JP2018004893A - Toner and developing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that can reduce white streaks on a medium including rough paper and provide a good image even when used for a long period in a high-temperature and high-humidity environment.SOLUTION: The present invention is a toner including toner particles each containing a vinyl resin, amorphous polyester resin, colorant, and mold release agent. The amorphous polyester resin includes a unit derived from an alcohol component and a unit derived from a straight-chain aliphatic dicarboxylic acid having 6 to 12 carbon atoms; the unit derived from a straight-chain aliphatic dicarboxylic acid is contained in an amount of 10 mol% or more and 50 mol% or less relative to the unit derived from the entire carboxylic acid component; on a toner cross-section observed by a transmission electron microscope, the vinyl resin forms a matrix; the amorphous polyester resin forms domains; and the mold release agent is a dicarboxylic diester compound.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in an image forming method such as an electrophotographic method, an electrostatic recording method, and a magnetic recording method, and a developing device.

  In recent years, printers and copiers that use electrophotography have been demanded to increase printing speed and save energy. For this reason, toners that are excellent in low-temperature fixability are required. Furthermore, various media support is required. In particular, when printing on a medium called rough paper with many irregularities on the surface of the paper, a part of the solid image is peeled off from the paper, and the image is badly whitened. It is easy to happen. This image detriment is caused by the fact that the toner placed in the concave portion of the rough paper melts in a state where it is difficult to receive pressure from a fixing member such as a fixing roller, so that the adhesion between the toner and the paper or between the toners becomes weak. .

  In order to suppress this adverse image effect, there is a method to improve the low-temperature fixability of the toner by lowering and softening the melt viscosity of the toner, but an external additive present on the surface of the toner is used. The toner is liable to be deteriorated such as being buried in the toner or the toner itself being cracked. In addition, as an electrophotographic process, there is a technology for reducing the size of the apparatus by adopting a cleaner-less system in which a cleaning member (hereinafter referred to as a cleaning blade) that removes transfer residual toner is omitted and the transfer residual toner is collected by a developing unit. is there. In this cleanerless system, the toner is stressed, and thus the above-described toner deterioration is likely to occur. In addition, when used in a high temperature and high humidity environment for a long period of time, image defects such as fogging due to poor charging due to moisture absorption are likely to occur. In view of the above, there is a demand for a toner having excellent durability while being excellent in low-temperature fixability.

  As a technology that achieves both low-temperature fixability and durability, there are a technology that uses a sharp melt property of a crystalline material for a toner, and a technology that improves a wax (release agent). In Patent Literature 1, low temperature fixability and durability are improved by controlling ester wax and crystalline polyester and using an inorganic fine particle external additive in combination with a certain particle size. Patent Document 2 describes a toner having improved low-temperature fixability using a plastic wax containing a polyfunctional ester compound.

JP2011-237801A JP 2001-281909 A

  When the present inventors examined the toner of Patent Document 1, when an inorganic fine particle external additive is used, the low temperature fixing property and durability may be obstructed due to the hardness and heat capacity of the inorganic fine particles. It was found that there is room for further improvement in terms of coexistence. Further, since the plastic wax described in Patent Document 2 has a low melting point and high compatibility with the binder resin, the toner is easy to soften and is durable at room temperature when the toner is subjected to stress such as a stirring member in the cartridge. Was not enough. Therefore, there is room for improvement in terms of both durability and low-temperature fixability. In any of these documents, there is a problem and there is room for improvement in the electrophotographic process that is particularly resistant to toner deterioration such as a cleanerless system and the improvement of white spots on media such as rough paper.

  An object of the present invention is to provide a toner that improves white spots on a medium such as rough paper and that can provide a good image even when used for a long time in a high-temperature and high-humidity environment, and a developing device having the toner. It is.

The present invention is a toner having toner particles containing a vinyl resin, an amorphous polyester resin, a colorant, and a release agent,
The amorphous polyester resin has a unit derived from an alcohol component, and a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms,
The unit derived from the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is contained in an amount of 10 mol% to 50 mol% with respect to the units derived from all carboxylic acid components in the amorphous polyester resin.
In the toner cross section observed with a transmission electron microscope,
The vinyl resin constitutes a matrix, the amorphous polyester resin constitutes a domain,
The release agent is an ester of a dicarboxylic acid and an aliphatic monoalcohol.

The present invention also provides a toner for developing an electrostatic latent image formed on an image carrier,
A toner carrying body that carries the toner and conveys the toner to the image carrier,
The present invention relates to a developing device, wherein the toner is the toner.

  According to the present invention, there are provided a toner that improves white spots on media such as rough paper and that can provide a good image even when used for a long time in a high-temperature and high-humidity environment, and a developing device having this toner. Can do.

1 is a schematic cross-sectional view of a developing device that can be used in the present invention. 1 is a schematic cross-sectional view illustrating an example of an image forming apparatus that can be used in the present invention. 2 is an example of a developing device in which a magnet is disposed inside a toner carrier.

Hereinafter, embodiments for carrying out the present invention will be described in detail.
The toner of the present invention is a toner having toner particles containing a vinyl resin, an amorphous polyester resin having a specific structure, a colorant, and a release agent. In the cross section of the toner observed with a transmission electron microscope (TEM), the vinyl resin forms a matrix, the amorphous polyester resin forms a domain, and the release agent is an ester of a dicarboxylic acid and an aliphatic monoalcohol. It is characterized by being. Hereinafter, an ester of a dicarboxylic acid and an aliphatic monoalcohol is also referred to as a dicarboxylic acid diester compound.

  The present inventors have found that a toner having excellent low-temperature fixability such as white spots and excellent durability can be obtained by the above-described configuration of the present invention. The present inventors consider the effects of the present invention as follows.

  In order to achieve both low-temperature fixability and durability as a toner, it is necessary to control the plastic state of the toner at normal temperature and during fixing. In other words, it is necessary that the toner has a certain toner strength at the normal temperature when stress is applied from the toner stirring blade in the cartridge and is not easily plastically deformed. In fixing (when heated at high temperature), it is necessary that the toner is plasticized and softened to promote adhesion between paper and toner.

  In the toner of the present invention, the vinyl resin forms a matrix, and the amorphous polyester resin forms a domain. As a matrix, vinyl resin tends to easily obtain good durability against external stresses such as heat and pressure. Further, unlike the case where the amorphous polyester resin is present on the toner surface like a shell, the formation of the domain makes it easy to improve durability against stress such as heat and pressure from the outside. With such a configuration, the strength of the toner is maintained, and the plastic deformation of the toner at normal temperature is difficult.

  Furthermore, the toner of the present invention has a dicarboxylic acid diester compound as a release agent. Moreover, an amorphous polyester resin has a unit derived from an alcohol component and a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms. Furthermore, the unit derived from the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is contained in an amount of 10 mol% to 50 mol% with respect to the units derived from all carboxylic acid components of the amorphous polyester resin. The dicarboxylic acid diester compound tends to be highly compatible with the above-mentioned domain and the above-mentioned specific amorphous polyester resin, and becomes compatible with each other at the time of fixing (at high temperature), and has a high plastic effect on the toner. Demonstrate. As a result, the present inventors consider that adhesion between the toners and adhesion between the toner and the paper are promoted, and it becomes easy to suppress fixing problems such as white spots on rough paper with many irregularities.

  Since the degree of compatibility with the amorphous polyester resin varies depending on the structure of the release agent, it is considered that the effect of low-temperature fixability may not be sufficiently obtained. For example, when a release agent having a different structure such as monoester, hexaester, or paraffin wax is used as the release agent, it becomes difficult to be compatible with the amorphous polyester resin, and the effect of low-temperature fixing tends to be inferior.

  The dicarboxylic acid diester compound which is a mold release agent is an ester of a dicarboxylic acid and an aliphatic monoalcohol. Examples of the dicarboxylic acid component include fumaric acid, terephthalic acid, adipic acid, sebacic acid, and the like. In particular, terephthalic acid is preferable. If terephthalic acid is included, the compatibility with the amorphous polyester resin having a benzene ring skeleton tends to be easily promoted, and it is considered that the effect of low-temperature fixability can be easily obtained. Subsequently, examples of the aliphatic monoalcohol component include myristyl alcohol, palmityl alcohol, stearyl alcohol, and behenyl alcohol.

