JP2019168529A - toner - Google Patents

Abstract

To provide a toner that achieves a mottle when printed at high speed and the suppression of toner splash under a hot and humid environment.SOLUTION: Provided is a toner including toner particles containing a binder resin, a crystalline resin, a wax and a colorant, wherein the interparticle force Fp(A) at 45°C of the toner measured by a method below is 80 nN or smaller and the interparticle force Fp(B) at 80°C of the toner is 290 nN or greater. [The Fp(A) is an interparticle force calculated from a maximum tensile fracture force when a load of 1.6 kN/mis applied to a toner at 45°C to form a toner compact and the toner compact is ruptured; the Fp(B) is an interparticle force calculated from a maximum tensile fracture force when a load of 10.0 kN/mis applied to a toner at 80°C to form a toner compact and the toner compact is ruptured.]SELECTED DRAWING: None

Description

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

In recent years, in printers and copiers, in addition to improving the printing speed, it is required to output high-quality images under various usage purposes and usage environments. However, pressure, rubbing, and heat are likely to occur at the contact point between the toner carrier and the seal member at the end thereof in various usage environments, for example, in a high temperature and high humidity environment. When the printing speed is high, it becomes more prominent.
Therefore, when the toner enters the contact point between the toner carrier and the seal member, the toner aggregates and is likely to be fused. As a result, the toner easily passes through the seal member and is scattered from the developing container. Therefore, from the viewpoint of suppressing toner scattering, improvement in durability against pressure and heat generated between members becomes a problem.

The following method has been proposed as one method that can solve the problems of suppressing the toner scattering and fusing the toner to the member.
In Patent Document 1, by controlling the force between two particles of toner (cohesive force) at 25 ° C. and 50 ° C., generation of transfer dust due to electric repulsion, transfer rate, transportability, and charging stability are controlled. A toner in which the decrease is suppressed is disclosed.
In Patent Document 2, a crystalline polyester resin and a monoester wax are dispersed in an amorphous polyester resin, and the dispersion diameter of the crystalline polyester resin and the monoester wax is controlled, so that the image sticks to the developing roller. There has been proposed a toner in which the toner is prevented.

JP 2011-13441 A JP 2017-83524 A

On the other hand, various image quality improvements are required for high image quality. Among them, mottle (density unevenness) is a problem in improving image quality.
For example, in a medium having a large unevenness on the surface, density unevenness (motor) due to the unevenness of the medium is remarkably generated from the halftone part to the solid image, which becomes a factor that hinders high image quality. The cause of the motor is the difference in the deformation width of the toner due to the pressure and heat applied to the convex and concave portions of the media during fixing.
Therefore, it is necessary to make the deformation width at the time of melting at the convex portion and concave portion of the toner close to some extent, that is, to maintain the viscoelasticity at a high temperature to some extent.
In addition, it is also important to suppress the proportion of toner present in the recesses when passing through the fixing nip.
For the above problems, it is essential to satisfy both the durability and heat resistance of the toner and the melting characteristics, but these characteristics often tend to be in a trade-off relationship.
Certainly, in the toner described in Patent Document 1, toner scattering can be improved by controlling the force between two particles of toner at 25 ° C. and 50 ° C. However, since the force between the two particles of the toner at 50 ° C. is reduced, the force between the two particles of the toner at 80 ° C. is lowered, and there is room for improvement of the mottle.

The toner described in Patent Document 2 is presumed that the crystalline polyester resin and the monoester wax form microdomains, so that the compatibility is high when sufficient heat is applied and the heat deformation is easy.
However, crystallization of crystalline polyester resin and monoester wax is insufficient, and there is room for improvement in heat resistance and durability in heat and rubbing generated from the seal member and the toner carrier in a high temperature environment. .
In addition, a certain amount of toner is present in the recess, and the toner in the recess is not easily melted and deformed, and there is room for improvement with respect to mottle.
That is, the present invention provides a toner that achieves both the motor when printing at high speed and the suppression of toner scattering in a high temperature and high humidity environment.

