Toner and its manufacturing method, toner storage unit, image forming apparatus, and image forming method

Abstract

To provide a toner that can achieve both low-temperature fixability and heat-resistant storage property at a high level and has satisfactory toner adhesion force, humidity-resistant thermal storage property, and cleaning property.SOLUTION: A toner has resin fine particles on a surface of a toner base particle containing at least a binder resin, a colorant, and wax. When a volume average primary particle diameter of the resin fine particles is M(nm) and a distance between the resin fine particles adjacent to each other and present on the surface of the toner base particle is L(nm), following (formula 1) to (formula 3) are satisfied. (Formula 1) M<L; (formula 2) 5(nm)<M≤60(nm); (formula 3)0.40≤[M(nm) / L(nm)]<0.90.SELECTED DRAWING: Figure 1

Description

[Technical Field]

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

[0002] An image forming method using electrophotography with toner involves forming an electrostatic latent image on the surface of a photoreceptor, developing the electrostatic latent image to form a toner image, transferring the toner image to a medium, and fixing the toner image.

[0003] In recent years, the toner has been required to have a smaller particle size and high-temperature offset resistance for improving the quality of output images, low-temperature fixability for energy saving, and heat-resistant storage stability that can withstand high temperatures and high humidity during storage and transportation after production. In particular, since the power consumption during fixation accounts for a large portion of the power consumption in the image forming process, improving the low-temperature fixability of the toner is extremely important. In order to improve the low-temperature fixability of a toner, it is necessary to use a material with a low melting point in the toner. However, a toner produced using a material with a low melting point has poor heat-resistant storage stability, and there is a trade-off between low-temperature fixability and heat-resistant storage stability.

[0004] Therefore, in order to achieve both low-temperature fixability and heat-resistant storage stability, a method for producing composite resin particles has been proposed, which includes, for example, forming composite resin particles in which resin microparticles containing two types of resin as constituent components within the same particle are attached to the surface of the resin particles, and then removing some or all of the resin from the resin microparticles (see, for example, Patent Documents 1 to 3). Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a toner that can achieve both low-temperature fixability and heat-resistant storage stability at high levels, and that has good toner adhesion, moist heat-resistant storage stability, and cleanability. [Means for solving the problem]

[0006] One aspect of the toner of the present invention as a means for solving the above problems is a toner having resin fine particles on the surface of toner base particles containing at least a binder resin, a colorant, and a wax, wherein when the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm), the following (Formula 1) to (Formula 3) are satisfied. When the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm), the following (Formula 1) to (Formula 3) are satisfied. (Formula 1) M < L (Formula 2) 5 (nm) < M ≤ 60 (nm) (Formula 3) 0.40 ≤ [M (nm) / L (nm)] < 0.90 Another aspect of the toner of the present invention as a means for solving the above problems is a toner having resin fine particles on the surface of toner base particles containing at least a binder resin, a colorant, and a wax, wherein when the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm), the following formula, M < L, is satisfied, and methacrylic acid detected by thermal decomposition gas chromatography of the toner is 1.0 mg / g or more and 4.0 mg / g or less with respect to the total amount of the toner. and methacrylic acid detected by thermal decomposition gas chromatography of the toner is 1.0 mg / g or more and 4.0 mg / g or less with respect to the total amount of the toner.

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a toner that can achieve both high-level low-temperature fixing properties and heat-resistant storage properties, and has good toner adhesion, heat and humidity-resistant storage properties, and cleaning properties.

Brief Description of the Drawings

[0008] [Figure 1] FIG. 1 is a schematic diagram showing the particle diameter M of the resin fine particles and the distance (linear distance connecting the centers) L between the resin fine particles defined in the present invention. [Figure 2] FIG. 2 is a schematic diagram showing an example of the process cartridge of the present invention. [Figure 3]FIG. 3 is a schematic diagram showing an example of an image forming apparatus according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] (toner) First, the first and second aspects of the resin particles of the toner of the present invention will be described.

[0010] [First aspect] The toner of the present invention contains toner base particles and, if necessary, further contains other components. On the surface of the toner base particle, the resin fine particles are present so as to satisfy the following formulas (1) to (3), where M (nm) is the volume average primary particle diameter of the resin fine particles and L (nm) is the distance between adjacent resin fine particles present on the surface of the toner base particle. (Formula 1)M <L (Formula 2)5(nm) <M≦60(nm) (Formula 3) 0.40≦[M(nm) / L(nm)]<0.90

[0011] <Resin fine particles> The resin particles are present on the surface of the toner base particles. The resin fine particles satisfy the following conditions. On the surface of the toner base particle, the resin fine particles are present so as to satisfy the following formulas (1) to (3), where M (nm) is the volume average primary particle diameter of the resin fine particles and L (nm) is the distance between adjacent resin fine particles present on the surface of the toner base particle. (Formula 1)M <L (Formula 2)5(nm) <M≦60(nm) (Formula 3) 0.40≦[M(nm) / L(nm)]<0.90

[0012] The M represents the volume average primary particle size of the resin fine particles. The volume average primary particle diameter of the resin fine particles is more than 5 nm and not more than 60 nm, and preferably more than 10 nm and not more than 50 nm. If the volume average primary particle diameter is 5 nm or less, the heat-resistant storage stability may be deteriorated, and if it is more than 60 nm, the low-temperature fixability may be deteriorated. The volume average primary particle size can be measured using a scanning electron microscope (SEM) image as described below.

[0013] The L represents the distance between adjacent resin particles. In the present invention, the distance between adjacent resin particles means the shortest distance between the center of one resin particle and the center of the other resin particle in two adjacent resin particles. The center of the resin fine particle is determined by observing the toner base particle with a scanning electron microscope, identifying the resin fine particle in the image obtained, and taking the center point as the center of gravity of the identified resin fine particle shape. The center point of the resin fine particle is determined as the intersection of the minor axis and the major axis, assuming that the resin fine particle is approximately spherical. In this case, the minor axis and the major axis do not need to intersect perpendicularly. The surface of the toner matrix is ​​not flat but slightly rounded (curved), and therefore the distance between adjacent resin particles is not the measured distance between resin particles on the toner matrix surface, but the shortest distance between resin particles on an image of the resin particles on the toner matrix surface photographed by SEM. The L is not particularly limited and can be appropriately selected depending on the purpose, but the L is preferably less than 30 nm. When the L spacing is less than 30 nm, deterioration of the moist heat resistant storage stability can be prevented.

[0014] Here, the relationship between M and L in the present invention will be explained in more detail with reference to the drawings. FIG. 1 is a schematic diagram showing the state of a toner surface. As shown in FIG. 1, resin fine particles 3 are present on the surface of a toner base particle 4. The resin fine particles 3 are composed of a core resin (b2) 2 and a shell resin (b1) 1, which will be described later. M represents the volume average primary particle diameter of the resin fine particles 3. L represents the distance between adjacent resin fine particles 3.

[0015] The M and L are measured by removing as much of the external additive as possible by ultrasonic liberation treatment to bring the particles into a state close to the toner base particles, and observing the particles with a scanning electron microscope (SEM) as follows. -Method for separating external additives- [1] Add 50 ml of a 5% by weight aqueous solution containing a surfactant (product name: Noigen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) to a 100 ml screw tube, add 3 g of toner to the mixture, and gently move it up and down and left and right. Then, mix it in a ball mill for 30 minutes to allow the toner to blend into the dispersion solution. [2] Then, using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS LLC), set the output to 40 W and apply ultrasonic energy for 60 minutes. -Ultrasonic conditions- Vibration time: 60 minutes continuous ·Amplitude: 40W ·Vibration start temperature: 23±1.5℃ ·Temperature during vibration: 23±1.5℃ [3] (1) The dispersion liquid is suction filtered using filter paper (product name: Qualitative Filter Paper (No. 2, 110 mm), manufactured by Advantec Toyo Co., Ltd.), washed twice with ion-exchanged water, filtered again, and the free additives are removed, after which the toner particles are dried. (2) The toner obtained in (1) is observed using a scanning electron microscope (SEM). First, external additives and fillers containing Si are detected by observing the backscattered electron image. (3) The image of (1) is binarized using image processing software (ImageJ) to remove the external additives and fillers. Next, the toner is observed at the same position as in (1) to obtain a secondary electron image. Since the resin fine particles are not observed in the backscattered electron image but only in the secondary electron image, the image is compared with the image obtained in (3), and the fine particles present in the portion other than the remaining external additives and filler (the portion other than that excluded in (3)) are determined to be resin fine particles. The volume average primary particle diameter of the resin fine particles and the distance between the resin fine particles (the distance between the centers of the particles) are measured using the image processing software. [Photography conditions] · Scanning electron microscope: SU-8230 (manufactured by Hitachi High-Technologies Corporation) · Magnification: 35,000 times · Captured image: SE(L): Secondary electron, BSE (Backscattered electron) · Accelerating voltage: 2.0 kV · Accelerating current: 1.0 μA · Probe current: Normal · Focus mode: UHR · WD: 8.0 mm The above measurement is performed on 100 binary images (one toner particle per image), and the average value is taken as the measurement result.

[0016] In the toner of the present invention, M and L satisfy the relationship of M < L. By M < L, the low-temperature fixing property can be improved. In the toner of the present invention, the ratio [M (nm) / L (nm)] of M to L is 0.40 or more and less than 0.90, preferably 0.50 or more and less than 0.80, and more preferably 0.60 or more and less than 0.70. If the ratio [M (nm) / L (nm)] is less than 0.40, the heat-resistant storage property and the cleaning property may deteriorate, and if the ratio [M (nm) / L (nm)] is 0.90 or more, the heat-resistant storage property may deteriorate.

[0017] The resin fine particles (hereinafter, may also be referred to as "resin fine particles (B)") preferably have a core resin (core part) and a shell resin (outer shell part) covering at least a part of the surface of the core resin, more preferably composed of a core resin and a shell resin, and still more preferably resin (b1) and resin (b2) having vinyl-based units. The vinyl-based units in the shell resin (hereinafter, also expressed as "resin (b1)") and the core resin (hereinafter, also expressed as "resin (b2)") are preferably polymers obtained by homopolymerizing or copolymerizing vinyl monomers.

[0018] Examples of the vinyl monomer include the following (1) to (10). (1) Vinyl hydrocarbon Examples of vinyl hydrocarbons include (1-1) aliphatic vinyl hydrocarbons, (1-2) alicyclic vinyl hydrocarbons, and (1-3) aromatic vinyl hydrocarbons.

[0019] (1-1) Aliphatic vinyl hydrocarbons Examples of the aliphatic vinyl hydrocarbon include alkenes and alkadienes. Specific examples of the alkene include ethylene, propylene, and α-olefins. Specific examples of the alkadienes include butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, and 1,7-octadiene.

[0020] (1-2) Alicyclic vinyl hydrocarbons Alicyclic vinyl hydrocarbons include mono- or di-cycloalkenes and alkadienes, and specific examples include (di)cyclopentadiene, terpene, and the like.

[0021] (1-3) Aromatic vinyl hydrocarbons Examples of aromatic vinyl hydrocarbons include styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substituted derivatives, and specific examples include α-methylstyrene, 2,4-dimethylstyrene, and vinylnaphthalene.

[0022] (2) Carboxyl group-containing vinyl monomers and their salts Examples of the carboxyl group-containing vinyl monomer and its salt include unsaturated monocarboxylic acids (salts) having 3 to 30 carbon atoms, unsaturated dicarboxylic acids (salts), and anhydrides (salts) thereof, and monoalkyl (carbon number 1 to 24) esters thereof or salts thereof. Specific examples include carboxyl group-containing vinyl monomers such as (meth)acrylic acid, (anhydride) maleic acid, maleic acid monoalkyl esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid, and metal salts thereof.

[0023] In the present invention, the term "(salt)" means an acid or a salt thereof. For example, an unsaturated monocarboxylic acid (salt) having 3 to 30 carbon atoms means an unsaturated monocarboxylic acid or a salt thereof. In the present invention, "(meth)acrylic" means methacrylic acid or acrylic acid. In the present invention, "(meth)acryloyl" means methacryloyl or acryloyl. In the present invention, "(meth)acrylate" means methacrylate or acrylate.

[0024] (3) Sulfonic acid group-containing vinyl monomers, vinyl sulfate monoesters, and their salts Examples of the sulfonic acid group-containing vinyl monomer, vinyl sulfate monoester, and salts thereof include C2-C14 alkene sulfonic acids (salts), C2-C24 alkyl sulfonic acids (salts), sulfo(hydroxy)alkyl-(meth)acrylates (salts), (meth)acrylamides (salts), and alkylaryl sulfosuccinic acids (salts). Specifically, an example of an alkene sulfonic acid having 2 to 14 carbon atoms is vinyl sulfonic acid (salt), an example of an alkyl sulfonic acid (salt) having 2 to 24 carbon atoms is α-methylstyrene sulfonic acid (salt), and an example of a sulfo(hydroxy)alkyl-(meth)acrylate (salt) or (meth)acrylamide (salt) is sulfopropyl (meth)acrylate (salt), sulfuric acid ester (salt), or sulfonic acid group-containing vinyl monomer (salt).

[0025] (4) Phosphate-containing vinyl monomers and their salts Examples of the phosphoric acid group-containing vinyl monomer and its salt include (meth)acryloyloxyalkyl (C1-24) phosphate monoester (salt), (meth)acryloyloxyalkyl (C1-24) phosphonic acid (salt), and the like. Specific examples of the (meth)acryloyloxyalkyl (having 1 to 24 carbon atoms) phosphate monoester (salt) include 2-hydroxyethyl (meth)acryloylphosphate (salt), phenyl-2-acryloyloxyethyl phosphate (salt), and the like. Specific examples of the (meth)acryloyloxyalkyl (carbon number 1 to 24) phosphonic acid (salt) include 2-acryloyloxyethyl phosphonic acid (salt).

[0026] Examples of the salts of (2) to (4) above include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, and quaternary ammonium salts.

[0027] (5) Hydroxyl group-containing vinyl monomer Examples of the hydroxyl group-containing vinyl monomer include hydroxystyrene, N-methylol(meth)acrylamide, hydroxyethyl(meth)acrylate, hydroxypropyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, (meth)allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1-buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, and sucrose allyl ether.

[0028] (6) Nitrogen-containing vinyl monomers Examples of the nitrogen-containing vinyl monomer include (6-1) amino group-containing vinyl monomer, (6-2) amide group-containing vinyl monomer, (6-3) nitrile group-containing vinyl monomer, (6-4) quaternary ammonium cation group-containing vinyl monomer, and (6-5) nitro group-containing vinyl monomer.

[0029] (6-1) Examples of amino group-containing vinyl monomers include aminoethyl (meth)acrylate.

[0030] (6-2) Examples of amide group-containing vinyl monomers include (meth)acrylamide and N-methyl(meth)acrylamide.

[0031] (6-3) Examples of nitrile group-containing vinyl monomers include (meth)acrylonitrile, cyanostyrene, and cyanoacrylate.

[0032] (6-4) Examples of quaternary ammonium cation group-containing vinyl monomers include quaternized products of tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, diethylaminoethyl (meth)acrylamide, and diallylamine (which are quaternized using a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, or dimethyl carbonate).

[0033] (6-5) Examples of nitro group-containing vinyl monomers include nitrostyrene.

[0034] (7) Epoxy group-containing vinyl monomer Examples of the epoxy group-containing vinyl monomer include glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and p-vinylphenyl phenyl oxide.

[0035] (8) Halogen-containing vinyl monomers Examples of the halogen-containing vinyl monomer include vinyl chloride, vinyl bromide, vinylidene chloride, allyl chloride, chlorostyrene, bromostyrene, dichlorostyrene, chloromethylstyrene, tetrafluorostyrene, and chloroprene.

[0036] (9) Vinyl esters, vinyl (thio)ethers, vinyl ketones Examples of the vinyl ester include vinyl acetate, vinyl butyrate, vinyl propionate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl 4-vinyl benzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth)acrylate, vinyl methoxyacetate, vinyl benzoate, ethyl α-ethoxyacrylate, alkyl (meth)acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth)acrylate], acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, octadecyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, etc.)], dialkyl fumarate (wherein the two alkyl groups are linear, branched, or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate, esters (the two alkyl groups are straight-chain, branched-chain, or alicyclic groups having 2 to 8 carbon atoms), poly(meth)allyloxyalkanes [diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane, etc.], vinyl monomers having polyalkylene glycol chains [polyethylene glycol (molecular weight 300) mono(meth)acrylate, polypropylene glycol (molecular weight 500) monoacrylate, methyl alcohol ethylene oxide 10 mole adduct (meth)acrylate, lauryl alcohol ethylene oxide 30 mole adduct (meth)acrylate, etc.], poly(meth)acrylates [poly(meth)acrylates of polyhydric alcohols: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate, etc.], and the like. Examples of vinyl (thio)ethers include vinyl methyl ether. Examples of vinyl ketones include vinyl methyl ketone.

[0037] (10) Other vinyl monomers Other vinyl monomers include, for example, tetrafluoroethylene, fluoroacrylate, isocyanatoethyl (meth)acrylate, and m-isopropenyl-α,α-dimethylbenzyl isocyanate.

[0038] In synthesizing the resin (b1), the vinyl monomers (1) to (10) may be used alone or in combination of two or more. As the resin (b1), from the viewpoint of low-temperature fixability, a styrene-(meth)acrylic acid ester copolymer and a (meth)acrylic acid ester copolymer are preferred, and a styrene-(meth)acrylic acid ester copolymer is more preferred. When the resin (b1) contains a carboxylic acid, an acid value is imparted to the resin, and it becomes easier to form toner particles in which the resin fine particles (B) adhere to the surface of the toner particles.

[0039] Examples of the vinyl monomer used in the resin (b2) include the same ones as those used in the resin (b1). In synthesizing the resin (b2), the vinyl monomers (1) to (10) listed for the resin (b1) may be used alone or in combination of two or more. As the resin (b2), from the viewpoint of low-temperature fixability, a styrene-(meth)acrylic acid ester copolymer and a (meth)acrylic acid ester copolymer are preferred, and a styrene-(meth)acrylic acid ester copolymer is more preferred.

[0040] The viscoelastic loss modulus G" of the resin (b1) at 100°C and a frequency of 1 Hz is preferably 1.5 MPa to 100 MPa, more preferably 1.7 MPa to 30 MPa, and even more preferably 2.0 MPa to 10 MPa. The loss modulus G" of the viscoelastic properties of the resin (b2) at a frequency of 1 Hz and 100°C is preferably 0.01 MPa to 1.0 MPa, more preferably 0.02 MPa to 0.5 MPa, and even more preferably 0.05 MPa to 0.3 MPa. When the viscoelastic loss modulus G" is within this range, it is easy to form toner particles in which the resin fine particles (B) containing the resin (b1) and the resin (b2) as constituent components in the same particle are adhered to the surface of the toner particle.

