30 mL of the aqueous electrolyte solution are placed in a 100 mL flat-bottomed beaker and 0.3 mL of a dilution of “Contaminon N” prepared by triple (mass) dilution with deionized water (a 10 wt% aqueous solution of a neutral pH 7 cleaning agent for cleaning precision measuring instruments, containing a non-ionic surfactant, an anionic surfactant and an organic builder, from Wako Pure Chemical Industries, Ltd.) is added as a dispersant. (3) An “Ultrasonic Dispersion System Tetora 150” (Nikkaki Bios Co., Ltd.), an ultrasonic dispersing device with an electrical power of 120 W, equipped with two oscillators (oscillation frequency = 50 kHz) arranged so that the phases are shifted by 180°, is prepared. 3.3 L of deionized water and 2 mL of Contaminon N are added to the water tank of the ultrasonic dispersing device. (4) The beaker described in (2) is inserted into the beaker holder opening of the ultrasonic disperser and the ultrasonic disperser is started. The vertical position of the beaker is adjusted so that the resonance state of the surface of the aqueous electrolyte solution in the beaker is at its maximum. (5) While the aqueous electrolyte solution in the beaker prepared according to (4) is sonicated with ultrasound, 10 mg of, for example, the toner, are added to the aqueous electrolyte solution in small aliquots and dispersed. The ultrasonic dispersion is continued for a further 60 seconds. The water temperature in the water tank is adjusted to a value of 10°C to 40°C during the ultrasonic dispersion. (6) The aqueous electrolyte solution prepared in (5), in which, for example, the toner is dispersed, is added dropwise with a pipette to the round-bottomed beaker, which is inserted into the sample rack as described in (1), whereby a measurement concentration of approximately 5% is established. The measurement is then carried out until the number of measured particles reaches 50,000. (7) The measurement data are analyzed by the special software supplied with the instrument and the weight-averaged particle diameter (D4) is calculated. If the special software is set to “Graph / Volume %”, the “average diameter” on the “Analysis / Volumetric Statistical Value (Arithmetic Mean)” screen is the weight-averaged particle diameter (D4).

[0147] Method for identifying the polyester with the structure represented by formula (1)

[0148] The structure represented by formula (1) is identified using the following procedure.

[0149] The hydrocarbon group represented by R in formula (1) and the silicon structure are represented by 13 C-NMR and solid-state 29 Si-NMR identified. 13 C-NMR measurement conditions Device: JNM-ECX500II, JEOL RESONANCE Sample tube: 3.2 mmΦ Sample: Deuterochloroform-soluble substances from the sample for NMR measurement Measurement temperature: Room temperature Pulse mode: CP / MAS Frequency of the measuring core: 123.25 MHz ( 13 C) Reference substance: Adamantane (external reference: 29.5 ppm) Sample spinning rate: 20 kHz Contact time: 2 ms Delay time: 2 s Number of scans: 1024

[0150] In this method, the hydrocarbon group represented by R in formula (1) is identified by the presence / absence of a signal, e.g., from the methyl group (Si-CH3) bonded to a silicon atom or the phenyl group (Si-C6H5).

[0151] The specific measurement conditions for the solid-state 29 Si NMRs are as follows. Instrument: JNM-ECX5002 (JEOL RESONANCE) Temperature: Room temperature Measurement method: DD / MAS method, 29 Si, 45° Sample tube: Zirconium dioxide 3.2 mmΦ Sample: filled into the sample tube as a powder Sample spinning rate: 10 kHz Relaxation delay: 180 s Scans: 2000

[0152] Method for measuring the content of crystalline polyester and the content of the structure represented by formula (2)

[0153] The content of crystalline polyester and the content of the structure represented by formula (2) are determined by 1 H-NMR determined using the device described above. 1 H-NMR measurement conditions Sample: substances soluble in deuterochloroform Pulse condition: 5.0 µs Frequency range: 10,500 Hz Number of scans: 64 Examples

[0154] The present disclosure is described below specifically with reference to manufacturing examples, examples, and comparative examples. However, the present disclosure is in no way limited to or by these. Unless expressly stated otherwise, the "parts" and "%" in the manufacturing examples, examples, and comparative examples always refer to the mass.