When the carbon number of the aliphatic monoalcohol of the release agent is C _A and the carbon number of the dicarboxylic acid is C _B , C _A is preferably 14 or more and 22 or less, and C _B is preferably 4 or more and 10 or less. . Furthermore, it is preferable that C _A / C _B is 1.7 or more and 4.5 or less. When C _A is 14 or more and 22 or less and C _B is 4 or more and 10 or less, the compatibility with the amorphous polyester resin is improved, which is preferable from the viewpoint of suppressing white spots. Furthermore, when the carbon number of C _A and C _B is controlled and C _A / C _B is 4.5 or less, compatibility between the release agent and the amorphous polyester resin is promoted during heating, and as a result, The effect of fixing plasticity is improved, and white spots are further suppressed. Further, when C _A / C _B is 1.7 or more, excessive promotion of toner plasticity at room temperature is suppressed, durability is improved, and fog is further suppressed.

  The content of the dicarboxylic acid diester compound is preferably 1% by mass or more and 25% by mass or less with respect to the total mass of the vinyl resin and the amorphous polyester resin.

  The melting point of the dicarboxylic acid diester compound is preferably 55 ° C. or higher and 90 ° C. or lower from the viewpoint of good heat-resistant storage stability and softening the amorphous polyester resin to exert an effect on low-temperature fixability. Furthermore, the weight average molecular weight (Mw) of the dicarboxylic acid diester compound is preferably 400 or more and 2000 or less from the viewpoints of heat resistant storage stability and low temperature fixability.

  In addition, the amorphous polyester resin has a unit derived from an alcohol component and a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms. And the content rate of the unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is 10 mol% or more and 50 mol% or less with respect to the units derived from all carboxylic acid components. Since the amorphous polyester resin contains a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms, compatibility with the dicarboxylic acid diester compound is easily promoted during fixing, and fixing such as white spots It is easy to exert an effect on inhibition. If the carbon number is 5 or less or 13 or more, the degree of compatibility with the dicarboxylic acid diester compound is weakened, and as a result, the effect of fixing plasticity is hardly obtained. More preferably, the linear aliphatic dicarboxylic acid has 6 to 10 carbon atoms.

  When the content ratio of the unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is less than 10 mol%, the effect of promoting compatibilization is difficult to obtain, and the fixing plasticity is weakened. It is difficult to obtain. If the content ratio is greater than 50 mol%, excessive compatibility with the amorphous polyester resin tends to occur excessively at room temperature, and toner deterioration tends to occur in a high-temperature and high-humidity environment. Evil is likely to occur. The content of the unit derived from the linear aliphatic dicarboxylic acid is more preferably 30 mol% or more and 50 mol% or less.

  The amorphous polyester resin can be obtained by polycondensation of an alcohol component and a carboxylic acid component containing a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms. The following are mentioned as an alcohol component. Examples of the divalent alcohol component include a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and a polyoxyethylene adduct of 2,2-bis (4-hydroxyphenyl) propane. Examples include alkylene oxide adducts of bisphenol A represented by the following formula (I), ethylene glycol, 1,3-propylene glycol, neopentyl glycol, and the like. Examples of the trivalent or higher alcohol component include sorbitol, pentaerythritol, dipentaerythritol, and the like. The dihydric alcohol component and the trihydric or higher polyhydric alcohol component can be used alone or in combination of a plurality of compounds.

(In formula, R shows a C2-C3 alkylene group. X and y show a positive number, and the sum of x and y is 1-16, Preferably it is 1.5-5. )

  Examples of the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms include adipic acid, suberic acid, sebacic acid, and dodecanedioic acid. Examples of the carboxylic acid other than the straight chain aliphatic dicarboxylic acid having 6 to 12 carbon atoms include the following. Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, glutaric acid, n-dodecenyl succinic acid, anhydrides of these acids, and lower alkyl esters. It is done. Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, emporic trimer acid and acid anhydrides thereof, lower Examples include alkyl esters.

  The amorphous polyester resin can be produced by esterification reaction or transesterification reaction using the above monomers. When polymerizing the raw material monomer, a known esterification catalyst such as dibutyltin oxide may be appropriately used in order to accelerate the reaction.

  The molar ratio of the alcohol component and the carboxylic acid component (carboxylic acid component / alcohol component), which is the raw material monomer of the amorphous polyester, is preferably 0.60 or more and 1.00 or less.

  The glass transition temperature (Tg) of the amorphous polyester resin is preferably 45 ° C. or higher and 70 ° C. or lower from the viewpoints of fixability and durability stability. The glass transition temperature (Tg) can be measured with a differential scanning calorimeter (DSC). The softening point of the amorphous polyester resin is preferably 80 ° C. or higher and 130 ° C. or lower, and more preferably 90 ° C. or higher and 120 ° C. or lower, from the viewpoint of low-temperature fixability of the toner.

  The acid value of the amorphous polyester resin is preferably 1.0 mgKOH / g or more and 10.0 mgKOH / g or less from the viewpoint of good charging characteristics of the toner and the abundance ratio of domains to the toner cross section described later. When the acid value of the amorphous polyester resin is 1.0 mgKOH / g or more, the domain tends to exist in the vicinity of the surface layer, and the low-temperature fixability is easily improved. It is suppressed that durability stability falls that the acid value of an amorphous polyester resin is 10.0 mgKOH / g or less. More preferably, it is 1.0 mgKOH / g or more and 7.0 mgKOH / g or less. In order to control the acid value of the amorphous polyester resin within the above range, the alcohol monomer component ratio / acid monomer component ratio at the time of resin production and / or the molecular weight should be adjusted, and a polyvalent such as trimellitic acid. It can be adjusted by the amount of the carboxylic acid monomer. In addition, the hydroxyl value of the amorphous polyester resin is preferably 2.0 mgKOH / g or more and 40.0 mgKOH / g or less from the viewpoint of fixability and storage stability.

  The weight average molecular weight (Mw) of the amorphous polyester resin is preferably 8000 or more and 13000 or less from the viewpoint of low-temperature fixability and durability of the toner. The toner of the present invention preferably has 5.0% by mass or more and 20.0% by mass or less of amorphous polyester with respect to the total of amorphous polyester resin and vinyl resin. By having 5.0% by mass or more of amorphous polyester, sufficient compatibility with the dicarboxylic acid diester compound as a mold release agent can be obtained. Further, when the amorphous polyester is 20.0% by mass or less, the durability of the toner can be sufficiently obtained.

  In the toner cross section observed with a transmission electron microscope (TEM), the domain is in a region within 25% of the distance between the outline and the center point of the cross section from the outline of the cross section to 40 area% with respect to the total area of the domain. More than 70 area% is preferable. In order to further suppress white spots, it is desirable to generate a plastic effect near the toner surface rather than the inner center of the toner in order to enhance the adhesion between the toner, the paper, and the toner. When the area ratio (hereinafter also referred to as “25% area ratio”) of a domain existing in a region within 25% of the distance between the outline and the center point of the cross section is within the above range from the cross section outline, This means that there are many domains of the conductive polyester resin near the surface of the toner. The present inventors believe that the release agent dicarboxylic acid diester is compatible with the domain in the vicinity of the surface, and the toner is plasticized, so that the adverse effect of white spots tends to be suppressed. . When the 25% area ratio is 40 area% or more, the release agent can have a more compatible effect with the amorphous polyester resin, and the low-temperature fixability is further improved. Further, when the 25% area ratio is 70 area% or less, durability is improved and fogging is further suppressed.

  Furthermore, it is preferable that the domain exists in an area within 50% of the distance between the outline and the center point of the cross section from the outline of the cross section to 80 area% to 100 area% with respect to the total area of the domain. . When the area ratio of the amorphous polyester domain existing within 50% of the distance between the contour and the center point of the cross section (hereinafter also referred to as “50% area ratio”) is 80 area% or more, Accordingly, the dicarboxylic acid diester as a release agent is more easily compatible. As a result, white spots can be further suppressed. More preferably, it is 90 area% or more and 100 area% or less.

  Next, the area of the domain existing within 25% of the distance between the contour and the center point of the cross section from the contour of the cross section becomes 25% to 50% of the distance between the contour and the center point of the cross section. It is preferably 1.05 times or more the area of the existing domain. This indicates that the domain is unevenly distributed on the toner surface. When the domain is unevenly distributed on the toner surface, it becomes easier to be compatible with the dicarboxylic acid diester of the release agent, and white spots are more easily suppressed. (From the cross-sectional contour of the toner, the area of the domain existing within 25% of the distance between the contour and the central point of the cross-section / From the contour of the cross-section, present within 25% to 50% of the distance between the contour and the central point of the cross-section. The area of the domain (hereinafter also referred to as the area ratio of the domain) is more preferably 1.20 times or more. On the other hand, the upper limit is not particularly limited, but is preferably 3.00 times or less.

