JP6918614B2 - Toner and its manufacturing method - Google Patents

Description

The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet recording method, or the like.

In recent years, copiers and printers using electrophotographic methods have come to be used in various countries and regions due to market expansion, and high-definition and high-quality images are stable even in a wide variety of environments and media. The printer obtained by the above is desired. In addition, various needs are required as the market scale expands, and for example, energy saving and miniaturization are considered as major technical issues.
In order to obtain a high-definition and high-quality image, in addition to increasing the resolution of the image, excellent dot reproducibility is desired as a toner, so a toner having a uniform charge is required.
Further, regarding the media, for example, when paper having low smoothness is used, pressure and heat are less likely to be applied to the recesses of the paper in the fixing step, and the toner deformation tends to be insufficient. Therefore, in order to improve the dot reproducibility, it is also necessary for the toner to be instantly melted and deformed by heat.
As for the miniaturization, it is mainly effective to miniaturize the fuser and the cartridge as the means.
In order to reduce the size of the fuser, film fixing makes it easy to simplify the heat source and the device configuration, and it is easy to apply. Such film fixing requires a toner that can be fixed with a small amount of heat and light pressure.
Further, since it is effective to reduce the size of the cartridge containing the developer, the one-component developing method is preferable to the two-component developing method using a carrier, and at the same time, the contact developing method is used to obtain a high-quality image. preferable. Therefore, in order to satisfy the above performance, the contact one-component developing method is an effective means.
In order to reduce the size of the contact one-component developing process cartridge, it is conceivable to reduce the diameter of the toner carrier or to eliminate the supply roller that supplies toner to the sleeve toner carrier. Here, when the supply roller is made less, the transportability of the toner to the sleeve toner carrier deteriorates, it becomes difficult to uniformly transport the toner to the regulation portion, and it becomes a strict condition for uniform charge application.
From the above, in order to obtain high-definition images for a wide variety of media while downsizing the printer, the toner has excellent charging characteristics in various environments and has excellent low-temperature fixability. Is desired.
As a method for imparting excellent charging characteristics to toner, Patent Document 1 proposes a method for producing toner matrix particles having a high circularity in order to make the charge amount distribution uniform in addition to a sharp particle size distribution. ..
This method includes a step of forming droplets of the polymerizable monomer composition and a step of polymerizing the polymerizable monomer composition to obtain toner mother particles, and a dispersion stabilizer is used in both steps. Use an aqueous medium containing. By using an aqueous medium containing a dispersion stabilizer also in the polymerization step, toner mother particles having a high circularity are obtained.
Further, as a method for improving low-temperature fixability, in Patent Document 2, a binder resin and a colorant containing an amorphous resin and an amorphous polyester resin (B) different from the amorphous resin (A). It has a domain-matrix structure in which the amorphous polyester resin (B) is dispersed as a domain phase in the matrix phase composed of the toner matrix particles containing However, in the observation image of the cross section of the toner mother particle, the number average domain diameter of the amorphous polyester resin (B) having a domain diameter of 100 nm or more is 100 to 200 nm, and the domain with respect to the total area of the domain phase. A toner for developing an electrostatic charge image, characterized in that the area ratio of the domain phase having a diameter of 500 nm or more is 0 to 10%, has been proposed.

Japanese Patent No. 3972709 JP-A-2015-152703

In the toner described in Patent Document 1, when an aqueous medium containing a dispersion stabilizer is used in the polymerization step, toner mother particles having a high circularity are certainly obtained, irregularly shaped particles are reduced, and the chargeability of the toner mother particles becomes high. It may be uniform and improved. However, in the above-mentioned film fixing, when fine wires are output using the toner on rough paper, for example, with low smoothness, the adhesive force between the toners at the time of heat welding tends to decrease in the fine wires with a small amount of toner. .. In addition, the toner existing in the recesses of the paper is less likely to receive sufficient pressure and heat. Therefore, it is easy to peel off from the paper and the reproducibility of fine lines is likely to deteriorate, and there is room for improvement.
In the toner described in Patent Document 2, since the polyester is exposed on the surface of the toner, it is difficult to uniformly charge the toner, it is difficult to obtain dot reproducibility, and there is room for improvement.
In addition, in the contact development method in which the supply roller is omitted, there is room for improvement in durability and charge stability due to environmental changes.
Further, since the polyester forms a small domain and is dispersed in the styrene acrylic resin, it is presumed that the compatibility is high when sufficient heat is applied and the polyester is easily deformed by heating. However, in a fixing machine such as the film fixing machine having a small amount of heat and a light pressure, the melt deformation of the toner in the recesses tends to be insufficient, and the adhesiveness between the paper and the toner tends to be insufficient. Therefore, the peeling of the molten toner tends to be more remarkable when a high-print image is output.
The present invention provides a toner that solves the above problems. More specifically, a toner having excellent fine line reproducibility and low temperature fixability in various environments is provided.

As a result of diligent studies, the present inventors, in addition to controlling the shape of the outermost surface of the toner matrix particles, adjust the existence state of the amorphous polyester (domain) in the vinyl resin (matrix) near the surface layer. The present invention was completed by finding a means for solving the above problems.
That is, the present invention is a toner having toner matrix particles containing a binder resin, a colorant, and an amorphous polyester.
In the toner cross section observed with a transmission electron microscope (TEM) of the toner, a matrix-domain structure is observed, the vinyl resin forms a matrix, and the amorphous polyester forms a plurality of domains.
The domain is present within 25% of the distance between the contour of the toner cross section and the center point of the toner cross section by 30 area% or more with respect to the total area of the domain of the amorphous polyester. The softening point (Tm) of the amorphous polyester is 85 ° C. or higher and 105 ° C. or lower.
^{The theoretical specific surface area A (m 2} / g) obtained from the particle size distribution and true density based on the number of toner mother particles and the specific surface area B (m ² / g) measured by the BET method are the following equations (1). , (2).
0.450 ≤ B ≤ 1.500 ... (1)
1.00 ≤ B / A ≤ 1.26 ... (2)
Further, the present invention is a method for producing a toner having the above configuration.
A polymerizable monomer composition containing a polymerizable monomer, a colorant, an amorphous polyester, and a vinyl polymer having an acid value of 5.0 mgKOH / g or more and 20.0 mgKOH / g or less is dispersed in an aqueous medium. , The step of forming the particles of the polymerizable monomer composition, and
Polymerization step of polymerizing the polymerizable monomer contained in the particles,
The present invention relates to a method for producing a toner having.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner capable of obtaining excellent fine line reproducibility and low temperature fixability even for a medium having low smoothness.

It is a figure which shows an example of a developing apparatus. This is an example of an image forming apparatus incorporating a developing apparatus. It is a schematic diagram of a flow curve.

As described above, the toner of the present invention is a toner having toner matrix particles containing a vinyl resin, an amorphous polyester, and a colorant, and a matrix-domain structure is observed in the toner cross section, and the amorphous polyester is observed. Is a toner in which the theoretical specific surface area A and the actual specific surface area B of the toner mother particles are adjusted to a specific range in addition to the fact that the domain is formed in the vicinity of the toner surface. It is characterized by.

The present inventors consider the reason why the present invention has solved the above problems as follows.

First, in order to solve the problem of the present invention, it is important that the vinyl resin has an amorphous polyester and that the vinyl resin has a plurality of domains.

The vinyl resin is, for example, a resin in which the rigidity of the toner can be easily controlled and the mechanical stress resistance of the toner can be easily improved. Further, since the amorphous polyester easily introduces a portion to be melted in a specific temperature range, it tends to be easy to improve the melting characteristics of the toner by changing the monomer composition or the like.

That is, the matrix-domain structure described above makes it possible for the toner to have both stress resistance and fixability characteristics.

In addition, when outputting an image in which toner such as fine lines does not exist densely on a medium with low smoothness, excellent charge uniformity, heat and pressure so that the toner can be properly transferred to the medium regardless of the unevenness of the paper. Excellent melt adhesion between toners is essential even in recesses where it is difficult to apply.

Therefore, in the present invention, in the melt adhesiveness, the thermal meltability is promoted by allowing the above-mentioned amorphous polyester domain to exist in the vicinity of the surface, and the unevenness of the toner itself is controlled to charge the toner. The above problem was solved by making the distribution uniform.

Considering the formation of toner mother particles in an aqueous medium, for example, the formation of toner mother particles by a suspension polymerization method, the polymerizable monomer composition repeats coalescence, shearing, and coalescence in the granulation step. In these two phenomena, when shearing is more likely to occur than coalescence, the amorphous polyester has a domain shape and exists near the surface of the toner droplet, which makes the droplet more likely to become unstable. , The formation of fine particles and the droplets themselves tend to be unstable. As a result, ultrafine irregularities are formed on the surface of the toner particle size.

In the present invention, it is necessary to uniformly cover the surface of the toner matrix particles with a polar resin having a high affinity for vinyl resin to suppress fine irregularities. Further, by controlling the interfacial tension of the polar resin and the amorphous polyester with respect to the aqueous phase, it is possible to easily suppress the variation between the toners of the amorphous polyester or inside the toner at the time of granulation. Therefore, the balance between shearing and coalescence of oil droplets formed by the polymerizable monomer composition in the granulation step can be controlled to some extent, and it becomes easy to suppress the generation of fine particles and the instability of toner. , I think that the unevenness of the surface could be suppressed.

From the viewpoint of enhancing the adhesiveness when melting between toners, the amorphous polyester domain is located within 25% of the distance between the contour and the center point of the cross section from the contour of the cross section, based on the total area of the domain. It is necessary that the area% or more and 70 area% or less exist.

The area ratio of the amorphous polyester domain (hereinafter, also referred to as "25% area ratio") existing within 25% of the distance between the contour and the center point of the cross section from the contour of the toner cross section is the melting of the toner at the time of melting. It is a parameter that has a high correlation with deformation, and if it is high, the adhesive force between toners or between toner and paper at the time of melting increases.

When the 25% area ratio is 30 area% or more, the adhesive force between the toners in the recesses at the time of melting and between the toner and the paper tends to increase, and the reproducibility of fine lines is improved. Further, when the area is 70 area% or less, the proportion of the amorphous polyester in the surface layer can be controlled within a desired range, so that the brittleness and chargeability of the toner can be easily maintained, and the toner tends to be particularly remarkable in a high humidity environment. .. From the viewpoint of further improving the above effect, the 25% area ratio is preferably 45 area% or more and 70 area%.

Next, as the amorphous polyester, it is important that the softening point of the amorphous polyester is 85 ° C. or higher and 105 ° C. or lower because the toner is easily deformed by heating. When the softening point of the amorphous polyester is 85 ° C. or higher, the brittleness of the toner is easily maintained, cracking and chipping of the toner is less likely to occur, and stable fine line reproducibility can be obtained for long-term image printing. It tends to be easy. Further, when the softening point is 105 ° C. or lower, it is easy to be melted and deformed by heat, so that the adhesive force between toners in the recesses is likely to be improved, and the reproducibility of fine lines on paper having low smoothness tends to be easily obtained. be.

As a means for controlling the softening point of the amorphous polyester within a preferable range of the present invention, there are a monomer unit derived from a linear aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms and a monomer unit derived from a dialcohol. It is preferable to use 10 mol% or more and 50 mol% or less of the content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms with respect to all the monomer units derived from the carboxylic acid of the amorphous polyester.

^{Further, the toner of the present invention has a theoretical specific surface area A (m 2} / g) obtained from the particle size distribution and true density based on the number of toner matrix particles, and a specific surface area B (m ² / g) measured by the BET method. Is essential to satisfy the following equations (1) and (2).
0.450 ≤ B ≤ 1.500 ... (1)
1.00 ≤ B / A ≤ 1.26 ... (2)

Since this B / A (hereinafter referred to as the surface unevenness index) is a value calculated from the BET specific surface area measured by the BET multipoint method, it is a numerical value of a nanometer-order ultrafine unevenness shape. be. The theoretical specific surface area A is a numerical value when all the particles are true spheres. Therefore, the more the surface unevenness index deviates from 1.00, the more unevenness is formed on the particle surface. As a result of studies by the present inventors, it is possible to impart uniform chargeability to the toner matrix particles by suppressing the generation of these ultrafine irregularities from the surface of the toner matrix particles, so that even in a medium having low smoothness. Since it tends to be easy to transfer with high accuracy, it tends to be easy to obtain high reproducibility of fine particles.