The present invention
A toner having toner particles containing a binder resin, a crystalline resin, a wax and a colorant,
The two-particle force Fp (A) at 45 ° C. of the toner measured by the following method is 80 nN or less,
The toner has a two-particle force Fp (B) at 80 ° C. of 290 nN or more.
[Fp (A) is calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 1.6 kN / m ² at 45 ° C. and the toner compact is broken. Is the force between two particles,
The Fp (B) is calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 10.0 kN / m ² at 80 ° C. and the toner compact is broken. It is the force between two particles. ]

  According to the present invention, it is possible to provide a toner that achieves both the mottle during high-speed printing and the suppression of toner scattering in a high-temperature and high-humidity environment.

The figure which shows an example of the apparatus used for the measurement of the force between two particles The figure which shows an example of an image forming apparatus Diagram showing domain existence

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
A crystalline material is a material in which an endothermic peak is observed in differential scanning calorimetry (DSC).

The present invention
A toner having toner particles containing a binder resin, a crystalline resin, a wax and a colorant,
The two-particle force Fp (A) at 45 ° C. of the toner measured by the following method is 80 nN or less,
The toner has a two-particle force Fp (B) at 80 ° C. of 290 nN or more.
[Fp (A) is calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 1.6 kN / m ² at 45 ° C. and the toner compact is broken. Is the force between two particles,
The Fp (B) is calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 10.0 kN / m ² at 80 ° C. and the toner compact is broken. It is the force between two particles. ]

Wax is excellent in the performance of plasticizing the resin at the time of melting, and the crystalline resin is excellent in melting characteristics and has an effect of maintaining the viscosity when the toner is melted.
Therefore, by combining the two, the melting of the toner can be promoted and the viscosity at the time of melting can be adjusted appropriately. Can be improved.
However, in media with large surface irregularities, the toner present in the recesses tends to be insufficiently deformed when melted, causing mottle.
Further, when the adhesion between the toner particles is low, the toner on the medium easily moves to the concave portion before passing through the fixing nip, which is considered to be one of the causes of the toner being settled in the concave portion.

Accordingly, it is assumed that the toner can be prevented from moving to the concave portion if the adhesion between the toner particles is increased assuming a small amount of heat, for example, a temperature (80 ° C.) before passing through the fixing nip.
Further, in a high temperature and high humidity environment (for example, 32.5 ° C., 85% RH), if the output is performed at a high speed, in addition to the temperature rise in the apparatus, heat generated by rubbing between the members such as the toner carrier and the seal member ( 45 ° C.), the toner particles gradually tend to aggregate.
As a result, toner aggregates are generated at the seal portion, and toner scattering is likely to occur. Therefore, it is presumed that generation of toner aggregates can be suppressed by reducing the adhesion force between the toner particles assuming the heat and pressure applied between the members.

The adhesion force between the toners measured under the different conditions is defined herein as a force between two particles (hereinafter referred to as a force between two particles).
The two-particle force at 45 ° C. and the two-particle force at 80 ° C. of the toner tend to trade off, and it is difficult to control both to the preferred range at the same time.
However, by controlling the dispersion state (domain diameter) of wax and crystalline resin, the state of crystallization, and the presence of external additives, the above conditions are satisfied, and in high-temperature printing and high-temperature and high-humidity environments. It has been found that both toner scattering suppression can be achieved.

Hereinafter, although it demonstrates in detail, it is not necessarily limited to these.
The toner is applied with a load of 1.6 kN / m ² at 45 ° C. to form a toner compact, and the two-particle force Fp (A calculated from the maximum tensile breaking force when the toner compact is broken. ) Is 80 nN or less.
The load of 1.6 kN / m ² assumes a load applied when the toner compacted in the process cartridge passes through the regulating portion.
When the force between two particles Fp (A) is 80 nN or less, toner aggregation is difficult to occur due to rubbing and heat generated between members, and toner scattering is suppressed.
The Fp (A) is preferably 10 nN or more and 80 nN or less, and more preferably 30 nN or more and 80 nN or less. When Fp (A) is 10 nN or more, the fluidity can be adjusted in a range in which the toner does not form an aggregate, and therefore, rapid entry of the toner into the seal member and slipping of the seal member are suppressed. preferable.