  The presence state of these domains of the amorphous polyester resin can be controlled by the acid value of the amorphous polyester resin.

  Next, the number average diameter of the amorphous polyester domains is preferably 0.3 μm or more and 3.0 μm or less. More preferably, it is 0.3 μm or more and 2.0 μm or less. When the number average diameter of the domain is 0.3 μm or more, the dicarboxylic acid diester of the release agent becomes easy to be compatible, and when melted at the time of fixing, adhesion to media such as paper and adhesion between toner particles is improved. It improves and it becomes easier to suppress white spots. When the number average diameter of the domains is 3.0 μm or less, it becomes easy to control the existence state of the domains in the toner particles. In addition, domain variation between toner particles can be reduced.

  Thus, in order to control the number average diameter of the non-crystalline polyester in the vicinity of the toner surface and to control the number average diameter of the domain, for example, in the case of suspension polymerization, the acid value and hydroxyl value of the non-crystalline polyester are used. It can be controlled with. Further, it can be adjusted by controlling the softening point of the amorphous polyester or by controlling the annealing conditions during toner production.

  The toner contains a vinyl resin. In addition to the vinyl resin, a known resin may be used as the binder resin to the extent that the effects of the present invention are not impaired. Vinyl resin is easy to achieve to maintain rigidity and viscosity.

  Examples of the vinyl resin include the following.

Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof;
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-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methacrylic acid Dimethylaminoethyl acid copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Maleic acid copolymerization , Styrene - styrene copolymer and maleic acid ester copolymers;
Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, polyacrylic acid resin, and the like can be used. These can be used alone or in combination of two or more. Among these, styrene copolymers, and styrene-butyl acrylate copolymers are particularly preferable from the viewpoints of development characteristics and ease of control of fixability.

  Next, the production method for obtaining the toner of the present invention and the material structure of the toner will be described in detail.

  The toner of the present invention is preferably produced in an aqueous medium such as a dispersion polymerization method, an association aggregation method, a dissolution suspension method, or a suspension polymerization method. In the present invention, in order to control the 25% area ratio of the amorphous polyester resin domain, the polymerizable monomer composition is granulated in an aqueous medium to form particles of the polymerizable monomer composition. The toner is preferably produced by a suspension polymerization method. The suspension polymerization method includes a polymerizable monomer capable of forming a vinyl resin, an amorphous polyester resin, a release agent, a colorant, and (if necessary, a polymerization initiator, a crosslinking agent, a charge control agent. , Other additives) are dissolved or dispersed to obtain a polymerizable monomer composition. Thereafter, this polymerizable monomer composition is added to an aqueous medium (which may contain a dispersion stabilizer as required). Then, particles of the polymerizable monomer composition are formed in an aqueous medium, and the polymerizable monomer contained in the particles is polymerized. This is a method for obtaining toner particles.

  As the polymerizable monomer, a vinyl monomer capable of radical polymerization is used. A monofunctional monomer or a polyfunctional monomer can be used as the vinyl monomer.

  Monofunctional monomers include styrene; styrene derivatives such as α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene; methyl Acrylic polymerizable monomers such as acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, dibutyl Methacrylic polymerizable monomers such as phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate and vinyl propionate; vinyl methyl ether; Sulfonyl ethyl ether, vinyl ether such as vinyl isobutyl ether; vinyl methyl ketone, vinyl hexyl ketone, and vinyl ketones such as vinyl isopropyl ketone. Among the above, the polymerizable monomer preferably contains styrene or a styrene derivative.

  Examples of the polyfunctional monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinyl ether and the like.

  Monofunctional monomers may be used alone or in combination of two or more, or monofunctional monomers and polyfunctional monomers may be used in combination. Polyfunctional monomers can also be used as crosslinking agents.

  As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. Further, it is preferable to carry out the polymerization reaction at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer because toner particles having appropriate strength and melting characteristics can be obtained.

  Examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile). ), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and other azo or diazo polymerization initiators; benzoyl peroxide, t-butylperoxy 2-ethyl Hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichloro Peroxidation of benzoyl peroxide, lauroyl peroxide, etc. System polymerization initiators and the like.

  In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  As the dispersion stabilizer, various surfactants, organic dispersants, and inorganic dispersants can be used. Among these, inorganic dispersants can be preferably used because they do not easily generate ultrafine powder and have obtained dispersion stability due to their steric hindrance. Examples of the inorganic dispersant include trivalent calcium phosphates such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, and hydroxyapatite, carbonates such as calcium carbonate and magnesium carbonate, calcium metasilicate, calcium sulfate, and barium sulfate. And inorganic salts such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

  These inorganic dispersants are desirably used in an amount of 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Moreover, the said dispersion stabilizer may be used independently and may use multiple types together. Further, a surfactant may be used in combination.

  In the present invention, a dicarboxylic acid diester compound is contained as a release agent, but a release agent other than the dicarboxylic acid diester compound may be used in combination as necessary.

  As a mold release agent used in combination with a dicarboxylic acid diester, from the viewpoint of high releasability, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax and ester waxes other than dicarboxylic acid, For example, monoester, pentaester, hexaester, octaester and the like are preferable.

  As addition amount of mold release agents other than dicarboxylic acid diester, it is 1.0 mass part or more and 30.0 mass parts or less with respect to 100 mass parts of vinyl resins, More preferably, 3.0 mass parts or more and 15.0 mass parts or less It is preferable to contain a mold release agent.

  The toner particles of the present invention may be magnetic toner particles or non-magnetic toner particles. From the viewpoint of fixability, magnetic toner particles containing a magnetic material are preferred.

  The magnetic material is preferably composed mainly of magnetic iron oxide such as triiron tetroxide and γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. .

  The shape of the magnetic body includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scaly shape, but a polyhedron, an octahedron, a hexahedron, a sphere, and the like having a low anisotropy increase the image density. In addition, it is preferable. The magnetic material preferably has a number average particle diameter of 0.10 μm or more and 0.40 μm or less from the viewpoint of uniform dispersibility and color in the toner.

  As for the presence state of the magnetic substance in the toner particles, it is preferable that the magnetic substance is not exposed on the surface of the toner particle but is present inside the toner particle. In addition, it is preferable that the abundance and existence state of the magnetic material between the toner particles is uniform. As a toner having such a dispersed state of a magnetic material, for example, there is a method of performing a desired hydrophobic treatment on the magnetic material. Examples of the surface treatment agent include silane compounds, titanate compounds, and aluminate compounds, but silane compounds are preferred. Examples of the silane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyl Dimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, n-butyltrimethyl Xysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane, hydroxypropyltrimethoxysilane, n-hexadecyltri Examples include methoxysilane and n-octadecyltrimethoxysilane. Moreover, these hydrolysates etc. are mentioned.

  Magnetic fine particles can be produced, for example, by the following method. An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide in an amount equivalent to or greater than the iron component to the ferrous salt aqueous solution. Air was blown in while maintaining the pH of the prepared aqueous solution at pH 7 or higher, and ferrous hydroxide was oxidized while heating the aqueous solution to 70 ° C. or higher. First, seed crystals serving as the core of the magnetic iron oxide powder were formed. Generate.

  Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. While maintaining the pH of the solution at 5 to 10, the reaction of ferrous hydroxide proceeds while blowing air to grow a magnetic iron oxide powder with the seed crystal as a core. At this time, the shape and magnetic characteristics of the magnetic fine particles can be controlled by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but the pH of the liquid is preferably not less than 5. The magnetic fine particles can be obtained by filtering, washing, and drying the magnetic fine particles thus obtained by a conventional method.

  The amount of magnetic iron oxide contained in the toner particles is preferably 25 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the binder resin.

  When producing non-magnetic toner particles, carbon black or other known pigments or dyes can be used as the colorant. Further, only one kind of pigment or dye may be used, or two or more kinds may be used in combination.

  Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155, 168, 180, 185, 214.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  The colorant contained in the toner is preferably 0.1 parts by mass or more and 60.0 parts by mass or less, more preferably 0.5 parts by mass with respect to 100 parts by mass in total of the vinyl resin and the amorphous polyester resin. It is not less than 50.0 parts by mass.

