Toner

Abstract

This invention relates to toners. A toner comprises toner particles containing a binder resin, wherein the toner particles further comprise a compound represented by formula (1) and a pigment having a quinacridone structure; wherein, in formula (1), R represents a straight-chain or branched alkyl group having 4 to 22 carbon atoms, and n is an integer from 1 to 4.

Description

Technical Field

[0001] This disclosure relates to a toner that can be used to form a toner image by developing an electrostatic latent image formed by methods such as electrophotography, electrostatic recording, or toner spraying recording. Background Technology

[0002] With the development of equipment, user demands for electrophotographic technologies used in copiers, printers, and fax machines have become increasingly stringent over the years. In recent years, advertising and design applications have expanded, demanding high color reproduction in output images. Therefore, there is a strong need for toners used in image formation to expand the color gamut and improve tinting strength.

[0003] A means of improving the tinting strength of a toner can be exemplified by a method for improving the dispersibility of the colorants contained in the toner. In electrophotographic technology, a toner is fixed to a medium such as paper by receiving heat and pressure from a fixing device. By improving the dispersibility of the colorants contained in the toner, the opacity of the colorants on the surface of the medium is improved, and thus the tinting strength is improved. Dispersants are commonly used as a means of improving the dispersibility of colorants.

[0004] For example, Japanese Patent Application Publication No. 2018-084774 discloses a toner in which a polymeric dispersant is incorporated to improve the dispersibility of the colorant. Furthermore, Japanese Patent Application Publication No. 2013-205593 discloses a toner using a block copolymer having vinylpyridine monomer blocks as a dispersant. Summary of the Invention

[0005] These techniques were thought to improve the dispersibility of colorants. However, it has been found that when using dispersants with high molecular weights, a polymer bridges between two colorant particles, causing aggregation and preventing adequate dispersibility. Furthermore, bridging between colorant particles increases the cross-linking density within the toner, making it difficult for the toner to melt and thus reducing its fixing properties on paper.

[0006] In addition, pigments with a quinacridone structure, possessing weather resistance and bright colors, are commonly used as toners and colorants. The quinacridone structure is considered to have excellent weather resistance because intermolecular hydrogen bonds are formed between the carbonyl and imino groups, and because the structure exhibits strong crystalline properties. However, it has been found that when pigments with a quinacridone structure are used as colorants, aggregation due to hydrogen bonding easily occurs, and the tinting strength decreases.

[0007] This disclosure provides a toner that, even when using pigments with a quinacridone structure, exhibits improved pigment dispersibility and improved tinting strength without degrading the fixing properties of paper.

[0008] This disclosure relates to a toner comprising toner particles containing a binder resin, wherein

[0009] Toner particles further include:

[0010] The compound represented by the following formula (1), and

[0011] Pigments with a quinacridone structure;

[0012] In formula (1), R represents a straight-chain or branched alkyl group with 4 to 22 carbon atoms, and n is an integer from 1 to 4.

[0013]

[0014] According to this disclosure, a toner can be provided that exhibits improved pigment dispersibility and improved tinting strength even when using pigments having a quinacridone structure without degrading the fixing properties of paper. Further features of the invention will become apparent from the following description of exemplary embodiments. Detailed Implementation

[0015] Unless otherwise stated, descriptions of numerical ranges in this disclosure, such as "from XX to YY" or "XX to YY", include the numbers at the upper and lower limits of the range. When describing numerical ranges in segments, the upper and lower limits of the ranges can be combined arbitrarily.

[0016] The implementation plan will be described in detail below.

[0017] This disclosure relates to a toner comprising toner particles containing a binder resin, wherein

[0018] Toner particles further include:

[0019] The compound represented by the following formula (1), and

[0020] Pigments with a quinacridone structure;

[0021] In formula (1), R represents a straight-chain or branched alkyl group with 4 to 22 carbon atoms, and n is an integer from 1 to 4.

[0022]

[0023] The inventors have discovered that, as a result of including a compound represented by formula (1) (hereinafter also referred to as compound (1)) and a pigment having a quinacridone structure (hereinafter also referred to as quinacridone pigment), a toner with high tinting strength is obtained without deteriorating the fixing properties of paper. The inventors believe the detailed mechanism is as follows.

[0024] The toner melts and deforms under the heat and pressure of the fixing device and is fixed onto paper. During this melting and deformation, the quinacridone pigment dispersed within it is subjected to strong external forces. It is believed that when the quinacridone pigment is subjected to these forces, intermolecular hydrogen bonds arising from the carbonyl and imino groups of the quinacridone structure come into play, causing aggregation. That is, the pigment dispersibility decreases after fixing onto paper, and the tinting strength also decreases.

[0025] However, it is believed that the presence of compound (1) other than quinacridone pigment can inhibit pigment aggregation and improve dispersibility. Specifically, when quinacridone pigment is subjected to external force during fixing, compound (1) is also subjected to external force, but since compound (1) exists as a molecule, it easily moves within the binder resin. It is speculated that the ether moiety and hydroxyl group of compound (1) specifically coordinate with the imino and carbonyl groups, thus inhibiting the aggregation of quinacridone pigment.

[0026] In formula (1), R represents a straight-chain or branched alkyl group with 4 to 22 carbon atoms, and n is an integer from 1 to 4. In compound (1), when the number of carbon atoms in R is less than 4, steric hindrance due to coordination of compound (1) is unlikely to occur, and the inhibition of aggregation of quinacridone pigment is insufficient, resulting in reduced pigment dispersibility and tinting strength after fixing. Furthermore, when the number of carbon atoms in R exceeds 22, the molecular weight is large, and movement within the binder resin is restricted, making it impossible to obtain the inhibition effect of pigment aggregation, resulting in reduced pigment dispersibility and tinting strength after fixing.

[0027] Furthermore, in compound (1), charge leakage and fogging are prone to occur when n exceeds 4. In addition, due to the ease of coordination with the imino and carbonyl groups of quinacridone pigments, the pigment dispersibility after fixing decreases, and the tinting strength decreases.

[0028] The preferred form of the toner will be described below. The amount of the compound represented by formula (1) in the toner is preferably 5 ppm to 500 ppm by mass. When the amount of compound (1) is 5 ppm or more, the dispersibility of the pigment is easily improved. At the same time, when the amount of compound (1) is 500 ppm or less, the hygroscopicity of the toner caused by the hydrophilic part of compound (1) is appropriately maintained, and the decrease in charge in high humidity environments is suppressed. More preferably, the amount of compound (1) is 10 ppm to 250 ppm. The amount of compound (1) can be controlled by its addition amount.