A toner compact is formed by applying a load of 10.0 kN / m ² at 80 ° C., and the interparticle force Fp (B calculated from the maximum tensile breaking force when the toner compact is broken. ) Is 290 nN or more.
The weight of 10.0 kN / m ² is a value assuming a load applied to the toner existing near the fixing nip.
When the two-particle force Fp (B) is 290 nN or more, the toner is prevented from shifting to the concave portion in the vicinity of the fixing nip, and the generation of mottle is suppressed.
The Fp (B) is preferably 290 nN or more and 500 nN or less, more preferably 340 nN or more and 500 nN or less.
When Fp (B) is 500 nN or less, the adhesiveness between the toners due to heat can be controlled within a certain range. Therefore, when the papers immediately after printing are stacked, the papers are caused by the toner melted by the amount of heat accumulated. It is effective for adhering and discharging paper.
As described above, Fp (A) and Fp (B) tend to trade off. In order to simultaneously control the above two numerical values within the above range, there is a method in which in a system containing a certain amount of wax, a crystalline material is finely dispersed inside toner particles to promote crystallization.
It is also possible to adjust Fp (A) and Fp (B) by externally adding inorganic fine particles to the toner particle surface for the modification of the toner particle surface (reduction of contact area between toner particles, spacer effect). It is.
Specifically, the melting point of the wax and the crystalline resin, the content thereof, the dispersion diameter (domain diameter) in the toner particles, and the kind and amount of the external additive can be adjusted.

As described above, the toner particles preferably contain a crystalline polyester resin from the viewpoint of suppressing mottle. More preferably, the crystalline resin is a crystalline polyester resin.
Here, the structure of the crystalline polyester resin will be described. The crystalline polyester preferably has a structure having a hydrocarbon chain as a main chain that is long to some extent. The crystalline polyester resin preferably has a structure represented by the following formula (1).

式中、ｍは４〜１４の整数であり、ｎは６〜１６の整数である。

In the formula, m is an integer of 4 to 14, and n is an integer of 6 to 16.

  The length of the main chain is determined by the values of m and n in the partial structure, but m is preferably 4 or more and n is 6 or more from the viewpoint of enhancing affinity with wax and promoting compatibility. Further, from the viewpoint of increasing the solubility of the crystalline polyester itself, specifically, m is preferably 14 or less, and n is preferably 16 or less.

As the crystalline polyester resin, a known one can be used, but it is preferably a polycondensate of an aliphatic dicarboxylic acid and an aliphatic diol. Further, saturated polyester is more preferable. Hereinafter, examples of the monomer that can be used will be given.
Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and the like.
Specific examples of the aliphatic diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, neopentyl glycol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11 -Undecanediol, 1,12-dodecanediol, etc. are mentioned.

The crystalline polyester resin can be produced by a normal polyester synthesis method. For example, it can be obtained by subjecting a dicarboxylic acid component and a dialcohol component to an esterification reaction or a transesterification reaction, and then subjecting it to a polycondensation reaction in accordance with a conventional method under reduced pressure or introducing nitrogen gas.
In the esterification or transesterification reaction, an ordinary esterification catalyst or transesterification catalyst such as sulfuric acid, tertiary butyl titanium butoxide, dibutyl tin oxide, manganese acetate, and magnesium acetate can be used as necessary. As for polymerization, it is possible to use a conventional polymerization catalyst, for example, known ones such as tertiary butyl titanium butoxide, dibutyl tin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. it can. The polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.
The catalyst is preferably a titanium catalyst, more preferably a chelate-type titanium catalyst. The reactivity of the titanium catalyst is appropriate, and a polyester having a preferable molecular weight distribution can be obtained.

The weight average molecular weight (Mw) of the crystalline polyester resin is preferably 10,000 or more and 60,000 or less, and more preferably 20,000 or more and 50,000 or less. This is because when the weight average molecular weight is within this range, the crystallinity of the crystalline polyester resin can be kept high, and the plasticizing effect of the crystalline polyester resin can be obtained quickly in the fixing step.
The weight average molecular weight (Mw) of the crystalline polyester resin can be controlled by various production conditions of the crystalline polyester resin.
The melting point of the crystalline polyester resin is preferably 60 to 100 ° C, more preferably 65 to 85 ° C.
The content of the crystalline polyester resin is preferably 1.0 part by mass or more and 10.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.