[0155] Production example of binder resin 1 - Bisphenol A / ethylene oxide (2.2 mol adduct): 50.0 mol parts - Bisphenol A / propylene oxide (2.2 mol adduct): 50.0 mol parts - Terephthalic acid: 90.0 mol parts - Trimellitic anhydride: 10.0 mol parts

[0156] 97.0 parts of this monomer for the formation of the polyester segment and 3.0 parts of a silicone oil with the hydroxy group at both ends (KF-6000, Shin-Etsu Chemical Co., Ltd.) were placed together with 500 ppm titanium tetrabutoxide in a 5-L autoclave and mixed.

[0157] A reflux condenser, a water separator, an N2 gas inlet line, a thermometer and a stirrer were then installed on the autoclave and a condensation polymerization reaction was carried out at 230°C while N2 gas was introduced into the autoclave.

[0158] The reaction time was adjusted to achieve the desired softening point; after completion of the reaction, the mixture was removed from the container, cooled, and pulverized to obtain a polyester 1 with the structure represented by formula (1). This polyester 1 had a softening point (Tm) of 130°C and a glass transition temperature (Tg) of 55°C. The polyester 1 was designated as binder resin 1.

[0159] The content of the structure of formula (2) in the polyester with the structure of formula (1) was 3.0 wt%; all R in formula (1) were the methyl group; and n was 26. Production example of binder resin 2

[0160] A polyester 2 was obtained according to the preparation method of binder resin 1, except that the silicone oil with the hydroxy group at both ends was replaced by 4.0 parts of a silicone oil (KF-6002, Shin-Etsu Chemical Co., Ltd.). This polyester 2 was designated binder resin 2. The content of the structure of formula (2) in the polyester with the structure of formula (1) was 4.0 wt%; all R in formula (1) were the methyl group; and n was 63. Production example of binder resins 3 to 10

[0161] Polyesters 3 to 10 were prepared according to the preparation method of binder resin 1, except that the silicone oil with the hydroxy group at both ends was replaced by a silicone oil (KF-6001, Shin-Etsu Chemical Co., Ltd.), the amount of silicone oil added was changed as shown in Table 1, and the softening point (Tm) and glass transition temperature (Tg) were adjusted by modifying the reaction time. These polyesters 3 to 10 were designated as binder resins 3 to 10. All R in formula (1) were the methyl group and n was 38. [Table 1] Table 1 Binder resin no. Polyester No. Amount of silicone oil added (parts by mass) Content of the structure of formula (2) (mass-%) 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 Production example of binder resin 11

[0162] An unmodified polyester 11 was prepared according to the preparation example of binder resin 1, except that the amount of added silicone oil was changed to 0 and the softening point (Tm) and glass transition temperature (Tg) were adjusted by modifying the reaction time. The unmodified polyester 11 had a softening point (Tm) of 113°C and a glass transition temperature (Tg) of 44°C. This unmodified polyester 11 was designated binder resin 11. Production example of binder resin 12

[0163] An unmodified polyester 12 was prepared according to the preparation example of binder resin 11, except that the softening point (Tm) and the glass transition temperature (Tg) were adjusted by modifying the reaction time. The unmodified polyester 12 had a softening point (Tm) of 150°C and a glass transition temperature (Tg) of 65°C. This unmodified polyester 12 was designated binder resin 12. Manufacturing example of crystalline polyester 1

[0164] 100.0 mol of 1,10-decanedicarboxylic acid as the carboxylic acid monomer and 100.0 mol of 1,9-nonanediol as the alcohol monomer were placed in a reactor with a nitrogen inlet, water separator tube, stirrer, and thermocouple. The temperature was increased to 140°C while stirring, and the reaction was heated to 140°C for eight hours under a nitrogen atmosphere. The water was then distilled off under normal pressure.