[0041] The loss modulus G″ of the viscoelastic properties of the resins (b1) and (b2) at a frequency of 1 Hz and 100°C can be adjusted by changing the types and composition ratio of the constituent monomers or by adjusting the polymerization conditions (types and amounts of initiator and chain transfer agent, reaction temperature, etc.). Specifically, for example, by using the following composition, it is possible to adjust each G″ to fall within the above-mentioned range. (1) Regarding the glass transition temperature (Tg1) calculated from the constituent monomers of resin (b1) and the glass transition temperature (Tg2) calculated from the constituent monomers of resin (b2), Tg1 is preferably 0°C to 150°C, more preferably 50°C to 100°C, and Tg2 is preferably -30°C to 100°C, more preferably 0°C to 80°C, and most preferably 30°C to 60°C. The glass transition temperature (Tg) calculated from the constituent monomers is a value that can be calculated by the Fox method. Here, the Fox method [TGFox, Phys. Rev., 86, 652 (1952)] is a method for estimating the Tg of a copolymer from the Tg of each homopolymer, which is represented by the following formula: 1 / Tg=W1 / Tg1+W2 / Tg2++Wn / Tgn [In the formula, Tg is the glass transition temperature (expressed in absolute temperature) of the copolymer, Tg1, Tg2...Tgn are the glass transition temperatures (expressed in absolute temperature) of the homopolymers of each monomer component, and W1, W2...Wn are the weight fractions of each monomer component.] (2) Regarding the calculated acid value (AV1) of the resin (b1) and the calculated acid value (AV2) of the resin (b2), (AV1) is preferably 75 mgKOH / g to 400 mgKOH / g, more preferably 150 mgKOH / g to 300 mgKOH / g, and (AV2) is 0 mgKOH / g to 50 mgKOH / g, more preferably 0 mgKOH / g to 20 mgKOH / g, and most preferably 0 mgKOH / g. The calculated acid value is a theoretical acid value calculated from the molar amount of acidic groups contained in the constituent monomers and the total weight of the constituent monomers.

[0042] As for the resin (b1), an example of a constituent monomer that satisfies the conditions (1) and (2) is a resin that contains, as a constituent monomer, preferably 10% by mass to 80% by mass, and more preferably 30% by mass to 60% by mass of styrene, and preferably a total of 10% by mass to 60% by mass, and more preferably a total of 30% by mass to 50% by mass of methacrylic acid and / or acrylic acid, based on the total mass of the resin (b1). Furthermore, examples of resin (b2) include resins that contain, as constituent monomers, preferably 10% by mass to 100% by mass, more preferably 30% by mass to 90% by mass of styrene based on the total mass of resin (b2), and preferably 0% by mass to 7.5% by mass in total, more preferably 0% by mass to 2.5% by mass of methacrylic acid and / or acrylic acid based on the total mass of resin (b2).

[0043] (3) The polymerization conditions (type and amount of initiator and chain transfer agent, reaction temperature, etc.) are adjusted. Specifically, with respect to the number average molecular weights (Mn1) and (Mn2) of resin (b1) and resin (b2), (Mn1) is preferably set to 2,000 to 2,000,000, more preferably 20,000 to 200,000, and (Mn2) is preferably set to 1,000 to 1,000,000, more preferably 10,000 to 100,000.

[0044] The loss modulus G″ of the viscoelastic properties in the present invention is measured, for example, using the following viscoelasticity measuring device. Apparatus: ARES-24A (Rheometrics) Jig: 25mm parallel plate Frequency: 1Hz Distortion rate: 10% Heating rate: 5℃ / min

[0045] The acid value (AVb1) of the resin (b1) is preferably from 75 mgKOH / g to 400 mgKOH / g, more preferably from 150 mgKOH / g to 300 mgKOH / g. If the acid value is within this range, the resin fine particles (B) containing vinyl units, in which the resin (b1) and the resin (b2) are contained as constituent components in the same particle, are likely to form particles adhered to the surface of the toner. Resin (b1) having an acid value within this range is a resin that contains methacrylic acid and / or acrylic acid in a total amount of preferably 10% by mass to 60% by mass, and more preferably 30% by mass to 50% by mass, based on the total mass of resin (b1).

[0046] The acid value (AVb2) of the resin (b2) is preferably 0 mgKOH / g to 50 mgKOH / g, more preferably 0 mgKOH / g to 20 mgKOH / g, and even more preferably 0 mgKOH / g, from the viewpoint of low-temperature fixability. Resin (b2) having an acid value within this range is a resin that contains methacrylic acid and / or acrylic acid in a total amount of preferably 0% to 7.5% by mass, and more preferably 0% to 2.5% by mass, based on the total mass of resin (b2). The acid value in the present invention is measured by the method of JIS K0070:1992.

[0047] The glass transition temperature of the resin (b1) is preferably higher than the glass transition temperature of the resin (b2), more preferably 10° C. or more higher, and even more preferably 20° C. or more higher. Within this range, the ease of forming toner particles in which the resin fine particles (B) adhere to the surface of the toner and the low-temperature fixability of the toner particles of the present invention are well balanced.

[0048] The glass transition temperature (hereinafter abbreviated as Tg) of the resin (b1) is preferably from 0°C to 150°C, more preferably from 50°C to 100°C. If the glass transition temperature is 0° C. or higher, the heat-resistant storage stability can be improved, and if the glass transition temperature is 150° C. or lower, there is little inhibition of low-temperature fixability. The Tg of the resin (b2) is preferably −30° C. to 100° C., more preferably 0° C. to 80° C., and even more preferably 30° C. to 60° C. If the glass transition temperature is −30° C. or higher, the heat-resistant storage stability can be improved, and if it is 100° C. or lower, there is little inhibition of low-temperature fixability.

[0049] In the present invention, Tg is measured by the method (DSC) specified in ASTM D3418-82 using a "DSC20, SSC / 580" [manufactured by Seiko Instruments Inc.].

[0050] The solubility parameter (hereinafter abbreviated as SP value) of the resin (b1) is set to 9 to 13 (cal / cm) from the viewpoint of ease of forming toner particles. 3 )1 / 2 is preferable, and 9.5 to 12.5 (cal / cm 3 )1 / 2 is more preferable, and 10.5 to 11.5 (cal / cm 3 )1 / 2 is more preferred. The SP value of the resin (b1) can be adjusted by changing the types and composition ratio of the constituent monomers. The SP value of the resin (b2) is set to 8.5 to 12.5 (cal / cm 3 ) from the viewpoint of ease of forming toner particles. 3 )1 / 2 is preferable, and 9 to 12 (cal / cm 3 )1 / 2 is more preferable, and 10 to 11 (cal / cm 3 )1 / 2 is more preferred. The SP value of the resin (b2) can be adjusted by changing the types and composition ratio of the constituent monomers.

[0051] The SP value in the present invention is calculated by the method by Fedors [Polym. Eng. Sci. 14(2)152, (1974)].

[0052] From the viewpoint of Tg of the resin (b1) and copolymerizability with other monomers, the resin (b1) preferably contains 10% by mass to 80% by mass, and more preferably 30% by mass to 60% by mass of styrene as a constituent monomer, based on the total mass of the resin (b1). From the viewpoint of Tg of the resin (b2) and copolymerizability with other vinyl monomers, the resin (b2) preferably contains 10% by mass to 100% by mass, and more preferably 30% by mass to 90% by mass of styrene as a constituent monomer, based on the total mass of the resin (b2).

[0053] The number average molecular weight (Mn) of the resin (b1) is preferably 2,000 to 2,000,000, and more preferably 20,000 to 200,000. If the number average molecular weight is 2,000 or more, the heat-resistant storage stability is improved, and if it is 2,000,000 or less, the low-temperature fixability of the toner is less hindered.

[0054] The weight-average molecular weight of the resin (b1) is preferably larger than that of the resin (b2), more preferably 1.5 times or more larger than that of the resin (b2), and even more preferably 2.0 times or more larger than that of the resin (b2). Within this range, an excellent balance between ease of toner particle formation and low-temperature fixability is achieved.

[0055] The weight average molecular weight (Mw) of the resin (b1) is preferably 20,000 to 20,000,000, and more preferably 200,000 to 2,000,000. If the weight average molecular weight is 20,000 or more, the heat-resistant storage stability is improved, and if it is 20,000,000 or less, the low-temperature fixability is less hindered.

[0056] The Mn of the resin (b2) is preferably 1,000 to 1,000,000, and more preferably 10,000 to 100,000. When Mn is 1,000 or more, the heat-resistant storage stability of the toner is improved, and when Mn is 1,000,000 or less, the low-temperature fixability of the toner is less hindered.

[0057] The Mw of the resin (b2) is preferably 10,000 to 10,000,000, and more preferably 100,000 to 1,000,000. When the Mw is 10,000 or more, the heat-resistant storage stability of the toner is improved, and when it is 10,000,000 or less, the low-temperature fixability of the toner is less hindered.

[0058] Among these, it is preferred that the Mw of the resin (b1) is 200,000 to 2,000,000, the Mw of the resin (b2) is 100,000 to 500,000, and the "Mw of (b1)" is greater than the "Mw of (b2)".

[0059] In the present invention, Mn and Mw can be measured using gel permeation chromatography (GPC) under the following conditions. Device (example): "HLC-8120" [manufactured by Tosoh Corporation] Column (example): "TSK GEL GMH6" [manufactured by Tosoh Corporation] x 2 Measurement temperature: 40℃ Sample solution: 0.25% by weight tetrahydrofuran solution (insoluble matter filtered off with a glass filter) Solution injection volume: 100μl Detector: Refractive index detector Reference material: 12 standard polystyrenes (TSK standard POLYSTYRENE) (molecular weights: 500, 1,050, 2,800, 5,970, 9,100, 18,100, 37,900, 96,400, 190,000, 355,000, 1,090,000, 2,890,000) [manufactured by Tosoh Corporation]

[0060] The weight ratio of the resin (b1) to the resin (b2) in the resin fine particles (B) is preferably 5 / 95 to 95 / 5, more preferably 25 / 75 to 75 / 25, and even more preferably 40 / 60 to 60 / 40. When the weight ratio of the resin (b1) to the resin (b2) is 5 / 95 or more, the toner has excellent heat-resistant storage stability, and when the weight ratio of the resin (b1) to the resin (b2) is 95 / 5 or less, the toner particles in which the resin fine particles (B) adhere to the surfaces of the toner resin particles are easily formed.

[0061] The resin fine particles (B) can be produced by known production methods, such as the following production methods (I) to (V). (I) A method of seed polymerization of constituent monomers of resin (b2) using fine particles of resin (b1) in an aqueous dispersion as seeds. (II) A method of seed polymerization of constituent monomers of resin (b1) using fine particles of resin (b2) in an aqueous dispersion as seeds. (III) A method in which a mixture of resin (b1) and resin (b2) is emulsified in an aqueous medium to obtain an aqueous dispersion of resin fine particles. (IV) A method in which a mixture of resin (b1) and constituent monomers of resin (b2) is emulsified in an aqueous medium, and then the constituent monomers of resin (b2) are polymerized to obtain an aqueous dispersion of resin fine particles. (V) A method in which a mixture of resin (b2) and the constituent monomers of resin (b1) is emulsified in an aqueous medium, and then the constituent monomers of resin (b1) are polymerized to obtain an aqueous dispersion of resin fine particles.

[0062] The fact that the resin microparticles (B) contain the shell resin (b1) and the core resin (b2) as constituent components within the same particle can be confirmed by observing an element mapping image of a cross section of the resin microparticles (B) using a known surface elemental analyzer (such as TOF-SIMSEDX-SEM), and by observing a cross section of the resin microparticles (B) stained with a stain corresponding to the functional groups contained in the resins (b1) and (b2) using an electron microscope. Furthermore, the resin microparticles obtained by this method may be obtained as a mixture containing, in addition to the resin microparticles (B) containing the resin (b1) and the resin (b2) as constituent components within the same particle, resin microparticles whose only constituent resin component is the resin (b1) and resin microparticles whose only constituent resin component is the resin (b2). In the composite process described below, the mixture may be used as is, or only the resin microparticles (B) may be isolated and used.

[0063] Specific examples of (I) include a method in which the constituent monomers of (b1) are polymerized dropwise to produce an aqueous dispersion of resin microparticles containing (b1), and then this is used as a seed to perform seed polymerization of the constituent monomers of (b2); and a method in which (b1) produced in advance by solution polymerization or the like is emulsified and dispersed in water, and then this is used as a seed to perform seed polymerization of the constituent monomers of (b2).

[0064] Specific examples of (II) include a method in which the constituent monomers of (b2) are polymerized dropwise to produce an aqueous dispersion of resin microparticles containing (b2), and then this is used as a seed to perform seed polymerization of the constituent monomers of (b1); and a method in which (b2) produced in advance by solution polymerization or the like is emulsified and dispersed in water, and then this is used as a seed to perform seed polymerization of the constituent monomers of (b1).

[0065] A specific example of (III) is a method in which solutions or melts of (b1) and (b2) previously prepared by solution polymerization or the like are mixed together, and then the mixture is emulsified and dispersed in an aqueous medium.

[0066] Specific examples of (IV) include a method in which (b1), which has been produced in advance by solution polymerization or the like, is mixed with constituent monomers of (b2), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b2) are polymerized; and a method in which (b1) is produced in the constituent monomers of (b2), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b2) are polymerized.

[0067] Specific examples of (V) include a method in which (b2), which has been produced in advance by solution polymerization or the like, is mixed with the constituent monomers of (b1), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b1) are polymerized; and a method in which (a2) is produced in the constituent monomers of (b1), the mixture is emulsified and dispersed in an aqueous medium, and then the constituent monomers of (b1) are polymerized.

[0068] In the present invention, any of the above production methods (I) to (V) is suitable.

[0069] The resin fine particles (B) are preferably used in the form of an aqueous dispersion. The substance (aqueous medium) used in the aqueous dispersion is not particularly limited as long as it is soluble in water and can be appropriately selected depending on the purpose, and examples thereof include surfactants (D), buffers, protective colloids, etc. These may be used alone or in combination of two or more. The aqueous medium used in the aqueous dispersion is not particularly limited as long as it is a liquid that essentially contains water, and examples thereof include an aqueous solution containing water.

[0070] Examples of the surfactant (D) include nonionic surfactants (D1), anionic surfactants (D2), cationic surfactants (D3), amphoteric surfactants (D4), and other emulsifying dispersants (D5).

[0071] Examples of the nonionic surfactant (D1) include AO (alkylene oxide) addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. Examples of the AO-addition type nonionic surfactant include EO adducts of aliphatic alcohols having 10 to 20 carbon atoms, EO adducts of phenols, EO (ethylene oxide) adducts of nonylphenols, EO adducts of alkylamines having 8 to 22 carbon atoms, and EO adducts of poly(oxypropylene) glycols. Examples of the polyhydric alcohol-type nonionic surfactant include fatty acid (8 to 24 carbon atoms) esters of polyhydric (tri- to octahydric or higher) alcohols (2 to 30 carbon atoms) (e.g., glycerin monostearate, glycerin monooleate, sorbitan monolaurate, sorbitan monooleate, etc.), alkyl (4 to 24 carbon atoms) poly(degree of polymerization 1 to 10) glycosides, and the like.

[0072] Examples of the anionic surfactant (D2) include ethercarboxylic acids having a hydrocarbon group of 8 to 24 carbon atoms or salts thereof, sulfates or ether sulfates having a hydrocarbon group of 8 to 24 carbon atoms and salts thereof, sulfonates having a hydrocarbon group of 8 to 24 carbon atoms, sulfosuccinates having one or two hydrocarbon groups of 8 to 24 carbon atoms, phosphates or ether phosphates having a hydrocarbon group of 8 to 24 carbon atoms and salts thereof, fatty acid salts having a hydrocarbon group of 8 to 24 carbon atoms, and acylated amino acid salts having a hydrocarbon group of 8 to 24 carbon atoms. Examples of ethercarboxylic acids or salts thereof having a hydrocarbon group with 8 to 24 carbon atoms include sodium lauryl ether acetate and (poly)oxyethylene (number of moles added: 1 to 100) sodium lauryl ether acetate. Examples of sulfates or ether sulfates having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof include sodium lauryl sulfate, (poly)oxyethylene (number of moles added: 1 to 100) sodium lauryl sulfate, (poly)oxyethylene (number of moles added: 1 to 100) triethanolamine lauryl sulfate, and (poly)oxyethylene (number of moles added: 1 to 100) sodium coconut oil fatty acid monoethanolamide sulfate. Examples of sulfonates having a hydrocarbon group with 8 to 24 carbon atoms include sodium dodecylbenzenesulfonate. Examples of the phosphate ester or ether phosphate ester having a hydrocarbon group with 8 to 24 carbon atoms and salts thereof include sodium lauryl phosphate and sodium (poly)oxyethylene (addition mole number 1 to 100) lauryl ether phosphate. Examples of fatty acid salts having a hydrocarbon group with 8 to 24 carbon atoms include sodium laurate and triethanolamine laurate. Examples of acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms include sodium coconut oil fatty acid methyl taurate, sodium coconut oil fatty acid sarcosine, triethanolamine coconut oil fatty acid sarcosine, triethanolamine N-coconut oil fatty acid acyl-L-glutamate, sodium N-coconut oil fatty acid acyl-L-glutamate, and sodium lauroylmethyl-β-alanine.

[0073] Examples of the cationic surfactant (D3) include quaternary ammonium salt types and amine salt types. Examples of the quaternary ammonium salt type include stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, and lanolin fatty acid aminopropylethyldimethylammonium ethyl sulfate. Examples of the amine salt type include stearic acid diethylaminoethylamide lactate, dilaurylamine hydrochloride, and oleylamine lactate.

[0074] Examples of the amphoteric surfactant (D4) include betaine-type amphoteric surfactants and amino acid-type amphoteric surfactants. Examples of the betaine-type amphoteric surfactant include coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, and lauryl hydroxysulfobetaine. Examples of amino acid type amphoteric surfactants include sodium β-laurylaminopropionate.

[0075] Other emulsifying dispersants (D5) include, for example, reactive activators. The reactive activator is not particularly limited as long as it has radical reactivity and can be appropriately selected depending on the purpose. Examples include ADEKA REASOAP (registered trademark) SE-10N, SR-10, SR-20, SR-30, ER-20, and ER-30 (all manufactured by ADEKA Corporation), AQUALON (registered trademark), HS-10, KH-05, KH-10, and KH-1025 (all manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), ELEMINOL (registered trademark) JS-20 (manufactured by Sanyo Chemical Industries, Ltd.), and LATEMUL (registered trademark) D-104, PD-420, and PD-430 (all manufactured by Examples of suitable emulsifying dispersants include those manufactured by Kao Corporation, IONET (registered trademark) MO-200 (manufactured by Sanyo Chemical Industries, Ltd.), polyvinyl alcohol, starch and its derivatives, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose, and hydroxyethyl cellulose, and carboxyl group-containing (co)polymers such as polysodium acrylate, and emulsifying dispersants having urethane groups or ester groups described in U.S. Pat. No. 5,906,704 (for example, those in which polycaprolactone polyol and polyether diol are linked with polyisocyanate).

[0076] As the surfactant (D), from the viewpoint of stabilizing oil droplets during emulsification and dispersion, obtaining a desired shape, and sharpening the particle size distribution, (D1), (D2), (D5), and combinations of these are preferred, and a combination of (D1) and (D5), and a combination of (D2) and (D5) are more preferred.

[0077] Examples of the buffering agent include sodium acetate, sodium citrate, and sodium bicarbonate. Examples of the protective colloid include water-soluble cellulose compounds and alkali metal salts of polymethacrylic acid.