Next, the wax will be described.
Examples of the wax include the following.
Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, Fischer-Tropsch wax, paraffin wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof ; Waxes mainly composed of fatty acid esters such as carnauba wax and montanic acid ester wax, and deoxidized part or all of fatty acid esters such as deoxidized carnauba wax; palmitic acid, stearic acid, montanic acid, etc. Saturated straight chain fatty acids; Unsaturated fatty acids such as brandic acid, eleostearic acid, parinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, merisyl Saturated alcohols such as alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide; Saturated fatty acid bisamides such as hexamethylene bisstearic acid amide; unsaturated fatty acids such as ethylene bis oleic acid amide, hexamethylene bis oleic acid amide, N, N ′ dioleyl adipic acid amide, N, N ′ dioleyl sebacic acid amide Amides; aromatic bisamides such as m-xylene bis-stearic acid amide and N, N ′ distearyl isophthalic acid amide; aliphatic gold such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate Salts (generally called metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and polyhydric alcohol moieties Esterified product: methyl ester compound having a hydroxy group obtained by hydrogenation of vegetable oil or the like.

In order to control Fp (A) and Fp (B) to desired values, the wax preferably contains an ester wax.
By containing the ester wax, it is considered that when heated, the ester wax dissolves first, and the exposure of the crystalline polyester resin to the toner particle surface and plasticity can be assisted.

Hereinafter, preferable ester wax will be described. The functional number described below indicates the number of ester groups contained in one molecule. For example, behenyl behenate is a monofunctional ester wax, and dipentaerythritol hexabehenate is a hexafunctional ester wax.
As the monofunctional ester wax, a condensate of an aliphatic alcohol having 16 to 24 carbon atoms and a long chain carboxylic acid, or a condensate of an aliphatic carboxylic acid having 14 to 22 carbon atoms and a long chain alcohol can be used. Here, any long-chain carboxylic acid or long-chain alcohol can be used, but it is preferable to combine monomers that can satisfy the following carbon number. Specifically, the number of carbon atoms when the aliphatic carboxylic acid and the long chain alcohol are added is preferably 36 to 44.

Examples of the aliphatic alcohol include 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, undecyl alcohol, and lauryl alcohol.
Examples of the aliphatic carboxylic acid include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, and decanoic acid.

As the bifunctional ester wax, a combination of dicarboxylic acid and monoalcohol or diol and monocarboxylic acid can be used.
Examples of the dicarboxylic acid include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
Examples of the diol include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12- Dodecanediol is mentioned.
The monoalcohol condensed with the dicarboxylic acid is preferably an aliphatic alcohol. Specific examples include tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, octacosanol and the like. .
As monocarboxylic acid condensed with diol, aliphatic carboxylic acid is preferable. Specific examples of the fatty acid include lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, lignoceric acid, and serotic acid.
In addition, although linear fatty acid and linear alcohol were illustrated here, you may have a branched structure.

Tri- or higher functional ester waxes can also be used. Here, the example in the case of obtaining trifunctional or more functional ester wax is given.
Examples of the trifunctional SL wax include a condensate of a glycerin compound and a monofunctional aliphatic carboxylic acid. Examples of the tetrafunctional ester wax include a condensate of pentaerythritol and a monofunctional aliphatic carboxylic acid, and a condensate of diglycerin and a carboxylic acid. Examples of pentafunctional ester waxes include condensates of triglycerin and monofunctional aliphatic carboxylic acids. Examples of the hexafunctional ester wax include a condensate of dipentaerythritol and a monofunctional aliphatic carboxylic acid, and a condensate of tetraglycerin and a monofunctional aliphatic carboxylic acid.

From the viewpoint of melting characteristics and durability, the melting point of the ester wax is preferably 60 to 80 ° C, more preferably 65 to 75 ° C.
Among these ester waxes, a monoester wax having a single ester bond in the molecular structure because of its high affinity with the crystalline resin and easy enhancement of the compatibility between the crystalline resin and the binder resin. It is preferable to contain.
By containing the monoester wax, the crystallization of the crystalline resin and the compatibilization of the crystalline resin and the binder resin when heated are promoted, and two types of force between two particles (Fp (A), Fp) are promoted. It becomes easy to control (B)) to a more preferable value.
The content of the monoester wax is preferably 10.0 parts by mass or more and 40.0 parts by mass or less, preferably 20.0 parts by mass or more and 35.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin. It is more preferable that The mass ratio of the crystalline resin to the monoester wax (crystalline resin / monoester wax) is preferably 0.05 or more and 0.33 or less, more preferably 0.05 or more and 0.20 or less. .