[0029] Furthermore, it is preferred that the adhesive resin has an SP value (cal / cm²) of 9.50 to 11.50. 3 ) 0.5When the SP value is within the above range, compound (1) is easily mobile, and the inhibition effect on the aggregation of quinacridone pigment is high. The SP value is more preferably 9.60 to 10.60. The SP value of the binder resin can be controlled by the type and proportion of monomers constituting the resin.

[0030] Furthermore, the mass ratio (pigment / compound of formula (1)) of the amount of pigment having a quinacridone structure in the toner to the amount of the compound represented by formula (1) is preferably 100 to 10,000. This is because it can suppress the decrease in charge under high humidity conditions and simultaneously exhibit an inhibitory effect on pigment aggregation. More preferably, this ratio is 200 to 5,000.

[0031] Furthermore, the pigment having a quinacridone structure is preferably at least one selected from the group consisting of CI Pigment Red 122, CI Pigment Red 202, and CI Pigment Violet 19, and more preferably at least one selected from the group consisting of CI Pigment Red 122 and CI Pigment Violet 19. This is because compound (1) is readily and specifically coordinated due to the absence of strong hydrogen bond sites other than imino and carbonyl groups.

[0032] Furthermore, the compound represented by formula (1) preferably has n of 1 or 2, and more preferably 1. When n is 1, the compound has low hydrophilicity, can easily move within the binder resin, and readily exhibits specific coordination with quinacridone pigments.

[0033] Furthermore, R in the compound represented by formula (1) is preferably a straight-chain alkyl group, and more preferably a straight-chain alkyl group with 8 to 14 carbon atoms. This is because compound (1) can easily move within the adhesive resin while exhibiting an inhibitory effect on pigment aggregation. More preferably, the straight-chain alkyl group has 10 to 12 carbon atoms.

[0034] Furthermore, in viscoelasticity measurements, the toner preferably has a storage modulus of elasticity of 5,000 Pa to 25,000 Pa at 100°C. This is because compound (1) can readily move within the binder resin while maintaining separation from the fixing device and paper during fixing and fixing properties to the paper. More preferably, the storage modulus of elasticity is 7,000 Pa to 20,000 Pa. The storage modulus of elasticity can be controlled by adjusting the type and amount of crystalline materials, such as crystalline polyesters or waxes, or the Tg and molecular weight of the binder resin.

[0035] There are no particular restrictions on the production method of the toner particles, and known methods can be used. From the viewpoint of effectively incorporating compound (1) into the binder resin, methods for producing toner particles in an aqueous medium, such as suspension polymerization, emulsion aggregation, or dissolution suspension, are preferred.

[0036] Adhesive resin

[0037] There are no particular limitations on the binder resin, and resins commonly used in toners can be used. Examples include polyester resins, vinyl ester resins, polyamide resins, furan resins, epoxy resins, xylene resins, and silicone resins. From the viewpoint of SP value, the binder resin preferably includes at least one selected from the group consisting of vinyl ester resins and polyester resins. Vinyl ester resins are more preferred as the binder resin. In a preferred embodiment, the toner particles have a core-shell structure having a core particle and a shell on the surface of the core particle. Preferably, the binder resin contained in the core particle is a vinyl ester resin and the shell is a polyester resin.

[0038] Examples of polymerizable monomers that can form vinyl resins include styrene monomers such as styrene, α-methylstyrene, and divinylbenzene; unsaturated carboxylic acid esters such as methyl acrylate, butyl acrylate, methyl methacrylate, 2-hydroxyethyl methacrylate, tert-butyl methacrylate, and 2-ethylhexyl methacrylate (e.g., alkyl (meth)acrylates having 1 to 24 carbon atoms in the alkyl group); unsaturated dicarboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid; unsaturated dicarboxylic acid anhydrides such as maleic anhydride; nitrile vinyl monomers such as acrylonitrile; halogenated vinyl monomers such as vinyl chloride; and nitrovinyl monomers such as nitrostyrene; etc.

[0039] These can be used alone or in combination. Vinyl resins are preferably copolymers comprising styrene monomers and unsaturated carboxylic acid esters.

[0040] Crosslinking agents can also be used in toner particles to control the molecular weight of the constituent molecules of the toner particles. As crosslinking agents, compounds having two or more polymerizable double bonds can be used. Specific examples include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups. These crosslinking agents can be used alone or as a mixture of two or more.

[0041] These crosslinking agents are preferably used in the range of 0.05 to 10 parts by mass relative to 100 parts by mass of polymerizable monomers, more preferably 0.10 to 5 parts by mass.

[0042] When using polyester resins, known polyester resins may be used. Specific examples include condensation polymers of diacids or their derivatives (carboxylic acid halides, esters, anhydrides) and diols. If desired, polybasic acids of three or more diacids and their derivatives (carboxylic acid halides, esters, anhydrides), monobasic acids, alcohols of three or more diacids, and monohydric alcohols may be used.

[0043] Examples of dicarboxylic acids include, for instance, aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, oxalic acid, malonic acid, succinic acid, dodecyl succinic acid, dodecenyl succinic acid, adipic acid, azelaic acid, sebacic acid, and decane-1,10-dicarboxylic acid; and aromatic dicarboxylic acids such as phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, hexamethylenetetrafluoroethylene (HET) acid, hymic acid, isophthalic acid, terephthalic acid, and 2,6-naphthalenedicarboxylic acid; etc.

[0044] Examples of derivatives of dicarboxylic acids include carboxylic acid halides, esters, and anhydrides of the aforementioned aliphatic and aromatic dicarboxylic acids.

[0045] Examples of diols include, for instance, acyclic aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, and neopentanediol; bisphenols such as bisphenol A and bisphenol F; bisphenol A ethylene oxide adducts and bisphenol A propylene oxide adducts; arylene alkyl diols such as dimethylbenzene diethylene glycol; and isosorbide; etc.

[0046] Examples of polybasic acids with three or more nucleotides and their anhydrides include trimellitic acid, trimellitic anhydride, benzopyrene, and benzopyrene.

[0047] Colorant

[0048] There are no particular limitations on quinacridone pigments, and known pigments having a quinacridone structure can be used. A quinacridone structure refers, for example, a quinacridone skeleton represented by formula (A). A pigment having a quinacridone structure is, for example, a pigment having a quinacridone skeleton represented by formula (A). A pigment having a quinacridone structure is preferably at least one selected from the group consisting of unsubstituted pigments represented by formula (A) and pigments in which any hydrogen atom of formula (A) is substituted by any substituent. Any substituent is at least one selected from the group consisting of alkyl groups having 1 to 4 carbon atoms (preferably 1 or 2, more preferably 1), halogen atoms (preferably Cl), and oxo groups (=O).