[0078] The resin microparticles (B) may contain, in addition to the shell resin (b1) and the core resin (b2), other resin components, an initiator (and its residue), a chain transfer agent, an antioxidant, a plasticizer, a preservative, a reducing agent, an organic solvent, etc.

[0079] Examples of the other resin components include vinyl resins other than the resins used for the shell resin (b1) and the core resin (b2), polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenolic resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like.

[0080] Examples of the initiator (and its residue) include known radical polymerization initiators, and specific examples include persulfate initiators such as potassium persulfate and ammonium persulfate; azo initiators such as azobisisobutyronitrile; organic peroxides such as benzoyl peroxide, cumene hydroperoxide, tertiary butyl hydroperoxide, tertiary butyl peroxyisopropyl monocarbonate, and tertiary butyl peroxybenzoate; and hydrogen peroxide.

[0081] Examples of the chain transfer agent include n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, 2-ethylhexyl thioglycolate, 2-mercaptoethanol, β-mercaptopropionic acid, and α-methylstyrene dimer.

[0082] Examples of antioxidants include phenol compounds, paraphenylenediamine, hydroquinone, organic sulfur compounds, and organic phosphorus compounds.

[0083] Examples of phenol compounds include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,2′-methylene-bis-(4-methyl-6-t-butylphenol), 2,2′-methylene-bis-(4-ethyl-6-t-butylphenol), 4,4′-thiobis-(3-methyl-6-t-butylphenol), 4,4′-butylidenebis-(3-methyl-6-t-butylphenol), t-butyl-6-t-butylphenol), 1,1,3-tris-(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'-bis(4'-hydroxy-3'-t-butylphenyl)butyric acid]glycol ester, tocopherol, etc.

[0084] Examples of paraphenylenediamines include N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N,N'-di-isopropyl-p-phenylenediamine, and N,N'-dimethyl-N,N'-di-t-butyl-p-phenylenediamine.

[0085] Examples of hydroquinones include 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, and 2-(2-octadecenyl)-5-methylhydroquinone.

[0086] Examples of the organic sulfur compounds include dilauryl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, and ditetradecyl-3,3'-thiodipropionate.

[0087] Examples of the organic phosphorus compound include triphenylphosphine, tri(nonylphenyl)phosphine, tri(dinonylphenyl)phosphine, tricresylphosphine, and tri(2,4-dibutylphenoxy)phosphine.

[0088] Examples of the plasticizer include phthalate esters, aliphatic dibasic acid esters, trimellitate esters, phosphate esters, and fatty acid esters. Examples of phthalate esters include dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, and diisodecyl phthalate. Examples of the aliphatic dibasic acid ester include di-2-ethylhexyl adipate and 2-ethylhexyl sebacate. Examples of trimellitic acid esters include tri-2-ethylhexyl trimellitate and trioctyl trimellitate. Examples of the phosphate ester include triethyl phosphate, tri-2-ethylhexyl phosphate, and tricresyl phosphate. An example of the fatty acid ester is butyl oleate.

[0089] Examples of the preservatives include organic nitrogen sulfur compound preservatives and organic sulfur halide preservatives.

[0090] Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose, and formaldehyde sulfoxylate metal salts; and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite.

[0091] Examples of the organic solvent include ketone solvents such as acetone and methyl ethyl ketone (hereinafter abbreviated as MEK); ester solvents such as ethyl acetate and γ-butyrolactone; ether solvents such as THF (tetrahydrofuran); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactam; alcohol solvents such as isopropyl alcohol; and aromatic hydrocarbon solvents such as toluene and xylene.

[0092] The content of the resin fine particles is preferably 0.2% to 5% by mass based on the toner. When the sum of resin (b1) and resin (b2) is within this range, the low-temperature fixing property and the heat-resistant storage property are improved. When it is 0.2 wt% or more based on the toner, the problem of deterioration of the heat-resistant storage property can be prevented, and when it is 5 wt% or less, the problem of deterioration of the low-temperature fixing property can be prevented.

[0093] [Second Aspect] In the second aspect of the toner of the present invention, on the surface of the toner base particles, when the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm), the following formula, M < L, is satisfied, and methacrylic acid detected by thermal decomposition gas chromatography of the toner is 1.0 mg / g or more and 4.0 mg / g or less based on the total amount of the toner, and it has resin fine particles. In the second aspect of the toner of the present invention, regarding the same description as in the first aspect, it is the same as that described in the first aspect.

[0094] The thermal decomposition gas chromatography of the toner is performed under the following conditions. [Conditions] · Gas chromatograph device: 7890B (manufactured by Agilent Technologies) · Thermal decomposition device: EGA / PY-3030D (manufactured by Frontier Lab) · Thermal decomposition condition temperature: 600 °C · Interface temperature: 400 °C · Detector temperature: 320 °C Oven temperature flow: <1> 50℃(10min) <2> Temperature rise: 10℃ / min <3> 150℃(0min) <4> Temperature rise: 20℃ / min <5> 320℃ (3.5 min) Column: UA5-30M-1F (30m x 0.25mm i.d., 1.0μm film) Detector: FID

[0095] In the toner of the present invention, the amount of methacrylic acid detected by pyrolysis gas chromatography of the toner is 1.0 mg / g or more and 4.0 mg / g or less relative to the toner. If the amount of methacrylic acid detected by pyrolysis gas chromatography of the toner is less than 1.0 mg / g relative to the toner, problems such as deterioration of humidity and heat resistance storage stability may occur, and if it exceeds 4.0 mg / g, problems may occur in low-temperature fixability.

[0096] <Toner base particles> The toner base particles (hereinafter, sometimes referred to as "toner base" or "base particles") contain a binder resin, a colorant, and a wax, and further contain other components as required.

[0097] <<Binder resin>> The binder resin is not particularly limited and can be appropriately selected depending on the purpose. Examples include polyester resins, styrene-acrylic resins, polyol resins, vinyl resins, polyurethane resins, epoxy resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. These may be used alone or in combination of two or more. Among these, polyester resins are preferred because they can impart flexibility to the toner.

[0098] <<<Polyester resin>>> The polyester resin is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include crystalline polyester resins, amorphous polyester resins, modified polyester resins, etc. These may be used alone or in combination of two or more.

[0099] -Amorphous polyester resin- The amorphous polyester resin (hereinafter also referred to as "amorphous polyester," "amorphous polyester," "amorphous polyester resin," "unmodified polyester resin," or "polyester resin component A") is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include an amorphous polyester resin obtained by reacting a polyol with a polycarboxylic acid. In the present invention, the amorphous polyester resin refers to a resin obtained by reacting a polyol with a polycarboxylic acid, as described above. Modified polyester resins, such as prepolymers described below, and modified polyester resins obtained by subjecting the prepolymers to a crosslinking and / or elongation reaction, are not included in the amorphous polyester resins of the present invention, but are treated as modified polyester resins. The amorphous polyester is a polyester resin component that is soluble in tetrahydrofuran (THF). The amorphous polyester (polyester resin component A) is preferably a linear polyester resin.

[0100] Examples of the polyol include diols. Examples of the diol include alkylene (carbon number 2 to 3) oxide (average number of added moles 1 to 10) adducts of bisphenol A such as polyoxypropylene(2.2)-2,2-bis(4-hydroxyphenyl)propane and polyoxyethylene(2.2)-2,2-bis(4-hydroxyphenyl)propane; ethylene glycol, propylene glycol; hydrogenated bisphenol A, and alkylene (carbon number 2 to 3) oxide (average number of added moles 1 to 10) adducts of hydrogenated bisphenol A. These may be used alone or in combination of two or more. Among these, the polyol preferably contains 40 mol % or more of alkylene glycol.

[0101] Examples of the polycarboxylic acid include dicarboxylic acids. Examples of the dicarboxylic acid include alkyl groups having 1 to 20 carbon atoms, such as adipic acid, phthalic acid, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, dodecenylsuccinic acid, and octylsuccinic acid; and succinic acid substituted with an alkenyl group having 2 to 20 carbon atoms. These may be used alone or in combination of two or more. Among these, the polycarboxylic acid preferably contains 50 mol % or more of terephthalic acid.

[0102] The polyester resin component A may contain a trivalent or higher carboxylic acid and / or a trivalent or higher alcohol, a trivalent or higher epoxy compound, or the like at the end of its resin chain in order to adjust the acid value and hydroxyl value. Among these, it is preferable to contain a trihydric or higher aliphatic alcohol, from the viewpoint that unevenness is unlikely to occur and sufficient gloss and image density can be obtained. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, and acid anhydrides thereof. Examples of the trihydric or higher alcohol include glycerin, pentaerythritol, and trimethylolpropane.

[0103] The molecular weight of the polyester resin component A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably in the following range. The weight average molecular weight (Mw) of the polyester resin component A is preferably from 3,000 to 10,000, and more preferably from 4,000 to 7,000. The number average molecular weight (Mn) of the polyester resin component A is preferably from 1,000 to 4,000, and more preferably from 1,500 to 3,000. The molecular weight ratio (Mw / Mn) of the polyester resin component A is preferably from 1.0 to 4.0, more preferably from 1.0 to 3.5. The molecular weight can be measured by GPC (gel permeation chromatography). The reason why the molecular weight is preferably within the above range is that if the molecular weight is too low, the toner may be inferior in heat-resistant storage stability and durability to stress such as stirring in a developing machine, while if the molecular weight is too high, the toner may have high viscoelasticity when melted, resulting in poor low-temperature fixability.Furthermore, if the amount of components having a molecular weight of 600 or less is too large, the toner may be inferior in heat-resistant storage stability and durability to stress such as stirring in a developing machine, while if the amount of components having a molecular weight of 600 or less is too small, the toner may be inferior in low-temperature fixability.

[0104] The THF-soluble component having a molecular weight of 600 or less is preferably 2% by mass to 10% by mass. As a method for adjusting the content of this component, a method of extracting polyester resin component A with methanol, removing components having a molecular weight of 600 or less, and purifying the product can be given.

[0105] The acid value of the polyester resin component A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 mgKOH / g to 50 mgKOH / g, and more preferably 5 mgKOH / g to 30 mgKOH / g. If the acid value is 1 mgKOH / g or more, the toner tends to be negatively charged, and further, the affinity between the toner and paper during fixing to paper is improved, thereby improving low-temperature fixability. On the other hand, if the acid value is 50 mgKOH / g or less, the problem of reduced charge stability, particularly with respect to environmental changes, can be prevented.

[0106] The hydroxyl value of the polyester resin component A is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 mgKOH / g or more.

[0107] The Tg of the polyester resin component A is preferably 40° C. to 65° C., more preferably 45° C. to 65° C., and even more preferably 50° C. to 60° C. When the Tg is 40° C. or higher, the toner has improved heat-resistant storage stability and durability against stress such as stirring in a developing machine, and also has improved filming resistance. On the other hand, when the Tg is 65° C. or lower, the toner is less susceptible to deformation due to heat and pressure during fixing, and low-temperature fixability is improved.

[0108] The content of the polyester resin component A is preferably 80 parts by mass to 90 parts by mass with respect to 100 parts by mass of the toner.

[0109] -Modified polyester- The modified polyester resin (hereinafter sometimes referred to as "modified polyester" or "polyester resin component C") is not particularly limited and can be appropriately selected depending on the purpose. For example, it may be a reaction product of an active hydrogen group-containing compound and a polyester resin (hereinafter sometimes referred to as "prepolymer" or "polyester prepolymer") having a site capable of reacting with the active hydrogen group-containing compound. The modified polyester is a polyester resin insoluble in tetrahydrofuran (THF). The polyester resin component insoluble in tetrahydrofuran (THF) reduces Tg and melt viscosity, ensuring low-temperature fixability, and has a branched structure in the molecular skeleton, forming a three-dimensional network structure in the molecular chain, resulting in rubber-like properties in that it deforms but does not flow at low temperatures. Since the polyester resin component C has an active hydrogen group-containing compound and a site capable of reacting with the active hydrogen group-containing compound, these sites behave like pseudo-crosslinking points, enhancing the rubber-like properties of the amorphous polyester resin A, and enabling the production of a toner with excellent heat-resistant storage stability and high-temperature offset resistance.

[0110] --Compounds containing active hydrogen groups-- The active hydrogen group-containing compound is a compound that reacts with a polyester resin having a site capable of reacting with the active hydrogen group-containing compound.

[0111] The active hydrogen group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, etc. These may be used alone or in combination of two or more.

[0112] The active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose. However, when the polyester resin having a site capable of reacting with the active hydrogen group-containing compound is a polyester resin containing an isocyanate group, amines are preferred in that they can increase the molecular weight of the polyester resin by an elongation reaction, a crosslinking reaction, or the like with the polyester resin. The amines are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, blocked amino groups of these, etc. These may be used alone or in combination of two or more. Among these, diamines and mixtures of diamines with small amounts of trivalent or higher amines are preferred.

[0113] The diamine is not particularly limited and can be selected appropriately depending on the purpose, and examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines. The aromatic diamine is not particularly limited and can be selected appropriately depending on the purpose, and examples thereof include phenylenediamine, diethyltoluenediamine, and 4,4'-diaminodiphenylmethane. The alicyclic diamine is not particularly limited and can be selected appropriately depending on the purpose, and examples thereof include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, and isophoronediamine. The aliphatic diamine is not particularly limited and can be selected appropriately depending on the purpose, and examples thereof include ethylenediamine, tetramethylenediamine, and hexamethylenediamine.

[0114] The trivalent or higher amine is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diethylenetriamine and triethylenetetramine.

[0115] The amino alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ethanolamine and hydroxyethylaniline.

[0116] The amino mercaptan is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.

[0117] The amino acid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include aminopropionic acid and aminocaproic acid.

[0118] The compound in which the amino group is blocked is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include ketimine compounds and oxazolizone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

[0119] --Polyester resin having a site capable of reacting with an active hydrogen group-containing compound-- The polyester resin having a site capable of reacting with the active hydrogen group-containing compound is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a polyester resin containing an isocyanate group (hereinafter, sometimes referred to as a "polyester prepolymer having an isocyanate group"). The polyester resin having an isocyanate group is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid with a polyisocyanate.

[0120] The polyol is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include diols, trihydric or higher alcohols, mixtures of diols and trihydric or higher alcohols, etc. These may be used alone or in combination of two or more. Among these, diols and mixtures of diols with a small amount of trihydric or higher alcohols are preferred.

[0121] The diol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include chain alkylene glycols, diols having an oxyalkylene group, alicyclic diols, bisphenols, alkylene oxide adducts of alicyclic diols, and alkylene oxide adducts of bisphenols. Examples of the chain alkylene glycol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Examples of the diol having an oxyalkylene group include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the alicyclic diol include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A. Examples of the bisphenols include bisphenol A, bisphenol F, and bisphenol S. Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene oxide. The number of carbon atoms in the chain alkylene glycol is not particularly limited and can be appropriately selected depending on the purpose, but 2 to 12 is preferred. Among these, at least one of a chain alkylene glycol having 2 to 12 carbon atoms and an alkylene oxide adduct of a bisphenol is preferred, and an alkylene oxide adduct of a bisphenol and a mixture of an alkylene oxide adduct of a bisphenol and a chain alkylene glycol having 2 to 12 carbon atoms are more preferred.

[0122] The trihydric or higher alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. The trihydric or higher aliphatic alcohol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and sorbitol. The trivalent or higher polyphenols are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include trisphenol PA, phenol novolak, and cresol novolak. Examples of the alkylene oxide adducts of the trivalent or higher polyphenols include those obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, or butylene oxide to a trivalent or higher polyphenol. When the diol and the trihydric or higher alcohol are used as a mixture, the mass ratio of the trihydric or higher alcohol to the diol (trihydric or higher alcohol / diol) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01 mass % to 10 mass %, more preferably 0.01 mass % to 1 mass %.

[0123] The polycarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include dicarboxylic acids, tri- or higher carboxylic acids, mixtures of dicarboxylic acids and tri- or higher carboxylic acids, etc. These may be used alone or in combination of two or more. Among these, dicarboxylic acids and mixtures of dicarboxylic acids with a small amount of trivalent or higher polycarboxylic acids are preferred.

[0124] The dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include divalent alkanoic acids, divalent alkenoic acids, and aromatic dicarboxylic acids. The divalent alkanoic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include succinic acid, adipic acid, and sebacic acid. The divalent alkenoic acid is not particularly limited and can be appropriately selected depending on the purpose, but is preferably a divalent alkenoic acid having 4 to 20 carbon atoms. The divalent alkenoic acid having 4 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include maleic acid and fumaric acid. The aromatic dicarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, but is preferably an aromatic dicarboxylic acid having 8 to 20 carbon atoms. The aromatic dicarboxylic acid having 8 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid.

[0125] The trivalent or higher carboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include trivalent or higher aromatic carboxylic acids. The trivalent or higher aromatic carboxylic acid is not particularly limited and can be appropriately selected depending on the purpose, but is preferably a trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms. The trivalent or higher aromatic carboxylic acid having 9 to 20 carbon atoms is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include trimellitic acid and pyromellitic acid.

[0126] As the polycarboxylic acid, an acid anhydride or a lower alkyl ester of any of a dicarboxylic acid, a tri- or higher carboxylic acid, and a mixture of a dicarboxylic acid and a tri- or higher carboxylic acid can also be used. The lower alkyl ester is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include methyl ester, ethyl ester, and isopropyl ester. When the dicarboxylic acid and the tri- or higher carboxylic acid are used in combination, the mass ratio of the tri- or higher carboxylic acid to the dicarboxylic acid (tri- or higher carboxylic acid / dicarboxylic acid) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.01% by mass to 10% by mass, and more preferably 0.01% by mass to 1% by mass.

[0127] When polyol and polycarboxylic acid are polycondensed, the equivalent ratio of hydroxyl groups of polyol to carboxyl groups of polycarboxylic acid (hydroxyl groups of polyol / carboxyl groups of polycarboxylic acid) is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 to 2, more preferably 1 to 1.5, and particularly preferably 1.02 to 1.3.

[0128] The content of the polyol-derived structural units in the polyester prepolymer having an isocyanate group is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and particularly preferably 2% by mass to 20% by mass. If the content is less than 0.5% by mass, the hot offset resistance may decrease, making it difficult to achieve both heat-resistant storage stability and low-temperature fixability of the toner, and if the content exceeds 40% by mass, the low-temperature fixability may decrease.

[0129] The polyisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those obtained by blocking these with phenol derivatives, oximes, caprolactam, etc. The aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate. The alicyclic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate. The aromatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, and 4,4′-diisocyanato-diphenyl ether. The aromatic aliphatic diisocyanate is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include α,α,α',α'-tetramethylxylylene diisocyanate. The isocyanurates are not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include tris(isocyanatoalkyl)isocyanurate, tris(isocyanatocycloalkyl)isocyanurate, etc. These may be used alone or in combination of two or more.

[0130] When the polyisocyanate is reacted with a polyester resin having a hydroxyl group, the equivalent ratio (NCO / OH) of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 to 5, more preferably 1.2 to 4, and particularly preferably 1.5 to 2.5. If the equivalent ratio is less than 1, the hot offset resistance may decrease, and if it exceeds 5, the low-temperature fixability may decrease.