When B is 0.450 or more, the particle size can be controlled within a certain range without increasing the particle size, and the surface unevenness index tends to be easily controlled within the above range. Further, since it is easy to maintain the charge, the above-mentioned fine line reproducibility tends to be easily obtained. Further, when B is 1.500 or less, the particle size can be maintained without making the particle size small, so that the charge distribution can be easily sharpened and the toner can be transferred uniformly to the paper, so that fine line reproducibility can be obtained. It tends to be easy to get rid of.

Further, as an ideal state for the surface unevenness index, a state close to 1.00, which has a minimum of extremely fine unevenness, is most preferable.

The surface unevenness index required for the present invention is 1.26 or less. When it is 1.26 or less, fine irregularities can be suppressed, so that the chargeability tends to be uniform, dots tend to be easily reproducible for media having low smoothness, and fine line reproducibility can be obtained. It tends to be easy. When the surface unevenness index is preferably 1.00 or more and 1.19 or less, stable uniform chargeability tends to be easily obtained even in a high humidity environment.

In order to keep the surface unevenness index in the above range, it is preferable to have a material having a high affinity with the vinyl resin forming the matrix near the surface, and the polar resin is a vinyl resin in consideration of the chargeability of the toner matrix particles. It is preferably present on the surface of.

In addition, the surface unevenness index is controlled by controlling the interfacial tension of the polar resin and the amorphous polyester in the tricalcium phosphate aqueous solution, and controlling the distillation step in the suspension polymerization method, such as the heating step of the toner matrix particles. It is preferable to control.

Further, the specific surface area B measured by the BET method is preferably adjusted by controlling the toner mother particle size and the degree of fine unevenness of the particles.

Hereinafter, preferred embodiments of the toner of the present invention will be described.

As described above, the toner of the present invention contains a vinyl resin and an amorphous polyester.

Examples of the vinyl resin include the following.

Monopolymers of styrene such as polystyrene and polyvinyltoluene and their substitutes;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalin copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, dimethylaminoethyl styrene-acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methacryl Dimethylaminoethyl acid acid copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Styrene-based copolymers such as maleic acid copolymer and styrene-maleic acid ester copolymer;

Polymethylmethacrylate, polybutylmethacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, and polyacrylic acid resin can be used, and these can be used alone or in combination of two or more. Among these, a styrene-based copolymer and further a styrene-butyl acrylate copolymer are particularly preferable from the viewpoint of easy control of development characteristics and fixability.

The amorphous polyester that can be used for the toner of the present invention can be a condensate of an arbitrary dicarboxylic acid and a dialcohol, but from the viewpoint of achieving both low-temperature fixability and charge stability in various environments, the amorphous polyester in the toner is amorphous. It is preferable to control the presence state of the sex polyester in an arbitrary range.

Specifically, as described above, in the toner cross section observed with a transmission electron microscope (TEM), a matrix-domain structure is observed, the vinyl resin forms a matrix, and the amorphous polyester forms a plurality of domains. It is preferable that the 25% area ratio is 30 area% or more and 70 area% or less.

Next, the domain of the amorphous polyester is 80 area% or more and 100 area% or less based on the total area of the domain within 50% of the distance between the contour and the center point of the cross section from the contour of the cross section. It is preferable that it exists. More preferably, it is 90 area% or more and 100 area% or less.

When the area ratio of the amorphous polyester domain (hereinafter, also referred to as "50% area ratio") existing within 50% of the distance between the contour and the center point of the cross section from the contour of the toner cross section is 80 area% or more. If there is, it can be melted instantly at the time of fixing, so that the low-temperature fixing property and the fine line reproducibility in the concave portion tend to be improved. Further, the presence of 80 area% or more of domains can be rephrased as the abundance of domains in the region from the center point of the toner to 50% of the contour of the toner cross section is 20 area% or less. In such a state, brittleness can be easily maintained during long-term use, and good fine line reproducibility can be easily obtained even after long-term use. The domain formed by the amorphous polyester component preferably has a domain diameter of 0.3 μm or more and 3.0 μm or less, and more preferably 0.3 μm or more and 2.0 μm or less.

When the average diameter of the number of domains of the amorphous polyester is 0.3 μm or more, the adhesive force between the paper and the toner is improved when the amorphous polyester is melted at the time of fixing, and the fine line reproducibility can be further improved.

On the other hand, when the number average diameter of the domains of the amorphous polyester is 3.0 μm or less, it becomes easy to control the existence state of the domains of the amorphous polyester in the toner mother particles. In addition, the variation in the domain of the amorphous polyester among the toner mother particles can be reduced. Therefore, it becomes easier to improve the fine line reproducibility.

As a method for forming an amorphous polyester domain near the toner surface and controlling the number average diameter of the amorphous polyester domains, adjustment of the acid value of the amorphous polyester and the molecular chain end of the amorphous polyester Examples include the addition of an oil-based moiety, the adjustment of the softening points of the amorphous polyester and the toner, and the adjustment of the production conditions of the toner matrix particles.

The content of the amorphous polyester is preferably 5.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin. When it is 5.0 parts by mass or more, it is easy to control the domain state in the vinyl resin, and if it can be distributed near the surface layer, it is easy to exert the melting effect near the surface layer at the time of melting, and the low temperature fixability is improved. It becomes a tendency. Further, when it is 30.0 parts by mass or less, brittleness is likely to be improved.

Further, the amorphous polyester has an interfacial tension C (mN / m) in a pH 6.0 tricalcium phosphate aqueous solution of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio). Interfacial tension D (mN / m) measured by changing amorphous polyester to polar resin is 13 ≤ CD ≤ 25 ... (4)
Is preferable from the viewpoint of controlling the extremely fine uneven shape on the surface of the toner matrix particles.

As described above, considering the formation of toner matrix particles in an aqueous medium, for example, by a suspension polymerization method, the polymerizable monomer composition repeats coalescence, shearing, and coalescence in the granulation step. .. In these two phenomena, when shearing is more likely to occur than coalescence, the amorphous polyester has a domain shape and exists near the surface of the toner droplet, which makes the droplet more likely to become unstable. , The formation of fine particles and the droplets themselves tend to be unstable. As a result, particles having a rough surface of the toner particle size are formed. Although the reason is not clear, the interfacial tension C and the non-crystalline polyester in a pH 6.0 aqueous solution of tricalcium phosphate of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio) of the amorphous polyester. When the difference in the interfacial tension D measured by changing the crystalline polyester to the polar resin is 13 mN / m or more and 25 mN / m or less, the surface of the toner matrix particles is uniformly covered with the polar resin, and between the toners of the amorphous polyester. Alternatively, it is possible to suppress the variation inside the toner. Therefore, it is possible to control the balance between shearing and coalescence of oil droplets formed by the polymerizable monomer composition in the granulation step, and thus it is possible to suppress the generation of fine particles and the instability of toner. thinking.

Since a specific site can be easily introduced into the molecular chain of the amorphous polyester, as a method for controlling the relationship of the interfacial tension, the molecular chain structure and composition ratio in the chain of the amorphous polyester are used. It is preferable to change the terminal structure. Further, although the polar resin will be described later, it can be controlled by the polar part in the polar resin.

Therefore, as the amorphous polyester, from the viewpoint of controlling the surface unevenness index of the toner matrix particles, brittleness and low-temperature fixability, a monomer unit derived from a linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms and a dialcohol are used. The content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having the derived monomer unit and having 8 or more and 14 or less carbon atoms is 10 mol% or more and 50 mol% with respect to the total monomer unit derived from the carboxylic acid of the amorphous polyester. The following is preferable.

When the number of carbon atoms is 8 or more, it is easy to control the value of the interfacial tension C within a desired range, and it is easy to have a structure like a pseudo-crystal state. Therefore, while suppressing the unevenness of the surface, the resin tends to be easily plasticized, so that the fine line reproducibility is easily improved. Further, when the number of carbon atoms is 14 or less, it is easy to control the value of the interfacial tension C within a desired range, and it is easy to lower the softening point of the amorphous polyester in a state where the peak molecular weight of the amorphous polyester is high. Therefore, it is possible to easily improve the plasticity at the time of fixing while maintaining the durability as a resin, and to suppress the unevenness of the toner surface.

Next, the amorphous polyester preferably has a carboxylic acid component containing a linear aliphatic dicarboxylic acid in an amount of 10 mol% or more and 50 mol% or less with respect to the total carboxylic acid component. It is preferable that the amount of the linear aliphatic dicarboxylic acid is 10 mol% or more based on the total carboxylic acid component because the softening point is likely to be lowered. Further, when the linear aliphatic dicarboxylic acid is 50 mol% or less with respect to the total carboxylic acid component, it is difficult to reduce the peak molecular weight of the amorphous polyester, which is preferable from the viewpoint of improving the durability of the toner.

Examples of the carboxylic acid component for obtaining an amorphous polyester include a linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms and other carboxylic acids. Examples of the linear aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms include suberic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Examples of the carboxylic acid other than the linear aliphatic dicarboxylic acid having 8 or more and 14 or less 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, and anhydrides of these acids, lower alkyl esters, and the like. Be done. Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, empol trimeric acid and their acid anhydrides, lower grades. Examples thereof include alkyl esters. Among these, terephthalic acid is preferably used because it can maintain a high peak molecular weight and easily maintain durability.

Examples of the alcohol component for obtaining the amorphous polyester include a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A, and other alcohols include the following. Examples of the divalent alcohol component include ethylene glycol, 1,3-propylene glycol, neopentyl glycol and the like. Examples of the trihydric or higher alcohol component include sorbitol, pentaerythritol, dipentaerythritol and the like. The divalent alcohol component and the trihydric or higher polyhydric alcohol component can be used alone or in combination of a plurality of compounds. Among these, as the alcohol component, the alcohol component derived from bisphenol A is preferably used from the viewpoint of ease of controlling the presence state in the toner.

The amorphous polyester can be produced by an esterification reaction or a transesterification reaction using the above alcohol component and carboxylic acid component. In the case of polycondensation, a known esterification catalyst such as dibutyl tin oxide may be appropriately used in order to promote the reaction.
The molar ratio (carboxylic acid component / alcohol component) of the alcohol component and the carboxylic acid component, which are the raw material monomers of the amorphous polyester resin, is preferably 0.60 or more and 1.00 or less.

The method for producing the amorphous polyester is not particularly limited, and can be produced by an esterification reaction or a transesterification reaction using each of the above-mentioned monomers. When polymerizing the raw material monomer, a commonly used esterification catalyst such as dibutyl tin oxide may be appropriately used in order to accelerate the reaction.

The glass transition temperature (Tg) of the amorphous polyester is preferably 45 ° C. or higher and 75 ° C. or lower from the viewpoint of fixability and brittleness.

The peak molecular weight (Mp (P)) of the amorphous polyester is preferably 8000 or more and 13000 or less. When the peak molecular weight (Mp (P)) is 8000 or more, it becomes easy to suppress cracking and crushing of the toner during long-term use. Further, when the peak molecular weight (Mp (P)) is 13000 or less, melting by heat occurs instantly, so that the toner layer can be sufficiently adhered to the paper.

The acid value AvA of the amorphous polyester is preferably lower than the acid value AvB of the polar resin described later. Further, AvA is preferably 1.0 mgKOH / g or more and 10.0 mgKOH / g or less, and more preferably 3.0 mgKOH / g or more and 8.0 mgKOH / g or less. Within the above range, it tends to exist in the vicinity of the surface of the toner mother particles without hindering the formation of the shell of the polar resin.

Next, it is preferable that the hydroxyl value OHv of the amorphous polyester is 40.0 mgKOH / g or less. For example, when the toner is obtained by a suspension polymerization method, it is preferable that the hydroxyl value OHv of the amorphous polyester is 40.0 mgKOH / g or less because the amorphous polyester easily forms a plurality of domains in the vicinity of the toner surface. ..