[0049]

[0050] As a quinacridone pigment, for example, at least one selected from the group consisting of CI Pigment Red 122, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 209, CI Pigment Violet 19, CI Pigment Violet 42, CI Pigment Orange 48, and CI Pigment Orange 49 can be used. The quinacridone pigment is preferably a magenta or purple colorant.

[0051] The amount of colorant relative to 100.0 parts by weight of adhesive resin is preferably 0.1 parts by weight to 30.0 parts by weight, more preferably 1.0 parts by weight to 15.0 parts by weight, and even more preferably 3.0 parts by weight to 8.0 parts by weight.

[0052] wax

[0053] The toner particles preferably include waxes. Examples of waxes include the following: hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline waxes, paraffin wax, and Fischer-Tropsch wax; oxides or block copolymers of hydrocarbon waxes such as oxidized polyethylene wax; waxes containing fatty acid esters, such as carnauba wax as a major component; and partially or completely deoxygenated fatty acid esters such as deoxycarnauba wax.

[0054] In addition, the following can be mentioned: saturated straight-chain fatty acids such as palmitic acid, stearic acid, and linoleic acid; unsaturated fatty acids such as brassinolic acid, tungstic acid, and octadecanoic acid; saturated alcohols such as beeswax alcohol; polyols such as sorbitol; esters of fatty acids such as palmitic acid, stearic acid, benzyl acid, and linoleic acid, and alcohols such as stearyl alcohol, aralkyl alcohol, benzyl alcohol, cinnamyl alcohol, wax alcohol, and beeswax alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauryl acid amide; saturated fatty acid diamides such as methylene bis-stearamide, ethylidene bis-decanoic acid amide, ethylidene bis-lauric acid amide, and hexamethylene bis-stearamide; and ethylidene bis-oleic acid amide. Unsaturated fatty acid amides such as hexamethylene dioleamide, N,N'-dioleenyl adipicamide, and N,N'-dioleenyl sebacate amide; aromatic diamides such as m-xylene bis-stearamide and N,N'-bis-stearyl isophthalamide; fatty acid metal salts (commonly known as metal soaps) such as calcium stearate, calcium silicate, zinc stearate, and magnesium stearate; waxes obtained by grafting vinyl monomers such as styrene and acrylic acid onto aliphatic hydrocarbon waxes; partially esterified products of fatty acids and polyols such as betaine monoglycerides; and methyl esterified products with hydroxyl groups obtained by hydrogenation of vegetable oils.

[0055] Among these waxes, from the viewpoint of improving low-temperature fixing and fixing winding resistance, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, as well as fatty acid waxes such as palmitic acid, stearic acid, benzyl acid and linalic acid, and alcohol waxes such as stearyl alcohol, aralkyl alcohol, benzyl alcohol, cinnamyl alcohol, wax alcohol and beeswax alcohol are preferred.

[0056] More preferably, the colorant particles comprise ester wax. The amount of wax (preferably ester wax) relative to 100.0 parts by weight of binder resin is preferably 0.5 parts by weight to 25.0 parts by weight, more preferably 3.0 parts by weight to 20.0 parts by weight, even more preferably 4.0 parts by weight to 17.0 parts by weight, even more preferably 6.0 parts by weight to 14.0 parts by weight, and particularly preferably 8.0 parts by weight to 12.0 parts by weight.

[0057] Furthermore, from the viewpoint of achieving both storage stability and high-temperature stain resistance of the toner, the peak temperature of the wax's maximum endothermic peak, which exists in the temperature range of 30°C to 200°C on the endothermic curve measured by differential scanning calorimeter (DSC) during heating, is preferably 50°C to 110°C.

[0058] Charge control agent

[0059] If desired, the toner may include a charge control agent. Known charge control agents can be used as charge control agents. The charge control agent can be added internally or externally to the toner particles. The amount of charge control agent added is preferably 0.2 to 10.0 parts by weight relative to 100.0 parts by weight of the binder resin.

[0060] carrier

[0061] Toners can be mixed with magnetic carriers and used as two-component developers to obtain stable images over a long period. Known magnetic carriers can be used as such, including surface-oxidized iron powder, unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, and rare earth elements, their alloy particles, oxide particles, and magnetic materials such as ferrites, and magnetic material dispersion resin carriers (so-called resin carriers) that include magnetic materials and a binder resin in which the magnetic materials are held in a dispersed state.

[0062] Inorganic fine particles

[0063] If desired, the toner particles can be used as a toner as is or can be used as a toner by externally adding various inorganic fine particles to the toner particles. Examples of inorganic fine particles that can be used include, for example, silicon dioxide, metal oxides (e.g., strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, and chromium oxide), nitrides (e.g., silicon nitride), metal salts (e.g., calcium sulfate, barium sulfate, calcium carbonate), and fatty acid metal salts (e.g., zinc stearate and calcium stearate).

[0064] Inorganic fine particles can also be hydrophobized to improve the flowability of the toner and to homogenize its charge. Examples of treatment agents used to hydrophobize inorganic fine particles include unmodified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents can be used alone or in combination.

[0065] Any method can be used to produce toner particles, but suspension polymerization is preferred. For example, a polymerizable monomer for producing an adhesive resin, a compound represented by formula (1), a pigment having a quinacridone structure, and other additives such as waxes if desired, are mixed to obtain a polymerizable monomer composition. The polymerizable monomer composition is then added to a continuous phase (e.g., an aqueous medium which may optionally include a dispersing stabilizer). Particles of the polymerizable monomer composition are then formed in the continuous phase (in the aqueous medium), and the polymerizable monomers contained in the particles are polymerized. By doing so, toner particles can be obtained.

[0066] The following will describe the methods for measuring various physical properties.

[0067] Identification and quantification of adhesive resins and colorants

[0068] The composition and proportion of constituent compounds, such as resins and colorants, contained in the toner are identified using pyrolysis gas chromatography-mass spectrometry (hereinafter also referred to as "pyrolysis GC / MS") and NMR. If the resin contained in the toner is available individually, it can be measured separately.

[0069] When the sample is resin, pyrolysis GC / MS is used to analyze the types of constituent compounds of the resin. The types of constituent compounds are identified by analyzing the mass spectra of the components of the resin decomposition products generated when the resin is thermally decomposed at 550°C to 700°C. Specific measurement conditions are as follows.

[0070] Pyrolysis GC / MS Measurement Conditions

[0071] Pyrolysis unit: JPS-700 (Nippon Analytical Industry Co., Inc.)

[0072] Decomposition temperature: 590℃

[0073] GC / MS device: Focus GC / ISQ (Thermo Fisher Scientific Corp.)