[0131] The content of the polyisocyanate-derived structural unit in the polyester prepolymer having an isocyanate group is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and particularly preferably 2% by mass to 20% by mass. If the content is less than 0.5% by mass, hot offset resistance may decrease, and if it exceeds 40% by mass, low-temperature fixability may decrease.

[0132] The average number of isocyanate groups per molecule of the polyester prepolymer having isocyanate groups is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 or more, more preferably 1.5 to 3, and particularly preferably 1.8 to 2.5. If the average number is less than 1, the molecular weight of the modified polyester resin will be low, and the hot offset resistance may decrease.

[0133] The modified polyester resin can be produced by a one-shot method, etc. As an example, a method for producing a urea-modified polyester resin will be described. First, a polyol and a polycarboxylic acid are heated to 150°C to 280°C in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin oxide, and the resulting water is removed, if necessary, under reduced pressure, to obtain a polyester resin having hydroxyl groups. Next, the polyester resin having hydroxyl groups is reacted with a polyisocyanate at 40°C to 140°C to obtain a polyester prepolymer having isocyanate groups. Furthermore, the polyester prepolymer having isocyanate groups is reacted with amines at 0°C to 140°C to obtain a urea-modified polyester resin.

[0134] The number average molecular weight (Mn) of the modified polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1,000 to 10,000, more preferably 1,500 to 6,000, as measured by GPC (gel permeation chromatography). The weight average molecular weight of the modified polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 20,000 or more and 1,000,000 or less as measured by GPC (gel permeation chromatography). When the weight average molecular weight is 20,000 or more, the toner tends to flow easily at low temperatures, which can prevent the problems of poor heat-resistant storage stability and low viscosity when melted, which can prevent the problems of poor high-temperature offset properties.

[0135] When a polyester resin having a hydroxyl group is reacted with a polyisocyanate, or when a polyester prepolymer having an isocyanate group is reacted with an amine, a solvent may be used as needed. The solvent is not particularly limited and can be appropriately selected depending on the purpose. Examples include aromatic solvents, ketones, esters, amides, ethers, and other solvents that are inactive to isocyanate groups. Examples of the aromatic solvent include toluene and xylene. Examples of the ketones include acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples of the esters include ethyl acetate. Examples of the amides include dimethylformamide and dimethylacetamide. Examples of the ethers include tetrahydrofuran.

[0136] The glass transition temperature of the modified polyester resin is preferably -60°C or higher and 0°C or lower, and more preferably -40°C or higher and -20°C or lower. If the glass transition temperature is −60° C. or higher, the flow of the toner at low temperatures cannot be suppressed, which can prevent problems such as deterioration of heat-resistant storage stability and filming resistance. If the glass transition temperature is 0° C. or lower, the toner cannot be sufficiently deformed by the application of heat and pressure during fixing, and the problem of insufficient low-temperature fixing properties can be prevented.

[0137] The content of the modified polyester is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 to 15 parts by mass, more preferably 5 to 10 parts by mass, per 100 parts by mass of the toner. The molecular structures of the polyester resin components A and C can be confirmed by NMR measurement using a solution or solid, as well as X-ray diffraction, GC / MS, LC / MS, IR measurement, and the like. In the infrared absorption spectrum, 965±10 cm -1 and 990±10cm -1 One method is to detect amorphous polyester resins that do not have absorption due to olefin δCH (out-of-plane bending vibration).

[0138] -Crystalline polyester- The crystalline polyester resin (hereinafter also referred to as "crystalline polyester" or "polyester resin component D") is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include crystalline polyester resins obtained by reacting polyol with polycarboxylic acid.

[0139] The crystalline polyester resin has high crystallinity and therefore exhibits a heat melting property in which the viscosity drops sharply near the fixing start temperature. By using the crystalline polyester resin having such properties together with the amorphous polyester resin, the toner has good heat-resistant storage stability due to its crystallinity up to just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin melts, causing a sudden drop in viscosity (sharp melt), which causes it to become compatible with the amorphous polyester resin, and both resins are fixed due to a sudden drop in viscosity, resulting in a toner that combines good heat-resistant storage stability and low-temperature fixability. Furthermore, the toner also shows good results in terms of release width (the difference between the minimum fixing temperature and the temperature at which high-temperature offset occurs). In the present invention, the crystalline polyester resin refers to a resin obtained by reacting a polyol with a polycarboxylic acid, as described above, and modified polyester resins, such as the prepolymers and resins obtained by subjecting the prepolymers to a crosslinking and / or elongation reaction, do not fall under the category of crystalline polyester resins.

[0140] --Polyol-- The polyol is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include diols and trihydric or higher hydric polyols.

[0141] Examples of the diol include saturated aliphatic diols. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. These may be used alone or in combination of two or more. Among these, linear saturated aliphatic diols are preferred because they can improve crystallinity and prevent a decrease in melting point, and linear saturated aliphatic diols having 2 to 12 carbon atoms are more preferred.

[0142] Examples of the saturated aliphatic diols 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 1,14-eicosanediol. Among these, ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol are preferred because the crystalline polyester resin has high crystallinity and excellent sharp melting properties.

[0143] Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol.

[0144] --Polycarboxylic Acids-- The polycarboxylic acid is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include dicarboxylic acids and tricarboxylic or higher carboxylic acids.

[0145] Examples of the dicarboxylic acid include saturated aliphatic dicarboxylic acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, and 1,18-octadecanedicarboxylic acid; and aromatic dicarboxylic acids such as dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, and mesaconic acid; and further include anhydrides and lower (C1 to C3) alkyl esters of these.

[0146] Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, anhydrides thereof, and lower (carbon number 1 to 3) alkyl esters thereof.

[0147] The polycarboxylic acid may contain a dicarboxylic acid having a sulfonic acid group in addition to the saturated aliphatic dicarboxylic acid or aromatic dicarboxylic acid. Furthermore, the polycarboxylic acid may contain a dicarboxylic acid having a double bond in addition to the saturated aliphatic dicarboxylic acid or aromatic dicarboxylic acid. These may be used alone or in combination of two or more.

[0148] The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having from 4 to 12 carbon atoms and a linear saturated aliphatic diol having from 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having from 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having from 2 to 12 carbon atoms. This is preferable in that the resin has high crystallinity and excellent sharp melting properties, and can therefore exhibit excellent low-temperature fixability.

[0149] The presence or absence of crystallinity of the crystalline polyester resin of the present invention can be confirmed by a crystal analysis X-ray diffractometer (for example, X'Pert Pro MRD Philips). The measurement method is described below. First, the target sample is ground in a mortar to prepare a sample powder, which is then evenly applied to a sample holder.The sample holder is then placed in the diffraction device, measurements are performed, and a diffraction spectrum is obtained. If the peak half-width of the peak with the highest intensity among the diffraction peaks obtained in the range of 20°<2θ<25° is 2.0 or less, it is determined to be crystalline. In contrast to crystalline polyester resins, polyester resins that do not exhibit the above-mentioned state are referred to as amorphous polyester resins in the present invention. The conditions for measuring X-ray diffraction are as follows. [Measurement conditions] Tension kV: 45kV Current: 40mA MPSS Upper Gonio Scan mode: continuos Starting angle: 3° End angle: 35° Angle Step: 0.02° Lucident beam optics Divergence slit: Div slit 1 / 2 Diffraction beam optics Anti scatter slit: As fixed 1 / 2 Receiving slit: Prog rec slit

[0150] The melting point of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. If the melting point is 60° C. or higher, the crystalline polyester resin is likely to melt at low temperatures, preventing a problem of a decrease in the heat-resistant storage stability of the toner. If the melting point is 80° C. or lower, the crystalline polyester resin is not sufficiently melted by heating during fixing, preventing a problem of a decrease in low-temperature fixability.

[0151] The molecular weight of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose. The orthodichlorobenzene soluble portion of the crystalline polyester resin preferably has a weight average molecular weight (Mw) of 3,000 to 30,000, more preferably 5,000 to 15,000, as measured by GPC. The orthodichlorobenzene soluble portion of the crystalline polyester resin preferably has a number average molecular weight (Mn) of 1,000 to 10,000, more preferably 2,000 to 10,000, as measured by GPC. The molecular weight ratio Mw / Mn of the crystalline polyester resin is preferably 1.0 to 10, more preferably 1.0 to 5.0. This is because a toner having a sharp molecular weight distribution and a low molecular weight has excellent low-temperature fixability, and when there are a lot of low-molecular-weight components, the heat-resistant storage stability is reduced.

[0152] The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but from the viewpoint of affinity between paper and resin, in order to achieve the desired low-temperature fixability, the acid value is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, while in order to improve high-temperature offset resistance, the acid value is preferably 45 mgKOH / g or less.

[0153] The hydroxyl value of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose. In order to achieve the desired low-temperature fixability and good charging characteristics, the hydroxyl value is preferably 0 mgKOH / g to 50 mgKOH / g, and more preferably 5 mgKOH / g to 50 mgKOH / g.

[0154] The molecular structure of the crystalline polyester resin can be confirmed by NMR measurement of a solution or a solid, as well as by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. Conveniently, in an infrared absorption spectrum, -1 or 990±10cm -1 One example is a method for detecting a crystalline polyester resin that has absorption based on the δCH (out-of-plane bending vibration) of olefin.

[0155] The content of the crystalline polyester resin is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 3 to 20 parts by weight, more preferably 5 to 15 parts by weight, per 100 parts by weight of the toner. When the content is 3 parts by weight or more, the problem of poor low-temperature fixability due to insufficient sharp melting by the crystalline polyester resin can be prevented. Furthermore, when the content is 20 parts by weight or less, the problem of reduced heat-resistant storage stability and increased image fogging can be prevented.

[0156] <<Coloring agent>> The colorant is not particularly limited and can be appropriately selected depending on the purpose. Examples of the colorant include carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, yellow ochre, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Balkan fast yellow (5G, R), tartrazine lake, quinoline yellow lake, and anthrazan yellow BG. L, Isoindolinone Yellow, Bengala, Red Lead, Cinnabar, Cadmium Red, Cadmium Mercury Red, Antimony Vermilion, Permanent Red 4R, Para Red, Faise Red, Parachlor Orthonitroaniline Red, Lithol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Lithol Rubin GX, Permanent Red F5R, Brilliant Antcarmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkali Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine, Prussian Blue, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chromium Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake,Examples include malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc oxide, and lithopone.

[0157] The content of the colorant is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 to 15 parts by mass, more preferably 3 to 10 parts by mass, relative to 100 parts by mass of the toner.

[0158] The colorant can also be used as a masterbatch combined with a resin. Examples of resins to be used in the preparation of the masterbatch or kneaded together with the masterbatch include, in addition to the other polyester resins, polymers of styrene or its substitution products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, and styrene-α-chloromethyl methacrylate copolymer. styrene copolymers such as styrene-acrylonitrile copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers, styrene-maleic acid copolymers, and styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resins, epoxy polyol resins, polyurethanes, polyamides, polyvinyl butyral, polyacrylic acid resins, rosin, modified rosin, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used alone or in combination of two or more.

[0159] The masterbatch can be obtained by mixing and kneading a masterbatch resin and a colorant under high shear force. In this process, an organic solvent can be used to enhance the interaction between the colorant and the resin. A method known as the flushing method, in which an aqueous paste containing the colorant in water is mixed and kneaded with the resin and organic solvent, the colorant is transferred to the resin, and the water and organic solvent components are removed, is also preferably used because the wet cake of the colorant can be used as is, eliminating the need for drying. A high-shear dispersing device such as a three-roll mill is preferably used for mixing and kneading.

[0160] <<Wax>> The wax (release agent) is not particularly limited and can be appropriately selected from known waxes, for example, natural waxes, synthetic waxes, etc. These may be used alone or in combination of two or more.

[0161] Examples of the natural waxes include plant waxes such as carnauba wax, cotton wax, and rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cerusin; and petroleum waxes such as paraffin, microcrystalline, and petrolatum. Examples of the synthetic wax include synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; fatty acid amide compounds such as esters, ketones, ethers, 12-hydroxystearic acid amide, stearic acid amide, phthalimide anhydride, and chlorinated hydrocarbons; low-molecular-weight crystalline polymer resins such as polyacrylate homopolymers and copolymers (e.g., n-stearyl acrylate-ethyl methacrylate copolymers); and crystalline polymers having long alkyl groups in their side chains. Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferred.

[0162] The melting point of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 60° C. or higher and 80° C. or lower. If the melting point is 60° C. or higher, the release agent tends to melt at low temperatures, preventing the problem of poor heat-resistant storage stability. If the melting point is 80° C. or lower, even when the resin melts and is in the fixing temperature range, the release agent does not melt sufficiently, causing fixing offset and image defects.

[0163] The content of the release agent is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 2 to 10 parts by mass, and more preferably 3 to 8 parts by mass, relative to 100 parts by mass of the toner. When the content is 2 parts by mass or more, problems such as poor high-temperature offset resistance during fixing and poor low-temperature fixability can be prevented, and when it is 10 parts by mass or less, problems such as a decrease in heat-resistant storage stability and a tendency for image fogging to occur can be prevented.

[0164] The toner base particles are not particularly limited as long as they are those used in ordinary toner base particles, and may contain other components appropriately selected depending on the purpose. The content of the other components is not particularly limited as long as it does not impair the properties of the toner, and can be appropriately selected depending on the purpose.

[0165] <Other ingredients> The other components are not particularly limited as long as they are those used in ordinary toners and can be appropriately selected depending on the purpose. Examples of the other components include a charge control agent, an external additive, a flowability improver, a cleaning property improver, and a magnetic material.

[0166] -Charge control agent- The charge control agent is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substance or compounds, tungsten simple substance or compounds, fluorine-based activators, metal salicylate, and metal salts of salicylic acid derivatives.

[0167] Commercially available examples of the charge control agent include the nigrosine dye Bontron 03, the quaternary ammonium salt Bontron P-51, the metal-containing azo dye Bontron S-34, the oxynaphthoic acid metal complex E-82, the salicylic acid metal complex E-84, and the phenol condensate E-89 (all manufactured by Orient Chemical Industry Co., Ltd.), the quaternary ammonium salt molybdenum complexes TP-302 and TP-415 (all manufactured by Hodogaya Chemical Industry Co., Ltd.), LRA-901, and the boron complex LR-147 (all manufactured by Nippon Carlit Co., Ltd.).

[0168] The content of the charge control agent is determined by the type of binder resin, the presence or absence of optional additives, and the toner production method, including the dispersion method, and is not uniquely limited. However, it is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, per 100 parts by weight of the binder resin. If the content exceeds 10 parts by weight, the toner becomes too chargeable, reducing the effect of the main charge control agent and increasing the electrostatic attraction force with the developing roller, which may result in reduced developer fluidity and reduced image density. These charge control agents can be melt-kneaded with a masterbatch and resin and then dissolved and dispersed. Of course, they can also be added when directly dissolved or dispersed in an organic solvent, or they can be fixed on the surface of the toner after toner particle production. The external additive is not particularly limited and can be appropriately selected depending on the purpose. For example,

[0169] -External additives- Examples include silica fine particles, hydrophobic silica, fatty acid metal salts (e.g., zinc stearate, aluminum stearate, etc.), metal oxides (e.g., titania, alumina, tin oxide, antimony oxide, etc.), and fluoropolymers. These may be used alone or in combination of two or more. Among these, hydrophobized inorganic fine particles are preferred. Examples of silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.). Examples of titania microparticles include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-140 (manufactured by Fuji Titanium Kogyo Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation).

[0170] Examples of hydrophobized titanium oxide microparticles include T-805 (manufactured by Nippon Aerosil Co., Ltd.), STT-30A, STT-65S-S (all manufactured by Titanium Kogyo Co., Ltd.), TAF-500T, TAF-1500T (all manufactured by Fuji Titanium Kogyo Co., Ltd.), MT-100S, MT-100T (all manufactured by Teika Corporation), and IT-S (manufactured by Ishihara Sangyo Kaisha, Ltd.).

[0171] Hydrophobized oxide fine particles, hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles can be obtained, for example, by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, etc. Silicone oil-treated oxide fine particles and inorganic fine particles, which are treated with silicone oil and heated if necessary, to form inorganic fine particles, are also suitable.

[0172] Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methylhydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, methacrylic-modified silicone oil, and α-methylstyrene-modified silicone oil.

[0173] The average particle size of the primary particles of the external additive is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 100 nm or less, more preferably 1 nm to 100 nm, even more preferably 3 nm to 70 nm, and particularly preferably 5 nm to 70 nm. When the average particle size of the primary particles is within this range, it is possible to prevent the inorganic fine particles from being buried in the toner, making it difficult for them to effectively exhibit their functions, and the photoreceptor surface from being unevenly damaged. The external additive preferably contains at least one type of inorganic fine particles that have been hydrophobized and have an average primary particle size of 20 nm or less, and at least one type of inorganic fine particles that have an average primary particle size of 30 nm or more. The specific surface area of ​​the external additive by the BET method is 20 m 2 / g~500m 2 / g is preferred.

[0174] The content of the external additive is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, relative to 100 parts by mass of the toner.

[0175] -Flow improver- The flowability improver is not particularly limited as long as it is capable of performing a surface treatment to increase hydrophobicity and prevent deterioration of flowability and charging properties even under high humidity conditions, and can be appropriately selected depending on the purpose. Examples of the flowability improver include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. It is particularly preferable that the silica and titanium oxide are surface-treated with such a flowability improver and used as hydrophobic silica and hydrophobic titanium oxide.

[0176] -Cleaning improver- The cleaning property improver is not particularly limited as long as it is added to the toner in order to remove the developer remaining on the photosensitive member or the primary transfer medium after transfer, and can be appropriately selected depending on the purpose. Examples of the cleaning property improver include fatty acid metal salts such as zinc stearate, calcium stearate, and stearic acid, and polymer fine particles produced by soap-free emulsion polymerization, such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer particles preferably have a relatively narrow particle size distribution, and preferably have a volume average particle size of 0.01 μm to 1 μm.

[0177] -Magnetic materials- The magnetic material is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include iron powder, magnetite, ferrite, etc. Among these, white materials are preferred in terms of color tone.

[0178] The glass transition temperature (Tg1st) of the toner at the first temperature rise in differential scanning calorimetry (DSC) is preferably 40°C to 65°C. The glass transition temperature (Tg1st) of the component of the toner that is insoluble in tetrahydrofuran (THF) at the first temperature rise in DSC is preferably from -45°C to 5°C. The glass transition temperature (Tg2nd) of the THF-soluble component of the toner at the second temperature rise in DSC is preferably 20°C to 65°C. It is preferable that the glass transition temperature (Tg1st) in the first temperature rise and the glass transition temperature (Tg2nd) in the second temperature rise in differential scanning calorimetry (DSC) of the toner satisfy Tg1st-Tg2nd≧10[°C], as this improves low-temperature fixability and heat-resistant storage stability.

[0179] Here, the glass transition temperature of the toner can be measured using, for example, a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation). For example, a DSC curve is measured using the differential scanning calorimeter. From the obtained DSC curves, an analysis program is used to select the DSC curve during the first heating run, and the glass transition temperature Tg1st during the first heating run can be determined using the endothermic shoulder temperature in the analysis program. A DSC curve during the second heating run can be selected, and the glass transition temperature Tg2nd during the second heating run can be determined using the endothermic shoulder temperature.