In order to control the acid value Av of the amorphous polyester to 1.0 mgKOH / g or more and 10.0 mgKOH / g or less and the hydroxyl value OHv to 40.0 mgKOH / g or less, the end of the molecular chain of the amorphous polyester It is preferable to have a lipophilic part.

Since the end of the molecular chain of the amorphous polyester has a lipophilic site, it is easy to interact with the vinyl resin, so that it is easy to control the size of the domain.

The amorphous polyester preferably has an alkyl moiety at the end of the amorphous polyester from the viewpoint of adjusting the acid value and the hydroxyl value and controlling the interfacial tension C.

Further, at the end of the amorphous polyester, at least one of an aliphatic monocarboxylic acid having a peak carbon number of 25 or more and 102 or less and an aliphatic monoalcohol having a peak carbon number of 25 or more and 102 or less (hereinafter, It is preferable that these two have a structure derived from (generally referred to as "long-chain monomer") at the end, and these long-chain monomers are preferably condensed at the end. Specifically, when a carboxyl group is present at the end of the amorphous polyester before the long-chain monomer is bonded, a condensation reaction with a monoalcohol occurs and a bond is generated. Further, when a hydroxy group is present at the end of the amorphous polyester before the long-chain monomer is bonded, a condensation reaction with a monocarboxylic acid occurs and a bond is generated. Here, the "peak value of carbon number" is the carbon number calculated from the main peak molecular weight of the long-chain monomer.

Further, here, when the amorphous polyester has a branched chain, the “terminal” also includes the end of the branched chain. In the present invention, the amorphous polyester has a branched chain, and the form condensed at the end of the branched chain is one of the preferred embodiments.

By binding a long-chain monomer to the end of the amorphous polyester, an alkyl moiety can be introduced at the end of the amorphous polyester. As a result, it is presumed that the alkyl moiety has a structure that is easy to fold, so that the amorphous polyester also takes a pseudo-crystallized state, so that it becomes easy to form a domain. Further, the above-mentioned interfacial tension C of the amorphous polyester tends to be easily controlled, and the surface unevenness index tends to be easily controlled.

Further, from the viewpoint of controlling the softening point and the interfacial tension C of the amorphous polyester, the peak value of the carbon number of the aliphatic monocarboxylic acid and the aliphatic monoalcohol is preferably 25 or more and 102 or less.

The total content ratio of the long-chain monomers is preferably 2.0 mol% or more and 10.0 mol% or less based on all the monomer units from the viewpoint of adjusting the acid value of the amorphous polyester and the interfacial tension.

The long-chain monomer is industrially obtained by alcohol- or acid-denaturing an aliphatic hydrocarbon as a raw material. For example, in the case of alcohol-modified products, alcohol is obtained by liquid-phase oxidizing an aliphatic hydrocarbon having 27 or more and 102 or less carbon atoms with a molecular oxygen-containing gas in the presence of a catalyst such as boric acid, anhydrous boric acid, or metaboric acid. It is known that it can be converted to. The amount of the catalyst added is preferably 0.01 mol or more and 0.5 mol or less with respect to 1 mol of the raw material aliphatic hydrocarbon.

As the molecular oxygen-containing gas to be blown into the reaction system, oxygen, air or a wide range of gases obtained by diluting them with an inert gas can be used, but the oxygen concentration is preferably 3% or more and 20% or less. The reaction temperature is 100 ° C. or higher and 200 ° C. or lower.

Further, when the long-chain monomer is modified with alcohol or acid, each unmodified component may also be generated. In order to prevent the charge amount from being lowered by this unmodified component, the modification rate of the aliphatic hydrocarbon component is preferably in the range of 85% or more, more preferably 90% or more. By optimizing the reaction conditions and performing purification work after the denaturation reaction, the unmodified aliphatic hydrocarbon component can be removed and the denaturation rate can be controlled.

If necessary, the toner mother particles may contain a charge control agent in order to improve the charge characteristics. Various types of charge control agents can be used, but a charge control agent that has a high charge speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner is produced by a suspension polymerization method as described later, a charge control agent having low polymerization inhibitory property and substantially no solubilized product in an aqueous dispersion medium is particularly preferable.

As a charge control agent
Metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid;
Metal salts or metal complexes of azo dyes or azo pigments;
High molecular weight compound having a sulfonic acid or carboxylic acid group in the side chain;
Boron compound;
Urea compound;
Silicon compound;
Calixarene and so on.

When a toner is produced by the suspension polymerization method, if a polymer compound having a sulfonic acid or a carboxylic acid group in the side chain (hereinafter, also referred to as a polar resin) is used as a charge control agent, the type and acid value, etc. It is more preferable because it is possible to form toner matrix particles having various structures by adjusting the polarity of. For example, by adjusting the acid value of the polar resin to be higher than the acid value of the amorphous polyester, the domain of the amorphous polyester is formed near the surface layer while forming a thin shell of the polar resin on the toner matrix particles. can do. As a result, it is possible to impart excellent chargeability and melting characteristics at a low calorific value to the toner mother particles.

Further, as described above, in order to make the surface unevenness index of the toner matrix particles within a desired range, the difference between the interfacial tension C of the amorphous polyester and the interfacial tension D measured by changing the amorphous polyester to a polar resin is It is preferably 13 mN / m or more and 25 mN / m or less.

By adjusting to the above range, it is possible to suppress the generation of fine particles and the instability of toner droplets during granulation in the suspension polymerization method, and it is possible to reduce the surface unevenness index.

Further, it is preferable that the polar resin is a vinyl polymer because it can cover the surface of the toner matrix particles more uniformly and the chargeability tends to be uniform.

Of the vinyl polymers, styrene copolymers are more preferred. The polymerizable monomer used together with the styrene monomer for forming the styrene copolymer includes acrylate, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, and acrylate-2. -A monocarboxylic acid having a double bond such as ethylhexyl, phenylacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylnitrile, acrylamide; or a substitute thereof; malein. Dicarboxylic acids with double bonds such as acids, butyl maleate, methyl maleate, dimethyl maleate and their substitutions; vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate; such as ethylene, propylene, butylene. Ethylene-based olefins; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; sulfonic acid group-containing monomers such as styrene sulfonic acid.

It is also possible to add a cross-linking agent to the polar resin. As the cross-linking agent, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinylaniline, Divinyl compounds such as divinyl ether, divinyl sulfide, and divinyl sulfone; compounds having three or more vinyl groups can be mentioned. These cross-linking agents can be used alone or as a mixture.

The content of the polar resin is preferably 0.10 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.10 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

By containing 0.10 parts by mass or more, the unevenness of the surface of the toner matrix particles can be easily controlled, and excellent chargeability can be imparted. Therefore, excellent charge stability can be obtained through long-term use in various environments. Excellent fine line reproducibility. Further, by containing 3.0 parts by mass or less, excellent charge stability can be obtained while suppressing charge-up even in a low temperature and low humidity environment.

Further, as described above, it is preferable to prepare the acid value AvB (mgKOH / g) of the polar resin to be higher than the acid value AvA (mgKOH / g) of the amorphous polyester. For example, in a toner produced by an aqueous medium, the polar resin is more likely to be uniformly present on the surface of the toner, which is preferable. The acid value AvB of the polar resin is preferably 5.0 mgKOH / g or more and 20.0 mgKOH / g or less, and more preferably 10.0 mgKOH / g or more and 20.0 mgKOH / g or less. When it is within the above range, the shielding property as a shell is enhanced, so that the charging property is likely to be stable.

Next, the release agent will be described. As the release agent, a known wax can be used as long as it is a wax for the purpose of imparting releasability and plasticity.

For example, petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof;
Montan wax and its derivatives;
Hydrocarbon wax by Fischer-Tropsch method and its derivatives;
Polyolefin waxes such as polyethylene and their derivatives;
Examples thereof include natural waxes such as carnauba wax and candelilla wax and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, fatty acids such as higher fatty alcohols, stearic acid and palmitic acid, acid amide waxes, ester waxes, hardened castor oil and its derivatives, vegetable waxes, animal waxes and the like can also be used.

Among these waxes, paraffin wax is preferably used from the viewpoint of compatibility with vinyl resin and releasability.

The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less, and 3.0 parts by mass or more and 25.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin. Is more preferable.

Next, the colorant will be described. As the black colorant, carbon black, magnetic fine particles, and those colored black using yellow, magenta, and cyan colorants described later are used.

When magnetic one-component development is adopted in the one-component development method, it is preferable to use magnetic fine particles having high transportability with respect to the toner carrier containing the magnet roller as the black colorant. Further, even when the supply roller for supplying the toner in the cartridge to the toner carrier is omitted, it is preferable to use magnetic fine particles having high transportability as the black colorant.

Further, in order to obtain uniform adhesion and high adhesiveness of the external additive, it is more preferable to use a magnetic toner using magnetic fine particles having a large specific gravity. We speculate that the reason for this high stickiness is as follows.

As a method of adhering the external additive to the toner matrix particles, it is preferable to use a mixing device using a stirring blade or the like from the viewpoint of mixing property and shearing force. In such an external addition step, the portion mainly processed is in the vicinity of the stirring blade. It is considered that the magnetic toner having a large specific density has a larger load during the external addition treatment in the vicinity of the stirring blade than the non-magnetic toner, and the probability of being treated is higher. Therefore, it is considered that the magnetic toner can obtain higher adhesiveness than the non-magnetic toner.

The magnetic fine particles are mainly composed of magnetic iron oxide such as triiron tetraoxide and γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum and silicon. These magnetic fine particles preferably have a BET specific surface area of ² to 30 m 2 / g by the nitrogen adsorption method, and more preferably 3 to 28 m ² / g. Further, those having a Mohs hardness of 5 to 7 are preferable. The shape of the magnetic fine particles includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scaly shape. Preferred above.

The magnetic fine particles preferably have a number average particle size of 0.10 μm or more and 0.40 μm or less. When the number average particle size is 0.10 μm or more, the magnetic fine particles are less likely to aggregate, and the uniform dispersibility of the magnetic fine particles in the toner mother particles is improved. Further, when the number average particle size is 0.40 μm or less, the coloring power of the toner is improved.

The number average particle diameter of the magnetic fine particles can be measured using a transmission electron microscope. Specifically, after sufficiently dispersing the toner to be observed in the epoxy resin, it is cured in an atmosphere at a temperature of 40 ° C. for 2 days to obtain a cured product. The obtained cured product is used as a flaky sample by a microtome, and the diameters of 100 magnetic fine particles in the field of view are measured with a photograph at a magnification of 10,000 to 40,000 times with a transmission electron microscope (TEM). Then, the number average particle diameter is calculated based on the equivalent diameter of the circle equal to the projected area of the magnetic fine particles. It is also possible to measure the particle size with an image analyzer.

The 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 to the ferrous salt aqueous solution in an equivalent amount or an equivalent amount or more with respect to the iron component. Air is blown while maintaining the pH of the prepared aqueous solution at 7 or higher, and the ferrous hydroxide oxidation reaction is carried out while heating the aqueous solution to 70 ° C. or higher to first form seed crystals that are the core of the magnetic iron oxide powder. 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 liquid at 5 to 10, the reaction of ferrous hydroxide is promoted while blowing air, and the magnetic iron oxide powder is grown around the seed crystal. At this time, it is possible to control the shape and magnetic characteristics of the magnetic fine particles by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction progresses, the pH of the liquid shifts to the acidic side, but it is preferable that the pH of the liquid is not less than 5. Magnetic fine particles can be obtained by filtering, washing, and drying the magnetic fine particles thus obtained by a conventional method.