When the mass ratio is 0.05 or more, the viscosity at the time of melting is easily controlled, and mottle is easily suppressed. On the other hand, when it is 0.33 or less, the electrostatic offset in a low temperature and low humidity environment (15 ° C., 10 RH%) is improved. The electrostatic offset is a phenomenon in which image distortion occurs when toner on a medium is attracted to a fixing member when passing through the fixing nip and transferred to the fixing member. The occurrence of electrostatic offset is particularly noticeable in a low-temperature and low-humidity environment where chargeability tends to accumulate.
In addition, as a reason for the occurrence of electrostatic offset, there is a tendency to be easily affected by non-uniformity of toner chargeability. The reason why the electrostatic offset can be improved by adjusting the mass ratio of the crystalline resin to the monoester wax within a desired range is estimated as follows.

  When the mass ratio of the crystalline resin to the monoester wax is in the above range, the crystalline resin can ooze out on the toner particle surface in a form containing a large amount of wax before the fixing nip (about 80 ° C.). As a result, it is assumed that the wax can function as a leakage site for charging the toner. Therefore, it is estimated that non-uniform charging of the toner can be suppressed and adhesion between the toner particles at 80 ° C. can be increased, and as a result, adhesion to the fixing member can be suppressed.

  In addition, in the DSC curve obtained in the process of raising the temperature once to 180 ° C. by the differential scanning calorimetry DSC of the toner and then lowering the temperature, the region of the maximum exothermic peak temperature ± 5 ° C. of the monoester wax obtained by the same conditions Where A is the maximum heat generation peak temperature + 5 ° C. or more and the heat generation amount in the region of the maximum heat generation peak temperature + 15 ° C. or less is B, B / A is preferably 0.5 or more and 4.0 or less. More preferably, it is 1.0 or more and 2.5 or less. By controlling to the above range, both fixing tailing and paper discharge adhesion can be achieved. The inventors presume this reason as follows.

B / A is the ratio of the peak of crystallized exotherm when the temperature is lowered after the temperature is raised by DSC.
The temperature rise assumes fixing, and when B / A is low, it indicates that a lot of non-wax mixture is precipitated. Fixing tailing is a phenomenon in which when paper with a line image transferred enters the fixing nip, water vapor contained in the paper explodes in the concave portion of the paper and blows off the subsequent line image. It is. That is, a phenomenon in which toner is scattered due to high energy when water vapor explodes with respect to the adhesive force between toner particles.
Note that an environment in which moisture is easily absorbed by paper, and a room temperature and high humidity environment, which is an environment unfavorable for temperature rise, are more severe environments.
In order to suppress the tailing, it is required to adjust the two-particle force Fp (B) of the 80 ° C. toner described above to a high range. In some cases, melting may be promoted, affecting the adhesion of the discharged paper. Therefore, it is presumed that by adjusting the value of B / A, it is possible to achieve both tailing and paper discharge adhesion by promoting recrystallization even in the compatible component of the toner after fixing. B / A can be controlled by the kind and amount of the crystalline resin and the wax, the ratio of the crystalline resin and the wax, and manufacturing conditions such as annealing described later.

In order to control the two-particle force Fp (B) of the toner within a desired range and to improve the fixing property of the toner, the wax and the crystalline resin, which are crystalline materials, form minute domains Thus, it is preferably dispersed inside the toner particles. Specifically, in the cross section of the toner particle observed with a transmission electron microscope TEM, the crystalline resin and the wax form a micro domain, and the number average value of the major axis of the crystalline resin and the micro domain of the wax is 5 nm or more. It is preferably 350 nm or less, and more preferably 20 nm or more and 300 nm or less.
When the major axis of the domain is very small as described above, the domain can be rapidly melted even at a high temperature rise, and the surrounding binder resin can be easily plasticized.
The size and number of the micro domains can be adjusted by the content and type of the crystalline resin and the wax and the toner production method described later.
The cross section of the toner particle is dyed so that the crystalline material can be easily observed, and a region having a lamellar structure confirmed by observation with a transmission electron microscope in the cross section is defined as a crystalline material domain. Furthermore, a domain having a major axis of 10 nm or more and 1000 nm or less is referred to as a microdomain in the present invention. A domain having a major axis exceeding 1000 nm is called a large domain. A detailed method for measuring the microdomain will be described later.