  The toner of the present invention may contain a charge control agent for improving charging characteristics. Various types of charge control agents can be used, and charge control agents that can quickly maintain a constant charge amount with a high charging speed are particularly preferable. Further, when the toner is produced using a polymerization method as described later, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Examples of charge control agents include metal compounds of aromatic carboxylic acids such as salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid and dicarboxylic acid; metal salts or metal complexes of azo dyes or azo pigments; sulfonic acid or carboxylic acid groups Examples include a polymer compound having a chain; a boron compound; a urea compound; a silicon compound; and a calixarene.

  The amount of these charge control agents used is preferably 0.1 parts by weight or more and 10.0 parts by weight or less with respect to a total of 100 parts by weight of the vinyl resin and the amorphous polyester resin when added inside the toner particles. It is used in the range. When added outside the toner particles, the amount is preferably 0.005 parts by mass or more and 1.0 parts by mass or less with respect to 100 parts by mass of the toner.

  Furthermore, in addition to the above materials, a known conductivity imparting agent, lubricant, abrasive, etc. may be added to the toner of the present invention.

  In the step of polymerizing the polymerizable monomer, the polymerization temperature is preferably set to 40 ° C or higher, and generally 50 ° C to 90 ° C.

  In order to obtain a toner having a preferred amorphous polyester domain of the present invention by suspension polymerization, it is preferable to have the following steps.

  After obtaining a colored particle by polymerizing a polymerizable monomer, in the state where the colored particle is dispersed in an aqueous medium, near the softening point of the amorphous polyester (for example, the softening point of the amorphous polyester + 10 ° C.), specifically Specifically, the temperature is raised to about 100 ° C., and the temperature is preferably maintained for 30 minutes or more. The upper limit is not particularly limited, but is preferably maintained for 24 hours or less from the viewpoint of production tact.

  Further, it is preferable to perform the following operation in the subsequent cooling step. Specifically, the aqueous medium is preferably cooled at a cooling rate of 5.0 ° C./min or higher, more preferably at a cooling rate of 20 ° C./min or lower, to a glass transition temperature (Tg) or lower of the toner. It is more preferable to cool at a rate of 100 ° C./min or more. The upper limit of the cooling rate is about 500 ° C./min or less from the viewpoint of production tact.

  Moreover, after cooling at the cooling rate, it is preferable to hold at that temperature for 30 minutes or more. The holding time is more preferably 60 minutes or more, and further preferably 120 minutes or more. The upper limit of the holding time is not particularly limited, but is about 24 hours or less from the viewpoint of production tact.

  A toner can be obtained by mixing the toner particles with an inorganic fine powder as a fluidity improver if necessary and adhering it to the surface.

  As the inorganic fine particles used in the present invention, fine particles such as silica, titanium oxide, and alumina can be used. Examples of the silica fine particles include so-called dry silica produced by vapor phase oxidation of silicon halides or dry silica called fumed silica, and so-called wet silica produced from water glass.

However, dry silica having fewer silanol groups on the surface and inside the silica fine particles and less production residue such as Na ₂ O and SO ₃ ²⁻ is more preferable. In dry silica, it is also possible to obtain fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. , Including them.

  The addition amount of the inorganic fine particles is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, more preferably 0.10 parts by mass or more and 4.0 parts by mass or less with respect to 100 parts by mass of the toner particles. is there.

  In the present invention, it is preferable that the inorganic fine particles have been subjected to a hydrophobic treatment since the environmental stability of the toner can be improved. Examples of the treatment agent used for the hydrophobic treatment of the inorganic fine particles include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, and silane coupling agents. In addition, treatment agents such as other organosilicon compounds and organotitanium compounds are listed. These can be used alone or in combination of two or more.

  Among the above-mentioned treatment agents, those treated with silicone oil are preferred, and those treated with silicone oil are more preferred at the same time as or after hydrophobizing inorganic fine particles with a silane compound. As the silicone oil, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.

  As a method of treating inorganic fine particles with silicone oil, for example, a method of directly mixing inorganic fine particles treated with a silane compound and silicone oil using a mixer such as a Henschel mixer, or spraying silicone oil onto inorganic fine particles A method is mentioned. Alternatively, after dissolving or dispersing silicone oil in a suitable solvent, inorganic fine particles may be added and mixed to remove the solvent. A spraying method is more preferable in that the formation of aggregates of inorganic fine particles is relatively small.

  The treatment amount of the silicone oil is preferably 1 part by mass to 40 parts by mass with respect to 100 parts by mass of the inorganic fine particles from the viewpoint of hydrophobicity.

Inorganic fine particles used in the present invention, in order to impart good fluidity to the toner, the specific surface area measured by the BET method by nitrogen adsorption is preferred in the 350 meters 2 / ^g range 20 m 2 / ^g. The specific surface area is calculated using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics Co., Ltd.) according to the BET method.

  If necessary, other external additives may be added to the toner. For example, charging aids, conductivity-imparting agents, anti-caking agents, release agents at the time of fixing of fixing rollers, lubricants, and resin fine particles and inorganic fine particles functioning as an abrasive.

  Examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder. Of these, polyvinylidene fluoride powder is preferred. Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder.

In the toner of the present invention, Tg _1st is 51.0 ° C. or more, further 52, when the glass transition point at the first temperature rise obtained by differential scanning calorimetry (DSC) measurement of the toner is Tg _1st (° C.). It is preferable that the temperature is 0.0 ° C. or higher, particularly 55.0 ° C. or higher. In DSC, when the glass transition point at the second temperature rise is Tg _2nd , Tg _2nd is preferably 46.0 ° C. or lower, more preferably 43.0 ° C. or lower, and particularly preferably 42.0 ° C. or lower.

The present inventors consider Tg _1st and Tg _2nd of the toner in the present invention as follows. First, Tg _1st is considered to be an index representing the degree of plasticity when the toner gives stress from a member such as a stirring member from normal temperature. A value of a certain value or more is more durable and storable. It is considered preferable from the viewpoint. Next, Tg _2nd indicates the degree to which the amorphous polyester resin and the dicarboxylic acid diester of the release agent are compatible when the toner receives heat at the time of fixing, and as a result, is an index of the degree of plasticization to the toner. I believe. Therefore, a value of Tg _2nd below a certain value indicates that the toner is effectively plasticized, and is considered preferable when considering low-temperature fixability.

  Next, a developing device and an image forming apparatus preferably used in the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view illustrating an example of a developing device. FIG. 2 is a schematic cross-sectional view showing an example of an image forming apparatus in which a developing device is incorporated.

  In FIG. 1 or FIG. 2, an electrostatic latent image carrier 45, which is an image carrier on which an electrostatic latent image is formed, is rotated in the direction of arrow R1. The toner carrier 47 rotates in the direction of the arrow R2 to convey the toner 57 to the development area where the toner carrier 47 and the electrostatic latent image carrier 45 are opposed to each other. Further, a toner supply member 48 is in contact with the toner carrier, and the toner 57 is supplied to the surface of the toner carrier by rotating in the direction of arrow R3.

  Around the electrostatic latent image carrier 45, a charging roller 46, a transfer roller 50, a fixing device 51, a pickup roller 52, and the like are provided. The electrostatic latent image carrier 45 is charged by the charging roller 46. Then, exposure is performed by irradiating the electrostatic latent image carrier 45 with laser light by the laser generator 54, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the electrostatic latent image carrier 45 is developed with toner in the developing device 49 to obtain a toner image. The toner image is transferred onto a transfer material (paper) 53 by a transfer roller 50. The transfer material (paper) 53 on which the toner image is placed is conveyed to the fixing device 51 and fixed on the transfer material (paper) 53.

  In the charging process in the developing device, the electrostatic latent image carrier and the charging roller form a contact portion and come into contact with each other, and a predetermined charging bias is applied to the charging roller to bring the surface of the electrostatic latent image carrier to a predetermined potential. It is preferable to use a contact charging device for charging.

  Next, a method for measuring other physical properties of the toner particles and toner of the present invention is as follows. Also in the examples described later, the physical property values are measured based on these methods.

  Next, it is preferable that the thickness of the toner layer on the toner carrier is regulated by the toner regulating member coming into contact with the toner carrier via the toner. By doing so, it is possible to obtain a high image quality without any defective regulation. As a toner regulating member that abuts on the toner carrier, a regulating blade is generally used and can be suitably used in the present invention.

  The developing step is preferably a step of applying a developing bias to the toner carrier and transferring the toner to the electrostatic latent image on the electrostatic latent image carrier to form a toner image. A voltage obtained by superimposing an alternating electric field on a DC voltage may be used.