Further, when the toner is produced by the suspension polymerization method, it is very preferable to hydrophobize the surface of the magnetic fine particles because it is easy to enclose the magnetic fine particles in the toner. When surface treatment is performed by a dry method, the magnetic fine particles that have been washed, filtered, and dried are treated with a coupling agent. When the surface treatment is performed wet, the dried iron oxide is redispersed after the oxidation reaction is completed, or the iron oxide obtained by washing and filtering after the oxidation reaction is completed in another aqueous medium without drying. Is redistributed and the coupling process is performed. Specifically, the coupling treatment is performed by adding a silane coupling agent while sufficiently stirring the redispersion solution to raise the temperature after hydrolysis, or by adjusting the pH of the dispersion solution to an alkaline range after hydrolysis. .. Among these, from the viewpoint of performing a uniform surface treatment, it is preferable to perform surface treatment by reslurrying as it is without drying after completion of the oxidation reaction, filtration and washing.

In order to treat the surface treatment of the magnetic fine particles wet, that is, to treat the magnetic fine particles with a coupling agent in an aqueous medium, first sufficiently disperse the magnetic fine particles in the aqueous medium so as to have a primary particle size, and prevent sedimentation and aggregation. Stir with a stirring blade or the like. Next, an arbitrary amount of the coupling agent is added to the dispersion liquid, and the surface treatment is performed while hydrolyzing the coupling agent. It is more preferable to perform surface treatment while dispersing.

Here, the aqueous medium is a medium containing water as a main component. Specific examples thereof include water itself, water to which a small amount of surfactant is added, water to which a pH adjuster is added, and water to which an organic solvent is added. As the surfactant, a nonionic surfactant such as polyvinyl alcohol is preferable. The surfactant is preferably added in an amount of 0.1% by mass or more and 5.0% by mass or less with respect to water. Examples of the pH adjuster include inorganic acids such as hydrochloric acid. Examples of the organic solvent include alcohols and the like.

Examples of the coupling agent that can be used in the surface treatment of the magnetic fine particles in the present invention include a silane coupling agent, a silane compound, and a titanium coupling agent. More preferably used are silane coupling agents and silane compounds, which are represented by the general formula (1).
R _m SiY _n General formula (1)
[In the formula, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents a functional group such as an alkyl group, a phenyl group, a vinyl group, an epoxy group, an acrylic group, and a methacryl group, and n is 1. Indicates an integer of ~ 3. However, m + n = 4. ]

Examples of the silane coupling agent and silane compound represented by the general formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and β- (3,4 epoxycyclohexyl) ethyltri. Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltri Methoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, n-butyltri Methoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltrimethoxysilane, n-decyltrimethoxysilane, hydroxypropyltrimethoxysilane, n-hexadecyl Examples thereof include trimethoxysilane and n-octadecyltrimethoxysilane.

Among these, from the viewpoint of imparting high hydrophobicity to the magnetic fine particles, it is preferable to use an alkyltrialkoxysilane coupling agent represented by the following general formula (2).
C _p H _{2p + 1} −Si− (OC _q H _{2q + 1} ) ₃ General formula (2)
[In the formula, p indicates an integer of 2 to 20, and q indicates an integer of 1 to 3. ]

When p in the above formula is 2 or more, it is easy to sufficiently impart hydrophobicity to the magnetic fine particles. Further, when p is 20 or less, the hydrophobicity becomes sufficient, and coalescence of magnetic fine particles can be prevented. When q is 3 or less, the reactivity of the silane coupling agent is good, and hydrophobization is sufficiently performed. Therefore, alkyltrialkoxysilanes in which p in the equation represents an integer of 2 to 20 (more preferably an integer of 3 to 15) and q represents an integer of 1 to 3 (more preferably an integer of 1 or 2). It is preferable to use a coupling agent.

When the above silane coupling agent is used, it can be treated alone or in combination of a plurality of types. When a plurality of types are used in combination, they may be treated individually with each coupling agent or may be treated at the same time.

In the present invention, other colorants may be used in combination with the magnetic fine particles. Examples of the colorant that can be used in combination include the above-mentioned known dyes and pigments, as well as magnetic or non-magnetic inorganic compounds. Specifically, ferromagnetic metal particles such as cobalt and nickel, or alloys obtained by adding chromium, manganese, copper, zinc, aluminum, rare earth elements, etc. to these. Particles such as hematite, titanium black, niglosin dye / pigment, carbon black, phthalocyanine and the like can be mentioned. These are also preferably surface-treated and used.

The content of the magnetic fine particles in the toner mother particles is preferably 20 parts by mass or more and 200 parts by mass or less, and more preferably 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or vinyl resin. ..

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 can be mentioned.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, 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. Pigment Bio Red 19.

Examples of the cyan colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

These colorants can be used alone or in the form of a solid solution. The colorant is selected in terms of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in toner matrix particles. The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or vinyl resin that produces the vinyl resin.

In the present invention, the toner mother particles can be produced by any known method. First, a case of manufacturing by a pulverization method will be described.

When the toner mother particles are produced by the pulverization method, for example, the toner components such as vinyl resin, colorant, mold release agent, amorphous polyester and crystalline polyester, and other additives are mixed with a Henschel mixer, a ball mill, or the like. Mix well by machine. Then, it is melt-kneaded using a heat kneader such as a heating roll, a kneader, or an extruder to disperse or melt the above-mentioned materials, cool and solidify them, pulverize them, classify them, and perform surface treatment as necessary. Toner mother particles can be obtained. Either of the order of classification and surface treatment may come first. In the classification process, it is preferable to use a multi-division classifier from the viewpoint of production efficiency.

The crushing step can be performed by a method using various crushing devices such as a mechanical impact type and a jet type. Further, in order to obtain the toner (toner mother particles) having a preferable circularity used in the present invention, it is preferable to further apply heat to pulverize the toner or perform a treatment of applying an auxiliary mechanical impact. Further, a hot water bath method in which finely pulverized (classified if necessary) toner matrix particles are dispersed in hot water, a method in which the toner matrix particles are passed through a hot air stream, or the like may be used.

Examples of the method of applying the mechanical impact force include a method of using a mechanical impact type crusher such as a cryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industries, Ltd. Another method is to apply a mechanical impact force to the toner by centrifugally pressing the toner inside the casing with blades that rotate at high speed, such as the method used by devices such as the Mechanofusion system manufactured by Hosokawa Micron. ..

In order to control the dispersed state of the vinyl resin and the amorphous polyester by the pulverization method, it is preferable to perform a treatment such as adding an amorphous polyester externally.

The toner mother particles can be produced by the pulverization method as described above, but the toner mother particles obtained by this pulverization method are generally amorphous and have low fluidity in the regulation section. There is a tendency. In addition, it is difficult to control the presence state of the resin in the toner matrix particles described above. Further, for example, when a magnetic material is used, the magnetic material is easily exposed to the surface, so that the charging stability is lowered and the concentration is likely to be lowered. Therefore, in the present invention, it is preferable to produce toner mother particles in an aqueous medium such as a dispersion polymerization method, an association aggregation method, a dissolution suspension method, and a suspension polymerization method, and among them, the suspension polymerization method is more preferable. ..

The suspension polymerization method is a polymerizable monomer in which a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a cross-linking agent, a charge control agent, and other additives) are dissolved or dispersed. Obtain the composition. The polymerizable monomer composition is then added into a continuous phase (eg, an aqueous medium (which may optionally contain a dispersion stabilizer)). Then, the particles of the polymerizable monomer composition are formed in the continuous phase (in the aqueous medium), and the polymerizable monomer contained in the particles is polymerized. By doing so, it is a method of obtaining toner. Toners obtained by the suspension polymerization method (hereinafter, also referred to as "polymerized toners") have almost spherical shapes of individual toner matrix particles, so that the fluidity at the regulation part is easily improved and uniform friction is achieved. Since it is easy to be charged, the image quality is easily improved.

Examples of the polymerizable monomer used for producing the polymerized toner include the following.

As a polymerizable monomer,
Styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene;
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, Acrylic acid esters such as phenyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylic acid esters such as dimethylaminoethyl and diethylaminoethyl methacrylate;
And so on. In addition, acrylonitrile, methacrylonitrile, acrylamide and the like can also be mentioned. These can be used alone or in combination of two or more.

Among the above-mentioned polymerizable monomers, it is preferable to use styrene or a styrene derivative alone or in combination of two or more from the viewpoint of toner development characteristics and durability.

The polymerization initiator used in the production of the toner by the polymerization method used in the present invention preferably has a half-life of 0.5 hours or more and 30.0 hours or less during the polymerization reaction. Further, when the polymerization reaction is carried out by using an addition amount of 0.5 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, the toner can be given desired strength and appropriate melting characteristics. can.

Specific examples of the polymerization initiator are 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, and 1,1'-azobis (cyclohexane-1). -Carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile and other azo or diazo polymerization initiators, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxide-based polymerization initiators such as peroxycarbonate, cumenehydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy2-ethylhexanoate, and t-butylperoxypivalate. Can be mentioned.

When the toner used in the present invention is produced by a polymerization method, a cross-linking agent may be added, and a preferable addition amount is 0.01 parts by mass or more and 5.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is less than a part.

Here, as the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used, and for example, a compound having two or more polymerizable double bonds is used.
Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene;
Carboxylate ester having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate;
Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone;
Compounds having three or more vinyl groups are used alone or as a mixture of two or more.

In the method for producing the toner used in the present invention by a polymerization method, if necessary, the above-mentioned toner composition or the like is added and uniformly dissolved or dispersed by a disperser to obtain a polymerizable monomer composition. Examples of the disperser include a homogenizer, a ball mill, and an ultrasonic disperser. The obtained polymerizable monomer composition is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size of the obtained toner matrix particles becomes sharper when the desired toner size is set at once by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser. The polymerization initiator may be added at the same time as the other additives are added to the polymerizable monomer, or may be mixed immediately before suspension in the aqueous medium. It is also possible to add a polymerization initiator immediately after granulation and before starting the polymerization reaction.

After granulation, a normal stirrer may be used to stir the particles to the extent that the state of the particles is maintained and the floating and sedimentation of the particles are prevented.

When producing the toner used in the present invention, various surfactants, organic dispersants and inorganic dispersants can be used as dispersion stabilizers. Among them, the inorganic dispersant can be preferably used because it is less likely to generate harmful ultrafine powder and has obtained dispersion stability due to its steric hindrance. Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other phosphoric acid polyvalent metal salts, calcium carbonate, magnesium carbonate and other carbonates, calcium metasilicate, calcium sulfate and sulfuric acid. Examples thereof include inorganic salts such as barium, and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

It is desirable to use 0.2 parts by mass or more and 20.0 parts by mass or less of these inorganic dispersants with respect to 100 parts by mass of the polymerizable monomer. Further, the dispersion stabilizer may be used alone or in combination of two or more. Further, a surfactant may be used in combination.

In the step of polymerizing the above-mentioned polymerizable monomer, the polymerization temperature is set to 40 ° C. or higher, generally 50 ° C. or higher and 90 ° C. or lower. When the polymerization is carried out in this temperature range, the release agent to be sealed inside is precipitated by phase separation, and the encapsulation becomes more complete.

In order to obtain the toner having the preferred amorphous polyester domain of the present invention by the suspension polymerization method, the following steps are important.

Further, after the completion of the polymerization step, it is preferable to carry out the distillation step in order to efficiently remove the remaining unreacted polymerizable monomer and to adjust the surface unevenness index to a desired range.
The distillation step is preferably carried out at a temperature equal to or higher than the glass transition temperature of the binder resin of the toner, preferably 60 ° C. or higher and 100 ° C. or lower, and more preferably 80 ° C. or higher and 100 ° C. or lower. preferable.

Further, as the holding time of the distillation step, in order to control the surface unevenness index within a desired range, it is preferable to hold the toner in a range in which coarseness of the toner matrix particles does not occur. It is preferably 60 minutes or more, and more preferably 120 minutes or more.

In order to form the domain of amorphous polyester, it is preferable to carry out the following steps.

After the polymerization of the above-mentioned polymerizable monomer is completed to obtain colored particles, in a state where the colored particles are dispersed in an aqueous medium, the amorphous polyester is in the vicinity of the softening point (softening point to softening point + 10 ° C.), specifically. It is preferable to raise the temperature to about 100 ° C. and keep the temperature 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 about 24 hours or less in relation to manufacturing efficiency.