In addition, in the cross section of the toner particle observed with a transmission electron microscope, the domain of the crystalline material such as wax and crystalline resin, more preferably the crystalline polyester resin, is obtained from the outline of the cross section. It is preferable that it is present in the range of 60% to 100% by number within 25% of the distance between them. More preferably, it is 65 number% or more and 100 number% or less.
As shown in FIG. 3, the number% means that 60% or more of the total number of domains of the crystalline substance exists in the region near the surface of the toner particles. Thus, when 60% by number or more of the domains are present in the vicinity of the toner particle surface, the amount of the crystalline material domain effective for the low-temperature fixability can be ensured.
The ratio (number%) of domains of the crystalline material existing within 25% of the distance between the contour and the center of gravity of the cross section from the outline of the toner particle cross section is called a 25% ratio. Examples of methods for controlling the 25% ratio within a preferable range include types of crystalline materials and manufacturing methods such as cooling means and annealing, which are crystallization methods for crystalline materials described later.

The binder resin used in the toner is a homopolymer of styrene such as polystyrene or polyvinyltoluene or a substituted product thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene. -Methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methacrylic Acid methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl Ether copolymer, styrene Nylmethyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-maleic acid copolymers, styrene-maleic acid ester copolymers, and other styrene copolymers; polymethyl methacrylate, poly Examples thereof include butyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, and polyacrylic acid resin.
These can be used alone or in combination of two or more. Of these, styrene copolymers represented by styrene-butyl acrylate are particularly preferred in terms of durability and fixability.

The following can be illustrated as a polymerizable monomer which forms a styrene-type copolymer.
Examples of the styrene polymerizable monomer include styrene; styrene polymerizable monomers such as α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, and p-methoxy styrene. .
Examples of acrylic polymerizable monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl. Examples thereof include acrylic polymerizable monomers such as acrylate, n-octyl acrylate, and cyclohexyl acrylate.
Examples of methacrylic polymerizable monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, and 2-ethylhexyl. Examples thereof include methacrylic polymerizable monomers such as methacrylate and n-octyl methacrylate.
In addition, the manufacturing method of a styrene-type copolymer is not specifically limited, A well-known method can be used. The content of the styrene copolymer relative to the total amount of the binder resin is preferably 70% by mass or more, and more preferably 80% by mass or more. The binder resin may be used in combination with other known resins.

A colorant can be used for the toner as needed. Examples of the colorant include the following organic pigments, organic dyes, and inorganic pigments.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds.
Examples of the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds.
Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
Examples of the black colorant include carbon black, the yellow colorant, the magenta colorant, the cyan colorant, and those that are toned to black using a magnetic material.
These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, lightness, light resistance, OHP transparency, and dispersibility in the toner particles. The content of the colorant is preferably 0.1 parts by mass or more and 60.0 parts by mass or less, more preferably 0.5 parts by mass or more and 50.0 parts by mass or less with respect to 100 parts by mass of the binder resin. It is.

The colorant is preferably a magnetic material from the viewpoint of ease of application to the toner manufacturing method. The toner can be produced by any known method, but is preferably produced in an aqueous medium.
When a magnetic material is used for the toner, the magnetic material is mainly composed of magnetic iron oxide such as triiron tetroxide and γ-iron oxide, and phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, silicon An element such as may be included. These magnetic materials preferably has a BET specific surface area by nitrogen adsorption method is 2~30m ² / g, more preferably 3~28m ² / g. Further, those having a Mohs hardness of 5 to 7 are preferred. The shape of the magnetic body includes a polyhedron, an octahedron, a hexahedron, a sphere, a needle, and a scale. Preferred above.

The magnetic material preferably has a number average particle diameter of 0.10 to 0.40 μm from the viewpoint of a balance between coloring power and cohesiveness. The number average particle diameter of the magnetic material can be measured using a transmission electron microscope. Specifically, after sufficiently dispersing the toner particles to be observed in the epoxy resin, a cured product obtained by curing in an atmosphere at a temperature of 40 ° C. for 2 days is obtained.
The obtained cured product is used as a flaky sample by a microtome, and the diameter of 100 magnetic particles in the field of view is measured with a transmission electron microscope (TEM) at a magnification of 10,000 to 40,000 times. Then, the number average particle diameter is calculated based on the equivalent diameter of a circle equal to the projected area of the magnetic material. It is also possible to measure the particle size with an image analyzer.