[0165] Then, 0.57 parts of tin dioctylate per 100 parts of the total amount of the carboxylic acid monomer and the alcohol monomer were added, followed by a reaction while heating to 200°C at 10°C / hour. After the two-hour reaction, once 200°C had been reached, the pressure in the reactor was reduced to 5 kPa or less, and the reaction was carried out at 200°C while monitoring the molecular weight to obtain the crystalline polyester 1. The crystalline polyester 1 had a melting point of 75°C and a weight-averaged molecular weight of 2.5 × 10⁻⁶. 4 . Manufacturing example of crystalline polyester 2

[0166] Crystalline polyester 2 was produced as in the production example for crystalline polyester 1, except that the weight-averaged molecular weight was modified by adjusting the reaction time. Crystalline polyester 2 had a melting point of 75°C and a weight-averaged molecular weight of 1.5 × 10⁻⁶. 4 . Manufacturing example of crystalline polyester 3

[0167] Crystalline polyester 3 was prepared as in the preparation example for crystalline polyester 1, except that the carboxylic acid monomer was replaced by sebacic acid and the alcohol monomer by 1,4-butanediol. Crystalline polyester 3 had a melting point of 65°C and a weight-averaged molecular weight of 1.5 × 10⁻⁶ 4 .

[0076] Production example of toner 1 - Binder resin 1 100 pieces - crystalline polyester 1 5 parts - Fischer-Tropsch wax (melting point: 90°C) 6 parts - CI Pigment Blue 15:3 4 parts

[0168] The above-mentioned materials were first mixed in a Henschel mixer and then melt-kneaded in a twin-screw extruder at 160°C.

[0169] The kneaded material was cooled and coarsely pulverized with a hammer mill and finely pulverized with a turbo mill.

[0170] The resulting finely powdered material was classified using a multi-stage classifier based on the Coanda effect to obtain a negatively triboelectrically charged toner particle 1 with a weight-averaged particle diameter (D4) of 6.0 µm.

[0171] 2.0 parts hydrophobized silicon dioxide fine particles (specific surface area of ​​140 m²) 2 / g, measured by the BET method using nitrogen adsorption) were added externally to 100 parts of toner particle 1 and mixed with them, and sieving through a sieve with a mesh size of 150 µm then yielded toner 1. Toner 1 had a ΔH1 of 4.9 J / g and a ΔH2 of 3.5 J / g. Toner 1 had a glass transition temperature (Tg) of 53°C, measured by differential scanning calorimetry in the second heating step.

[0172] Example of the production of magnetic core particles for use as carriers - Fe2O3 62.7 pieces - MnCO3 29.5 pieces - Mg(OH)2 6.8 pieces - SrCO3 1.0 parts

[0173] The materials listed above were weighed out as ferrite starting materials in the composition ratio specified above.

[0174] The material was then mixed and pulverized for five hours using a dry vibratory mill and stainless steel balls with a diameter of 1 / 8 inch. The resulting pulverized material was then processed into pellets with an edge length of approximately 1 mm using a roller press.

[0175] From these pellets, the coarse powder was removed using a vibrating sieve with a mesh size of 3 mm, and the fines were removed using a vibrating sieve with a mesh size of 0.5 mm. The pellets were then fired in a kiln under a nitrogen atmosphere (0.01 vol% oxygen concentration) for four hours at a temperature of 1000°C to produce pre-fired ferrite. The composition of the resulting pre-fired ferrite was as follows. (MnO) a (MgO) b (SrO) c (Fe2O3) d

[0176] In the formula, a = 0.257, b = 0.117, c = 0.007, d = 0.393.

[0177] The resulting pre-burned ferrite was pulverized to approximately 0.3 mm using a crusher. Thirty parts of water per 100 parts of pre-burned ferrite were then added, and the mixture was pulverized for one hour using a wet ball mill with 1 / 8-inch diameter zirconium dioxide balls. The resulting slurry was then pulverized for four hours using a wet ball mill with 1 / 16-inch diameter aluminum oxide balls to obtain a ferrite slurry (a fine pulverized version of the pre-burned ferrite).

[0178] For every 100 parts of pre-burned ferrite, 1.0 part of ammonium polycarboxylate was added as a dispersant and 2.0 parts of polyvinyl alcohol as a binder. The mixture was then granulated into spherical particles using a spray dryer (manufacturer: Ohkawara Kakohki Co., Ltd.). The particle size of the resulting particles was adjusted, and the mixture was subsequently heated for two hours at 650°C in a rotary kiln to remove the organic components, such as the dispersant and the binder.