Further, in order to achieve the dispersed state of the amorphous polyester as described above, it is preferable to perform the following operations in the subsequent cooling step. Specifically, it is preferable to cool the aqueous medium to Tg or less of the toner at a cooling rate of 5.00 ° C./min or more, more preferably at a cooling rate of 20 ° C./min or more, and a cooling rate of 100 ° C./min or more. It is more preferable to cool with the above. The upper limit of the cooling rate is not particularly limited, but is preferably 500 ° C./min or less.

After cooling at the above cooling rate, it is preferable to keep the temperature 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 about 24 hours or less in relation to manufacturing efficiency. In addition, Tg or less means from Tg to about Tg-5 ° C.

Toner matrix particles are obtained by filtering, washing, and drying the obtained polymer particles.

The toner mother particles may be used as they are as the toner, or may be used as a toner in which the inorganic fine particles adhere to the surface of the toner mother particles by externally adding inorganic fine particles as described later. It is also possible to insert a classification step in the manufacturing process (before mixing the inorganic fine particles) to cut the coarse powder and fine powder contained in the toner matrix particles.

Further, in the toner of the present invention, as a fluidizing agent, inorganic fine particles having an average number of primary particles of 4 nm or more and 80 nm or less, more preferably 6 nm to 40 nm are added (externally added) to the toner matrix particles. preferable. Further, it is more preferable to use inorganic fine particles having an average number of primary particles of 80 nm or more and 200 nm or less in combination. By externally adding the toner, the fluidity of the toner can be ensured through durability, uniform and stable triboelectricity can be obtained, and the concentration can be easily improved. Inorganic fine particles are added to improve the fluidity of the toner and equalize the charge of the toner. Inorganic fine particles are treated to hydrophobize the inorganic fine particles to adjust the amount of charge in the toner and improve environmental stability. It is also a preferable form to give.

In the present invention, the method for measuring the number average diameter of the primary particles of the inorganic fine particles is performed by using a photograph of the toner magnified by a scanning electron microscope.

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 a silicon halide or fumed silica, and so-called wet silica produced from water glass or the like.

However, dry silica having less 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 preferable.} Further, in dry silica, it is also possible to obtain composite 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 manufacturing process. , Including them.

The amount of the inorganic fine particles added is preferably 0.1 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the toner mother particles. The content of the inorganic fine particles can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

In the present invention, it is preferable that the inorganic fine particles are hydrophobized because 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. Further, other treatment agents such as organosilicon compounds and organotitanium compounds can be mentioned. These can be used alone or in combination of two or more.

Among the above-mentioned treatment agents, those treated with silicone oil are preferable, and those treated with silicone oil at the same time or after treating the inorganic fine particles with a silane compound are more preferable. As a method for treating such inorganic fine particles, for example, as a first-stage reaction, a silylation reaction is carried out with a silane compound to eliminate silanol groups by a chemical bond, and then as a second-stage reaction, silicone oil is applied to the surface. A hydrophobic thin film can be formed.

The silicone oil is preferably a viscosity at 25 ° C. is 10 mm ² / s or more 200,000 mm ² / s or less things, more preferably the following 3,000 mm ² / s or more 80,000mm ² / s.

As the silicone oil used, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorphenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.

Examples of the method of treating the inorganic fine particles with silicone oil include a method of directly mixing the inorganic fine particles treated with a silane compound and silicone oil using a mixer such as a Henschel mixer, or a method of spraying the inorganic fine particles with silicone oil. The method can be mentioned. Alternatively, a method may be used in which the silicone oil is dissolved or dispersed in an appropriate solvent, and then inorganic fine particles are added and mixed to remove the solvent. A method of spraying is more preferable because 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, preferably 3 parts by mass to 35 parts by mass with respect to 100 parts by mass of the inorganic fine particles, and good hydrophobicity can be easily obtained.

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 include: 20 m ² / g or more 350 meters ² / g Preferably, 25 m ² / More preferably, it is g or more and 300 m ^{2 / g or less.} The specific surface area is calculated by adsorbing nitrogen gas on the sample surface using the specific surface area measuring device "Gemini 2375 Ver.5.0" (manufactured by Shimadzu Corporation) according to the BET method and using the BET multipoint method. ..

The toner of the present invention includes still other additives such as, for example.
Lubricants particles such as fluororesin particles, zinc stearate particles, polyvinylidene fluoride particles;
Abrasives such as cerium oxide particles, silicon carbide particles, strontium titanate particles;
Fluidity-imparting agents such as titanium oxide particles and aluminum oxide particles;
Anti-caking agent;
A small amount of organic fine particles and inorganic fine particles having opposite polarities can also be used as a developable improver. It is also possible to hydrophobize the surface of these additives before use.

The developing apparatus to which the toner of the present invention can be preferably applied will be described in detail with reference to the drawings.

FIG. 1 is a schematic cross-sectional view showing an example of a developing device. Further, FIG. 2 is a schematic cross-sectional view showing an example of an image forming apparatus incorporating a developing apparatus.

In FIG. 1 or 2, the electrostatic latent image carrier 45, which is an image carrier on which the electrostatic latent image is formed, is rotated in the direction of arrow R1. By rotating the toner carrier 47 in the direction of arrow R2, the toner 57 is conveyed to the developing region where the toner carrier 47 and the electrostatic latent image carrier 45 face each other. Further, the 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.

A charging roller 46, a transfer member (transfer roller) 50, a fixing device 51, a pickup roller 52, and the like are provided around the electrostatic latent image carrier 45. The electrostatic latent image carrier 45 is charged by the charging roller 46. Then, the laser beam 54 irradiates the electrostatic latent image carrier 45 with laser light to perform exposure, 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 the toner in the developer 49 to obtain a toner image. The toner image is transferred onto the transfer material (paper) 53 by the transfer member (transfer roller) 50 that is in contact with the electrostatic latent image carrier 45 via the transfer material. The transfer material (paper) 53 on which the toner image is placed is carried to the fixing device 51 and fixed on the transfer material (paper) 53.

<Measuring method of softening point (Tm) of toner and amorphous polyester>
The softening points of toner and amorphous polyester are measured using a constant load extrusion type thin tube rheometer "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 a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve showing the relationship between and temperature can be obtained.

In the present invention, the softening point is the "melting temperature in the 1/2 method" described in the manual attached to the "flow characteristic evaluation device flow tester CFT-500D". The melting temperature in the 1/2 method is calculated as follows. First, 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time when the outflow starts is obtained (this is defined as X. X = (Smax-Smin) / 2). Then, the temperature of the flow curve when the amount of descent of the piston is the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method (a schematic diagram of the flow curve is shown in FIG. 3).

The measurement sample is about 60 g of toner or amorphous polyester at about 10 MPa in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NPA System Co., Ltd.). A columnar product having a diameter of about 8 mm is used by compression molding for seconds.

The measurement conditions of CFT-500D are as follows.
Test mode: Hot compress start temperature: 50 ° C
Achieved temperature: 200 ° C
Measurement interval: 1.0 ° C
Heating rate: 4.0 ° C / min
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: 1.0 mm

<Measuring method of weight average particle size (D4) and number average particle size (D1) of toner>
The weight average particle size (D4) and number average particle size (D1) of the toner are the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman Coulter 3) by the pore electric resistance method equipped with an aperture tube of 100 μm. Calculated by performing measurement and analysis using Coulter) and the attached dedicated software "Beckman Coulter Particle 3 Version 3.51" (Beckman Coulter) for setting measurement conditions and analyzing measurement data. ..

As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1 part by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.

Before measuring and analyzing, the dedicated software was set as follows.

In the dedicated software "Change standard measurement method (SOM) screen", set the total count number in the control mode to 50,000 particles, measure once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). The value obtained using (manufactured by) is set. By pressing the threshold / noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check the flush of the aperture tube after measurement.

In the "pulse to particle size conversion setting screen" of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.

The specific measurement method is as follows.
(1) Approximately 200 ml of the electrolytic aqueous solution is placed in a 250 ml round bottom beaker made of glass dedicated to ultisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the dedicated software.
(2) Approximately 30 ml of the electrolytic aqueous solution is placed in a 100 ml flat-bottomed beaker made of glass, and "Contaminone N" (nonionic surfactant, anionic surfactant, and organic builder) as a dispersant is used as a dispersant for precise measurement of pH 7. Add about 0.3 ml of a diluted solution obtained by diluting a 10% by mass aqueous solution of a neutral detergent for cleaning a vessel, manufactured by Wako Pure Chemical Industries, Ltd.) with ion-exchanged water 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are built in with the phase shifted by 180 degrees, and are placed in the water tank of the ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios) with an electrical output of 120 W. A certain amount of ion-exchanged water is added, and about 2 ml of the Contaminone N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) The electrolytic aqueous solution (5) in which toner is dispersed is dropped onto the (1) round bottom beaker installed in the sample stand using a pipette, and the measured concentration is adjusted to about 5%. Then, the measurement is performed until the number of particles to be measured reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) and the number average particle size (D1) are calculated. In addition, when the graph / number% and graph / volume% are set by the dedicated software, the "arithmetic diameter" on the analysis / number statistical value (arithmetic mean) and analysis / volume statistics (arithmetic mean) screens is the number average. The particle size (D1) and the weight average particle size (D4).

<Measurement method of true density of toner matrix particles>
When measuring the true density of the toner matrix particles in a toner in which an external additive is added to the toner matrix particles, it is necessary to remove the external additive. B / A calculation method> is as described.

The true density of the toner matrix particles was measured by a dry automatic densitometer auto pycnometer (manufactured by Yuasa Ionics Co., Ltd.). The conditions are as follows.
Cell: SM cell (10 ml)
Sample amount: Approximately 2.0 g

This measuring method measures the true density of solids and liquids based on the gas phase replacement method. Similar to the liquid phase substitution method, it is based on Archimedes' principle, but since gas (argon gas) is used as the substitution medium, the accuracy for micropores is high.

<Calculation method of surface unevenness index B / A>
The surface unevenness index is obtained from the theoretical specific surface area A and the BET specific surface area B of the toner matrix particles (= B / A). In addition, when measuring the surface unevenness index of the toner mother particles in the toner in which the external additive is externally added to the toner mother particles, it is necessary to remove the external additive. Specific methods include, for example, the following. The method can be mentioned.

-When the toner is magnetic toner (1) Put 45 mg of magnetic toner in a sample bottle and add 10 mL of methanol.
(2) Disperse the sample for 1 minute with an ultrasonic cleaner to separate the external additive.
(3) Suction filtration (10 μm membrane filter) is performed to separate the magnetic toner mother particles and the external additive. Alternatively, a magnet may be placed on the bottom of the sample bottle to fix the magnetic toner mother particles and separate only the supernatant liquid.
(4) The above (2) and (3) are performed a total of three times, and the obtained magnetic toner mother particles are sufficiently dried in a vacuum dryer at room temperature. By observing the magnetic toner mother particles from which the external additive has been removed with a scanning electron microscope, it can be confirmed that the external additive has disappeared. If the external additive is not sufficiently removed, repeat steps (2) and (3) until the external additive is sufficiently removed. As another method for removing the external additive instead of the above (2) and (3), there is a method of dissolving the external additive with an alkaline solution. As the alkali, an aqueous sodium hydroxide solution is preferable.

-For non-magnetic toner Add 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve in a water bath to prepare a sucrose concentrate. 31 g of the sucrose concentrate and 6 mL of Contaminone N are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.

The centrifuge tube is shaken with the shaker for 20 minutes under the condition of 350 reciprocations per minute. After shaking, the solution is replaced with a glass tube for a swing rotor (50 mL), and centrifugation is performed at 3500 rpm for 30 minutes with a centrifuge. In the glass tube after centrifugation, the toner matrix particles are present in the uppermost layer and the silica fine particles are present on the aqueous solution side of the lower layer, so that only the toner matrix particles in the uppermost layer are recovered.

If the external additive has not been sufficiently removed, centrifugation is repeated as necessary, and after sufficient separation, the toner solution is dried to collect toner matrix particles.

Each calculation method is as follows.