  As the waveform of the alternating electric field, a sine wave, a rectangular wave, a triangular wave, or the like can be used as appropriate. Further, it may be a pulse wave formed by periodically turning on / off a DC power source. As described above, a bias whose voltage value periodically changes can be used as the waveform of the alternating electric field.

  In the present invention, when a method of conveying toner by magnetism without using a toner supply member is used, it is preferable to arrange a magnet inside the toner carrier (reference numeral 59 in FIG. 3). In this case, the toner carrier preferably has a fixed magnet having multiple poles inside, and preferably has 3 to 10 magnetic poles.

<Measurement Method of 25% Area Ratio, 50% Area Ratio, and Domain Area Ratio>
The toner is sufficiently dispersed in a visible light curable resin (Aronix LCR series D800), and then cured by irradiation with short wavelength light. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to produce a 250-nm flaky sample. Next, the cut out sample was enlarged at a magnification of 40000 to 50000 times using a transmission electron microscope (Electron Microscope JEM-2800 manufactured by JEOL Ltd.) (TEM-EDX), the cross section of the toner particles was observed, and EDX was used. Element mapping.

  The cross section of the toner to be observed is selected as follows. First, the cross-sectional area of the toner is obtained from the cross-sectional image of the toner, and the diameter (equivalent circle diameter) of a circle having an area equal to the cross-sectional area is obtained. Only a toner cross-sectional image in which the absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is within 1.0 μm is observed.

  The mapping conditions are a storage rate of 9000 to 13000 and an integration count of 120. Among the domains derived from the resin confirmed from the observed image, the spectrum intensity derived from the C element and the spectrum intensity derived from the O element are measured. It is a domain of amorphous polyester. After specifying the amorphous polyester domain, the toner cross-sectional image is binarized. Thereafter, the area of the amorphous polyester domain existing within 25% of the distance between the outline and the center point of the cross section from the outline of the cross section of the toner to the total area of the amorphous polyester domains existing in the toner cross section Calculate the ratio (area%). For the binarization process, Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) is used.

  The calculation method is as follows. In the TEM image, the contour and center point of the toner cross section are obtained. The outline of the toner cross section is assumed to be along the surface of the toner observed in the TEM image. The center point of the toner cross section is the center of gravity of the toner cross section.

  A line is drawn from the obtained center point to a point on the contour of the toner cross section. On the line, the position of 25% of the distance between the outline and the center point of the cross section is specified from the outline.

  Then, this operation is performed once for the contour of the toner cross section, and a boundary line of 25% of the distance between the contour and the center point of the cross section is clearly shown from the contour of the toner cross section.

  Based on the TEM image in which the 25% boundary line is clearly defined, the area of the amorphous polyester domain existing in the region surrounded by the outline of the toner cross section and the 25% boundary line is measured. . Then, the total area of the amorphous polyester domains present in the toner cross section is measured, and the area% based on the total area is calculated.

(50% area ratio)
Similarly to the measurement of the 25% area ratio described above, a boundary line of 50% of the distance between the contour and the center point of the cross section is clearly shown from the contour of the toner cross section. The area of the amorphous polyester domain existing in the region surrounded by the outline of the cross section of the toner and the boundary line of 50% is measured, and area% based on the total domain area is calculated.

(Area ratio of domain)
Further, the area of the domain existing within 25% of the distance between the contour and the center point of the cross section from the contour of the cross section, and 25% to the distance between the contour and the center point of the cross section from the cross section contour. The ratio to the area of the domain existing at 50% (area ratio of the domain) is obtained by the following formula using the calculated value obtained above.
Domain area ratio =
(25% area ratio (area%)) / [(50% area ratio (area%)) − (25% area ratio (area%))]
<Measuring method of number average diameter (D1) of domains of amorphous polyester>
Elemental mapping is performed using EDX in the same manner as described above to specify an amorphous polyester domain.

  The number average diameter of the domains is obtained by calculating the equivalent circle diameter from the area of the domains. The number of measurements is 100, and the arithmetic average value of the equivalent circle diameters of 100 domains is the number average diameter of the domains. The toner for calculating the number average diameter of the domains is determined as follows.

  First, the cross-sectional area of the toner is obtained from the cross-sectional image of the toner, and the diameter (equivalent circle diameter) of a circle having an area equal to the cross-sectional area is obtained. The domain diameter is calculated only for the toner cross-sectional image in which the absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is within 1.0 μm. Since the domain diameter may vary depending on the particle diameter of the toner, the average domain diameter can be calculated in this way.

<Method for Measuring Tg of Toner and Tg of Amorphous Polyester Resin>
The Tg (Tg _1st , Tg _2nd ) of the toner and the amorphous polyester resin Tg are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (manufactured by TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 3 mg of toner or about 2 mg of amorphous polyester is precisely weighed and placed in an aluminum pan. An empty aluminum pan is used as a reference, and a measurement temperature range of 20 to 180 ° C. The measurement is performed at a heating rate of 10 ° C./min. In the measurement, the temperature is once raised from 20 ° C. to 180 ° C., then the temperature is lowered from 180 ° C. to 10 ° C. at a temperature drop rate of 10 ° C./min, and then the temperature is raised again. For the toner, a specific heat change can be obtained in the temperature range of 30 ° C. to 90 ° C. in the first and second temperature raising processes. With respect to the amorphous polyester resin, a specific heat change is obtained in the temperature range of 30 ° C. to 90 ° C. in the second temperature raising process. At this time, the intersection of the intermediate point line of the baseline before and after the change in specific heat and the differential heat curve are defined as the glass transition temperature Tg of the toner and the glass transition temperature Tg of the amorphous polyester resin. As for the glass transition temperature of the toner, Tg obtained at the first temperature rise is Tg _1st (° C.), and Tg obtained at the second temperature rise is Tg _2nd (° C.).

<Method for measuring softening point of amorphous polyester resin>
The softening point of the amorphous polyester resin is measured using a constant-load extrusion type capillary rheometer “Flow Characteristic Evaluation Device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of descending piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.

  As a measurement sample, about 1.0 g of a sample is compression-molded at about 10 MPa for about 60 seconds using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising method temperature rising rate: 4.0 ° C./min
Starting temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Method for measuring acid value of amorphous polyester resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value of the amorphous polyester resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) Preparation of reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethanol (95% by volume), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution. 7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethanol (95% by volume) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 2.0 g of a crushed amorphous polyester resin sample is precisely weighed in a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added over 5 hours. Dissolve. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.

(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measuring method of hydroxyl value of amorphous polyester resin>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. Although the hydroxyl value of an amorphous polyester resin is measured according to JIS K 0070-1992, specifically, it measures according to the following procedures.

(1) Preparation of reagent 25 g of special grade acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.

  Dissolve 1.0 g of phenolphthalein in 90 ml of ethanol (95% by volume) and add ion-exchanged water to 100 ml to obtain a phenolphthalein solution.

  Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethanol (95% by volume) to make 1 liter. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.5 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.5 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.

(2) Operation (A) Main test 1.0 g of a crushed amorphous polyester resin sample is precisely weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylating reagent is accurately added to the sample using a whole pipette. . At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.

  A small funnel is placed on the mouth of the flask, and the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.

  After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 ml of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5 ml of ethanol.

  Add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.

(B) Blank test Titration similar to the above operation is performed except that a sample of an amorphous polyester resin is not used.

(3) Substituting the obtained results into the following formula to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mg KOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g), D: acid value (mgKOH / g) of amorphous polyester resin.

<Measuring method of melting point of release agent>
The melting point of the mold release agent is the peak temperature of the maximum endothermic peak in the DSC curve measured according to ASTM D3418-82 using a differential scanning calorimeter “Q2000” (TA Instruments). The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. Specifically, about 2 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised from 30 ° C. to 200 ° C., then the temperature is lowered from 200 ° C. to 30 ° C. at a rate of temperature drop of 10 ° C./min, and then the temperature is raised again. The maximum endothermic peak temperature of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the melting point.

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner is determined based on the precise particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) having a 100 μm aperture tube. Using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting and analyzing the measurement data, the measurement data is measured with 25,000 effective channels. Analysis was performed and calculated.