[0074] Column: HP-5MS, length 60m, inner diameter 0.25mm, film thickness 0.25μm

[0075] Inlet temperature: 200℃

[0076] Flow pressure: 100 kPa

[0077] Split: 50 mL / min

[0078] MS ionization: EI

[0079] Ion source temperature: 200℃, mass range 45-650

[0080] Subsequently, the abundance ratio of the constituent compounds of the identified resin was measured and analyzed by solid-state analysis. 1 Calculations were performed using H-NMR. Nuclear magnetic resonance spectroscopy was employed. 1 The structure was determined by H-NMR [400MHz, CDCl3, room temperature (25℃)].

[0081] Measuring apparatus: JNM-EX400 FT NMR instrument (manufactured by JEOL Ltd.)

[0082] Measurement frequency: 400MHz

[0083] Pulse condition: 5.0 μs

[0084] Frequency range: 10,500Hz

[0085] Total number of times: 1024

[0086] The mol ratio of each monomer is obtained from the integral value of the obtained spectrum, and the composition ratio (mass%) is calculated based on it.

[0087] The amount of compound represented by equation (1)

[0088] Preparation of extracted samples

[0089] Add a total of 2g of toner and 18g of ethanol, homogenize by hand, and then irradiate with ultrasound for 5 minutes. Incubate the resulting composition in a constant temperature chamber at 60°C for 24 hours, and then further incubate at room temperature for 3 days. Collect the supernatant of the resulting sample and filter it through a PTFE syringe filter (250nm pore size), and use the filtrate as the extraction sample.

[0090] GC / MS Analysis

[0091] The GC / MS instrument was a GC TRACE-1310 (manufactured by Thermo Fisher Scientific Corp.), the detector was a single quadrupole analyzer MS ISQ LT (manufactured by Thermo Fisher Scientific Corp.), and the autosampler was a TRIPLUS RSH (manufactured by Thermo Fisher Scientific Corp.). Measurements were performed under the conditions shown below.

[0092] Sample volume: 1 μL (liquid spraying)

[0093] Column: HP5-MS (manufactured by Agilent Technologies, Inc.)

[0094] Length: 30m, Inner diameter: 0.25mm, Film thickness: 0.25μm

[0095] Flow split ratio: 10

[0096] Flow rate: 15 mL / min

[0097] Inlet temperature: 250℃

[0098] Helium flow rate in the column: 1.5 mL / min

[0099] MS ionization: EI

[0100] Column temperature conditions: Hold at 40°C for 3 minutes, then increase to 300°C at a rate of 10°C / min and hold for 10 minutes.

[0101] Ion source temperature: 250℃

[0102] Quality range: m / z 45-1000

[0103] Conveyor line temperature: 250℃

[0104] Creating calibration curves

[0105] Samples were prepared for creating calibration curves such that the concentrations of compound (1) in ethanol solutions were 10 ppm, 50 ppm, 100 ppm, and 250 ppm. These samples were measured under the above conditions, and calibration curves were created from the peak area values ​​derived from the fatty alcohols. The structures of the compounds were determined using an FT NMR instrument, JNM-EX400 (manufactured by JEOL Ltd.). 1 H-NMR 400MHz, CDCl3, room temperature (25℃)] (Also used 13The extract was determined by analysis using methods such as C-NMR. Based on the information obtained by the above methods, the amount of the compound relative to the toner (by mass) was calculated.

[0106] SP value calculation method

[0107] SP values ​​are obtained according to the calculation method proposed by Fedors as follows. For each polymerizable monomer, the evaporation energy (Δei) (cal / mol) and molar volume (Δvi) (cm³) are obtained from "Polym. Eng. Sci., 14(2), 147-154(1974)" for atoms and groups in the molecular structure. 3 / mol), and (ΣΔei / ΣΔvi) 0.5 Defined as SP value (cal / cm) 3 ) 0.5 .

[0108] For the SP value of the adhesive resin, the evaporation energy (Δei) and molar volume (Δvi) of the monomer unit derived from the polymerizable monomers constituting the adhesive resin are obtained for each monomer unit. The product of the molar ratio (j) of each monomer unit in the adhesive unit is calculated, and the total evaporation energy of the monomer unit is divided by the total molar volume to obtain {(Σj×ΣΔei) / (Σj×ΣΔvi)}. 0.5 It is defined as the SP value (cal / cm). 3 ) 0.5 .

[0109] Storage elastic modulus of toner

[0110] As the measuring apparatus, a rotating flat-plate rheometer "ARES" (manufactured by TA INSTRUMENTS) was used. The measured samples were obtained by pressing 0.1 g of toner into a circular plate with a diameter of 7.9 mm and a thickness of 2.0 ± 0.3 mm using a benchtop molding machine at 25°C. The pressing conditions were 15 MPa and 60 seconds.

[0111] The sample is mounted on a parallel plate, and the temperature is increased from room temperature (25°C) to 120°C over 15 minutes to adjust the sample shape. The sample is then cooled to the viscoelastic measurement start temperature to begin the measurement. At this point, the sample is set such that the initial normal force is zero. Furthermore, as described below, in subsequent measurements, the effect of the normal force can be counteracted by setting the automatic tension adjustment to ON.

[0112] Measurements were taken under the following conditions.

[0113] (1) Use a parallel plate with a diameter of 7.9 mm.

[0114] (2) The frequency is 1.0 Hz.

[0115] (3) The initial strain value is set to 0.1%.

[0116] (4) Measurements were taken between 30°C and 200°C at a ramp rate of 2.0°C / min. Measurements were taken under the following automatic strain control settings. Measurements were taken in Auto Strain mode.

[0117] (5) The maximum applied strain is set to 20.0%.

[0118] (6) The maximum allowable torque is set to 200.0 g·cm and the minimum allowable torque is set to 0.2 g·cm.

[0119] (7) The strain adjustment is set to 20.0% of the current strain. During the measurement, the automatic tension adjustment mode is used.

[0120] (8) The Auto Tension Direction is set to Compression.

[0121] (9) The initial static force is set to 10.0g and the automatic tension sensitivity is set to 40.0g.

[0122] (10) The operating conditions for automatic tensioning are as follows: sample modulus is 1.0 × 10⁻⁶. 3 (Pa) or above.

[0123] The storage elastic modulus at 100°C was determined by the above measurements.

[0124] Method for measuring the weight-average particle size (D4) of toner particles

[0125] The weight-average particle size (D4) of the toner particles was calculated and analyzed using a precision particle size distribution measuring device, the "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman-Coulter Inc.), equipped with a 100 μm orifice and based on the micropore resistance method, and dedicated software, "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman-Coulter Inc.), for setting measurement conditions and analyzing measurement data at 25,000 effective measurement channels. The electrolyte solution used for measurement was prepared by dissolving premium sodium chloride in ion-exchanged water to a concentration of approximately 1% by mass. For example, "ISOTON II" (manufactured by Beckman-Coulter Inc.) could be used.