<< Calculation method of theoretical specific surface area A of toner matrix particles >>
In the same manner as in the measurement of the number average particle size (D1), the particle size distribution based on the number of toner mother particles was measured. However, in the analysis using "Beckman Coulter Particle 3 Version 3.51" (manufactured by Beckman Coulter), measurement targets are from 2.0 μm to 32.0 μm, and 12 channels (2.00 to 2.520 μm, 2.520 to 3.175 μm, 3.175 to 4.000 μm, 4.000 to 5.040 μm, 5.040 to 6.350 μm, 6.350 to 8.000 μm, 8,000 to 10.079 μm, 10. 079 to 12.699 μm, 12.699 to 16.000 μm, 16.000 to 20.159 μm, 20.159 to 25.398 μm, 25.398 to 32.000 μm) rice field.

After that, using the median value of each channel (for example, if the median value is 2.00 to 2.520 μm, the median value is 2.260 μm), it is determined that the toner mother particle of the median value of each channel is a true sphere. Find the theoretical surface area (= 4 × π × (median of each channel) ² ) in the assumed case. By multiplying the theoretical surface area by the number ratio of the particles belonging to each channel obtained above, the average theoretical surface area (a) of one particle assuming that the measured toner mother particle is a true sphere is obtained.

Next, the theoretical mass (= 4/3 × π) assuming that the toner mother particles at the median value of each channel are true spheres from the median value of each channel and the true density of the measured toner mother particles in the same manner. × (median value of each channel) ³ × true density) is calculated. The average theoretical mass (b) of one particle is obtained from the theoretical mass and the number ratio of the particles belonging to each channel obtained earlier.

As described above, the theoretical specific surface area A (= a / b) of the toner mother particle is calculated from the average theoretical surface area and the average theoretical mass of one particle.

<< Measurement method of BET specific surface area B of toner matrix particles >>
The specific surface area BET of the toner matrix particles can be determined by a low temperature gas adsorption method based on a dynamic constant pressure method according to the BET method (preferably the BET multipoint method). For example, by adsorbing nitrogen gas on the sample surface using the specific surface area measuring device "Gemini 2375 Ver.5.0" (manufactured by Shimadzu Corporation) and measuring using the BET multipoint method, the BET specific surface area (BET specific surface area) m ² / g) was calculated. Specifically, the measurement is performed by the following procedure.

After measuring the mass of the empty sample cell, the sample cell is filled with 1.0 g of the measurement sample. Further, a sample cell filled with a sample is set in the degassing device, and degassing is performed at room temperature for 7 hours. After degassing, the mass of the entire sample cell is measured, and the exact mass of the sample is calculated from the difference from the empty sample cell. Next, empty sample cells are set in the balance port and analysis port of the BET measuring device. A dewar bottle containing liquid nitrogen is set at a predetermined position, and P0 is measured by a saturated vapor pressure (P0) measurement command. After the P0 measurement is completed, the degassed sample cell is set in the analysis port, the sample mass and P0 are input, and then the measurement is started by the BET measurement command. After that, the BET specific surface area is automatically calculated.

<Measurement method of 25% area ratio and 50% area ratio>
(25% area ratio)
After the toner is sufficiently dispersed in a visible light curable resin (trade name, Aronix LCR series D-800; manufactured by Toagosei Co., Ltd.), it is cured by irradiating it with short wavelength light. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to prepare a flaky sample of 250 nm. Next, the cut-out sample was magnified using a transmission electron microscope (JEM-2800 manufactured by JEOL Ltd.) (TEM-EDX) at a magnification of 40,000 to 50,000 times, the cross section of the particles was observed, and the EDX was used. Perform element mapping.

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

As the mapping conditions, the storage rate is 9000 to 13000, and the number of integrations is 120 times. Among the resin-derived domains confirmed from the observation images, the spectral intensity derived from the C element and the spectral intensity derived from the O element are measured, and the domain in which the spectral intensity of the C element with respect to the O element is 0.05 or more is found. It is a domain of amorphous polyester. After identifying the amorphous polyester domain, the toner is binarized to 25, which is the distance between the contour and the center point of the cross section from the contour of the toner cross section with respect to the total area of the amorphous polyester domain existing in the toner cross section. Calculate the area ratio (area%) of the amorphous polyester domain present within%. Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) is used for the binarization process.

The calculation method is as follows. In the above TEM image, the contour and center point of the toner cross section are obtained. The contour of the toner cross section shall 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.

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

Then, this operation is performed for one round of 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 indicated from the contour of the toner cross section.

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

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

<Measuring method of the number average diameter of amorphous polyester domains>
Element mapping is performed using EDX in the same manner as above to identify the amorphous polyester domain. The domain diameter is obtained by obtaining the circle-equivalent diameter from the area of the domain. The number of measurements is 100, and the arithmetic mean value of the circle-equivalent diameter of 100 domains is defined as the number average diameter of the domains. The domain for which the domain diameter is calculated is determined as follows.

First, the cross-sectional area of the toner is obtained from the toner cross-sectional image, and the diameter of a circle having an area equal to the cross-sectional area (circle equivalent diameter) 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 1.0 μm or less. Since the domain diameter may change depending on the particle size of the toner, the average domain diameter can be calculated by doing so.

<Method of measuring acid value Av of amorphous polyester and polar resin>
The acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of the sample is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.

(1) Preparation of Reagents 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion-exchanged water is added to make 100 ml to obtain a phenolphthalein solution.

Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it 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 that 25 ml of 0.1 mol / l hydrochloric acid was placed in a triangular flask, several drops of the phenolphthaline solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, those prepared according to JIS K 8001-1998 are used.

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

(B) Blank test Titration is performed in the same manner as described above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).

(3) Substitute the obtained result into the following formula to calculate the acid value.
A = [(CB) x f x 5.61] / S

Here, A: acid value (mgKOH / g), B: addition amount of potassium hydroxide solution in blank test (ml), C: addition amount of potassium hydroxide solution in this test (ml), f: potassium hydroxide Solution factor, S: sample (g).

<Measurement method of hydroxyl value OHv of amorphous polyester and long chain monomer>
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when acetylating 1 g of a sample. The hydroxyl value of the sample is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure.

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

1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion-exchanged water is added to make 100 ml to obtain a phenolphthalein solution.

Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it 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 that 25 ml of 0.5 mol / l hydrochloric acid was placed in a triangular flask, several drops of the phenolphthaline solution were added, titrated with the potassium hydroxide solution, and the hydroxylation required for neutralization was performed. Obtained from the amount of potassium solution. As the 0.5 mol / l hydrochloric acid, those prepared according to JIS K 8001-1998 are used.

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

A small funnel is placed on the mouth of the flask, and about 1 cm of 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 thick paper having a round hole.

After 1 hour, remove the flask from the glycerin bath and allow to cool. After allowing to cool, add 1 ml of water from the funnel and shake to hydrolyze acetic anhydride. The flask is heated again in a glycerin bath for 10 minutes for further complete hydrolysis. After allowing to cool, wash the walls of the funnel and flask with 5 ml of ethyl alcohol.

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

(B) Blank test Titration is performed in the same manner as above except that no sample is used.

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

<Measurement by changing to interfacial tension C and polar resin in tricalcium phosphate aqueous solution of pH 6.0 of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio) by the suspension method. Measurement of interfacial tension D>
(1) After warming to put to 60 ° C. 0.1 mol / L-Na ₃ PO ₄ aqueous solution 450 parts to 720 parts Preparation of ion-exchanged water of the aqueous phase, 1.0 mol / L-CaCl ₂ aqueous solution 67 Add 7 parts to obtain an aqueous medium containing a dispersion stabilizer. Measure the pH (hereinafter also referred to as the aqueous phase) and confirm that it is 6.0 ± 0.2.

(2) Preparation of oil phase 1 g of a sample is added to 8 g of styrene and 2 g of n-butyl acrylate and dissolved to prepare a styrene / butyl acrylate dispersion (hereinafter, also referred to as an oil phase).

(2) Interfacial tension measurement The interfacial tension was measured by the suspension method described below. Specifically, in an environment of a temperature of 25 ° C., a FACE solid-liquid interface analyzer Drop Master 700 manufactured by Kyowa Interface Science Co., Ltd. was used, and the measurement was performed with WIDE1 as the field of view of the lens portion. First, the tip of a thin tube having an inner diameter of 0.4 mm is inserted into the aqueous phase downward in the vertical direction. Next, the thin tube is connected to the syringe section. A pre-prepared oil phase is placed in the syringe section. Next, by connecting the syringe part to AUTO DISPENSER AD-31 manufactured by Kyowa Interface Science Co., Ltd. and extruding the oil phase from the thin tube, droplets can be created at the tip of the thin tube in the aqueous phase. Then, the interfacial tension is calculated from the shape of the droplet. The control and calculation methods for creating droplets were performed using a measurement and analysis system manufactured by Kyowa Interface Science Co., Ltd. The density difference between the aqueous phase and the oil phase required for the calculation was 0.10 g / cm ³ , which is the density difference between water and styrene. The final measurement result of the interfacial tension was the average value of the measured values of 10 times.

Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on Examples. However, this does not limit any embodiment of the present invention. Unless otherwise specified, the number of copies and% in the examples are based on mass.

<Preparation of toner carrier 1>
(Preparation of substrate 1)
As the substrate 1, a core metal having a diameter of 6 mm made of SUS304 is coated with a primer (trade name, DY35-051; manufactured by Toray Dow Corning) and baked.

(Making elastic rollers)
The substrate 1 prepared as described above is placed in a mold, and an addition type silicone rubber composition mixed with the following materials is injected into a cavity formed in the mold.
-Liquid silicone rubber material (trade name, SE6724A / B; manufactured by Toray Dow Corning)
100 copies, carbon black (trade name, Talker Black # 4300; manufactured by Tokai Carbon Co., Ltd.)
15 parts ・ Silica particles as heat resistance imparting agent 0.2 parts ・ Platinum catalyst 0.1 parts Next, the mold is heated and the silicone rubber is vulcanized and cured at a temperature of 150 ° C. for 15 minutes. After the substrate 1 having the cured silicone rubber layer formed on the peripheral surface is removed from the mold, the substrate 1 is further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. In this way, an elastic roller having a silicone rubber elastic layer having a diameter of 12 mm formed so as to cover the outer peripheral surface of the substrate is produced.

(Preparation of surface layer 1)
(Synthesis of isocyanate group-terminated prepolymer 1)
Polypropylene glycol-based polyol (trade name: Excelol 4030; manufactured by Asahi Glass Co., Ltd.) 100 with respect to 17.7 parts of toluene diisocyanate (TDI) (trade name: Cosmonate T80; manufactured by Mitsui Chemicals, Inc.) in a nitrogen atmosphere. .0 parts are gradually added dropwise while maintaining the temperature inside the reaction vessel at 65 ° C. After completion of the dropping, the reaction is carried out at a temperature of 65 ° C. for 2 hours. The obtained reaction mixture is cooled to room temperature to obtain an isocyanate group-terminated prepolymer 1 having an isocyanate group content of 3.8% by mass.

(Synthesis of Amino Compound 1)
In a reaction vessel equipped with a stirrer, a thermometer, a perfusion tube, a dropping device and a temperature controller, 100.0 parts (1.67 mol) of ethylenediamine and 100 parts of pure water are heated to 40 ° C. while stirring. Next, while maintaining the reaction temperature at 40 ° C. or lower, 425.3 parts (7.35 mol) of propylene oxide is gradually added dropwise over 30 minutes. The reaction is carried out with stirring for another hour to obtain a reaction mixture. The obtained reaction mixture is heated under reduced pressure to distill off water to obtain 1426 g of an amino compound.

As a surface layer material
-Isocyanate group-terminated prepolymer 1 617.9 parts-Amino compound 1 34.2 parts-Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Co., Ltd.) 117.4 parts-Urethane resin fine particles (trade name, Artpearl C-400) ; Made by Negami Kogyo Co., Ltd.)
Stir 130.4 parts and mix.