[0180] (developer) The developer of the present invention contains at least the toner of the present invention, and optionally contains other appropriately selected components such as a carrier, etc. The developer may be a one-component developer or a two-component developer, but when used in a high-speed printer or the like that corresponds to the recent improvement in information processing speed, a two-component developer is preferred because of its improved lifespan.

[0181] <Career> The carrier is not particularly limited and can be appropriately selected depending on the purpose, but it is preferable that the carrier has a core material and a resin layer that covers the core material.

[0182] -Core material- The material for the core is not particularly limited and can be selected appropriately depending on the purpose. Examples include manganese-strontium-based materials with a density of 50 to 90 emu / g and manganese-magnesium-based materials with a density of 50 to 90 emu / g. To ensure image density, it is preferable to use high-magnetization materials such as iron powder with a density of 100 emu / g or more and magnetite with a density of 75 to 120 emu / g. It is also preferable to use low-magnetization materials such as copper-zinc-based materials with a density of 30 to 80 emu / g, as these materials can reduce the impact of the developer in a standing state on the photoreceptor and are advantageous for achieving high image quality. These may be used alone or in combination of two or more.

[0183] The volume average particle diameter of the core material is not particularly limited and can be selected appropriately depending on the purpose, but is preferably 10 to 150 μm, more preferably 40 to 100 μm. If the volume average particle diameter is less than 10 μm, the amount of fine powder in the carrier increases, which can reduce the magnetization per particle and cause carrier scattering. On the other hand, if the volume average particle diameter exceeds 150 μm, the specific surface area decreases, which can cause toner scattering, and in full-color printers with many solid areas, the reproduction of the solid areas can be particularly poor.

[0184] The toner of the present invention can be mixed with the carrier and used in a two-component developer. The content of the carrier in the two-component developer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 90 to 98 parts by mass, more preferably 93 to 97 parts by mass, relative to 100 parts by mass of the two-component developer. The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

[0185] (Toner manufacturing method) The toner production method of the present invention is a method for producing the above-described toner. The toner manufacturing method includes a composite particle forming step and a removing step, and may further include other steps as necessary.

[0186] <Composite particle formation process> The composite particle forming step is a step of adhering resin fine particles to the surfaces of toner base particles to form composite particles. Examples of the method for forming the composite particles include a known dissolution suspension method in which an oil phase containing components of the toner base particles, such as the binder resin, colorant, and wax, is dispersed in an aqueous medium containing resin fine particles to form granules.

[0187] As an example of the dissolution suspension method, a method of forming composite particles while generating a polyester resin by an elongation reaction and / or crosslinking reaction between the prepolymer and the curing agent will be described. In this method, an aqueous medium is prepared, an oil phase containing a toner base particle material is prepared, the toner base particle material is emulsified or dispersed, and the organic solvent is removed.

[0188] -Preparation of aqueous medium (aqueous phase)- The aqueous medium can be prepared, for example, by dispersing resin fine particles in the aqueous medium. The amount of the resin fine particles added to the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 0.5 to 10 parts by mass per 100 parts by mass of the aqueous medium. The aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. Examples include water, a solvent miscible with water, and a mixture thereof. These may be used alone or in combination of two or more. Among these, water is preferred.

[0189] The water-miscible solvent is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, lower ketones, etc. Examples of the alcohol include methanol, isopropanol, ethylene glycol, etc. Examples of the lower ketones include acetone, methyl ethyl ketone, etc.

[0190] -Preparation of oil phase- The oil phase can be prepared by dissolving or dispersing the toner base particle material, which contains a binder resin, a colorant, and a wax, and further contains a curing agent, etc., as required, in an organic solvent.

[0191] The organic solvent is not particularly limited and can be appropriately selected depending on the purpose, but organic solvents having a boiling point of less than 150° C. are preferred in terms of ease of removal.

[0192] Examples of the organic solvent having a boiling point of less than 150°C include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These may be used alone or in combination of two or more. Of these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride, etc. are preferred, and ethyl acetate is more preferred.

[0193] -Emulsification or dispersion- The toner materials can be emulsified or dispersed by dispersing an oil phase containing the toner materials in the aqueous medium. When the toner materials are emulsified or dispersed, the curing agent and the prepolymer can undergo an elongation reaction and / or a crosslinking reaction.

[0194] The reaction conditions (reaction time, reaction temperature) for producing the prepolymer are not particularly limited and can be appropriately selected depending on the combination of the curing agent and the prepolymer. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 to 24 hours. The reaction temperature is preferably 0°C to 150°C, more preferably 40°C to 98°C.

[0195] The method for stably forming a dispersion containing the prepolymer in the aqueous medium is not particularly limited and can be appropriately selected depending on the purpose. For example, there is a method in which an oil phase prepared by dissolving or dispersing toner materials in a solvent is added to an aqueous medium phase, and the resulting mixture is dispersed by shear force.

[0196] The dispersing machine used for the dispersion is not particularly limited and can be appropriately selected depending on the purpose. Examples include low-speed shear dispersing machines, high-speed shear dispersing machines, friction dispersing machines, high-pressure jet dispersing machines, and ultrasonic dispersing machines. Among these, high-speed shear dispersing machines are preferred because they can control the particle size of the dispersed material (oil droplets) to 2 to 20 μm.

[0197] When using the high-speed shear disperser, conditions such as the rotation speed, dispersion time, and dispersion temperature can be appropriately selected depending on the purpose. The rotation speed is preferably 1,000 to 30,000 rpm, and more preferably 5,000 to 20,000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes. The dispersion temperature under pressure is preferably 0°C to 150°C, and more preferably 40°C to 98°C. Generally, the higher the dispersion temperature, the easier the dispersion.

[0198] The amount of the aqueous medium used when emulsifying or dispersing the toner materials is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight, per 100 parts by weight of the toner materials. If the amount of the aqueous medium used is less than 50 parts by weight, the dispersion state of the toner materials may be poor and toner base particles with the specified particle size may not be obtained, and if it exceeds 2,000 parts by weight, production costs may increase.

[0199] When the oil phase containing the toner materials is emulsified or dispersed, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersed oil droplets and the like, forming them into a desired shape, and sharpening the particle size distribution. The dispersant is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include surfactants, poorly water-soluble inorganic compound dispersants, and polymeric protective colloids. These may be used alone or in combination of two or more. Among these, surfactants are preferred.

[0200] The surfactant is not particularly limited and can be appropriately selected depending on the purpose. For example, anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc. can be used. Examples of the anionic surfactants include alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters. Among these, those having a fluoroalkyl group are preferred.

[0201] -Removal of organic solvents- The method for removing the organic solvent from the dispersion liquid such as the emulsified slurry is not particularly limited and can be appropriately selected depending on the purpose. Examples of the method include a method in which the temperature of the entire reaction system is gradually increased to evaporate the organic solvent in the oil droplets, and a method in which the dispersion liquid is sprayed into a dry atmosphere to remove the organic solvent in the oil droplets. Once the organic solvent is removed, composite particles are formed.

[0202] <Removal process> The removal step is a step of removing at least a portion of the resin fine particles from the composite particles, and it is preferable to remove a portion or all of the shell resin (resin (b1)) in the resin fine particles. An example of the step of removing at least a portion of the resin fine particles is a washing step of washing the composite particles. Therefore, the removing step can also be called a washing step.

[0203] In the washing step, examples of a method for removing part or all of the resin (b1) include a method for removing part or all of (b1) by a chemical method. The chemical method may include, for example, washing the composite particles with a basic aqueous solution, which can dissolve part or all of the shell resin (b1). By carrying out the washing step, a toner that satisfies the above-mentioned (formula 3) can be obtained.

[0204] The basic aqueous solution is not particularly limited as long as it is basic and can be appropriately selected depending on the purpose, and examples thereof include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, ammonia, etc. These may be used alone or in combination of two or more. Among these, potassium hydroxide and sodium hydroxide are preferred from the viewpoint of ease of dissolving the shell resin (b1). The pH of the basic aqueous solution is preferably 8 to 14, more preferably 10 to 12.

[0205] The mixing of the composite particles with the alkaline aqueous solution in the washing step can be carried out by, for example, adding the basic aqueous solution dropwise to the composite slurry under stirring. After the basic aqueous solution is added dropwise, an acidic aqueous solution may be added dropwise to neutralize the solution.

[0206] <Other processes> The other steps are not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a drying step and a classification step. The drying step is not particularly limited as long as it can remove the solvent from the composite particles, and can be appropriately selected depending on the purpose. The classification step may be carried out by removing fine particles in a liquid using a cyclone, decanter, centrifugal separation, or the like, or the classification operation may be carried out after drying.

[0207] The obtained composite particles may be mixed with particles of the external additive, the charge control agent, etc. In this case, by applying a mechanical impact force, it is possible to prevent the particles of the external additive, etc. from being detached from the surface of the toner base particles. The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include a method for applying an impact force to the mixture using blades rotating at high speed, and a method for introducing the mixture into a high-speed air stream and accelerating it to cause particles to collide with each other or with an appropriate collision plate.

[0208] The apparatus used in the above method is not particularly limited and can be appropriately selected depending on the purpose. Examples include an Ang Mill (manufactured by Hosokawa Micron Corporation), an apparatus obtained by modifying an I-type Mill (manufactured by Nippon Pneumatic Co., Ltd.) to reduce the grinding air pressure, a Hybridization System (manufactured by Nara Machinery Works), a Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

[0209] (Toner storage unit) The toner storage unit in the present invention refers to a unit having a function of storing toner and storing the toner. Examples of the toner storage unit include a toner storage container, a developing unit, and a process cartridge. The toner container refers to a container that contains the toner of the present invention. The developing device has a means for storing toner and developing the toner. The process cartridge is a cartridge that integrates at least an image carrier and a developing unit, contains toner, and is detachably mountable to an image forming apparatus. The process cartridge may further include at least one selected from a charging unit, an exposure unit, and a cleaning unit.

[0210] Next, one embodiment of the process cartridge is shown in Figure 2. As shown in Figure 2, the process cartridge of this embodiment has a built-in latent image carrier 101, a charging device 102, a developing device 104, and a cleaning unit 107, and may further have other means as necessary. In Figure 2, reference numeral 103 denotes exposure from an exposure device, and reference numeral 105 denotes recording paper. The latent image carrier 101 may be the same as an electrostatic latent image carrier in an image forming apparatus described later, and the charging device 102 may be any charging member. In the image forming process using the process cartridge shown in Figure 2, while the latent image carrier 101 rotates in the direction of the arrow, an electrostatic latent image corresponding to the exposed image is formed on its surface by charging with a charging device 102 and exposure 103 with an exposure means (not shown). This electrostatic latent image is developed with toner by a developing device 104, and the toner development is transferred to recording paper 105 by a transfer roller 108 and printed out. Next, the surface of the latent image carrier after the image transfer is cleaned by a cleaning unit 107, and further discharged by a discharge means (not shown), and the above operations are repeated again.

[0211] (Image forming apparatus and image forming method) The image forming apparatus of the present invention preferably has the above-mentioned toner storage unit, an electrostatic latent image carrier, an electrostatic latent image forming means, and a developing means, and further has other means as required. The image forming method according to the present invention includes at least an electrostatic latent image forming step and a development step, and may further include other steps as required.

[0212] <Electrostatic latent image carrier> The material, structure, and size of the electrostatic latent image bearing member are not particularly limited and can be appropriately selected from known materials, and examples of the material include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine, etc. Among these, amorphous silicon is preferred in terms of long life. The linear speed of the electrostatic latent image bearing member is preferably 300 mm / s or more.

[0213] <Electrostatic latent image forming means and electrostatic latent image forming process> The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected depending on the purpose. For example, it may be a means having at least a charging member that charges the surface of the electrostatic latent image carrier, and an exposure member that exposes the surface of the electrostatic latent image carrier to light in an imagewise manner.

[0214] The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image bearing member, and can be appropriately selected depending on the purpose. For example, the electrostatic latent image forming step can be performed by charging the surface of the electrostatic latent image bearing member and then exposing it to light in an imagewise manner, using the electrostatic latent image forming unit.

[0215] <<Charging materials and charging>> The charging member is not particularly limited and can be appropriately selected depending on the purpose. Examples thereof include a known contact charger equipped with a conductive or semiconductive roller, brush, film, rubber blade, etc., and a non-contact charger utilizing corona discharge such as a corotron or scorotron.

[0216] The charging can be carried out, for example, by applying a voltage to the surface of the electrostatic latent image bearing member using the charging member. The shape of the charging member may be a roller, a magnetic brush, a fur brush, or any other shape, and can be selected according to the specifications and shape of the image forming apparatus.

[0217] The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because it allows an image forming apparatus in which the amount of ozone generated from the charging member is reduced.

[0218] <<Exposure member and exposure>> The exposing member is not particularly limited and can be appropriately selected depending on the purpose as long as it can expose the surface of the electrostatic latent image bearing member charged by the charging member in the form of an image to be formed, and examples thereof include various exposing members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.

[0219] The light source used in the exposure member is not particularly limited and can be appropriately selected depending on the purpose, and examples thereof include general light-emitting materials such as fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light-emitting diodes (LEDs), semiconductor lasers (LDs), and electroluminescence (EL).

[0220] In order to irradiate only light in a desired wavelength range, various filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used.

[0221] The exposure can be carried out, for example, by exposing the surface of the electrostatic latent image bearing member to light in an imagewise manner using the exposure member. In the present invention, a backlight system may be employed in which exposure is performed imagewise from the back side of the electrostatic latent image bearing member.

[0222] <Developing means and developing process> The developing unit is not particularly limited as long as it is a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a toner image, which is a visible image, and is equipped with toner, and can be appropriately selected depending on the purpose. The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier with a toner to form a toner image, which is a visible image, and can be appropriately selected depending on the purpose. For example, the developing step can be performed by the developing unit. The developing means is preferably a developing device having an agitator that frictionally agitates the toner to charge it, a magnetic field generating means fixed inside, and a rotatable developer carrier that carries a developer containing the toner on its surface.

[0223] <Other means and other steps> Examples of the other means include a transfer means, a fixing means, a cleaning means, a discharging means, a recycling means, and a control means. Examples of the other steps include a transfer step, a fixing step, a cleaning step, a discharging step, a recycling step, and a control step.

[0224] <<Transfer means and transfer process>> The transfer means is not particularly limited as long as it is a means for transferring a visible image onto a recording medium, and can be selected appropriately depending on the purpose. However, a preferred embodiment has a primary transfer means for transferring the visible image onto an intermediate transfer body to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The transfer step is not particularly limited as long as it is a step of transferring a visible image onto a recording medium, and can be appropriately selected depending on the purpose. However, a preferred embodiment is one in which an intermediate transfer member is used, a visible image is primarily transferred onto the intermediate transfer member, and then the visible image is secondarily transferred onto the recording medium. The transfer step can be carried out by, for example, charging the visible image on the photosensitive member using a transfer charger, and can be carried out by the transfer unit.

[0225] Here, when the image to be secondarily transferred onto the recording medium is a color image made up of toners of multiple colors, the transfer means can be configured to sequentially overlay toners of each color on the intermediate transfer body to form an image on the intermediate transfer body, and the intermediate transfer means can secondarily transfer the image on the intermediate transfer body onto the recording medium all at once. The intermediate transfer body is not particularly limited and can be appropriately selected from known transfer bodies depending on the purpose, and a suitable example is a transfer belt.

[0226] The transfer means (the primary transfer means and the secondary transfer means) preferably includes at least a transfer device that peels and charges the visible image formed on the photosensitive member onto the recording medium. Examples of the transfer device include a corona transfer device that uses corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium is typically plain paper, but is not particularly limited as long as it can be used to transfer the unfixed image after development, and can be selected appropriately depending on the purpose. PET base for overhead projectors can also be used.

[0227] <<Fixing means and fixing process>> The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image on the recording medium, and can be appropriately selected depending on the purpose. For example, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt. The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected depending on the purpose. For example, the fixing step may be performed for each color toner transferred to the recording medium, or may be performed simultaneously for each color toner in a stacked state.

[0228] The fixing step can be carried out by the fixing means. The heating temperature in the heating and pressing member is preferably 80°C to 200°C. In the present invention, depending on the purpose, a known optical fixing device may be used together with or instead of the fixing means. The surface pressure in the fixing step is not particularly limited and can be appropriately selected depending on the purpose. 2 ~80N / cm 2 It is preferable that:

[0229] <<Cleaning means and cleaning process>> The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose, such as a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, or a web cleaner. The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected depending on the purpose. For example, it can be performed by the cleaning unit.

[0230] <<Static Charge Elimination Means and Static Charge Elimination Process>> The discharging means is not particularly limited as long as it is a means for discharging the photosensitive member by applying a discharging bias to the photosensitive member, and can be appropriately selected depending on the purpose. For example, a discharging lamp can be used. The charge-eliminating step is not particularly limited as long as it is a step of applying a charge-eliminating bias to the photosensitive member to eliminate charges, and can be appropriately selected depending on the purpose. For example, it can be performed by the charge-eliminating unit.

[0231] <<Recycling methods and processes>> The recycling means is not particularly limited as long as it is a means for recycling the toner removed by the cleaning step into the developing device, and can be appropriately selected depending on the purpose. For example, known conveying means can be used. The recycling step is not particularly limited as long as it is a step of recycling the toner removed by the cleaning step into the developing device, and can be appropriately selected depending on the purpose. For example, it can be performed by the recycling means.

[0232] Next, one embodiment of a method for forming an image using the image forming apparatus of the present invention will be described with reference to Fig. 3. Although a printer is shown as an example of the image forming apparatus of this embodiment, the image forming apparatus is not particularly limited as long as it is capable of forming an image using toner, such as a copier, facsimile, or multifunction machine. The image forming apparatus includes a paper feed unit 210, a conveying unit 220, an image forming unit 230, a transfer unit 240, and a fixing unit 250. The paper feed section 210 includes a paper feed cassette 211 in which the paper P to be fed is stacked, and a paper feed roller 212 that feeds the paper P stacked in the paper feed cassette 211 one sheet at a time.

[0233] The conveying section 220 includes a roller 221 that conveys the paper P fed by the paper feed roller 212 toward the transfer section 240, a pair of timing rollers 222 that hold the leading end of the paper P conveyed by the roller 221 and wait, sending the paper to the transfer section 240 at a predetermined timing, and a paper discharge roller 223 that discharges the paper P with the fixed color toner image onto a paper discharge tray 224.

[0234] The image forming section 230 includes, at predetermined intervals from left to right in the figure, an image forming unit Y that forms an image using a developer containing yellow toner, an image forming unit C that uses a developer containing cyan toner, an image forming unit M that uses a developer containing magenta toner, an image forming unit K that uses a developer containing black toner, and an exposure device 233. It should be noted that when referring to any of the image forming units (Y, C, M, K), it is referred to as an image forming unit.

[0235] The developer contains toner and carrier. The four image forming units (Y, C, M, K) have substantially the same mechanical configuration, except for the developer used in each.

[0236] The transfer unit 240 includes a drive roller 241 and a driven roller 242, an intermediate transfer belt 243 that can rotate counterclockwise in the figure as the drive roller 241 is driven, primary transfer rollers (244Y, 244C, 244M, 244K) that are arranged opposite the photosensitive drum 231 across the intermediate transfer belt 243, and secondary opposing rollers 245 and 246 that are arranged opposite each other across the intermediate transfer belt 243 at the position where the toner image is transferred to the paper.