[0126] Before performing measurements and analysis, configure the dedicated software as follows. On the "Change Standard Measurement Method (SOM) Screen" of the dedicated software, set the total count in the control mode to 50,000 particles, the number of measurement cycles to 1, and the Kd value to the value obtained using "Standard Particle 10.0 μm" (manufactured by 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, and the electrolyte to ISOTON II, and check the "Flush the port after measurement" option. On the "Pulse to Particle Size Conversion Setting Screen" of the dedicated software, set the element spacing to logarithmic particle size, the number of particle size elements to 256, and the particle size range to 2 μm to 60 μm. The specific measurement method is as follows.

[0127] (1) Place approximately 200 mL of electrolyte solution in a 250 mL glass round-bottom beaker provided with the Multisizer 3, place the beaker on the sample stage, and stir counterclockwise at 24 rpm using a stir bar. Then, remove dirt and air bubbles from the mouthpiece using the "mouthpiece rinse" function of the dedicated software.

[0128] (2) Place about 30 mL of electrolyte aqueous solution in a 100 mL flat-bottomed glass beaker and add about 0.3 mL of the following diluent as a dispersant.

[0129] - Diluent: Prepared by diluting "Contaminon N" (a 10% by mass aqueous solution of a neutral detergent for washing precision measuring instruments, consisting of nonionic surfactants, anionic surfactants, and organic additives, with a pH of 7, manufactured by Wako Pure Chemical Industries, Ltd.) three times by mass with ion-exchanged water.

[0130] (3) Place the predetermined amount of ion-exchanged water in a water tank with an ultrasonic diffuser that has two built-in oscillation frequencies of 50 kHz, a phase offset of 180 degrees and a power output of 120 W, and add about 2 mL of Contaminon N to the water tank.

[0131] - Ultrasonic Dispersion System Tetora 150 (manufactured by Nikkaki Bios Co., Ltd.)

[0132] (4) Place the beaker from (2) into the fixing hole of the ultrasonic disperser and start the ultrasonic disperser. Adjust the height of the beaker to maximize the resonance state of the electrolyte solution surface in the beaker.

[0133] (5) While irradiating the electrolyte solution in the beaker described in (4) with ultrasound, approximately 10 mg of toner was added little by little to the electrolyte solution and dispersed. Then, the ultrasonic dispersion treatment was continued for another 60 seconds. During ultrasonic dispersion, the water temperature in the bath was appropriately adjusted to 15°C to 40°C.

[0134] (6) Using a pipette, drop the electrolyte aqueous solution containing the toner from (5) above into a round-bottom beaker mounted on the sample stage in (1), and adjust the measurement concentration to about 5%. Then, perform the measurement until the number of particles measured reaches 50,000.

[0135] (7) Analyze the measurement data using the dedicated software provided with the device and calculate the weight-average particle size (D4). When the chart / volume % is set using the dedicated software, the "average diameter" on the analysis / volume statistics (arithmetic mean) screen is the weight-average particle size (D4).

[0136] Example

[0137] The present invention will now be described in more detail by way of examples. The present invention is not limited to the following examples. Unless otherwise stated, the quantities in the examples and comparative examples are all based on mass.

[0138] Production of polyester resin 1 for adhesive resin

[0139] The monomers used in the amounts shown in Table 1 were placed in a reaction vessel equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, and 1.5 parts of dibutyltin oxide were added as a catalyst to a total of 100 parts of monomers. Then, under atmospheric pressure and a nitrogen atmosphere, the mixture was rapidly heated to 180°C, and water was distilled off while heating from 180°C to 210°C at a rate of 10°C / h to carry out polycondensation. After reaching 210°C, the pressure inside the reaction vessel was reduced to below 5 kPa, and polycondensation was carried out at 210°C and below 5 kPa to obtain polyester resin 1.

[0140] Production of polyester resin 2 for adhesive resin

[0141] Except for changing the raw materials to those shown in Table 1, polyester resin 2 is produced by the same production method as polyester resin 1.

[0142] [Table 1]

[0143]

[0144] BPA-PO: Bisphenol A-propylene oxide (2 mol) adduct

[0145] The structure of the compound represented by formula (1)

[0146] Table 2 shows the structures of the compounds represented by formula (1).

[0147] [Table 2]

[0148] compound a Compound b Compound C compound d compound e compound f compound g compound h compound i compound j compound k n 1 1 1 1 1 2 3 4 3 3 5 R <![CDATA[C 12 H 25 ]]> <![CDATA[C8H 17 ]]> <![CDATA[C 14 H 29 ]]> <![CDATA[C4H9]]> <![CDATA[C 22 H 45 ]]> <![CDATA[C 12 H 25 ]]> <![CDATA[C 12 H 25 ]]> <![CDATA[C 12 H 25 ]]> <![CDATA[C3H7]]> <![CDATA[C 23 H 47 ]]> <![CDATA[C 12 H 25 ]]>

[0149] Production of Toner 1

[0150] Production of shell-grade polyester resin A

[0151] Add the following materials to an autoclave equipped with a pressure reducing device, a water separation device, a nitrogen introducing device, a temperature measuring device, and a stirrer.

[0152] -Terephthalic acid: 32.3 parts (50.0 mol%)

[0153] -Bisphenol A-propylene oxide (2 mol) adduct: 67.7 parts (50.0 mol%)

[0154] - Potassium titanium oxalate (catalyst): 0.02 parts

[0155] Subsequently, the reaction was carried out at 220°C under a nitrogen atmosphere and atmospheric pressure until the desired molecular weight was reached. Polyester resin A was obtained by pulverizing after cooling.

[0156] Preparation of dispersion

[0157] A sodium phosphate aqueous solution was prepared by adding 100.0 parts of ion-exchanged water, 2.0 parts of sodium phosphate, and 0.9 parts of 10% hydrochloric acid to a granulation tank and heating it to 50°C. A calcium chloride aqueous solution prepared by dissolving 1.2 parts of calcium chloride hexahydrate in 8.2 parts of ion-exchanged water was added to the granulation tank, and the mixture was stirred for 30 minutes at a circumferential speed of 25 m / s using a TK homogenizer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.). As a result, a dispersion (aqueous dispersion) of calcium phosphate (fine particles) as poorly water-soluble inorganic fine particles was obtained.