As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, dedicated software was set up as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
1. About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
2. About 30 ml of the electrolytic solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
3. Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and a predetermined amount of ions are contained in the water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. Add replacement water. About 2 ml of the aforementioned contamination N is added to this water tank.
4). 2. Is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
5. 4. above. In the state where the electrolytic aqueous solution in the beaker is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
6). The above 1. installed in the sample stand. The toner was dispersed in a round bottom beaker using a pipette. The aqueous electrolyte solution is dropped to adjust the measured concentration to about 5%. The measurement is performed until the number of measured particles reaches 50,000.
7). The fixed data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the analysis / volume statistics (arithmetic average) screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement method of weight average molecular weight of amorphous polyester resin and release agent>
The weight average molecular weight (Mw) of the amorphous polyester resin and the release agent is measured by gel permeation chromatography (GPC) as follows.

First, an amorphous polyester resin and a release agent are dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Equipment: High-speed GPC equipment “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: LF-604 double eluent: THF
Flow rate: 0.6 mL / min Oven temperature: 40 ° C
Sample injection amount: 0.020 mL
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way. In addition, all the parts in the following mixing | blending are a mass part.

<Example of production of amorphous polyester resin A1>
In a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, the kinds or amounts of carboxylic acid component and alcohol component shown in Table 1 were put. Thereafter, 1.5 parts of dibutyltin was added as a catalyst to 100 parts of the total amount of monomers. Next, the temperature was quickly raised to 180 ° C. under normal pressure in a nitrogen atmosphere, and then water was distilled off while heating from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour to perform polycondensation. After reaching 210 ° C., the pressure in the reaction vessel was reduced to 5 kPa or less, and polycondensation was performed under the conditions of 210 ° C. and 5 kPa or less to obtain amorphous polyester resin A1. At that time, the polymerization time was adjusted so that the resulting amorphous polyester resin A1 had a Tg (° C.) of around 60 ° C. and an acid value (mg KOH / g) of the values shown in the table. Table 2 shows the physical properties of the amorphous polyester resin A1.

<Production Example of Amorphous Polyester Resin A2 to A14>
Amorphous polyester resins A2 to A15 were obtained in the same manner as in the amorphous polyester tree A1, except that the types and amounts used of the carboxylic acid component and the alcohol component were changed as shown in Table 1. Table 2 shows the physical properties of the amorphous polyester resins A2 to A14.

<Example of production of amorphous polyester A15>
A four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 100 g of bisphenol A ethylene oxide 2 mol adduct, 189 g of bisphenol A propylene oxide 2 mol adduct, 51 g of terephthalic acid, 61 g of fumaric acid, adipine An acid 25 g and an esterification catalyst (tin octylate) 2 g were added, and a condensation polymerization reaction was performed at 230 ° C. for 8 hours. Furthermore, it was made to react at 8 kPa for 1 hour, and it cooled to 160 degreeC. Thereafter, a mixture of 6 g of acrylic acid, 70 g of styrene, 31 g of n-butyl acrylate and 20 g of a polymerization initiator (di-t-butyl peroxide) was added dropwise over 1 hour with a dropping funnel. After the dropping, the addition polymerization reaction was continued for 1 hour while maintaining the temperature at 160 ° C, and then the temperature was raised to 200 ° C and maintained at 10 kPa for 1 hour. Thereafter, unreacted acrylic acid, styrene, and n-butyl acrylate were removed to obtain amorphous polyester A15, which is a composite resin formed by bonding a vinyl polymer segment and a polyester polymer segment.

<Example of production of release agent 1>
A reactor equipped with a Dimroth, Dean-Stark water separator and a thermometer was charged with 300 mol parts of benzene, 200 mol parts of myristyl alcohol as an alcohol monomer, and 100 mol parts of terephthalic acid as an acid monomer. Further, 10 mol parts of p-toluenesulfonic acid was added, sufficiently stirred and dissolved, and then refluxed for 6 hours. Then, the valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the product was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized with benzene, washed and purified to obtain a release agent 1. Table 3 shows the physical properties of the release agent 1.

<Example of production of release agents 2-12>
Except having used the alcohol component and acid component which are shown in Table 3, it carried out similarly to the manufacture example of the mold release agent 1, and obtained the mold release agents 2-12. Table 3 shows the physical properties of release agents 2 to 12.

<Example of production of release agent 13>
A release agent 13 was obtained in the same manner as in the production example of the release agent 1 except that 100 mol parts of behenyl alcohol was used as the alcohol monomer and 100 mol parts of behenic acid was used as the acid monomer. Table 3 shows the physical properties of the release agent 13.

<Example of production of release agent 14>
A release agent 14 was obtained in the same manner as in the production example of the release agent 1 except that 100 mol parts of dipentaerythritol was used as the alcohol monomer and 600 mol parts of sebacic acid was used as the acid monomer. Table 3 shows the physical properties of the release agent 14.

<Production example of treated magnetic material>
During an aqueous ferrous sulfate solution, 1.0 to 1.1 equivalents of caustic soda solution with respect to an iron element, the amount of _P 2 _{O 5} to an iron element to be 0.15% by mass in terms of phosphorus, the iron element On the other hand, SiO ₂ in an amount of 0.50% by mass in terms of silicon element is mixed to prepare an aqueous solution containing ferrous hydroxide. The pH of the aqueous solution is set to 8.0, and an oxidation reaction is performed at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.

  Subsequently, ferrous sulfate aqueous solution is added to this slurry liquid so that it may become 0.9-1.2 equivalent with respect to the initial alkali amount (Na component of caustic soda), and then the slurry liquid is maintained at pH 7.6, and air is added. The slurry undergoes an oxidation reaction while blowing in to prepare a slurry liquid containing magnetic iron oxide. The slurry is filtered and washed, and this hydrous slurry liquid is once taken out. At this time, take a small amount of water sample and measure the water content. Next, this water-containing sample is put into another aqueous medium without being dried, stirred and redispersed with a pin mill while circulating the slurry, and the pH of the redispersed liquid is adjusted to about 4.8. Then, 1.6 parts of n-hexyltrimethoxysilane coupling agent was added to 100 parts of magnetic iron oxide with stirring (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing sample), and water was added. Decomposition was performed. Thereafter, the mixture was sufficiently stirred, and the dispersion was subjected to surface treatment at a pH of 8.6. The produced hydrophobic magnetic material is filtered with a filter press, washed with a large amount of water, dried at 100 ° C. for 15 minutes, and then at 90 ° C. for 30 minutes. A treated magnetic body of 0.21 μm was obtained.

<Production Example of Toner 1>
(Adjustment of the first aqueous medium)
3.1 parts of sodium phosphate dodecahydrate was added to 342.8 parts of ion-exchanged water and T.P. K. The mixture was heated to 60 ° C. with stirring using a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Thereafter, an aqueous calcium chloride solution in which 1.8 parts of calcium chloride dihydrate was added to 12.7 parts of ion-exchanged water and an aqueous sodium chloride solution in which 2.3 parts of sodium chloride were added to 14.5 parts of ion-exchanged water were added. Then, stirring was advanced to obtain a first aqueous medium containing a dispersion stabilizer.

(Adjustment of polymerizable monomer composition)
-Styrene 76.0 parts-N-butyl acrylate 24.0 parts-Amorphous polyester A1 18.0 parts-1-6 hexanediol diacrylate 0.5 parts-Aluminum salicylate compound (E-101: manufactured by Orient Chemical Co., Ltd.) 1.5 parts and treated magnetic material 1 65.0 parts The above materials were uniformly dispersed and mixed using an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.), then heated to 65 ° C, and then a release agent. 15.0 parts of 1 was added and mixed and dissolved to obtain a polymerizable monomer composition.

(Adjustment of the second aqueous medium)
To 164.7 parts of ion-exchanged water, 0.9 part of sodium phosphate 12 hydrate was added and heated to 60 ° C. with stirring using a paddle stirring blade. Thereafter, a calcium chloride aqueous solution in which 0.5 part of calcium chloride dihydrate was added to 3.8 parts of ion-exchanged water was added and the stirring was advanced to obtain a second aqueous medium containing the dispersion stabilizer B.

(Granulation)
A polymerizable monomer composition and 7.0 parts of t-butyl peroxypivalate as a polymerization initiator are charged into a first aqueous medium, and T. butyl is added at 60 ° C. in an N ₂ atmosphere. K. Granulation while stirring for 10 minutes at 15000 rpm with a homomixer, a suspension containing droplets of the polymerizable monomer composition was prepared.

(Polymerization / distillation / drying)
The suspension was put into the second aqueous medium and reacted at 74 ° C. for 4 hours while stirring with a paddle stirring blade. After completion of the reaction, the mixture was distilled at 98 ° C. for 3 hours, and then the suspension was cooled, washed with hydrochloric acid, filtered and dried to obtain toner particles having a weight average particle diameter of 7.9 μm.