The magnetic material can be manufactured, for example, by the following method. An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide in an amount equivalent to or greater than the iron component to the ferrous salt aqueous solution. Air was blown in while maintaining the pH of the prepared aqueous solution at pH 7 or higher, and ferrous hydroxide was oxidized while heating the aqueous solution to 70 ° C. or higher. Generate.
Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. While maintaining the pH of the solution at 5 to 10, the reaction of ferrous hydroxide proceeds while blowing air to grow a magnetic iron oxide powder with the seed crystal as a core. At this time, it is possible to control the shape and magnetic characteristics of the magnetic material by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but the pH of the liquid is preferably not less than 5. A magnetic material can be obtained by filtering, washing, and drying the magnetic material thus obtained by a conventional method.

  In addition, when the toner is produced in an aqueous medium, it is very preferable to subject the surface of the magnetic material to a hydrophobic treatment. When surface treatment is performed in a dry process, the coupling agent treatment is performed on the magnetic material that has been washed, filtered, and dried. When wet surface treatment is performed, after the oxidation reaction is completed, the dried material is redispersed, or after completion of the oxidation reaction, the magnetic substance obtained by washing and filtering is not dried but in another aqueous medium. Either a dry method or a wet method in which re-dispersion and coupling treatment are performed can be selected as appropriate.

Examples of the coupling agent that can be used in the surface treatment of the conductive powder include a silane coupling agent and a titanium coupling agent. More preferably used is a silane coupling agent, which is represented by the general formula (I).
R _m SiY _n (I)
[Wherein, R represents an alkoxy group (preferably having 1 to 6 carbon atoms), m represents an integer of 1 to 3, Y represents a functional group such as an alkyl group, a vinyl group, an epoxy group, or a (meth) acryl group. Represents a group, and n represents an integer of 1 to 3. However, m + n = 4. ]

Those where Y is an alkyl group can be preferably used. Among these, an alkyl group having 3 to 6 carbon atoms is preferable, and an alkyl group having 3 or 4 carbon atoms is particularly preferable.
In the case of using a silane coupling agent, it is possible to process alone or to use a plurality of types in combination. When using several types together, you may process separately with each coupling agent, and may process simultaneously.
The total amount of the coupling agent used is preferably 0.9 to 3.0 parts by mass with respect to 100 parts by mass of the magnetic material, and the amount of the processing agent depends on the surface area of the magnetic material and the reactivity of the coupling agent. It is important to adjust the amount.

In addition to the magnetic material, other colorants may be used in combination. Examples of the colorant that can be used in combination include magnetic or nonmagnetic inorganic compounds in addition to the above-described known dyes and pigments. Specifically, ferromagnetic metal particles such as cobalt and nickel, or alloys obtained by adding chromium, manganese, copper, zinc, aluminum, rare earth elements and the like to these. Examples thereof include particles such as hematite, titanium black, nigrosine dye / pigment, carbon black, and phthalocyanine. These are also preferably used by treating the surface.
The content of the magnetic body is preferably 40 parts by mass or more and 200 parts by mass or less with respect to 100.0 parts by mass of the binder resin. More preferably, it is 60 to 160 parts by mass.
Note that the content of the magnetic substance in the toner can be measured using a thermal analyzer, TGA7, manufactured by PerkinElmer. The measuring method is as follows. The toner is heated from room temperature to 900 ° C. at a temperature rising rate of 25 ° C./min in a nitrogen atmosphere. The weight loss mass% between 100 ° C. and 750 ° C. is defined as the binder resin amount, and the remaining mass is approximately defined as the magnetic material amount.

A charge control agent can be used for the toner as needed. As the charge control agent, known ones can be used, but a charge control agent that has a high tribocharging speed and can stably maintain a constant triboelectric charge amount is preferable. Further, when the toner particles are produced by a suspension polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous medium is preferable.
As the charge control agent, there are one that controls the toner to negative charge and one that controls the toner to positive charge. Examples of controlling the toner to be negatively charged include the following. Monoazo metal compound, acetylacetone metal compound, aromatic oxycarboxylic acid, aromatic dicarboxylic acid, oxycarboxylic acid or dicarboxylic acid-based metal compound, aromatic oxycarboxylic acid, aromatic mono- or polycarboxylic acid or metal salt thereof, Examples include anhydrides or esters, phenol derivatives such as bisphenol, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and charge control resins. .