[0237] The fixing device 250 has a heater installed inside and is equipped with a pressure roller 252 that forms a nip by rotatably pressing a fixing belt 251 that heats the paper P against the fixing belt 251. This applies heat and pressure to the color toner image on the paper P, fixing the color toner image. The paper P with the fixed color toner image is discharged to a paper discharge tray 224 by a paper discharge roller 223, completing the series of image formation processes. [Example]

[0238] Examples of the present invention will be described below, but the present invention is not limited to these examples. Unless otherwise specified, "parts" means parts by mass and "%" means % by mass.

[0239] <Production Example A1: Production of a particle dispersion (W0-1) of shell resin (resin b1-1)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 3,710 parts by weight of water and 200 parts by weight of polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ester ammonium (Aqualon KH-1025, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and stirred at 200 rpm to homogenize. The homogenized mixture was heated to raise the temperature of the system to 75°C, after which 90 parts by weight of a 10% by weight aqueous ammonium persulfate solution was added, followed by the dropwise addition of a mixture of 450 parts by weight of styrene, 250 parts by weight of butyl acrylate, and 300 parts by weight of methacrylic acid over a period of 4 hours. After the dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a microparticle dispersion (W0-1) containing resin (b1-1), a polymer copolymerized with the monomer and polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ester ammonium. The volume average particle size of the microparticles in the microparticle dispersion (W0-1) was measured by dynamic light scattering (light scattering electrophoresis apparatus: ELS-8000 manufactured by Otsuka Electronics Co., Ltd.) and was found to be 15 nm. A part of the particle dispersion (W0-1) was dried to isolate a resin (b1-1). The resin had a Tg of 53°C and an acid value of 195 mgKOH / g.

[0240] <Production Example A2: Production of a particle dispersion (W0-2) of shell resin (resin b1-2)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 3,760 parts by weight of water and 150 parts by weight of polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ammonium (Aqualon KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and stirred at 200 rpm to homogenize. The homogenized mixture was heated to 75°C, after which 90 parts by weight of a 10% by weight aqueous ammonium persulfate solution was added, followed by the dropwise addition of a mixture of 430 parts by weight of styrene, 270 parts by weight of butyl acrylate, and 300 parts by weight of methacrylic acid over a period of 4 hours. After the dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a microparticle dispersion (W0-2) containing resin (b1-2), a polymer copolymerized with the monomer and polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ammonium. The volume average particle size of the microparticles in the microparticle dispersion (W0-2) was measured in the same manner as in W0-1 and was found to be 30 nm. A part of the particle dispersion (W0-2) was dried to isolate a resin (b1-2). The resin had a Tg of 53°C and an acid value of 195 mgKOH / g.

[0241] <Production Example A3: Production of particle dispersion (W0-3) of shell resin (resin b1-3)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 3,810 parts by weight of water and 100 parts by weight of polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ester ammonium (Aqualon KH-1025, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and stirred at 200 rpm to homogenize. The homogenized mixture was heated to 75°C, after which 90 parts by weight of a 10% by weight aqueous ammonium persulfate solution was added, followed by the dropwise addition of a mixture of 400 parts by weight of styrene, 300 parts by weight of butyl acrylate, and 300 parts by weight of methacrylic acid over a period of 4 hours. After the dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a microparticle dispersion (W0-3) containing resin (b1-3), a polymer copolymerized with the monomer and polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ester ammonium. The volume average particle size of the microparticles in the microparticle dispersion (W0-3) was measured in the same manner as in W0-1 and was found to be 45 nm. A part of the particle dispersion (W0-3) was dried to isolate a resin (b1-3). The resin had a Tg of 53°C and an acid value of 195 mgKOH / g.

[0242] <Production Example A4: Production of particle dispersion (W0-4) of shell resin (resin b1-4)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 3,860 parts by weight of water and 50 parts by weight of polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ester ammonium (Aqualon KH-1025, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and stirred at 200 rpm to homogenize. The homogenized mixture was heated to 75°C, after which 90 parts by weight of a 10% by weight aqueous ammonium persulfate solution was added, followed by the dropwise addition of a mixture of 400 parts by weight of styrene, 300 parts by weight of butyl acrylate, and 300 parts by weight of methacrylic acid over a period of 4 hours. After the dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a microparticle dispersion (W0-4) containing resin (b1-4), a polymer copolymerized with the monomer and polyoxyethylene-1-(allyloxymethyl) alkyl ether sulfate ester ammonium. The volume average particle size of the microparticles in the microparticle dispersion (W0-4) was measured in the same manner as in W0-1 and was found to be 60 nm. A part of the particle dispersion (W0-4) was dried to isolate a resin (b1-4). The resin had a Tg of 53°C and an acid value of 195 mgKOH / g.

[0243] <Production Example B1: Production of particle dispersion (W-1) of resin particles (B-1)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 938 parts by weight of the particle dispersion (W0-1) and 46 parts by weight of water, and 0.053 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 8.1 parts by weight of styrene, 4.4 parts by weight of butyl acrylate, and 3.6 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours, using the particles (resin (b1-1)) in (W0-1) as seeds to obtain a particle dispersion (W-1) of resin particles (B-1) containing resin (b2-1), a copolymer of the monomers (styrene, butyl acrylate), and resin (b1-1) as constituent components within the same particle. The volume average particle size of the resin fine particles (B-1) was measured in the same manner as for W0-1 and was found to be 15.3 nm. The fine particle dispersion (W-1) was neutralized with 10% aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-1). The Tg of this resin was 53°C.

[0244] It was confirmed by observation using a transmission electron microscope that the microparticle dispersion (W-1) contained resin microparticles (B-1) containing resin (b1-1) and resin (b2-1) as constituent components within the same particle. Specifically, 2 parts by mass of gelatin (Cook Gelatin, manufactured by Morinaga Milk Industry Co., Ltd.) was dissolved in 15 parts by mass of water heated to 95°C to 100°C, and the gelatin solution was air-cooled to 40°C. The microparticle dispersion (W-1) was mixed in a 1:1 ratio with this gelatin solution, stirred well, and then cooled to 10°C for 1 hour to produce a hardened gel. This gel was sliced ​​into 80 nm thick sections using an ultramicrotome (Ultramicrotome UC7, FC7, Leica Microsystems) while maintaining the temperature at -80°C. The sections were then stained with a 2% aqueous solution of ruthenium tetroxide for 5 minutes and then observed under a transmission electron microscope (Hitachi Technologies, H-7100).

[0245] <Production Example B2: Production of particle dispersion (W-2) of resin particles (B-2)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 333 parts by weight of the particle dispersion (W0-1) and 497 parts by weight of water, and 0.533 parts by weight of tertiary butyl hydroperoxide (NOF Corporation, Perbutyl H) was added. The system was then heated to 70°C, and 86.7 parts by weight of styrene, 46.7 parts by weight of butyl acrylate, and 36.0 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-2) of resin particles (B-2) containing resin (b1-1) and resin (b2-2), a polymer formed by copolymerization of the monomers (styrene, butyl acrylate) using the particles (resin (b1-1)) in (W0-1) as seeds. The volume average particle size of the resin fine particles (B-2) was measured in the same manner as for W0-1 and was found to be 21.6 nm. The fine particle dispersion (W-2) was neutralized with 10% aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-2). The Tg of this resin was 53°C. It was confirmed by the same method as for the above-mentioned microparticle dispersion (W-1) that the microparticle dispersion (W-2) contains resin microparticles (B-2) that contain resin (b1-1) and resin (b2-2) as constituent components within the same particle.

[0246] <Production Example B3: Production of particle dispersion (W-3) of resin particles (B-3)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 875 parts by weight of the particle dispersion (W0-1) and 93 parts by weight of water, and 0.100 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 16.3 parts by weight of styrene, 8.8 parts by weight of butyl acrylate, and 6.8 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-3) of resin particles (B-3) containing resin (b2-3), a polymer formed by copolymerization of the monomers (styrene, butyl acrylate) using the particles (resin (b1-1)) in (W0-1) as seeds, and resin (b1-1) as constituent components within the same particle. The volume average particle size of the resin fine particles (B-3) was measured in the same manner as for W0-1 and was found to be 15.7 nm. The fine particle dispersion (W-3) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and then centrifuged to separate the precipitate, which was then dried to isolate resin (b2-3). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-3) contained resin microparticles (B-3) that contained resin (b1-1) and resin (b2-3) as constituent components within the same particle.

[0247] <Production Example B4: Production of particle dispersion (W-4) of resin particles (B-4)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 500 parts by weight of the particle dispersion (W0-1) and 373 parts by weight of water, and 0.400 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 65.0 parts by weight of styrene, 35.0 parts by weight of butyl acrylate, and 27.0 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-4) of resin particle (B-4) containing resin (b2-4), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-1)) in (W0-1) as seeds, and resin (b1-1) as constituent components within the same particle. The volume average particle size of the resin fine particles (B-4) was measured in the same manner as for W0-1 and was found to be 18.9 nm. The fine particle dispersion (W-4) was neutralized with 10% aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-4). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-4) contained resin microparticles (B-4) that contained resin (b1-1) and resin (b2-4) as constituent components within the same particle.

[0248] <Production Example B5: Production of particle dispersion (W-5) of resin particles (B-5)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 750 parts by weight of the particle dispersion (W0-1) and 186 parts by weight of water, and 0.200 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 32.5 parts by weight of styrene, 17.5 parts by weight of butyl acrylate, and 13.5 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-5) of resin particle (B-5) containing resin (b2-5), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-1)) in (W0-1) as seeds, and resin (b1-1) as constituent components within the same particle. The volume average particle size of the resin fine particles (B-5) was measured in the same manner as for W0-1 and was found to be 16.5 nm. The fine particle dispersion (W-5) was neutralized with a 10% by mass aqueous ammonia solution to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-5). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-5) contains resin microparticles (B-5) that contain resin (b1-1) and resin (b2-5) as constituent components within the same particle.

[0249] <Production Example B6: Production of particle dispersion (W-6) of resin particles (B-6)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 667 parts by weight of the particle dispersion (W0-1) and 248 parts by weight of water, and 0.267 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, and 43.3 parts by weight of styrene, 23.3 parts by weight of butyl acrylate, and 18.0 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-6) of resin particle (B-6) containing resin (b2-6), a polymer formed by copolymerization of the monomers (styrene, butyl acrylate) using the particles (resin (b1-1)) in (W0-1) as seeds, and resin (b1-1) as constituent components within the same particle. The volume average particle size of the resin fine particles (B-6) was measured in the same manner as for W0-1 and was found to be 17.2 nm. The fine particle dispersion (W-6) was neutralized with a 10% by weight aqueous ammonia solution to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-6). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-6) contains resin microparticles (B-6) that contain resin (b1-1) and resin (b2-6) as constituent components within the same particle.

[0250] <Production Example B7: Production of particle dispersion (W-7) of resin particles (B-7)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 600 parts by weight of the particle dispersion (W0-1) and 298 parts by weight of water, and 0.320 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 52.0 parts by weight of styrene, 28.0 parts by weight of butyl acrylate, and 21.6 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-7) of resin particle (B-7) containing resin (b2-7), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-1)) in (W0-1) as seeds, and resin (b1-1) as constituents within the same particle. The volume average particle size of the resin fine particles (B-7) was measured in the same manner as for W0-1 and was found to be 17.8 nm. The fine particle dispersion (W-7) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-7). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-7) contains resin microparticles (B-7) that contain resin (b1-1) and resin (b2-7) as constituent components within the same particle.

[0251] <Production Example B8: Production of particle dispersion (W-8) of resin particles (B-8)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 938 parts by weight of the particle dispersion (W0-2) and 46 parts by weight of water, and 0.053 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 8.1 parts by weight of styrene, 4.4 parts by weight of butyl acrylate, and 3.6 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-8) of resin particle (B-8) containing resin (b2-8), a polymer formed by copolymerization of the monomers (styrene, butyl acrylate) using the particles (resin (b1-2)) in (W0-2) as seeds, and resin (b1-2) as constituent components within the same particle. The volume average particle size of the resin fine particles (B-8) was measured in the same manner as for W0-1 and was found to be 30.7 nm. The fine particle dispersion (W-8) was neutralized with a 10% by weight aqueous ammonia solution to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-8). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-8) contains resin microparticles (B-8) that contain resin (b1-2) and resin (b2-8) as constituent components within the same particle.

[0252] <Production Example B9: Production of particle dispersion (W-9) of resin particles (B-9)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 875 parts by weight of the particle dispersion (W0-2) and 93 parts by weight of water, and 0.100 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 16.3 parts by weight of styrene, 8.8 parts by weight of butyl acrylate, and 6.8 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-9) of resin particle (B-9) containing resin (b2-9), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-2)) in (W0-2) as seeds, and resin (b1-2) as constituents within the same particle. The volume average particle size of the resin fine particles (B-9) was measured in the same manner as for W0-1 and was found to be 31.4 nm. The fine particle dispersion (W-9) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-9). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-9) contains resin microparticles (B-9) that contain resin (b1-2) and resin (b2-9) as constituent components within the same particle.

[0253] <Production Example B10: Production of particle dispersion (W-10) of resin particles (B-10)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 750 parts by weight of the particle dispersion (W0-2) and 186 parts by weight of water, and 0.200 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 32.5 parts by weight of styrene, 17.5 parts by weight of butyl acrylate, and 13.5 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-10) of resin particles (B-10) containing resin (b2-10), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-2)) in (W0-2) as seeds, and resin (b1-2) as constituents within the same particle. The volume average particle size of the resin fine particles (B-10) was measured in the same manner as for W0-1 and was found to be 33.0 nm. The fine particle dispersion (W-10) was neutralized with 10% by weight aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-10). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-10) contains resin microparticles (B-10) that contain resin (b1-2) and resin (b2-10) as constituent components within the same particle.

[0254] <Production Example B11: Production of Particle Dispersion (W-11) of Resin Particles (B-11)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 667 parts by weight of the particle dispersion (W0-2) and 248 parts by weight of water, and 0.267 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, and 43.3 parts by weight of styrene, 23.3 parts by weight of butyl acrylate, and 18.0 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-11) of resin particles (B-11) containing resin (b2-11), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-2)) in (W0-2) as seeds, and resin (b1-2) as constituents within the same particle. The volume average particle size of the resin fine particles (B-11) was measured in the same manner as for W0-1 and was found to be 34.3 nm. The fine particle dispersion (W-11) was neutralized with 10% by weight aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-11). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-11) contains resin microparticles (B-11) that contain resin (b1-2) and resin (b2-11) as constituent components within the same particle.

[0255] <Production Example B12: Production of particle dispersion (W-12) of resin particles (B-12)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 600 parts by weight of the particle dispersion (W0-2) and 298 parts by weight of water, and 0.320 parts by weight of tertiary butyl hydroperoxide (NOF Corporation, Perbutyl H) was added. The system was then heated to 70°C, and 52.0 parts by weight of styrene, 28.0 parts by weight of butyl acrylate, and 21.6 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-12) of resin particles (B-12) containing resin (b2-12), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-2)) in (W0-2) as seeds, and resin (b1-2) as constituents within the same particle. The volume average particle size of the resin fine particles (B-12) was measured in the same manner as for W0-1 and was found to be 35.6 nm. The fine particle dispersion (W-12) was neutralized with a 10% by weight aqueous ammonia solution to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-12). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-12) contains resin microparticles (B-12) that contain resin (b1-2) and resin (b2-12) as constituent components within the same particle.

[0256] <Production Example B13: Production of particle dispersion (W-13) of resin particles (B-13)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 938 parts by weight of the particle dispersion (W0-3) and 46 parts by weight of water, and 0.053 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 8.1 parts by weight of styrene, 4.4 parts by weight of butyl acrylate, and 3.6 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-13) of resin particles (B-13) containing resin (b2-13), a polymer formed by copolymerization of the monomers (styrene, butyl acrylate) using the particles (resin (b1-3)) in (W0-3) as seeds, and resin (b1-3) as constituents within the same particle. The volume average particle size of the resin fine particles (B-13) was measured in the same manner as for W0-1 and was found to be 46.0 nm. The fine particle dispersion (W-13) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-13). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-13) contains resin microparticles (B-13) that contain resin (b1-3) and resin (b2-13) as constituent components within the same particle.

[0257] <Production Example B14: Production of particle dispersion (W-14) of resin particles (B-14)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 875 parts by weight of the particle dispersion (W0-3) and 93 parts by weight of water, and 0.100 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 16.3 parts by weight of styrene, 8.8 parts by weight of butyl acrylate, and 6.8 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-14) of resin particles (B-14) containing resin (b2-14), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-3)) in (W0-3) as seeds, and resin (b1-3) as constituents within the same particle. The volume average particle size of the resin fine particles (B-14) was measured in the same manner as for W0-1 and was found to be 47.0 nm. The fine particle dispersion (W-14) was neutralized with a 10% by weight aqueous ammonia solution to a pH of 9.0, and then centrifuged to separate the precipitate, which was then dried to obtain a resin (b2-14). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-14) contains resin microparticles (B-14) that contain resin (b1-3) and resin (b2-14) as constituent components within the same particle.

[0258] <Production Example B15: Production of particle dispersion (W-15) of resin particles (B-15)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 750 parts by weight of the particle dispersion (W0-3) and 186 parts by weight of water, and 0.200 parts by weight of tertiary butyl hydroperoxide (NOF Corporation, Perbutyl H) was added. The system was then heated to 70°C, after which 32.5 parts by weight of styrene, 17.5 parts by weight of butyl acrylate, and 13.5 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-15) of resin particle (B-15) containing resin (b2-15), a polymer formed by copolymerization of the monomers (styrene, butyl acrylate) using the particles (resin (b1-3)) in (W0-3) as seeds, and resin (b1-3) as constituents within the same particle. The volume average particle size of the resin fine particles (B-15) was measured in the same manner as for W0-1 and was found to be 49.5 nm. The fine particle dispersion (W-15) was neutralized with 10% by weight aqueous ammonia to a pH of 9.0, and then centrifuged to separate the precipitate, which was then dried to isolate resin (b2-15). The Tg of this resin was 53°C. It was confirmed using the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-15) contained resin microparticles (B-15) that contained resin (b1-3) and resin (b2-15) as constituent components within the same particle.

[0259] <Production Example B16: Production of particle dispersion (W-16) of resin particles (B-16)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 667 parts by weight of the particle dispersion (W0-3) and 248 parts by weight of water, and 0.267 parts by weight of tertiary butyl hydroperoxide (NOF Corporation, Perbutyl H) was added. The system was then heated to 70°C, after which 43.3 parts by weight of styrene, 23.3 parts by weight of butyl acrylate, and 18.0 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-16) of resin particle (B-16) containing resin (b2-16), a polymer formed by copolymerization of the monomers (styrene, butyl acrylate) using the particles (resin (b1-3)) in (W0-3) as seeds, and resin (b1-3) as constituents within the same particle. The volume average particle size of the resin fine particles (B-16) was measured in the same manner as for W0-1 and was found to be 51.5 nm. The fine particle dispersion (W-16) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-16). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-16) contained resin microparticles (B-16) containing resin (b1-3) and resin (b2-16) as constituent components within the same particle.