(External additive mixing)
Mitsui Henschel obtained 100 parts of the toner particles obtained and 0.8 part of hydrophobized silica fine particles obtained by subjecting dry silica fine particles having a BET value of 300 m ² / g (number average particle diameter of primary particles 8 nm) to hexamethyldisilazane treatment. Toner 1 was obtained by mixing with a mixer (FM-10 model, manufactured by Mitsui Miike Chemical Co., Ltd.). Table 4 shows the release agent, amorphous polyester resin, colorant, and physical properties of Toner 1.

<Production Examples of Toners 2 to 20 and Comparative Toners 1 to 7>
In the production example of the toner 1, toners 2 to 20 and comparative toners 1 to 7 were produced in the same manner except that the types of the amorphous polyester and the release agent were changed. Table 4 shows release agents, amorphous polyester resins, and physical properties of the toners 2 to 20 and the comparative toners 1 to 7.

<Production Example of Toner 21>
In the toner 1 production example, toner 21 was produced in the same manner as in the toner 1 production example, except that the processed magnetic material 65.0 parts was changed to 8.0 parts carbon black as the colorant. Table 4 shows the release agent, amorphous polyester resin, colorant, and physical properties of the toner 21.

<Production Example of Comparative Toner 8>
Comparative toner 8 was obtained in the same manner as in toner 1 except that paraffin wax (HNP-51, manufactured by Nippon Seiwa Co., Ltd., melting point 77 ° C.) was used as a release agent. Table 4 shows the release agent, amorphous polyester resin, colorant, and physical properties of Comparative Toner 8.

<Production example of comparative toner 9>
In the toner 1 production example, the toner 1 was produced except that 65.0 parts of the treated magnetic material was changed to 8.0 parts of carbon black as a colorant and paraffin wax (HNP-51) was used as a release agent. Production was carried out in the same manner as in Example, and Comparative Toner 9 was obtained. Table 4 shows the release agent, amorphous polyester resin, colorant, and physical properties of Comparative Toner 9.

<Production Example of Comparative Toner 10>
<< Preparation of each dispersion liquid >>
(Resin particle dispersion (1))
-Styrene: 325 parts-n-butyl acrylate: 100 parts-Acrylic acid (manufactured by Rhodia Nikka Co., Ltd.): 13 parts-1,10-decanediol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.): 1.5 parts-Dodecanethiol ( Wako Pure Chemical Industries, Ltd.): 3.0 parts

  The above components are mixed in advance and dissolved to prepare a solution. A surfactant solution prepared by dissolving 9 parts of an anionic surfactant (Dowfax A211 manufactured by Dow Chemical Co., Ltd.) in 580 parts of ion-exchanged water is added to a flask. Accommodated. Next, 400 parts of the above-mentioned premixed solution was added, dispersed and emulsified, and slowly stirred and mixed for 10 minutes, and then 50 parts of ion-exchanged water in which 6 parts of ammonium persulfate was dissolved was added. Next, after sufficiently replacing the inside of the flask with nitrogen, the flask was heated with an oil bath while stirring the flask until it reached 75 ° C., and emulsion polymerization was continued for 5 hours to obtain a resin particle dispersion (1). It was.

  When the resin particles were separated from the resin particle dispersion (1) and examined for physical properties, the number average particle diameter was 195 nm, the solid content in the dispersion was 42%, the glass transition point was 51.5 ° C., and the weight average molecular weight Mw. Was 32,000.

(Resin particle dispersion (2))
The amorphous polyester A15 was dispersed using a disperser in which Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) was modified to a high temperature and high pressure type. Specifically, with a composition ratio of 79% by mass of ion-exchanged water, 1% by mass (as an active ingredient) of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK), and 20% by mass of amorphous polyester A15. The pH is adjusted to 8.5 with ammonia, the rotor is rotated at 60 Hz, the pressure is 5 kg / cm ² , and the heat is heated by a heat exchanger at 140 ° C., and the number average particle diameter is 290 nm. A resin fine particle dispersion (2) was obtained.

(Colorant dispersion)
・ Carbon black 20 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts ・ Ion-exchanged water 78 parts The above components were used at 3000 rpm using a homogenizer (IKA, Ultra Turrax T50). The pigment was blended in water for 2 minutes, further dispersed at 5000 rpm for 10 minutes, and then stirred for a whole day and night with a normal stirrer to degas. Thereafter, using a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006), dispersion was performed at a pressure of 240 MPa for about 1 hour to obtain a colorant dispersion (1). Further, the pH of the dispersion was adjusted to 6.5.

(Release agent dispersion)
・ 45 parts of hydrocarbon wax (Fischer-Tropsch wax, maximum endothermic peak; 78 ° C., Mw; 750)
・ Cationic surfactant (Neogen RK, Daiichi Kogyo Seiyaku) 5 parts ・ Ion-exchanged water 200 parts The above components were heated to 95 ° C. and sufficiently dispersed with a homogenizer (manufactured by IKA, Ultra Tarax T50). Dispersion treatment was performed with a pressure-discharge type gorin homogenizer to obtain a release agent dispersion having a number average diameter of 190 nm and a solid content of 25%.

(Example of toner particle production)
・ Ion-exchanged water 400 parts ・ Resin particle dispersion (1) 620 parts (resin particle concentration: 42%)
Resin particle dispersion (2) 279 parts (resin particle concentration: 20%)
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount: 60%)
1.5 parts (0.9 parts as an active ingredient)
The above components were put into a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. Thereafter, 88 parts of the colorant dispersion and 60 parts of the release agent dispersion were added and held for 5 minutes. As it was, a 1.0% nitric acid aqueous solution was added to adjust the pH to 3.0. Next, the stirrer and the mantle heater were removed, and a mixed solution of 0.33 part of polyaluminum chloride and 37.5 parts of 0.1% nitric acid aqueous solution was dispersed while being dispersed at 3000 rpm with a homogenizer (Ultra Tarax T50). 1/2 of this was added. Thereafter, the dispersion rotational speed was set to 5000 rpm, the remaining ½ was added over 1 minute, and the dispersion rotational speed was set to 6500 rpm to disperse for 6 minutes.

  A reactor is equipped with a stirrer and a mantle heater, and the temperature is increased to 42 ° C. at 0.5 ° C./min while appropriately adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. Hold for 15 minutes. Thereafter, the particle size was measured with a Coulter Multisizer every 10 minutes while raising the temperature at 0.05 ° C./min. When the weight average particle size reached 7.8 μm, a 5% sodium hydroxide aqueous solution was added. Used to bring the pH to 9.0. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles were almost spherical in the second hour. Solidified.

  Thereafter, the reaction product is filtered and washed with ion-exchanged water, and when the filtrate has a conductivity of 50 mS or less, cake-like particles are taken out and ion-exchanged water having an amount 10 times the mass of the particles is taken out. The mixture was added and stirred with a three-one motor. When the particles were sufficiently loosened, the pH was adjusted to 3.8 with a 1.0% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were pulverized by a sample mill and dried in an oven at 40 ° C. for 24 hours. Further, the obtained powder was pulverized with a sample mill and then further vacuum-dried in an oven at 40 ° C. for 5 hours to obtain comparative toner particles 10. In the same manner as in the production example of the toner 1, 0.8 parts of hydrophobized silica fine particles were added to the obtained comparative toner particles 10 to obtain a comparative toner 10.

表中の用語は、次に記載のことを意味する。ＮＤ：検知されず、ＣＢ：カーボンブラック

The terms in the table mean the following: ND: not detected, CB: carbon black

<Example of production of toner carrier 1>
(Synthesis of isocyanate group-terminated prepolymer)
Polypropylene glycol polyol (trade name: Exenol 4030; manufactured by Asahi Glass Co., Ltd.) 100 with respect to 17.7 parts of tolylene diisocyanate (TDI) (trade name: Cosmonate T80; manufactured by Mitsui Chemicals) in a reaction vessel under a nitrogen atmosphere 0.0 g was gradually added dropwise while maintaining the temperature in the reaction vessel at 65 ° C. After completion of the dropping, the reaction was carried out at a temperature of 65 ° C. for 2 hours. The resulting reaction mixture was cooled to room temperature to obtain an isocyanate group-terminated prepolymer having an isocyanate group content of 3.8% by mass.