[0158] Preparation of pigment dispersion compositions

[0159] - Polymerizable monomer (styrene): 39.0 parts

[0160] - Colorant (CI Pigment Red 122): 5.0 parts

[0161] -Compound a: 0.0028 parts

[0162] The above materials were introduced into a grinder (manufactured by Nippon Coke & Eng. Co., Ltd.) and stirred at 200 rpm for 180 minutes at 25°C using zirconia beads with a radius of 1.25 mm to prepare a pigment dispersion composition.

[0163] Preparation of colorant-containing compositions

[0164] Place the following materials in the same container and mix and disperse them at a circular speed of 20 m / s using a TK homogenizer (trade name, manufactured by TokushuKika Kogyo Co., Ltd.).

[0165] -The above pigment dispersion composition: 44.0028 parts

[0166] - Polymerizing monomer (styrene): 31.0 parts

[0167] - Polymerizing monomer (n-butyl acrylate): 30.0 parts

[0168] - Polyester resin A: 2.0 parts

[0169] - Crosslinking agent (divinylbenzene): 0.5 parts

[0170] In addition, after heating to 60°C, 10.0 parts of wax (betaine ester) were added, and the mixture was dispersed and mixed for 30 minutes to prepare a composition containing a colorant.

[0171] Preparation of polymeric monomer composition particles

[0172] The colorant-containing composition was placed in a dispersion comprising fine calcium phosphate particles and stirred at 30 m / s using a TK homogenizer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 60°C under a nitrogen atmosphere. A total of 9.0 parts of tert-butyl peroxypentanoate (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perbutyl PV", molecular weight: 174.2, 10-hour half-life temperature: 58°C) as a polymerization initiator were added to the stirred composition to prepare a dispersion comprising polymerizable monomer composition particles.

[0173] Next, the dispersion of the polymerizable monomer composition particles was transferred to another tank and heated to 70°C while stirring with a paddle stirrer. The reaction was carried out at 70°C for 5 hours, and then the temperature was set to 85°C and the reaction was carried out for another 2 hours. Then, while stirring, dilute hydrochloric acid was added until the pH reached 1.5 to dissolve the dispersion stabilizer. The solid fraction was separated by filtration, thoroughly washed with deionized water, and then vacuum dried at 40°C for 24 hours to obtain toner particles 1 with a weight-average particle size (D4) of 6.8 μm.

[0174] External addition steps

[0175] 1.5 parts of hydrophobic silica (RY50, manufactured by Nippon Aerosil Co., Ltd.) were added to 100 parts of toner granules 1 obtained as described above, and the mixture was mixed using a Mitsui Henschel mixer (manufactured by Mitsui MiikeMachinery Co., Ltd.). Toner 1 was then obtained by sieving using a vibrating sieve with an opening of 45 μm.

[0176] Production of colorants 2 to 13

[0177] In the preparation of the pigment dispersion composition of colorant 1, the type of colorant, the type of added compound, and the amount added are changed as shown in Table 3. In addition, colorants 2 to 13 are obtained in the same manner, except that the amount of wax (betaine acid) is changed in the preparation of the colorant-containing composition.

[0178] [Table 3]

[0179]

[0180] The abbreviations in the table are as follows.

[0181] PR122: CI Pigment Red 122

[0182] PV19: CI Pigment Violet 19

[0183] PR202: CI Pigment Red 202

[0184] PR238: CI Pigment Red 238

[0185] Production of Toner 14

[0186] In the preparation of the pigment dispersion composition of toner 1, the type of colorant is changed as shown in Table 3. Furthermore, toner 14 is obtained in the same manner, except that the polymerizable monomer is changed as follows in the preparation of the colorant-containing composition of toner 1.

[0187] - Polymerizing monomer (styrene): 16.0 parts

[0188] - Polymerizing monomer (sorbate acrylate): 35.0 parts

[0189] - Polymerizing monomer (methyl methacrylate): 10.0 parts

[0190] Production of Toner 15

[0191] In the preparation of the pigment dispersion composition of toner 1, the type of colorant is changed as shown in Table 3. Furthermore, toner 15 is obtained in the same manner, except that the polymerizable monomer is changed as follows in the preparation of the colorant-containing composition of toner 1.

[0192] - Polymerizable monomer (styrene): 26.0 parts

[0193] - Polymerizing monomer (sorbate acrylate): 30.0 parts

[0194] - Polymerizing monomer (methyl methacrylate): 5.0 parts

[0195] Production of Toner 16

[0196] Preparation of polyester resin particle dispersion

[0197] - Polyester resin 1: 200.0 parts

[0198] - Ion-exchanged water: 500.0 parts

[0199] The above materials were placed in a stainless steel container and heated and melted in a warm bath at 95°C. While thoroughly stirring at 7800 rpm using a homogenizer (Ultra-Turrax T50, manufactured by IKA), 0.1 mol / L sodium bicarbonate was added to raise the pH to greater than 7.0. Then, a mixed solution of 3 parts sodium dodecylbenzenesulfonate and 297 parts deionized water was gradually added dropwise to emulsify and disperse the mixture, obtaining a polyester resin particle dispersion. When the particle size distribution of this polyester resin particle dispersion was measured using a particle size analyzer (LA-950, manufactured by Horiba, Ltd.), the number average particle size of the contained polyester resin particles was 0.25 μm. No coarse particles larger than 1 μm were observed.

[0200] Preparation of wax particle dispersion

[0201] - Ion-exchanged water: 500.0 parts

[0202] - Succinate: 250.0 parts

[0203] The above materials were placed in a stainless steel container and heated and melted in a warm bath at 95°C. While thoroughly stirring at 7800 rpm using a homogenizer (Ultra-Turrax T50, manufactured by IKA), 0.1 mol / L sodium bicarbonate was added to raise the pH to greater than 7.0. Then, a mixed solution of 5 parts sodium dodecylbenzenesulfonate and 245 parts ion-exchanged water was gradually added dropwise to emulsify and disperse the mixture, obtaining a wax particle dispersion. When the particle size distribution of this wax particle dispersion was measured using a particle size analyzer (LA-920, manufactured by Horiba, Ltd.), the number average particle size of the contained wax particles was 0.35 μm. No coarse particles larger than 1 μm were observed.

[0204] Preparation of colorant particle dispersion

[0205] - Colorant (CI Pigment Red 122): 100.0 parts

[0206] - Sodium dodecylbenzenesulfonate: 5.0 parts

[0207] -Compound a: 0.85 parts

[0208] - Ion-exchanged water: 400.0 parts

[0209] The above materials were mixed and dispersed using a sand mill. When the particle size distribution of the colorant particles in the colorant particle dispersion was measured using a particle size measuring device (LA-920, manufactured by Horiba, Ltd.), the number average particle size of the contained colorant particles was 0.2 μm, and no coarse particles larger than 1 μm were observed.