[0260] <Production Example B17: Production of particle dispersion (W-17) of resin particles (B-17)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 600 parts by weight of the particle dispersion (W0-3) and 298 parts by weight of water, and 0.320 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 52.0 parts by weight of styrene, 28.0 parts by weight of butyl acrylate, and 21.6 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-17) of resin particle (B-17) containing resin (b2-17), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-3)) in (W0-3) as seeds, and resin (b1-3) as constituents within the same particle. The volume average particle size of the resin fine particles (B-17) was measured in the same manner as for W0-1 and was found to be 53.4 nm. The fine particle dispersion (W-17) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and then centrifuged to separate the precipitate, which was then dried to obtain resin (b2-17). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-17) contained resin microparticles (B-17) containing resin (b1-3) and resin (b2-17) as constituent components within the same particle.

[0261] <Production Example B18: Production of particle dispersion (W-18) of resin particles (B-18)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 500 parts by weight of the particle dispersion (W0-4) and 373 parts by weight of water, and 0.400 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 65.0 parts by weight of styrene, 35.0 parts by weight of butyl acrylate, and 27.0 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-18) of resin particle (B-18) containing resin (b2-18), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-4)) in (W0-4) as seeds, and resin (b1-4) as constituents within the same particle. The volume average particle size of the resin fine particles (B-18) was measured in the same manner as for W0-1 and was found to be 60.0 nm. The fine particle dispersion (W-18) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-18). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-18) contained resin microparticles (B-18) containing resin (b1-4) and resin (b2-18) as constituent components within the same particle.

[0262] <Production Example B19: Production of Particle Dispersion (W-19) of Resin Particles (B-19)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 667 parts by weight of the particle dispersion (W0-4) and 248 parts by weight of water, and 0.267 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 43.3 parts by weight of styrene, 23.3 parts by weight of butyl acrylate, and 18.0 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W-19) of resin particle (B-19) containing resin (b2-19), a polymer in which the monomers (styrene, butyl acrylate) were copolymerized using the particles (resin (b1-4)) in (W0-4) as seeds, and resin (b1-4) as constituents within the same particle. The volume average particle size of the resin fine particles (B-19) was measured in the same manner as for W0-1 and was found to be 47.6 nm. The fine particle dispersion (W-19) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2-19). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W-19) contained resin microparticles (B-19) containing resin (b1-4) and resin (b2-19) as constituent components within the same particle.

[0263] <Production Example C1: Production of particle dispersion (W'-1) of resin particles (B'-1)> The microparticle dispersion (W0-3) described in Production Example A3 was used alone to prepare a microparticle dispersion (W'-1) (a microparticle dispersion without a core-shell structure, volume average particle size: 45.0 nm, Tg: 53°C, acid value: 195 mgKOH / g).

[0264] <Production Example C2: Production of Aqueous Dispersion (W'-2) of Resin Particles (B'-2)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 963 parts by mass of the particle dispersion (W0-3) and 28 parts by mass of water, and 0.030 parts by mass of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 4.8 parts by mass of styrene, 2.6 parts by mass of butyl acrylate, and 2.0 parts by mass of a 1% by mass aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W'-2) of resin particle (B'-2) containing resin (b2'-2), a polymer formed by copolymerization of the monomers using the particles in (W0-3) as seeds, and resin (b1-3) as constituent components within the same particle. The volume average particle size of the resin fine particles (B'-2) was measured in the same manner as for W0-1 and was found to be 45.6 nm. The fine particle dispersion (W'-2) was neutralized with 10% by mass aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2'-2). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W'-2) contained resin microparticles (B'-2) containing resin (b1-3) and resin (b2'-2) as constituent components within the same particle.

[0265] <Production Example C3: Production of Aqueous Dispersion (W'-3) of Resin Particles (B'-3)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 250 parts by weight of the particle dispersion (W0-3) and 559 parts by weight of water, and 0.600 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 97.5 parts by weight of styrene, 52.5 parts by weight of butyl acrylate, and 40.5 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W'-3) of resin particle (B'-3), which contains resin (b2'-3), a polymer formed by copolymerization of the monomers using the particles in (W0-3) as seeds, and resin (b1-3) as constituent components within the same particle. The volume average particle size of the resin fine particles (B'-3) was measured in the same manner as for W0-1 and was found to be 71.4 nm. The fine particle dispersion (W'-3) was neutralized with 10% by weight aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2'-3). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W'-3) contained resin microparticles (B'-3) containing resin (b1-3) and resin (b2'-3) as constituent components within the same particle.

[0266] <Production Example C4: Production of Aqueous Dispersion (W'-4) of Resin Particles (B'-4)> A reaction vessel equipped with a stirrer, heating / cooling device, and thermometer was charged with 200 parts by weight of the particle dispersion (W0-2) and 596 parts by weight of water, and 0.640 parts by weight of tertiary butyl hydroperoxide (Perbutyl H, NOF Corporation) was added. The system was then heated to 70°C, after which 104.0 parts by weight of styrene, 56.0 parts by weight of butyl acrylate, and 43.2 parts by weight of a 1% by weight aqueous ascorbic acid solution were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 70°C for 4 hours to obtain a particle dispersion (W'-4) of resin particle (B'-4) containing resin (b2'-4), a polymer formed by copolymerization of the monomers using the particles in (W0-2) as seeds, and resin (b1-2) as constituent components within the same particle. The volume average particle size of the resin fine particles (B'-4) was measured in the same manner as for W0-1 and was found to be 47.6 nm. The fine particle dispersion (W'-4) was neutralized with 10% by weight aqueous ammonia to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2'-4). The Tg of this resin was 53°C. It was confirmed by the same method as for the microparticle dispersion (W-1) that the microparticle dispersion (W'-4) contained resin microparticles (B'-4) containing resin (b1-2) and resin (b2'-4) as constituent components within the same particle.

[0267] <Production Example C5: Production of particle dispersion (W'-5) of resin particles (B'-5)> A reaction vessel equipped with a stirrer, a heating / cooling device, and a thermometer was charged with 745 parts by mass of water and 0.800 parts by mass of tertiary butyl hydroperoxide (Perbutyl H, manufactured by NOF Corporation), and the mixture was heated to 70°C. Then, 130.0 parts by mass of styrene, 70.0 parts by mass of butyl acrylate, and 54.0 parts by mass of a 1% by mass aqueous solution of ascorbic acid were added dropwise over 2 hours. After the dropwise addition, the mixture was aged at 75°C for 4 hours to obtain a fine particle dispersion (W'-5) containing a resin (B'-5), which is a polymer formed by copolymerization of the monomers. The volume average particle size of the resin fine particles (B'-5) was measured in the same manner as for W0-1 and was found to be 45.0 nm. The fine particle dispersion (W'-5) was neutralized with 10% ammonia water to a pH of 9.0, and the precipitate was centrifuged and dried to isolate resin (b2'-5). The Tg of this resin was 53°C.

[0268] The physical properties of the microparticle dispersions (W0-1) to (W0-3) are shown in Table 1. The physical properties of the resin microparticles (B-1) to (B-17) and (B'-1) to (B'-5) are shown in Table 2.

[0269] [Table 1]

[0270] [Table 2]

[0271] [Table 3]

[0272] [Table 4]

[0273] [Table 5]

[0274] [Table 6]

[0275] Example 1 <Synthesis of amorphous polyester resin A-1> In a four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, bisphenol A ethylene oxide side 2 mole adduct, bisphenol A propylene oxide 3 mole adduct, terephthalic acid, adipic acid, and trimethylolpropane were added to form a mixture in which the molar ratio of the bisphenol A ethylene oxide side 2 mole adduct to the bisphenol A propylene oxide 3 mole adduct (bisphenol A ethylene oxide side 2 mole adduct / bisphenol A propylene oxide 3 mole adduct) was 85 / 15, and the molar ratio of the terephthalic acid to the adipic acid was 85 / 15. The monomers were charged so that the molar ratio (terephthalic acid / adipic acid) was 75 / 25, the amount of trimethylolpropane in all monomers was 1 mol%, and the molar ratio of hydroxyl groups to carboxyl groups (OH / COOH) was 1.2. This was reacted with titanium tetraisopropoxide (500 ppm relative to the resin components) at normal pressure and 230°C for 8 hours, and then reacted for a further 4 hours at a reduced pressure of 10 mmHg to 15 mmHg. After that, trimellitic anhydride was added to the reaction vessel so that the amount was 1 mol% relative to the total resin components, and this was reacted for 3 hours at normal pressure and 180°C to obtain [Amorphous Polyester Resin A-1]. The amorphous polyester resin A-1 had a Tg2nd of 55°C.

[0276] <Synthesis of Prepolymer C-1 (Modified Polyester Resin C-1)> Into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen inlet tube, 3-methyl-1,5-pentanediol, isophthalic acid, adipic acid, and trimellitic anhydride were charged together with titanium tetraisopropoxide (1,000 ppm relative to the resin component) so that the molar ratio of hydroxyl groups to carboxyl groups, OH / COOH, was 1.5, the diol component was 100 mol% 3-methyl-1,5-pentanediol, the dicarboxylic acid component was 40 mol% isophthalic acid and 60 mol% adipic acid, and the amount of trimellitic anhydride in all monomers was 1 mol%. Thereafter, the temperature was raised to 200°C over about 4 hours, and then to 230°C over 2 hours, and the reaction was continued until no water was discharged. Thereafter, the mixture was further reacted for 5 hours under a reduced pressure of 10 mmHg to 15 mmHg to obtain [Intermediate Polyester C-1]. Next, into a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, [intermediate polyester C-1] and isophorone diisocyanate (IPDI) were added at a molar ratio (isocyanate groups of IPDI / hydroxyl groups of intermediate polyester) of 2.0, and after diluting with ethyl acetate to make a 50% ethyl acetate solution, the mixture was reacted at 100°C for 5 hours to obtain [prepolymer C-1]. The Tg2nd of the prepolymer C-1 was -40°C.

[0277] <Synthesis of crystalline polyester resin D-1> Sebacic acid and 1,6-hexanediol were charged into a 5 L four-neck flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple so that the molar ratio of hydroxyl groups to carboxyl groups, OH / COOH, was 0.9, and the mixture was reacted with titanium tetraisopropoxide (500 ppm relative to the resin component) at 180°C for 10 hours, then heated to 200°C and reacted for 3 hours, and then further reacted at a pressure of 8.3 kPa for 2 hours to obtain [Crystalline Polyester Resin D-1]. The melting point (mp) of the crystalline polyester resin was 70°C.

[0278] The Tg2nd of the amorphous polyester resin A-1 and the prepolymer C-1, and the melting point (mp) of the crystalline polyester resin D-1 were measured as follows.

[0279] Approximately 5.0 mg of each resin was placed in an aluminum sample container, which was then placed on a holder unit and placed in an electric furnace. Next, under a nitrogen atmosphere, the sample was heated from -80°C to 150°C at a heating rate of 1.0°C / min (first heating). The sample was then cooled from 150°C to -80°C at a heating rate of 1.0°C / min, and further heated to 150°C at a heating rate of 1.0°C / min (second heating). DSC curves were measured during both the first and second heating periods using a differential scanning calorimeter (TA Instruments, model Q-200). From the obtained DSC curves, the DSC curve at the second temperature rise was selected using the analysis program in the Q-200 system, and the glass transition temperature Tg2nd of the target sample at the second temperature rise was determined. Furthermore, from the obtained DSC curves, the DSC curve during the second temperature increase was selected, and the endothermic peak top temperature during the second temperature increase of the target sample was determined as the melting point.

[0280] <Preparation of Crystalline Polyester Resin Dispersion> 50 parts by mass of [Crystalline polyester resin D-1] and 450 parts by mass of ethyl acetate were placed in a container equipped with a stirring rod and a thermometer, heated to 80°C while stirring, held at 80°C for 5 hours, and then cooled to 30°C over 1 hour. Dispersion was carried out using a bead mill (Ultraviscomill, manufactured by Imex) under conditions of a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, an 80% volume filling of 0.5 mm diameter zirconia beads, and 3 passes to obtain [Crystalline polyester resin dispersion].

[0281] <Preparation of Masterbatch (MB)> 1,200 parts by mass of water, 500 parts by mass of carbon black (Printex 35, manufactured by Degussa) [DBP oil absorption = 42 mL / 100 mg, pH = 9.5], and 500 parts by mass of [amorphous polyester resin C-1] were added, mixed with a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.), kneaded at 150 °C for 30 minutes using two rolls, rolled and cooled, and then pulverized with a pelletizer to obtain [masterbatch].

[0282] <Preparation of WAX dispersion liquid> 50 parts by mass of paraffin wax (manufactured by Nippon Seiro Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 °C, SP value 8.8) as a mold release agent 1 and 450 parts by mass of ethyl acetate were charged into a container equipped with a stirring rod and a thermometer, heated to 80 °C under stirring, held at 80 °C for 5 hours, cooled to 30 °C in 1 hour, and dispersed using a bead mill (Ultraviscomill, manufactured by Imex Co., Ltd.) under the conditions of a liquid feeding rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, 80% by volume filling of zirconia beads with a diameter of 0.5 mm, and 3 passes to obtain [WAX dispersion liquid 1].

[0283] <Synthesis of ketimine compound> 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged into a reaction vessel equipped with a stirring rod and a thermometer, and reacted at 50 °C for 5 hours to obtain [ketimine compound 1]. The amine value of [ketimine compound 1] was 418.

[0284] <Preparation of oil phase> 500 parts by mass of [WAX dispersion liquid 1], 750 parts by mass of [amorphous polyester resin A-1], 150 parts by mass of [prepolymer C-1], 500 parts by mass of [crystalline polyester resin dispersion liquid], 100 parts by mass of [masterbatch 1], and 2 parts by mass of [ketimine compound 1] as a curing agent were placed in a container and mixed with a TK homomixer (manufactured by Primix Corporation) at 7,000 rpm for 60 minutes to obtain [oil phase 1].

[0285] <Preparation of aqueous phase> 990 parts by mass of water, 83 parts by mass of [Resin Fine Particle Dispersion (W-1)], 37 parts by mass of a 48.5% aqueous solution of sodium dodecyldiphenyletherdisulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by mass of ethyl acetate were mixed and stirred to obtain a milky white liquid, which was designated as [Aqueous Phase 1].

[0286] <Emulsification / solvent removal> 1,200 parts by mass of [Aqueous Phase 1] was added to a container containing [Oil Phase 1] and mixed for 20 minutes at 13,000 rpm using a TK Homomixer to obtain [Emulsified Slurry 1]. Next, [Emulsified Slurry 1] was placed in a container equipped with a stirrer and thermometer, and the solvent was removed at 30°C for 8 hours, followed by aging at 45°C for 4 hours to obtain [Dispersed Slurry 1].

[0287] <Washing and drying> 100 parts by mass of [Dispersion Slurry 1] was filtered under reduced pressure, and then the following operations were carried out. (1) 100 parts by mass of ion-exchanged water was added to the filter cake, and the mixture was mixed with a TK homomixer (at a rotation speed of 12,000 rpm for 10 minutes) and then filtered. (2): A 10% aqueous solution of sodium hydroxide was added to the filter cake of (1) until the pH reached 10.5, and the mixture was mixed in a TK homomixer (at 12,000 rpm for 10 minutes), followed by filtration under reduced pressure. (3): 10% hydrochloric acid was added to the filter cake of (2) until the pH reached 4 to 5, and the mixture was mixed in a TK homomixer (at 12,000 rpm for 10 minutes) and then filtered. (4): 300 parts by mass of ion-exchanged water was added to the filter cake of (3), mixed with a TK homomixer (at 12,000 rpm for 10 minutes), and then filtered. This procedure (1) to (4) was repeated twice to obtain a filter cake. The filtered cake was dried in a circulating air dryer at 45° C. for 48 hours and sieved through a mesh with 75 μm openings to obtain toner base particles 1.

[0288] In the following explanation, the washing conditions in operation (2) are as follows: Washing strength (weak): Add 10% sodium hydroxide solution to the filter cake in (1) until the pH reaches 10.5, and mix with a TK homomixer (12,000 rpm for 10 minutes). Washing strength (medium): Add 10% sodium hydroxide solution to the filter cake (1) until the pH reaches 11.0, and mix with a TK homomixer (12,000 rpm for 10 minutes). Washing strength (strong): Add 10% sodium hydroxide solution to the filter cake (1) until the pH reaches 11.5, and mix with a TK homomixer (rotation speed: 12,000 rpm for 60 minutes).

[0289] <External additive treatment> 100 parts by mass of [toner base particles 1] were mixed with 0.6 parts by mass of hydrophobic silica having an average particle size of 100 nm, 1.0 part by mass of titanium oxide having an average particle size of 20 nm, and 0.8 parts by mass of hydrophobic silica fine powder having an average particle size of 15 nm in a Henschel mixer to obtain [toner 1].

[0290] Example 2 [Toner base particles 2] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-2)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 2] was produced using this [Toner base particles 2].

[0291] Example 3 [Toner base particles 3] were obtained in the same manner as in Example 2, except that the cleaning strength in the <Cleaning and drying> procedure (2) was changed to cleaning strength (weak). [Toner 3] was produced using this [Toner base particles 3].

[0292] Example 4 [Toner base particles 4] were obtained in the same manner as in Example 1, except that [Resin particle dispersion liquid (W-1)] was replaced with [Resin particle dispersion liquid (W-3)] in Example 1. [Toner 4] was produced using this [Toner base particles 4].

[0293] Example 5 [Toner base particles 5] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-4)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 5] was produced using this [Toner base particles 5].

[0294] Example 6 [Toner base particles 6] were obtained in the same manner as in Example 5, except that the cleaning strength in the <Cleaning and drying> procedure (2) was changed to cleaning strength (weak). [Toner 6] was produced using this [Toner base particles 6].

[0295] Example 7 [Toner base particles 7] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-5)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner base particles 7] was used to produce [Toner 7]. It was made.

[0296] Example 8 [Toner base particles 8] were obtained in the same manner as in Example 7, except that the cleaning strength in the <Cleaning and drying> procedure (2) was changed to cleaning strength (weak). [Toner 8] was produced using this [Toner base particles 8].

[0297] Example 9 [Toner base particles 9] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-6)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 9] was produced using this [Toner base particles 9].

[0298] Example 10 [Toner base particles 10] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-7)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 10] was produced using this [Toner base particles 10].

[0299] Example 11 [Toner base particles 11] were obtained in the same manner as in Example 10, except that the cleaning strength in the <Cleaning and drying> procedure (2) was changed to cleaning strength (strong). [Toner 11] was produced using this [Toner base particles 11].

[0300] Example 12 [Toner base particles 12] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-8)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (strong). [Toner base particles 12] was produced using this [Toner base particles 12].

[0301] Example 13 [Toner base particles 13] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-9)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (strong). [Toner base particles 13] was produced using this [Toner base particles 13].

[0302] Example 14 [Toner base particles 14] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-10)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 14] was produced using this [Toner base particles 14].

[0303] Example 15 [Toner base particles 15] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-11)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 15] was produced using this [Toner base particles 15].

[0304] Example 16 [Toner base particles 16] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-12)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 16] was produced using this [Toner base particles 16].