(Synthesis of amino compounds)
While stirring, 100.0 g (1.67 mol) of ethylenediamine and 100 parts of pure water were heated to 40 ° C. while stirring in a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a temperature controller. Next, while maintaining the reaction temperature at 40 ° C. or lower, 425.3 g (7.35 mol) of propylene oxide was gradually added dropwise over 30 minutes. The reaction was further stirred for 1 hour to obtain a reaction mixture. The resulting reaction mixture was heated under reduced pressure to distill off water, thereby obtaining 426 g of an amino compound.

(Preparation of substrate)
As a substrate, a primer (trade name, DY35-051; manufactured by Toray Dow Corning) was applied and baked on a ground aluminum cylindrical tube having an outer diameter of 10 mm (diameter) and an arithmetic average roughness Ra of 0.2 μm.

(Production of elastic roller)
The substrate prepared above was placed in a mold, and an addition type silicone rubber composition in which the following materials were mixed was injected into a cavity formed in the mold.
-100 parts of liquid silicone rubber material (trade name, SE6724A / B; manufactured by Toray Dow Corning)-15 parts of carbon black (trade name, Toka Black # 4300; manufactured by Tokai Carbon Co.)-Silica powder as a heat resistance imparting agent Body 0.2 part, platinum catalyst 0.1 part.

  Subsequently, the mold was heated to cure and cure the silicone rubber at a temperature of 150 ° C. for 15 minutes. The substrate on which the cured silicone rubber layer was formed on the peripheral surface was removed from the mold, and then the substrate was further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. Thus, an elastic roller having a silicone rubber elastic layer having a film thickness of 0.5 mm and a diameter of 11 mm formed on the outer periphery of the substrate was produced.

(Preparation of surface layer)
As the material of the surface layer, 36.1 parts of the amino compound, 117.4 parts of carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation), and urethane resin fine particles (617.9 parts of the isocyanate group-terminated prepolymer) 130.4 parts of a product name, Art Pearl C-400 (manufactured by Negami Kogyo Co., Ltd.) was mixed with stirring. Next, MEK (methyl ethyl ketone) was added so that the total solid content ratio was 30% by mass to prepare a coating material for forming a surface layer.

  Next, the rubber-free part of the previously produced elastic roller was masked and stood vertically, and rotated at 1500 rpm, and the paint was applied while lowering the spray gun at 30 mm / s. Subsequently, the coating layer was cured and dried by heating at a temperature of 180 ° C. for 20 minutes in a hot air drying oven, thereby obtaining a toner carrier 1 having a surface layer having a film thickness of about 8 μm on the outer periphery of the elastic layer.

<Example 1>
A Canon printer LBP7700C was modified and used for image output evaluation. As a remodeling point, the toner carrier 1 is changed, and the toner supply member of the developing device is rotated reversely to the toner carrier as shown in FIG. 1, and the voltage application to the toner supply member is turned off. . The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the electrostatic latent image carrier was 1.1 mm, and 120 g of toner was charged. Furthermore, the toner carrier was modified so that the voltage applied to the toner carrier could be 200 V higher than the product conditions. (For example, when the voltage applied to the toner carrier of the product is -600V, the condition that is 200V higher than the product condition is -400V.)
Further, as shown in FIG. 2, the cleaning blade was removed, and the process speed was modified to 35 ppm. By doing so, the area of the contact portion between the toner carrier and the electrostatic latent image carrier was reduced, and further, the process speed was increased to adjust to strict image forming conditions. Regarding image evaluation, the following images were drawn out and judged using each condition and index. The evaluation results are shown in Table 5.

<Low-temperature fixing evaluation (white spot evaluation)>
Fixing evaluation was performed in a normal temperature and high humidity environment (temperature: 27.0 ° C., relative humidity: 70%). This is an environment that assumes that the fixing film has been deprived of heat by moisture on the paper, and is a severe environment for evaluation of white spots. In this fixing evaluation, the fixing device is temporarily removed from the image forming apparatus and remodeled so that an unfixed image can be output. Evaluation paper of Business 4200 (Beck smoothness 56, basis weight 105 g / m ² , hereinafter referred to as plain paper) and NEENH CLASSIC LAID TEXT (Beck smoothness 5, basis weight 105 g / m ² , hereinafter referred to as rough paper) Was used to evaluate the fixing. The Beck smoothness indicating the roughness of the paper surface is smaller in the NEENAH CLASSIC LAID TEXT than in the Business 4200, and the presence of more concave portions in the paper makes it possible to make a more rigorous evaluation with respect to white spots in fixing. Note that the Beck smoothness of the paper is measured in accordance with JIS-P-8119.

As the fixing evaluation image, a solid image was used which was adjusted so that the left and right margins were 80 mm and the top and bottom margins were 10 mm. At this time, the applied voltage of the solid image was adjusted so that the applied amount of toner was 0.8 mg / cm ² . While changing the temperature range from 150 ° C. to 200 ° C. every 5 ° C., the presence or absence of white spots at each temperature was visually confirmed. The lowest temperature at which white spots did not occur was defined as the lower limit of fixing temperature, and ranking was performed as shown below.
A: Fixing temperature lower limit is less than 175 ° C. B: Fixing temperature lower limit is from 175 ° C. to less than 180 ° C. C: Fixing temperature lower limit is from 180 ° C. to less than 185 ° C. D: Fixing temperature lower limit is from 185 ° C. to less than 190 ° C.

<Fog immediately after a solid black image after repeated use in a high temperature and high humidity environment>
A repeated use test was conducted in a high temperature and high humidity environment (temperature: 32.5 ° C., relative humidity: 80%). The above-mentioned plain paper was used as the evaluation paper. One thousand sheets of images with a printing ratio of 1% were passed intermittently. Thereafter, an image is output in which the front 50 area% of the image is a solid black image and the rear end 50 area% is a solid white image, and the fog density (%) of the solid white image portion immediately after the solid black image is not passed. The difference was calculated. For fog measurement, TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.) was used, and the average value of 5 points was used as the fog density (%), and ranking was performed as shown below.
A: Fog less than 1.5% B: Fog 1.5% to less than 2.0% C: Fog 2.0% to less than 2.5% D: Fog 2.5% or more

<Examples 2 to 21 and Comparative Examples 1 to 10>
Evaluation was performed in the same manner as in Example 1 except that each toner was changed as shown in Table 5. The evaluation results are shown in Table 5.

45 electrostatic latent image carrier 47 toner carrier 57 toner 48 toner supply member 46 charging roller 50 transfer roller 51 fixing unit 52 pickup roller 54 laser generator 49 developing unit 53 transfer material

Claims (8)

A toner having toner particles containing a vinyl resin, an amorphous polyester resin, a colorant, and a release agent,
The amorphous polyester resin has a unit derived from an alcohol component, and a unit derived from a linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms,
The unit derived from the linear aliphatic dicarboxylic acid having 6 to 12 carbon atoms is contained in an amount of 10 mol% to 50 mol% with respect to the units derived from all carboxylic acid components in the amorphous polyester resin.
In the toner cross section observed with a transmission electron microscope,
The vinyl resin constitutes a matrix, the amorphous polyester resin constitutes a domain,
The toner, wherein the releasing agent is an ester of a dicarboxylic acid and an aliphatic monoalcohol. When the carbon number of the aliphatic monoalcohol of the release agent is C _A and the carbon number of the dicarboxylic acid is C _B ,
C _A is 14 or more and 22 or less, C _B is 4 or more and 10 or less,
The toner according to claim 1, wherein C _A / C _B is 1.7 or more and 4.5 or less.   The domain is present in an area within 25% of the distance between the outline and the center point of the cross section from the outline of the cross section to 40 area% or more and 70 area% or less with respect to the total area of the domain. Or the toner according to 2.   The domain is present in an area within 50% of the distance between the outline and the center point of the cross section from the outline of the cross section to 80 area% or more and 100 area% or less with respect to the total area of the domain. 4. The toner according to any one of items 1 to 3.   The area of the domain existing in an area within 25% of the distance between the contour and the center point of the cross section from the contour of the cross section is the distance between the contour and the center point of the cross section. The toner according to claim 1, wherein the toner is 1.05 times or more the area of the domain existing in a region of 25% to 50%.   6. The toner according to claim 1, wherein the number average diameter of domains of the amorphous polyester resin is 0.3 μm or more and 3.0 μm or less.   The toner according to any one of claims 1 to 6, wherein the acid value of the amorphous polyester resin is 1.0 mgKOH / g or more and 10.0 mgKOH / g or less. Toner for developing the electrostatic latent image formed on the image carrier;
A toner carrying body that carries the toner and conveys the toner to the image carrier,
The developing device according to claim 1, wherein the toner is the toner according to claim 1.

Images