[0210] Production of Toner Granules 16

[0211] - Polyester resin particle dispersion: 500.0 parts

[0212] - Colorant particle dispersion: 25.5 parts

[0213] - Wax particle dispersion: 40.0 parts

[0214] - Sodium dodecylbenzenesulfonate: 5.0 parts

[0215] Polyester resin particle dispersion, wax particle dispersion, and sodium dodecylbenzenesulfonate were placed in a reactor (a 1-liter flask with baffled anchor blades) and mixed uniformly. Simultaneously, colorant particle dispersion was uniformly mixed in a 500 mL beaker and gradually added to the reactor while stirring to obtain a mixed dispersion. While stirring the obtained mixed dispersion, 1 part of aluminum sulfate aqueous solution was added dropwise as a solid component to form aggregated particles.

[0216] After the addition was complete, the atmosphere inside the system was purged with nitrogen, and then maintained at 50°C for 1 hour, followed by 55°C for 1 hour. The temperature was then increased and maintained at 90°C for 30 minutes. The temperature was then decreased to 63°C and maintained for 3 hours to form fused particles. After the predetermined time, the toner particles 16 were obtained by cooling to room temperature (approximately 25°C) at a rate of 0.5°C per minute, washing, filtering, solid-liquid separation, and then drying using a vacuum dryer.

[0217] External addition steps

[0218] Except for the use of toner particles 16, toner 16 is obtained in the same manner as in the external addition step of toner particles 1.

[0219] Production of Toner 17

[0220] In the preparation of the polyester resin particle dispersion of colorant 16, polyester resin 2 is used instead of polyester resin 1. Furthermore, colorant 17 is obtained in the same manner, except that the amount of the compound is changed to 0.95 parts in the preparation of the colorant particle dispersion.

[0221] Production of Toner 18

[0222] Except that the amount of the compound was changed to 1.10 parts in the preparation of the colorant particle dispersion of colorant 16, colorant 18 was obtained in the same manner.

[0223] Production of Toner 19

[0224] Preparation of dispersion

[0225] A total of 250.0 parts of ion-exchanged water and 10.2 parts of magnesium chloride were dissolved in a granulation tank to prepare an aqueous solution of magnesium chloride. While stirring at a circumferential speed of 25 m / s using a TK homogenizer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.), an aqueous solution prepared by dissolving 6.2 parts of sodium hydroxide in 50.0 parts of ion-exchanged water was gradually added to the granulation tank to obtain a dispersion containing fine particles of magnesium hydroxide.

[0226] Preparation of pigment dispersion compositions

[0227] - Polymerizable monomer (styrene): 39.0 parts

[0228] - Colorant (CI Pigment Red 122): 5.0 parts

[0229] -Compound a: 0.003 parts

[0230] The above materials were introduced into a grinder (manufactured by Nippon Coke & Eng. Co., Ltd.) and stirred at 200 rpm for 180 minutes at 25°C using zirconia beads with a radius of 1.25 mm to prepare a pigment dispersion composition.

[0231] Preparation of colorant-containing compositions

[0232] Place the following materials in the same container and mix and disperse them at a circular speed of 20 m / s using a TK homogenizer (trade name, manufactured by TokushuKika Kogyo Co., Ltd.).

[0233] -The above pigment dispersion composition: 44.003 parts

[0234] - Polymerizing monomer (styrene): 31.0 parts

[0235] - Polymerizing monomer (n-butyl acrylate): 30.0 parts

[0236] - Charge control agent: FCA-5 (trade name, manufactured by Fujikura Kasei Co., Ltd.): 1.2 parts

[0237] - Crosslinking agent (divinylbenzene): 0.5 parts

[0238] In addition, after heating to 60°C, 10.0 parts of wax (betaine ester) were added, and the components were dispersed and mixed for 30 minutes to prepare a composition containing colorant.

[0239] Preparation of polymeric monomer composition particles

[0240] The colorant-containing composition was placed in a dispersion containing fine magnesium hydroxide particles and stirred at a circular speed of 30 m / s using a TK homogenizer (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.) at 60°C under a nitrogen atmosphere. A total of 9.0 parts of tert-butyl peroxypentanoate (manufactured by Nippon Oil & Fats Co., Ltd., trade name "Perbutyl PV", molecular weight: 174.2, 10-hour half-life temperature: 58°C) as a polymerization initiator were added to the stirred composition to prepare a dispersion containing polymerizable monomer composition particles.

[0241] Next, the dispersion of the polymerizable monomer composition particles was transferred to another tank and heated to 70°C while being stirred with a paddle stirrer to carry out the polymerization reaction. When the conversion rate of the polymerizable monomer reached 95%, the temperature was raised to 90°C, and 2.0 parts of methyl methacrylate as the polymerizable monomer and an aqueous solution prepared by dissolving 0.2 parts of 2,2'-azobis(N-butyl-2-methylpropionamide) in 10 parts of deionized water were added as the water-soluble initiator. The polymerization reaction was carried out at 90°C for 3 hours to obtain a polymerization reaction solution (polymerization slurry) including toner particles 19.

[0242] After cooling, sulfuric acid was added to bring the pH to below 6.5, and the mixture was stirred for 2 hours to dissolve the poorly water-soluble inorganic fine particles located on the surface of the toner particles. The dispersion of the toner particles was filtered, washed with water, and dried at 40°C for 48 hours to obtain toner particles 19 with a core-shell structure and a weight-average particle size (D4) of 6.8 μm.

[0243] External addition steps

[0244] A total of 100.0 parts of toner particles 19 and 1.5 parts of dry silica particles ("AEROSIL (registered trademark) REA90": positively charged hydrophobic silica particles) were mixed for 3 minutes using an FM mixer (Nippon Coke & Eng. Co., Ltd.) to allow the silica particles to adhere to the toner particles 19. Toner 19 was then obtained by sieving through a 300-mesh sieve (48 μm opening).

[0245] Production of colorant 20 to 24

[0246] In the preparation of the pigment dispersion composition of toner 1, the type of colorant, the type of compound added, and the amount added are changed as shown in Table 3. Furthermore, toners 20 to 24 are obtained in the same manner, except for those in the preparation of the colorant-containing composition of toner 1 where the polymerizable monomer is changed to toner 14. Toner 21, indicated by "none" in Table 3, does not contain compound (1).

[0247] Physical properties of toners 1 to 24

[0248] The above physical properties were measured using toners 1 to 24, and the obtained physical properties are shown in Table 4.