[0305] Example 17 [Toner base particles 17] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-13)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 17] was produced using this [Toner base particles 17].

[0306] Example 18 [Toner base particles 18] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-14)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 18] was produced using this [Toner base particles 18].

[0307] Example 19 [Toner base particles 19] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-15)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner base particles 19] was produced using this [Toner base particles 19].

[0308] Example 20 [Toner base particles 20] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-16)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 20] was produced using this [Toner base particles 20].

[0309] Example 21 [Toner base particles 21] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-17)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner base particles 21] was produced using this [Toner base particles 21].

[0310] Example 22 [Toner base particles 22] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-18)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 22] was produced using this [Toner base particles 22].

[0311] Example 23 [Toner base particles 23] were obtained in the same manner as in Example 1, except that [Resin particle dispersion (W-1)] was replaced with [Resin particle dispersion (W-19)] and the cleaning strength in the <Washing and drying> procedure (2) was changed to cleaning strength (medium). [Toner 23] was produced using this [Toner base particles 23].

[0312] (Comparative Example 1) [Toner base particles 24] were obtained in the same manner as in Example 1, except that [Resin particle dispersion liquid (W-1)] was replaced with [Resin particle dispersion liquid (W'-1)] in Example 1. [Toner 24] was produced using this [Toner base particles 24].

[0313] (Comparative Example 2) [Toner base particles 25] were obtained in the same manner as in Example 1, except that [Resin particle dispersion liquid (W-1)] was replaced with [Resin particle dispersion liquid (W'-2)] in Example 1. [Toner 25] was produced using this [Toner base particles 25].

[0314] (Comparative Example 3) [Toner base particles 26] were obtained in the same manner as in Example 1, except that [Resin particle dispersion liquid (W-1)] was replaced with [Resin particle dispersion liquid (W'-3)] in Example 1. [Toner 26] was produced using this [Toner base particles 26].

[0315] Comparative Example 4 [Toner base particles 27] were obtained in the same manner as in Example 1, except that [Resin particle dispersion liquid (W-1)] was replaced with [Resin particle dispersion liquid (W'-4)] in Example 1. [Toner 27] was produced using this [Toner base particles 27].

[0316] (Comparative Example 5) [Toner base particles 28] were obtained in the same manner as in Example 1, except that [Resin particle dispersion liquid (W-1)] was replaced with [Resin particle dispersion liquid (W'-5)] in Example 1. [Toner 28] was produced using this [Toner base particles 28].

[0317] <Measurement of interparticle distance> The inter-particle distance (L) and volume average primary particle diameter (M) of the obtained toner were measured by the following methods. The measurement results are shown in Table 7. -Method for separating external additives- [1] 50 ml of a 5% by weight aqueous solution containing a surfactant (product name: Noigen ET-165, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was added to a 100 ml screw tube, and 3 g of toner was added to the mixture and gently moved up and down and left and right. After that, the mixture was stirred in a ball mill for 30 minutes to allow the toner to blend into the dispersion solution. [2] Then, ultrasonic energy was applied for 60 minutes using an ultrasonic homogenizer (trade name homogenizer, model VCX750, CV33, manufactured by SONICS & MATERIALS LLC) with an output set to 40 W. -Ultrasonic conditions- Vibration time: 60 minutes continuous ·Amplitude: 40W ·Vibration start temperature: 23±1.5℃ ·Temperature during vibration: 23±1.5℃ [3] (1) The dispersion liquid was suction filtered using filter paper (trade name: Qualitative Filter Paper (No. 2, 110 mm), manufactured by Advantec Toyo Co., Ltd.), washed twice with ion-exchanged water, filtered again, and the free additives were removed, after which the toner particles were dried. (2) The toner obtained in (1) was observed using a scanning electron microscope (SEM). First, external additives and fillers containing Si were detected by observing the backscattered electron image. (3) The image of (2) was binarized using image processing software (ImageJ), and the external additives and fillers were removed. Next, a secondary electron image was observed at the same position as in (2). Since the resin fine particles cannot be observed in the backscattered electron image but can only be observed in the secondary electron image, the image was compared with the image obtained in (3), and the fine particles present in the areas other than the remaining external additives and filler (areas other than those excluded in (3)) were determined to be resin fine particles, and the volume average primary particle diameter (M) of the resin fine particles and the distance between the resin fine particles (the distance between the centers of the particles, L) were measured using the image processing software. [Photography conditions] Scanning electron microscope: SU-8230 Magnification: 35,000x Image capture: SE (L): Secondary electrons, BSE (backscattered electrons), Accelerating voltage: 2.0 kV Accelerating current: 1.0μA Probe current: Normal Focus mode: UHR WD: 8.0 mm This measurement was carried out for 100 binarized images (one toner particle per image), and the average value was taken as the average value of the distance between the resin particles.

[0318] [Table 7]

[0319] <Creating the carrier> A resin layer coating solution was prepared by adding 100 parts by weight of silicone resin (organostraight silicone), 5 parts by weight of γ-(2-aminoethyl)aminopropyltrimethoxysilane, and 10 parts by weight of carbon black to 100 parts by weight of toluene and dispersing the mixture for 20 minutes using a homomixer.The resin layer coating solution was applied to the surface of 1,000 parts by weight of spherical magnetite with an average particle size of 50 μm using a fluidized bed coating device to prepare a carrier.

[0320] <Preparation of developer> 5 parts by weight of each toner and 95 parts by weight of carrier were mixed using a ball mill to prepare a developer.

[0321] The toner and developer obtained above were evaluated as follows, and the results are shown in Table 8.

[0322] <Granulation property> Each of the obtained toners was dispersed in water, and the volume average particle diameter Mw and number average particle diameter Mn were measured using a Coulter Counter "Multisizer III" (manufactured by Beckman Coulter, Inc.) to determine the particle size distribution (Mw / Mn). The granulation properties were evaluated according to the following evaluation criteria. Regarding granulation properties, it is said that a particle size distribution of 1.24 or less is preferable. -Evaluation criteria- I: Particle size distribution is 1.18 or less II: Particle size distribution is 1.19 or more and 1.24 or less III: Particle size distribution of 1.25 or more

[0323] <Low temperature fixability> The developer was loaded into the image forming apparatus shown in FIG. 3, and a rectangular solid image of 2 cm x 15 cm was printed on PPC paper type 6000<70W>A4 T (manufactured by Ricoh Co., Ltd.) in monochrome mode with a toner adhesion amount of 0.40 mg / cm 2 The surface temperature of the fixing roller was changed to observe whether offset occurred, in which the residual image of the solid image was fixed in a location other than the desired location, and the fixing temperature at which offset occurred was measured and evaluated based on the following criteria. The solid image was also formed on the transfer paper at a position 3.0 cm from the leading edge in the paper feed direction. The speed of passing through the nip of the fixing device was 300 mm / s. -Evaluation criteria- A: The minimum fixing temperature is 130°C or less B: Minimum fixing temperature is greater than 130°C and less than or equal to 135°C C: Minimum fixing temperature is greater than 135°C and less than 140°C D: The minimum fixing temperature is higher than 140°C

[0324] <Heat-resistant storage stability> 10 g of toner was filled into a 50 mL glass container, and after storing the toner at 50°C for 8 hours, it was sieved through a 42 mesh sieve for 2 minutes, and the mass of the toner remaining on the wire mesh (sieve) was measured, and the toner residual rate was measured as the ratio to the mass of the toner placed in the sieve [(mass of toner remaining on the wire mesh / mass of toner placed in the sieve) x 100]. At this time, the better the heat-resistant storage stability of the toner, the smaller the residual rate. The evaluation criteria for heat-resistant storage stability were as follows: -Evaluation criteria- A: Residual rate is less than 5% B: Residual rate is 5% or more but less than 15% C: Residual rate is 15% or more but less than 30% D: Residual rate is 30% or more

[0325] <Toner adhesion> 160kN / m of toner 2The interparticle force (Fp) during compression was measured using an Agrobot (manufactured by Hosokawa Micron Corporation), a powder bed compression / tensile property measuring device, and the toner adhesion force was evaluated based on the following evaluation criteria. The measurement was carried out as follows. Under the following conditions, a certain amount of toner is filled into a cylindrical cell divided into two parts, top and bottom, and the toner is subjected to a force of 160 kN / m 2 The maximum tensile breaking force when the powder layer was broken by lifting the upper cell after holding it under a pressure of 1000 kJ / s, was calculated from the powder layer height during compression, the cell inner diameter, the average toner particle size, the toner true density, and the toner amount. Specifically, the toner amount was 8.00±0.02 g, the ambient temperature was 25±2°C, the humidity was 30±5% RH, the cell inner diameter was 25 mm, the cell temperature was 25°C, the spring wire diameter was 1.0 mm, the compression speed was 0.1 mm / sec, and the compression load was 8 kg (pressure: 160 kN / m 2 ), compression holding time: 60 seconds, tensile speed: 0.6 mm / sec, tensile sampling start time: 0 seconds, tensile sampling time: 25 seconds. The interparticle force (Fp) was calculated using the attached application software. The measurement was carried out after conditioning the toner at 23° C. and 53% RH for 24 hours. -Evaluation criteria- I: Good Fp≦350 II: Tolerance Level 350 <Fp≦500 III: NG level, breaking failure

[0326] <Heat and humidity resistance> Each toner was stored for 3 days at a temperature of 40°C and a relative humidity of 70%, and then sieved through a 42-mesh sieve for 2 minutes, and the amount (g) remaining on the wire mesh was measured. The remaining rate (%) was calculated from the amount (g) of toner before sieving and the amount (g) remaining after sieving, and evaluated according to the following criteria: The better the heat-resistant storage stability of the toner, the smaller the remaining rate. -Evaluation criteria- A: Residual rate is less than 10% B: Residual rate is 10% or more but less than 20% C: Residual rate is 20% or more but less than 30% D: Residual rate is 30% or more

[0327] <Cleaning ability (photoreceptor contamination)> Using the image forming apparatus, a chart with an image area ratio of 5% was printed 3 times per job in a laboratory environment of 21° C. and 65% RH, and 50,000 sheets (A4 size landscape) were output. Thereafter, in a laboratory environment of 32°C and 54% RH, 100 sheets of A4 size landscape paper with a 43 mm wide vertical band pattern (in the paper travel direction) and three charts were printed as evaluation images, and the resulting images were visually observed to evaluate the cleaning performance based on whether or not there were any image abnormalities due to poor cleaning. -Evaluation criteria- I: Toner that has slipped through due to poor cleaning cannot be visually confirmed on the printed paper or on the photosensitive drum, and no streaks of toner can be confirmed even when observing the photosensitive drum longitudinally with a microscope. II: Toner that has slipped through due to poor cleaning cannot be visually confirmed on the printed paper or on the photosensitive drum. III: Toner that has slipped through due to poor cleaning can be visually confirmed on the printed paper and on the photosensitive drum.

[0328] <Overall Judgment> The overall evaluation was determined based on the results of the above four evaluation items and the following criteria. -standard- A: All evaluation criteria are A and I. B: There is at least one B or II in each evaluation criterion, and no items rated C, D, or III. C: There is at least one C in each evaluation criterion, and no items rated D or III. D: There is an item rated D or III in any of the evaluation criteria.

[0329] [Table 8]

[0330] The present invention includes, for example, the following aspects. <1> A toner having resin fine particles on the surface of toner base particles containing at least a binder resin, a colorant, and a wax, When the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm), the toner is characterized by satisfying the following (Equation 1) to (Equation 3). (Equation 1) M < L (Equation 2) 5 (nm) < M ≤ 60 (nm) (Equation 3) 0.40 ≤ [M (nm) / L (nm)] < 0.90 <2> The toner according to <1>, which satisfies the following (Equation 1) to (Equation 3) when the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm). (Equation 1) M < L (Equation 2-1) 10 (nm) < M ≤ 50 (nm) (Equation 3-1) 0.50 ≤ [M (nm) / L (nm)] < 0.80 <3> The toner according to any one of <1> to <2>, which satisfies the following (Equation 1) to (Equation 4) when the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm). (Equation 1) M < L (Equation 2-2) 10 (nm) < M (Equation 3-2) 0.60 ≤ [M (nm) / L (nm)] < 0.70 (Equation 4) L < 35 (nm) <4> A toner having resin fine particles on the surface of toner base particles containing at least a binder resin, a colorant, and a wax, When the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particles is L (nm), it satisfies the following formula, M < L, and methacrylic acid detected by thermal decomposition gas chromatography of the toner is 1.0 mg / g or more and 4.0 mg / g or less with respect to the total amount of the toner. The toner is characterized by this. <5> The resin fine particles contain a resin having a vinyl-based unit, The resin having a vinyl unit contains methacrylic acid. <1> from <4> The toner according to any one of the above items. <6> The resin fine particles have a core resin (b2) and a shell resin (b1) that covers at least a part of the surface of the core resin. <1> from <5> The toner according to any one of the above items. <7> The shell resin contains a styrene-(meth)acrylic acid ester copolymer. <6> The toner is as described in <8> The content of the resin particles is 0.2% by mass to 5% by mass relative to the toner. <1> from <7> The toner according to any one of the above items. <9> the toner has a glass transition temperature (Tg1st) in the first temperature rise measured by differential scanning calorimetry (DSC) of 40°C to 65°C; The toner has a component insoluble in tetrahydrofuran (THF) that has a glass transition temperature (Tg1st) in the first temperature rise of DSC of -45°C to 5°C, The glass transition temperature (Tg2nd) of the THF-soluble component of the toner in the second temperature rise of DSC is 20°C to 65°C. <1> from <8> The toner according to any one of the above items. <10> The glass transition temperature (Tg1st) in the first temperature rise and the glass transition temperature (Tg2nd) in the second temperature rise in differential scanning calorimetry (DSC) of the toner are Tg1st-Tg2nd≧10[°C] <1> from <9> The toner according to any one of the above items. <11> The binder resin contains an amorphous polyester. <1> from <10> The toner according to any one of the above items. <12> The binder resin contains a modified polyester. <1> from <11> The toner according to any one of the above items. <13> The modified polyester is a polyester containing, as a constituent, a trivalent or tetravalent aliphatic polyhydric alcohol having 3 to 10 carbon atoms. <12> The toner is as described in <14> The modified polyester contains a diol as a constituent component, The diol has an odd number of carbon atoms in the main chain of 3 to 9 and an alkyl group in the side chain. <12> from <13> The toner according to any one of the above items. <15> The modified polyester has at least one of a urethane bond and a urea bond. <12> from <14> The toner according to any one of the above items. <16> The binder resin contains a crystalline polyester. <1> from <15> The toner according to any one of the above items. <17> The aforementioned <1> from <16> and a carrier. <18> The aforementioned <1> from <16> 1. A toner storage unit characterized by storing the toner according to any one of the above items. <19> The aforementioned <18> 10 is a diagram showing an image forming apparatus according to an embodiment of the present invention; <20> The aforementioned <1> from <16> An image forming method using the toner according to any one of an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner to form a toner image; a transfer step of transferring the toner image formed on the electrostatic latent image carrier to a medium; and a fixing step of fixing the toner image transferred onto the medium. <21> The aforementioned <1> from <16> A method for producing the toner according to any one of the above, a composite particle forming step of forming composite particles by adhering resin fine particles to the surfaces of toner base particles; and a removing step of removing at least a part of the resin fine particles from the composite particles. <22> The removing step is a step of washing with a basic aqueous solution. <21> 2. A method for producing the toner according to claim 1.

[0331] The aforementioned <1> from <16> The toner according to any one of <17> The developer according to <18> The toner storage unit according to <19> The image forming apparatus according to <20> and the image forming method described in <21> from <22> According to any one of the above toner production methods, the conventional problems can be solved and the object of the present invention can be achieved. [Explanation of symbols]

[0332] 10 Photosensitive drum 40 Developer 58 Corona charger 80 Transfer roller 90 Cleaning Device 110 Process cartridge 210 Paper feed section 211 Paper cassette 212 Paper feed roller 220 Conveyor 221 Laura 222 Timing roller 223 Paper ejection roller 224 Paper output tray 230 Image creation section 233 Exposure device 240 Transcription Unit 241 Drive roller 242 driven roller 243 Intermediate transfer belt 244 Primary transfer roller 245 Secondary opposing roller 246 Secondary transfer roller 250 Fixing unit 251 Fixing belt 252 pressure roller [Prior art documents] [Patent documents]

[0333] [Patent Document 1] Japanese Patent Application Laid-Open No. 2002-284881 [Patent Document 2] Japanese Patent Application Publication No. 2019-099809 [Patent Document 3] Japanese Patent Application Publication No. 2019-143128

Claims

1. A toner having resin fine particles on the surface of toner base particles containing at least a binder resin, a colorant, and a wax, When the volume average primary particle diameter of the resin fine particles is M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particle is L (nm), the following (Formula 1) to (Formula 3) are satisfied: the binder resin contains a crystalline polyester resin, the resin fine particles contain a resin having a vinyl unit, The toner is characterized in that the resin having a vinyl unit contains methacrylic acid. (Formula 1) M<L (Formula 2) 5(nm)<M≦60(nm) (Formula 3) 0.40≦[M(nm) / L(nm)]<0.90

2. 2. The toner according to claim 1, wherein the resin fine particles have a volume average primary particle diameter M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particle is L (nm), and the following (Formula 1) to (Formula 3) are satisfied: (Formula 1) M<L (Formula 2-1) 10(nm)<M≦50(nm) (Formula 3-1) 0.50≦[M(nm) / L(nm)]<0.80

3. 3. The toner according to claim 1, wherein the resin fine particles have a volume average primary particle diameter M (nm) and the distance between adjacent resin fine particles present on the surface of the toner base particle is L (nm), and the toner satisfies the following (Formula 1) to (Formula 4): (Formula 1) M<L (Formula 2-2) 10(nm)<M (Formula 3-2) 0.60≦[M(nm) / L(nm)]<0.70 (Formula 4) L<35 (nm)

4. 4. The toner according to claim 1, wherein the amount of methacrylic acid detected by pyrolysis gas chromatography of the toner is 1.0 mg / g or more and 4.0 mg / g or less based on the total amount of the toner.

5. 5. The toner according to claim 1, wherein the resin particles have a core resin and a shell resin that coats at least a part of the surface of the core resin.

6. 6. The toner according to claim 5, wherein the shell resin contains a styrene-(meth)acrylic acid-(meth)acrylic acid ester copolymer.

7. A toner storage unit containing the toner according to any one of claims 1 to 6.

8. An image forming apparatus comprising the toner storage unit according to claim 7.

9. An image forming method using the toner according to any one of claims 1 to 6, an electrostatic latent image forming step of forming an electrostatic latent image on an electrostatic latent image carrier; a developing step of developing the electrostatic latent image formed on the electrostatic latent image carrier with the toner to form a toner image; a transfer step of transferring the toner image formed on the electrostatic latent image carrier to a medium; a fixing step of fixing the toner image transferred onto the medium.

10. A method for producing the toner according to any one of claims 1 to 6, comprising the steps of: a composite particle forming step of forming composite particles by adhering resin fine particles to the surfaces of toner base particles; a removing step of removing at least a part of the resin fine particles from the composite particles.

11. The method for producing a toner according to claim 10, wherein the removing step is a step of washing with a basic aqueous solution.

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