Next, methyl ethyl ketone (hereinafter, also referred to as “MEK”) is added so that the total solid content ratio is 30% by mass, and then the mixture is mixed by a sand mill. Next, the viscosity is further adjusted to 10 cps or more and 13 cps or less with MEK to prepare a coating material for forming a surface layer.

The elastic roller 1 produced above is immersed in a paint for forming a surface layer to form a coating film of the paint on the surface of the elastic layer of the elastic roller 1 and dried. Further, a surface layer having a film thickness of 15 μm is provided on the outer periphery of the elastic layer by heat treatment at a temperature of 150 ° C. for 1 hour to prepare a toner carrier 1.

<Production example of long-chain monomer 1>
1200 g of an aliphatic hydrocarbon having a peak carbon number of 35 was placed in a cylindrical reaction vessel made of glass, 38.5 g of boric acid was added at a temperature of 140 ° C., and immediately, the oxygen concentration of 50% by volume of air and 50% by volume of nitrogen was about. A mixed gas of 10% by volume was blown at a rate of 20 liters per minute, reacted at 200 ° C. for 3.0 hours, then warm water was added to the reaction solution, and hydrolysis was performed at 95 ° C. for 2 hours. The reaction was taken. 20 parts of the modified product was added to 100 parts of n-hexane to dissolve and remove the unmodified component to obtain a long-chain monomer 1. The obtained long-chain monomer 1 had a denaturation rate of 93.5% and a hydroxyl value of 92.4 mgKOH / g.

<Production example of amorphous polyester 1>
After adjusting the amounts of raw material monomers shown in Table 1 so that the carboxylic acid component and alcohol component are shown in Table 1, they are placed in a reaction vessel equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. , 1.5 parts of dibutyltin is added as a catalyst to 100 parts of the total amount of the monomer. Then, after rapidly raising the temperature to 180 ° C. under normal pressure under a nitrogen atmosphere, water is distilled off while heating at a rate of 10 ° C./hour from 180 ° C. to 210 ° C. to carry out polycondensation. After reaching 210 ° C., the pressure inside the reaction vessel is reduced to 5 kPa or less, and polycondensation is performed under the conditions of 210 ° C. and 5 kPa or less to obtain amorphous polyester 1. At that time, the polymerization time is adjusted so that the peak molecular weight of the obtained amorphous polyester 1 becomes the value shown in Table 1. Table 1 shows the physical characteristics of the amorphous polyester 1.

<Production example of amorphous polyesters 2 to 13>
Amorphous polyesters 2 to 13 are obtained in the same manner as in amorphous polyester 1 except that the raw material monomer and the amount used are changed as shown in Table 1. The physical characteristics of these amorphous polyesters are shown in Table 1.

<Production example of amorphous polyester 14>
100 mol parts of bisphenol A ethylene oxide 2 mol addition, 173.6 mol part of bisphenol A propylene oxide 2 mol addition, 97.1 mol of terephthalic acid in a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. 2 parts of esterification catalyst (tin octylate) was added to 100 parts of 166.2 mol of fumaric acid, 54.1 mol of adipic acid, and 2 mol of bisphenol A ethylene oxide adduct, and polymerized at 230 ° C. for 8 hours. After further reacting at 8 kPa for 1 hour and cooling to 160 ° C., a mixture of 6 parts of acrylic acid, 70 parts of styrene, 31 parts of n-butyl acrylate and 20 parts of a polymerization initiator (di-t-butyl peroxide). Was dropped over 1 hour with a dropping funnel, and after the dropping, the addition polymerization reaction was continued for 1 hour while being held at 160 ° C., then the temperature was raised to 200 ° C. and held at 10 kPa for 1 hour, and then unreacted. By removing the acrylic acid, styrene and butyl acrylate of the above, an amorphous polyester 14 which is a composite resin formed by bonding a vinyl polymerized segment and a polyester polymerized segment was obtained.

<Manufacturing example of processed magnetic material>
In ferrous sulfate aqueous solution, 1.00 to 1.10 equivalents of caustic soda solution for iron element, 0.15 part of phosphorus element equivalent for iron element, _{P 2} O _{5 for iron element Amount of SiO 2} equivalent to 0.50 parts 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 carried out at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.

Next, a ferrous sulfate aqueous solution was added to this slurry liquid so that the amount was 0.90 to 1.20 equivalents with respect to the initial amount of alkali (sodium component of caustic soda), the slurry liquid was maintained at pH 7.6, and air was introduced. The oxidation reaction is promoted while blowing to obtain a slurry liquid containing magnetic iron oxide. After filtering and washing, the water-containing slurry liquid is once taken out. At this time, a small amount of a water content sample is taken and the water content is measured. Next, this water-containing sample is put into another aqueous medium without drying, and the pH of the redispersion liquid is adjusted to about 4.8 by redispersing with a pin mill while stirring and circulating the slurry. Then, while stirring, 1.6 parts of the n-hexyltrimethoxysilane coupling agent was added to 100 parts of magnetic iron oxide (the amount of magnetic iron oxide was calculated as the value obtained by subtracting the water content from the water content sample), and water was added. Disassemble. After that, the mixture is sufficiently stirred to adjust the pH of the dispersion to 8.6 and surface treatment is performed. 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 90 ° C. for 30 minutes, and the obtained particles are crushed to have a volume average particle size of 0. A processed magnetic material of .21 μm is obtained.

<Production example of toner mother particle 1>
473 parts of 0.1 mol / L-Na ₃ PO ₄ aqueous solution was added to 720 parts of ion-exchanged water and heated to 60 ° C., and then _{71.1 parts of 1.0 mol / L-CaCl 2} aqueous solution was added. , Obtain an aqueous medium containing a dispersion stabilizer.

・ 74.0 parts of styrene ・ 26.0 parts of n-butyl acrylate ・ 10.0 parts of amorphous polyester ・ 0.6 part of divinylbenzene ・ Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1. 5 parts, treated magnetic material 65.0 parts, polar resin 1
(Styrene-2-ethylhexyl acrylate copolymer containing 3% 2-acrylamide-2-methylpropanesulfonic acid, Tg = 78 ° C.) 2.0 parts Attritor (Mitsui Miike Machinery Co., Ltd.) Was uniformly dispersed and mixed using the above to obtain a monomer composition. This monomer composition is heated to 63 ° C., and 15 parts of paraffin wax (melting point 78 ° C.) is added and mixed thereto to dissolve the monomer composition. Then, 5.0 parts of the polymerization initiator tert-butylperoxypivalate is dissolved.

The aqueous medium of the above monomer composition was charged in, 60 ° C., T. under N ₂ atmosphere K. Granulate by stirring with a homomixer (Tokukika Kogyo Co., Ltd.) at 12000 rpm for 10 minutes. Then, the reaction is carried out at 70 ° C. for 4 hours while stirring with a paddle stirring blade. After completion of the reaction, it is confirmed that the colored particles are dispersed in the aqueous medium obtained here, and that calcium phosphate is attached to the surface of the colored particles as an inorganic dispersant.

At this point, the colored particles were analyzed by adding hydrochloric acid to an aqueous medium to wash and remove calcium phosphate, and then filtering and drying. As a result, the glass transition temperature Tg of the binder resin was 55 ° C.

Subsequently, the water-based medium in which the colored particles are dispersed is heated to 100 ° C. and held for 240 minutes. Then, 5 ° C. water is added to the water-based medium, and the mixture is cooled from 100 ° C. to 50 ° C. at a cooling rate of 100 ° C./min. Subsequently, the aqueous medium was held at 50 ° C. for 120 minutes.

Then, hydrochloric acid is added to the aqueous medium to wash and remove calcium phosphate, and then the mixture is filtered and dried to obtain toner matrix particles 1. Table 2 shows the production conditions of the toner mother particles 1.

<Production example of toner matrix particles 2-26>
In the production of the toner matrix particles 1, the same applies to the toner matrix particles 2 to the same except _{that the amorphous polyester, the polar resin, the colorant, the number of copies of the Na 3} PO ₄ aqueous solution, the number of copies of the CaCl _{2 aqueous solution, and the production conditions are changed.} 26 are manufactured. Table 2 shows the production conditions of the obtained toner matrix particles.

<Production example of toner matrix particles 27>
<< Preparation of each dispersion >>
-Resin particle dispersion liquid (1)-
・ Styrene (manufactured by Wako Junyaku Co., Ltd.): 325 parts ・ n Butyl acrylate (manufactured by Wako Junyaku Co., Ltd.): 100 parts ・ Acrylic acid (manufactured by Rhodia Nikka Co., Ltd.): 13 parts ・ 1,10-decanediol diacrylate (new Nakamura Kagaku Co., Ltd.): 1.5 parts, Dodecanethiol (Wako Junyaku Co., Ltd.): 3.0 parts The above components are mixed in advance and dissolved to prepare a solution, and an anionic surfactant (Dow Chemical). A surfactant solution prepared by dissolving 9 parts of Doufax A211) in 580 parts of ion-exchanged water is contained in a flask, and 400 parts of the above solution is added to disperse and emulsify, and the mixture is slowly stirred for 10 minutes. While mixing, 50 parts of ion-exchanged water in which 6 parts of ammonium persulfate was dissolved was added.

Next, after the inside of the flask was sufficiently replaced with nitrogen, the inside of the flask was heated with an oil bath while stirring until the inside of the flask reached 75 ° C., and emulsion polymerization was continued as it was for 5 hours to obtain a resin particle dispersion liquid (1). rice field.

When the physical properties of the resin particles were examined by separating them from the resin particle dispersion liquid (1), the number average particle size was 195 nm, the solid content in the dispersion liquid was 42%, the glass transition point was 51.5 ° C., and the weight average molecular weight Mw. Was 32000.

-Resin particle dispersion (2)-
The amorphous polyester 14 was dispersed using a disperser modified into a high-temperature and high-pressure type of Cavitron CD1010 (manufactured by Eurotec Ltd.). Specifically, the composition ratio is 79% of ion-exchanged water, 1% of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) (as an active ingredient), and 20% of solid content, and ammonia. The pH was adjusted to 8.5, the Cavitron was operated under the conditions of a rotor rotation speed of 60 Hz, a pressure of 5 kg / cm ² , and heating by a heat exchanger at 140 ° C. The dispersion liquid (2) was obtained.

-Colorant dispersion-
・ 20 parts of carbon black ・ 2 parts of anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) ・ 78 parts of ion-exchanged water Soak the pigment in water for 2 minutes, disperse it at 5000 rpm for 10 minutes, stir it with a normal stirrer for 1 day and night to defoam, and then use the high-pressure impact disperser Ultimateizer Co., Ltd., Sugino Machine Co., Ltd. Using HJP30006), the mixture was dispersed at a pressure of 240 MPa for about 1 hour to obtain a colorant dispersion liquid. Further, the pH of the dispersion was adjusted to 6.5.

-Release 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 Heat the above components to 95 ° C and disperse them sufficiently with a homogenizer (Ultratarax T50 manufactured by IKA). The dispersion treatment was carried out with a pressure discharge type Gorin homogenizer to obtain a release agent dispersion having an average number diameter of 190 nm and a solid content of 25%.

<< Manufacturing example of toner matrix particles >>
-Ion-exchanged water 400 parts-Resin particle dispersion liquid (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 active ingredient)
The above components were placed in a 3 liter reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and kept at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature from the outside with a mantle heater. Then, 88 parts of the colorant dispersion liquid and 60 parts of the release agent dispersion liquid were added and held for 5 minutes. As it was, a 1.0% aqueous nitric acid solution was added to adjust the pH to 3.0. Next, the stirrer and mantle heater were removed, and while dispersing at 3000 rpm with a homogenizer (manufactured by IKA Japan: Ultratarax T50), 0.33 parts of polyaluminum chloride and 37.5 parts of 0.1% nitric acid aqueous solution were added. After adding 1/2 of the mixed solution, the dispersion speed was set to 5000 rpm, the remaining 1/2 was added over 1 minute, and the dispersion speed was set to 6500 rpm for 6 minutes.