[0249] [Table 4]

[0250]

[0251] Image evaluation

[0252] As the image forming device, a color laser beam printer (HP LaserJet Enterprise Color M652n) manufactured by Hewlett-Packard Co. was used, and the processing speed was modified to 300 mm / s. An original HP 656X LaserJet toner cartridge (magenta) was used as the cartridge. The product toner was removed from the cartridge, the cartridge was cleaned with a blower, and then 300g of toner to be evaluated was filled. The toner was evaluated using the aforementioned cartridge through the following tests. Evaluation was conducted by installing the aforementioned cartridge on the magenta station and installing dummy cartridges on other stations. Since only toner 19 is a positively charged toner, various potential settings were varied to enable the development of the positively charged toner.

[0253] Evaluation of fogging

[0254] A total of 300g of toner was placed in a thermostat at 40°C and 95% RH for 30 days, and the toner's performance after this harsh condition was evaluated. As an evaluation criterion, the reflectance (%) of non-image areas was measured using a "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.) under high temperature and high humidity conditions (temperature 32°C / humidity 85% RH). The evaluation was performed using a value (%) obtained by subtracting the obtained reflectance from the reflectance (%) of unused printed output paper (standard paper) measured in the same manner. A lower value indicates better suppression of image hazing. Plain paper (HP Brochure Paper 200g, glossy, manufactured by HP Co., 200g / m²) was used. 2Evaluation was conducted using the glossy paper model.

[0255] Evaluation criteria

[0256] A: The difference in reflectivity is less than 0.5%.

[0257] B: The difference in reflectance is greater than 0.5% and less than 1.5%.

[0258] C: The difference in reflectance is greater than 1.5% and less than 3.0%.

[0259] D: The difference in reflectance is greater than 3.0%.

[0260] Image density

[0261] The tinting strength of the toner is demonstrated by the solid image (toner loading: 0.8 mg / cm²). 2 Image density was evaluated. A Macbeth Reflectance Density Meter RD918 (manufactured by Macbeth) was used to measure image density, and the relative density of the white background portion with an original density of 0.00 was measured relative to the output image. As the recording medium, letter-size plain paper (XEROX 4200, manufactured by XEROX Corp., 75 g / m²) was used. 2 ).

[0262] Evaluation criteria

[0263] A: Image density is above 1.45.

[0264] B: Image density is above 1.30 and below 1.45.

[0265] C: Image density is above 1.15 and below 1.30.

[0266] D: Image density less than 1.15

[0267] Low temperature fixing

[0268] As the recording medium, plain paper of letter size (XEROX 4200, manufactured by XEROX Corp., 75 g / m²) was used. 2 Next, using a filled toner, an unfixed image, 2.0 cm long and 15.0 cm wide, is formed on a portion 1.0 cm from the top relative to the paper's direction, such that the toner loading is 0.20 mg / cm². 2 Next, the extracted fixing unit was modified to allow adjustment of the fixing temperature and processing speed, and fixing experiments were conducted on unfixed images using the modified fixing unit.

[0269] First, unfixed images were fixed at various temperatures under normal temperature and humidity conditions (23°C, 60% RH) by setting the processing speed to 300 mm / s and the fixing line pressure to 27.4 kgf. The evaluation criteria for low-temperature fixing performance are as follows. The low-temperature fixing start temperature is when 4.9 kPa (50 g / cm³) is applied. 2 The lowest temperature at which the image density reduction rate before and after rubbing the image surface 5 times with a load of Silbon paper (Dusper K-3) at a speed of 0.2 m / s was less than 10.0% (low-temperature side fixing start temperature). Without proper fixing, the image density reduction rate tends to increase.

[0270] Evaluation criteria

[0271] A: The starting temperature for low-temperature side fixing is below 120℃.

[0272] B: The starting temperature for low-temperature side fixing is above 120℃ and below 135℃.

[0273] C: The starting temperature for low-temperature side fixing is above 135℃ and below 150℃.

[0274] D: The starting temperature for low-temperature side fixing is above 150℃.

[0275] Separability

[0276] Toner separation was evaluated by visually observing whether entanglement occurred during fixing. The separation was assessed under high temperature and high humidity conditions (32°C / 85% RH) on ordinary paper (XEROX 4200, manufactured by XEROX Corp., 75 g / m²). 2 To output a solid image, a 3mm tip edge is opened along the length direction (toner loading: 0.8mg / cm). 2 The fixing process is performed at each fixing temperature while gradually increasing the set temperature by 5°C. The upper limit temperature at which tangling does not occur is defined as the separation temperature during fixing. The separation temperature during fixing is evaluated according to the following evaluation criteria.

[0277] Evaluation criteria

[0278] A: The separation temperature during fixing is above 160℃.

[0279] B: The separation temperature during fixing is above 150℃ and below 160℃.

[0280] C: The separation temperature during fixing is above 140℃ and below 150℃.

[0281] D: The separation temperature during fixing is below 140℃.

[0282] Examples 1 to 19

[0283] In Examples 1 to 19, toners 1 to 19 were used for the above evaluation. The evaluation results are shown in Table 5.

[0284] Comparative Examples 1 to 5

[0285] In Comparative Examples 1 to 5, toners 20 to 24 were used for the above evaluation. The evaluation results are shown in Table 5.

[0286] [Table 5]

[0287]

[0288] Although the invention has been described with reference to exemplary embodiments, it should be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the appended claims should be interpreted in the broadest sense to cover all such modifications and equivalent structures and functions.

Claims

1. A toner comprising toner particles containing a binder resin, characterized in that, The toner particles further comprise: The compound represented by the following formula (1), and Pigments with a quinacridone structure; In formula (1), R represents a straight-chain or branched alkyl group with 8 to 14 carbon atoms, and n is an integer of 1 or 2. The amount of the compound represented by formula (1) in the toner is 5 to 500 ppm by mass, and In viscoelasticity measurements, the toner has a storage elastic modulus of 5,000 to 25,000 Pa at 100°C.

2. The toner according to claim 1, wherein the binder resin has an SP value (cal / cm 3 ) 0.5 .

3. The toner according to claim 1 or 2, wherein the amount of the pigment having the quinacridone structure in the toner is, by mass, the amount of the compound represented by the formula (1) being 100 to 10,000.

4. The toner according to claim 1 or 2, wherein the pigment having a quinacridone structure is at least one selected from the group consisting of CI Pigment Red 122, CI Pigment Red 202, and CI Pigment Violet 19.

5. The toner according to claim 1 or 2, wherein in formula (1), n ​​is 1.

6. The toner according to claim 1 or 2, wherein the binder resin has an SP value (cal / cm²) of 9.60 to 10.

60. 3 ) 0.5 .

7. The toner according to claim 1 or 2, wherein the toner particles further comprise ester waxes.

8. The colorant according to claim 7, wherein the amount of the ester wax is 6.0 to 14.0 parts by weight relative to 100.0 parts by weight of the binder resin.

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