[0179] To control the firing atmosphere, the temperature was increased from room temperature to 1300°C over two hours using an electric furnace under a nitrogen atmosphere (1.00% oxygen concentration by volume), and then fired for four hours at 1150°C. The temperature was then reduced to 60°C over four hours, the material was returned from the nitrogen atmosphere to the atmosphere, and removed at a temperature of 40°C or below.

[0180] The aggregated particles were crushed; the product with low magnetic force was then removed by a magnetic force classifier; and the coarse particles were removed by sieving on a sieve with an opening of 250 µm to obtain magnetic core particles with a particle diameter of 50% (D50) on a volume basis of 37.0 µm.

[0181] Manufacturing example of coating resin for use with a substrate material - Cyclohexyl methacrylate monomer 26,8% - Methyl methacrylate monomer 0,2% - Methyl methacrylate macromonomer 8,4%

[0182] (Macromonomer with the methacryloyl group at one end and with a weight-averaged molecular weight of 5000) - toluene 31,3% - Methyl ethyl ketone 31,3% - Azobisisobutyronitrile 2,0%

[0183] Of these materials, the cyclohexyl methacrylate monomer, the methyl methacrylate monomer, the methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were placed in a separable four-necked flask equipped with a reflux condenser, a thermometer, a nitrogen supply line, and a stirrer. Nitrogen gas was introduced into the separable flask to create a nitrogen atmosphere. The mixture was then heated to 80 °C, azobisisobutyronitrile was added, and polymerization was carried out under reflux for five hours.

[0184] Hexane was poured into the resulting reaction product to precipitate the copolymer.

[0185] The resulting precipitate was separated by filtration and dried in a vacuum to obtain a resin.

[0186] 30 parts of this resin were dissolved in a solvent mixture of 40 parts toluene and 30 parts methyl ethyl ketone to obtain a resin solution (solids concentration = 30%). Production of coating resin solution - Resin solution (30% solids concentration) 33,3% - toluene 66,4% - Carbon black (Regal 330, Cabot Corporation) 0,3% (number-average primary particle diameter: 25 nm, specific surface area due to nitrogen adsorption: 94 m²) 2 / g, DBP absorption: 75 mL / 100 g)

[0187] The materials listed above were placed in a paint shaker and dispersed with 0.5 mm diameter zirconium dioxide beads for one hour. The resulting dispersion was filtered through a 5.0 µm membrane filter to obtain a coating resin solution. Manufacturing example of a magnetic carrier

[0188] The coating resin solution and the magnetic core particles (the amount of coating resin solution was 2.5 parts as resin component per 100 parts of the magnetic core particles) were introduced into a vacuum degassing kneader which was kept at normal temperature.

[0189] After introduction, the mixture was stirred for 15 minutes at a stirring speed of 30 rpm and the solvent was evaporated by at least a prescribed amount (80 wt%), then the temperature was increased to 80°C while stirring at reduced pressure, the toluene was distilled off over two hours and cooled.

[0190] The product with low magnetic force was separated from the resulting magnetic carrier using a magnetic force classifier, and the magnetic carrier was then sieved through a sieve with an opening of 70 µm and classified using a wind force classifier to obtain a magnetic carrier with a particle diameter of 50% (D50) on a volume basis of 38.2 µm. Manufacturing example from developer 1

[0191] A developer 1 was prepared by mixing the toner 1 and the magnetic carrier using a V-mixer (model V-10, Tokuju Seisakusho Co., Ltd.) and conditions of 0.5 s -1 and produced with a rotation time of five minutes and using 10 parts toner 1 per 90 parts of the magnetic carrier. The following assessments were carried out with the resulting developer 1. Example 1: Evaluation of low-temperature fixability