A stirrer and a mantle heater are installed in the reaction vessel, and the temperature is raised to 42 ° C. at 0.5 ° C./min while appropriately adjusting the rotation speed of the stirrer so that the slurry is sufficiently agitated, and at 42 ° C. After holding for 15 minutes, the particle size was measured with a Coulter Multisizer every 10 minutes while raising the temperature at 0.05 ° C./min, and when the weight average particle size was 7.4 μm, 5% water was used. The pH was adjusted to 9.0 using an aqueous sodium oxide solution. Then, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a heating rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed with an optical microscope and a scanning electron microscope (FE-SEM) every 30 minutes, the particles became almost spherical in the second hour, so the temperature was lowered to 20 ° C. at 1 ° C./min to cool the particles. Solidified.

Then, the reaction product is filtered, washed with water through ion-exchanged water, and when the conductivity of the filtrate becomes 50 mS or less, the cake-shaped particles are taken out and the amount of ion-exchanged water is 10 times the particle weight. The particles were charged, stirred with a three-one motor, and when the particles were sufficiently loosened, the pH was adjusted to 3.8 with a 1.0% aqueous nitrate solution and held for 10 minutes. After that, it was filtered and washed with water again, and when the conductivity of the filtrate became 10 mS or less, the water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were crushed with a sample mill and dried in an oven at 40 ° C. for 24 hours. Further, the obtained powder was crushed by a sample mill and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain toner matrix particles 27.

<Production example of toner matrix particles 28>
Toner mother particles were produced according to Example 1 of JP-A-2006-184746 to obtain toner mother particles 28.

<Making toner>
<Manufacturing example of toner 1>
To 100 parts of the toner mother particles 1, 0.3 parts of sol-gel silica fine particles having an average number of primary particles of 115 nm were added and mixed using Mitsui Henschel Mixer (Mitsui Miike Machinery Co., Ltd.). Then, silica having an average number of primary particles with an average diameter of 12 nm was treated with hexamethyldisilazane and then treated with silicone oil, and 0.9 parts of hydrophobic silica fine particles ^{having a BET specific surface area value of 120 m 2 / g after the treatment were formed.} The particles were added and mixed in the same manner using Mitsui Henchel Mixer (Mitsui Miike Kakoki Co., Ltd.) to prepare Toner 1. Table 3 shows the physical characteristics of the obtained toner 1.

<Manufacturing examples of toners 2 to 23 and comparison toners 1 to 5>
In the production of the toner 1, the toner matrix particles were changed as shown in Table 3 to obtain toners 2 to 23 and comparative toners 1 to 5. Table 3 shows the physical characteristics of the obtained toners 2 to 23 and the comparative toners 1 to 5.

[Example 1]
The printer LBP7700C (manufactured by Canon Inc.), whose fixing method is an on-demand fixing method based on film fixing, was modified and used for image output evaluation. As a modification point, the toner carrier 1 was changed, the toner supply member of the developing apparatus (toner supply roller shown in FIG. 1: 48) was removed, and the voltage application to the toner supply member was turned off. The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the photosensitive drum was 1.0 mm.

In this way, by removing the supply roller, the transportability of the toner to the carrier is tightened, and by reducing the area of the contact portion between the toner carrier and the electrostatic latent image carrier, the durability against the toner is being improved. Since it is possible to increase the stress of the toner, it is possible to strictly evaluate the change in the fine line reproducibility and the fine line reproducibility due to the durability.

The developing apparatus modified as described above was filled with 100 g of toner 1 to be evaluated, and the developing apparatus was produced using the toner carrier 1. The produced developing apparatus was set in a cyan station and / or a black station, and image evaluation was performed. As the durable print image, a horizontal line having a printing rate of 1% was used, and as a durable condition, a test was conducted using two sheets of intermittent paper. The evaluation results are shown in Table 4.

[Evaluation of fine line reproducibility] In (1) to (3), the check image has a basis weight of 90 g / m 2 for FOX RIVER BOND (manufactured by FOX RIVER Paper), and the 3000 printed images have a basis weight of 75 ^{g / m 2.} This ^{is done using m 2} businesss 4200 (manufactured by Xerox).

(1) Evaluation of fine line reproducibility of the initial image in a normal temperature and humidity environment and the image after printing 3000 sheets The developing device filled with toner is left in a normal temperature and humidity environment (23 ° C./50% RH) for 48 hours. ..

The fine line reproducibility was evaluated for the initial check image and the check image after printing 3000 horizontal lines with the modified machine.

A grid pattern (1 cm interval) on a 100 μm (latent image) line was imaged, and the scattering was visually evaluated using an optical microscope.
A: The line is very sharp and there is almost no splattering B: The line is relatively sharp with a slight splattering C: There is a little splattering and the line feels vague D: It is less than the level of C

(2) Evaluation of Fine Line Reproducibility of Initial Image in Room Temperature and High Humidity The toner-filled developing device is left in a room temperature and high humidity environment (23 ° C./85% RH) for 48 hours.

The fine line reproducibility of the initial check image was evaluated by the modified machine. A grid pattern (1 cm interval) on a 100 μm (latent image) line was imaged, and the scattering was visually evaluated using an optical microscope.
A: The line is very sharp and there is almost no splattering B: The line is relatively sharp with a slight splattering C: There is a little splattering and the line feels vague D: It is less than the level of C

(3) Evaluation of fine line reproducibility of check image after printing 3000 sheets in a low temperature and low humidity environment A developing device that prints 3000 sheets in a normal temperature and humidity environment with the above-mentioned remodeling machine is placed in a low temperature and low humidity environment (15 ° C., 10% RH). ) Was left for 48 hours, a check image was printed, and the fine line reproducibility was evaluated. A grid pattern (1 cm interval) on a 100 μm (latent image) line was imaged, and the scattering was visually evaluated using an optical microscope.
A: The line is very sharp and there is almost no splattering B: The line is relatively sharp with a slight splattering C: There is a little splattering and the line feels vague D: It is less than the level of C

[Low temperature fixability (tape peeling)]
The toner-filled developing apparatus is left to stand in a normal temperature and humidity environment (23 ° C./50% RH) for 48 hours. After that, the developing device is set in the cyan station and / or the black station, the fixing device is temporarily removed from the image forming device, and the unfixed image is modified so that it can flow. The image is a solid image with a tip margin of 10 mm and 50 mm x 50 mm on a GF-104 (basis weight 104 g / m ² , Canon A4 size) evaluation paper so that the toner loading amount is 0.90 mg / cm ^2. The solid black unfixed image was adjusted.

An "external fuser" set in a cyan station and / or a black station, the fuser was removed from the evaluation machine, and the fixing temperature of the fixing device could be set arbitrarily was attached to the evaluation machine.

Under the above environment, the fixability was evaluated while changing the set temperature control of the sleeve surface temperature of the external fuser in a temperature range from 170 ° C. to 220 ° C. every 5 ° C.

The image density of the solid black image portion of the obtained unfixed image was measured at 5 points and averaged to obtain an "initial density". Then, a polyester tape (No. 5515 manufactured by Nichiban Co., Ltd.) was attached to the solid black image portion, and a load of 100 g was reciprocated three times on the polyester tape to bring the polyester tape into close contact with the image. Then, after peeling off the polyester tape, the image density of the fixed image was measured at 5 points and averaged to obtain "density after tape peeling". The image density was measured using X-Rite (X-Rite, 500 series, density measurement mode).

Then, the difference between the initial concentration and the concentration after tape peeling was divided by the initial concentration and multiplied by 100 to obtain the concentration retention rate (%) after tape peeling. The temperature at which the concentration retention rate after tape peeling was less than 10% was defined as the temperature at which the fixability was excellent, and was ranked A to D according to the following criteria.
A: The concentration retention rate (%) after tape peeling is less than 10.0% even at 180 ° C.
B: The concentration retention rate (%) after tape peeling is less than 10.0% even at 190 ° C.
C: The concentration retention rate (%) after tape peeling is less than 10.0% even at 200 ° C.
D: The concentration retention rate (%) after tape peeling is less than 10.0% even at 210 ° C.

[Examples 2 to 23]
The toner was changed according to Table 4, and image drawing evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4.

[Comparative Examples 1 to 5]
The toner was changed according to Table 4, and image drawing evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4.

45: Electrostatic latent image carrier, 46: Charging roller, 47: Toner carrier, 48: Toner supply member, 49: Developer, 50: Transfer member (transfer roller), 51: Fixer, 52: Pickup roller, 53: Transfer material (paper), 54: Laser generator, 55: Toner control member, 56: Metal plate, 57: Toner, 58: Stirring member

Claims (11)

A toner having toner matrix particles containing a vinyl resin, a colorant, and an amorphous polyester.
In the toner cross section observed with a transmission electron microscope (TEM) of the toner, a matrix-domain structure is observed, the vinyl resin forms a matrix, and the amorphous polyester forms a plurality of domains.
The domain is within 25% of the distance between the contour and the center point of the toner cross section from the contour of the toner cross section, and is 30 area% or more and 70 area% or less with respect to the total area of the domain of the amorphous polyester. It is present and the softening point (Tm) of the amorphous polyester is 85 ° C. or higher and 105 ° C. or lower.
^{The theoretical specific surface area A (m 2} / g) obtained from the particle size distribution and true density based on the number of toner mother particles and the specific surface area B (m ² / g) measured by the BET method are the following equations (1). , (2) is satisfied.
0.450 ≤ B ≤ 1.500 ... (1)
1.00 ≤ B / A ≤ 1.26 ... (2) The toner according to claim 1, wherein the theoretical specific surface area A of the toner mother particles and the specific surface area B measured by the BET method satisfy the following formula (3).
1.00 ≤ B / A ≤ 1.19 ... (3) The vinyl resin is a styrene-butyl acrylate copolymer.
The toner mother particles are coated with a polar resin and are coated with a polar resin.
The polar resin is a vinyl polymer having an acid value of 5.0 mgKOH / g or more and 20.0 mgKOH / g or less.
Interfacial tension C (mN / m) of the amorphous polyester in a pH 6 tricalcium phosphate aqueous solution of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio), and the polar resin. styrene / butyl acrylate = 80/20 interfacial tension D in a tricalcium phosphate aqueous pH6 of the polar resin dissolved in (mass ratio) (mN / m) is, claim to satisfy the following formula (4) The toner according to 1 or 2.
13 ≤ CD ≤ 25 ... (4) The toner according to any one of claims 1 to 3, wherein the toner has 5.0 parts by mass or more and 30.0 parts by mass or less of the amorphous polyester with respect to 100 parts by mass of the vinyl resin. The toner according to any one of claims 1 to 4, wherein the acid value of the amorphous polyester is 1.0 mgKOH / g or more and 10.0 mgKOH / g or less. The amorphous polyester resin has a monomer unit derived from a linear aliphatic dicarboxylic acid having 8 or more carbon atoms and 14 or less carbon atoms, and a monomer unit derived from dialcohol.
Claim 1 in which the content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having 8 or more and 14 or less carbon atoms is 10 mol% or more and 50 mol% or less with respect to all the monomer units derived from the carboxylic acid of the amorphous polyester. The toner according to any one of 5 to 5. The toner according to any one of claims 1 to 6, wherein the specific surface area B (m ^{2 / g) is 0.450 or more and 0.705 or less.} The method for producing toner according to any one of claims 1 to 7.
A polymerizable monomer composition containing a polymerizable monomer, a colorant, an amorphous polyester, and a vinyl polymer having an acid value of 5.0 mgKOH / g or more and 20.0 mgKOH / g or less is dispersed in an aqueous medium. , A step of forming particles of the polymerizable monomer composition, and a polymerization step of polymerizing the polymerizable monomer contained in the particles,
A method for producing toner having. The method for producing toner according to claim 8, further comprising a distillation step of performing distillation at a temperature of 80 ° C. or higher and 100 ° C. or lower and a holding time of 60 minutes or longer after the polymerization step. The method for producing toner according to claim 8 or 9, wherein after the distillation step, the toner is cooled to a temperature of Tg or less at a cooling rate of 5.00 ° C./min or more. The method for producing toner according to claim 10, wherein after the distillation step, the toner is cooled to a temperature of Tg or less of the toner at a cooling rate of 100 ° C./min or more.

Images