[0192] A Canon, Inc. imageRUNNER ADVANCE C5051 commercial digital printer was used as the imaging device. It was modified to allow for free adjustment of the fusing temperature and processing speed. Developer 1 was introduced into the cyan position of the developer unit of this modified device. The electrostatic latent image carrier (DC voltage VDC), the electrostatic latent image carrier charging voltage VD, and the laser power were adjusted to achieve the desired toner deposition level on the paper. The following evaluation was then performed. - Paper: CS-680 (A4, 68.0 g / m 2 ) (sold by Canon Marketing Japan Inc.) - Toner application level on paper: 0.90 mg / cm² 2 - Evaluation image: Placement of a 10 cm 2 large image in the middle of the A4 paper - Fixation test environment: low temperature, low humidity: Temperature of 15°C / humidity of 10% RH (“L / L” below)

[0193] The processing speed was set to 450 mm / s; the fixing temperature was adjusted; the fixed image was output and the condition of the fixed image was visually assessed. Evaluation criteria A: Fixation is possible in the temperature range below 115°C. B: Fixing is possible in a temperature range of 115°C or higher and less than 120°C. C: Fixing is possible in a temperature range of 120°C or higher and less than 125°C. D: Fixing is possible in a temperature range of 125°C or higher and less than 130°C. E: Fixation is only possible in a temperature range of 130°C or higher. Evaluation of image storage capability

[0194] A safe fixing temperature was set at 20°C above the lower limit of the fixing temperature, using GF-C104 (A4, 104 g / cm²). 2 ) (distributed by Canon Marketing Japan Inc.), a general-purpose paper for color copiers and printers, two printouts of a solid color image (5 cm × 5 cm) with a toner application level of 0.90 mg / cm² were made. 2 The image was created on one side of an A4 sheet of paper. The recording paper on which the solid color image had been created was stacked with the sides facing each other so that the solid color images were in contact, and left for one day in an environment with a temperature of 65°C, a relative humidity of 40%, and under a vertical load of 100 g / cm². 2 stored. The images on the two prints were then separated and the defects were removed.

[0195] The presence or absence of gloss variation on the image surface, resulting from image adhesion, was evaluated. The percentage of the area exhibiting gloss variation (i.e., the percentage of the area with gloss variation) was determined by binarization using image processing. Evaluation criteria A: There are no image defects. B: Gloss unevenness is present in the image. (The percentage of the area exhibiting a fluctuation in gloss value is less than 2%) C: Gloss unevenness is present in the image. (The percentage of the area exhibiting a variation in gloss value is at least 2% but less than 5%) D: Gloss unevenness is present in the image. (The percentage of the area exhibiting a variation in gloss value is at least 5% but less than 10%) E: The image is peeling off.

[0196] Developer 1 received a grade of A for each of the evaluation points described above. Examples 2 to 10: Manufacturing example of toner cartridges 2 to 10

[0197] Toners 2 to 10 were produced as in the manufacturing example of toner 1, with the type and quantity of the addition of the binder resin and the crystalline polyester being changed as shown in Table 2. [Table 2] Table 2 Toner No. Binder resin no. crystalline polyester No. Amount of crystalline polyester added (parts by mass) Content of crystalline polyester (parts by mass) Toner temperature (°C) ΔH1(J / g) ΔH2(J / g) ΔH2 / ΔH1 1 1 1 5 5 53 4,9 3,5 0,71 2 2 1 8 8 50 7,3 5,1 0,70 3 3 1 3 3 55 2,8 2,0 0,71 4 4 1 8 8 55 6,3 4,4 0,70 5 5 1 8 8 55 5,0 3,5 0,70 6 6 2 2 2 55 1,2 0,6 0,50 7 7 2 12 12 55 10,5 5,4 0,51 8 8 2 14 14 45 12,1 6,1 0,50 9 9 2 14 14 60 12,1 6,1 0,50 10 10 3 14 14 44 0,5 0,2 0,40

[0198] The content (parts by mass) for the crystalline polyester in the table is the value per 100 parts by mass of the binder resin. Manufacturing example from developers 2 to 10

[0199] Developers 2 through 10 were produced as in the manufacturing example for Developer 1, with the toner being changed as specified in Table 3. The same evaluations were performed as in Example 1. The results of the evaluations are listed in Table 3. [Table 3] Table 3 Example No. Toner No. Developer No. Lower fixing temperature limit (°C) Evaluation of low-temperature fixability Percentage of area showing a fluctuation in gloss value (%) Assessment of image storability 1 1 1 110 A 0 A 2 2 2 110 A 0 A 3 3 3 110 A 0 A 4 4 4 115 B 0 A 5 5 5 115 B 0 A 6 6 6 117 B 1,2 B 7 7 7 117 B 1,4 B 8 8 8 117 B 3,4 C 9 9 9 117 B 3,6 C 10 10 10 120 C 3,6 C Comparison examples 1 to 4

[0200] Production example of toners 11 to 14

[0201] Toners 11 to 14 were produced as in the manufacturing example for toner 1, with the type and quantity of binder resin and crystalline polyester being changed as specified in Table 4. [Table 4] Table 4 Toner No. Binder resin no. crystalline polyester No. Amount of crystalline polyester added (parts by mass) Content of crystalline polyester (parts by mass) Toner temperature (°C) ΔH1(J / g) ΔH2(J / g) ΔH2 / ΔH1 11 9 - 0 0 65 0,0 0,0 - 12 11 2 14 14 42 11,5 4,6 0,40 13 12 - 0 0 65 0,0 0,0 - 14 11 - 0 0 44 0,0 0,0 -

[0202] The content (parts by mass) for the crystalline polyester in the table is the value per 100 parts by mass of the binder resin. Manufacturing example from developers 11 to 14

[0203] Developers 11 through 14 were produced as in the manufacturing example for Developer 1, with the toner being changed as specified in Table 5. The same evaluations were performed as in Example 1. The results of the evaluations are listed in Table 5. [Table 5] Table 5 Comparative example Toner No. Developer No. Lower fixing temperature limit (°C) Evaluation of low-temperature fixability Area percentage that shows a fluctuation in gloss value (%) Assessment of image storability 1 11 11 125 D 4,3 C 2 12 12 123 C 8,2 D 3 13 13 140 E 4,4 C 4 14 14 117 B The image has peeled off. E

Claims

[1] Toner comprising a toner particle comprising a binder resin and a crystalline polyester, wherein the binder resin contains a polyester with a structure represented by the following formula (1), wherein the content of the polyester with the structure of formula (1) in the binder resin is at least 50 wt%: In formula (1), the Rs each represent hydrogen, a methyl group or a phenyl group independently of one another; A represents a polyester segment; B represents a polyester segment or functional group selected from the group consisting of -R 1 EAR 1 COOH, and -R 1 NH2, where R 1 a single bond or a C 1-4 represents an alkylene group; and an average number of repetitions n is between 10 and 80, and wherein the content of the structure represented by the following formula (2) in the polyester with the structure represented by formula (1) is from 0.5 wt% to 5.0 wt%: In formula (2) the Rs each independently represent hydrogen, a methyl group or a phenyl group and n is the average value of the number of repeats of the siloxane unit and ranges from 10 to 80. [2] Toner according to claim 1, which has a glass transition temperature in a second heating step, measured on the toner by differential scanning calorimetry, of 45°C to 60°C. [3] Toner according to claim 1 or 2, wherein using ΔH1 for the endothermic amount originating from the crystalline polyester in a first heating step, measured on the toner by differential scanning calorimetry, and using ΔH2 for the endothermic amount originating from the crystalline polyester in a second heating step, measured on the toner by differential scanning calorimetry, ΔH1 ranges from 1.0 J / g to 10.0 J / g and the ratio of ΔH2 to ΔH1 (ΔH2 / ΔH1) is between 0.50 and 1.

00. [4] Toner according to any one of claims 1 to 3, wherein the content of the crystalline polyester in the toner is from 2.0 parts by mass to 12.0 parts by mass per 100 parts by mass of the binder resin. [5] Toner according to any one of claims 1 to 4, wherein each of the Rs is the methyl group. [6] Toner according to any one of claims 1 to 5, wherein the crystalline polyester is a polycondensate of an aliphatic diol having 6 to 18 carbons with an aliphatic dicarboxylic acid compound having 6 to 18 carbons.