Examples of the charge control agent that controls the toner to be positively charged include the following. Guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts that are analogs thereof And these lake pigments; triphenylmethane dye and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and Ferrocyanide); metal salt of higher fatty acid; charge control resin.
Said charge control agent can be used individually or in combination of 2 or more types.
Among these charge control agents, metal-containing salicylic acid compounds are preferable, and those in which the metal is aluminum or zirconium are particularly preferable.
The addition amount of the charge control agent is preferably 0.01 to 20.0 parts by mass, more preferably 0.5 to 10.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

As the charge control resin, it is preferable to use a polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group. The polymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group preferably contains a sulfonic acid group-containing acrylamide monomer or a sulfonic acid group-containing methacrylamide monomer in a copolymerization ratio of 2% by mass or more. . More preferably, it is 5% by mass or more in terms of copolymerization ratio.
The charge control resin has a glass transition temperature (Tg) of 35 ° C. or more and 90 ° C. or less, a peak molecular weight (Mp) of 10,000 or more and 30,000 or less, and a weight average molecular weight (Mn) of 25,000 or more and 50,000 or less. Some are preferred. When this charge control resin is used, preferable triboelectric charging characteristics can be imparted without affecting the thermal characteristics required of the toner particles. Furthermore, since the charge control resin contains a sulfonic acid group, the dispersibility of the charge control resin itself in the dispersion of the colorant, and the dispersibility of the colorant are improved, and the coloring power, transparency, and The triboelectric charging characteristics can be further improved.

In order to control the force between the two particles of the toner, Fp (A), Fp (B) to a desired range, it is preferable to add silica fine particles, which are inorganic fine particles, to externally mix and adhere to the surface of the toner particles.
Further, from the viewpoint of controlling the force between the two particles within a desired range, the particle size distribution on the basis of the number of silica fine particles on the toner particle surface observed with a scanning electron microscope (SEM) is between 30 nm and 90 nm. It preferably has a peak. More preferably, it is 40 nm or more and 70 nm or less. For example, silica fine particles having a primary particle number average particle size of 30 to 90 nm (more preferably 40 to 70 nm) are preferably added to the toner particles.
The number average particle diameter of the primary particles of the silica fine particles is measured using a photograph of toner magnified by a scanning electron microscope. As the silica fine particles, for example, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass can be used. .
Further, from the viewpoint of enhancing the durability, the aspect ratio (minor axis / major axis) of the silica fine particles on the toner particle surface is 0.70 to 1.00 (more preferably 0.80 to 1.00). preferable.
When the aspect ratio of the silica fine particles is within the above range, the fluidity of the toner is easily improved. The content of silica fine particles is preferably 0.10 to 1.00 parts by mass per 100 parts by mass of toner particles. More preferably, it is 0.30-1.00 mass part.

  In addition to the silica fine particles, other inorganic fine particles can be added to improve the fluidity of the toner and to make the charge of the toner particles uniform. It is also a preferred form to impart functions such as adjustment of the charge amount of the toner and improvement of environmental stability by hydrophobizing the inorganic fine particles. Treatment agents used for the hydrophobic treatment of inorganic fine particles include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. You may use independently and may use 2 or more types together.

  For the toner, other additives such as lubricant powder such as fluororesin powder, zinc stearate powder, polyvinylidene fluoride powder; abrasive such as cerium oxide powder, silicon carbide powder, strontium titanate powder; Flowability imparting agents such as powder and aluminum oxide powder; anti-caking agent; or organic fine particles and inorganic fine particles having opposite polarity can be used in small amounts as a developability improver. It is also possible to use the surface of these additives after hydrophobizing them.

  The toner can be produced by any known method, but it is preferable to produce the toner in an aqueous medium in order to control the presence of the crystalline resin or wax. The suspension polymerization method is preferable because it easily controls the dispersion state of the crystalline material and controls the formation of domains on the order of several nm.

The suspension polymerization method will be described below.
The suspension polymerization method is a polymerizable monomer capable of forming a binder resin, a crystalline resin, a wax, and a colorant (in addition, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary). Is uniformly dissolved or dispersed to obtain a polymerizable monomer composition. Thereafter, the polymerizable monomer composition is dispersed and granulated in a continuous layer containing a dispersant (for example, an aqueous phase) using an appropriate stirrer, and the resulting polymerizable monomer composition is obtained. A polymerization reaction of the polymerizable monomer contained in the droplets is performed to obtain toner particles having a desired particle size. The toner particles obtained by this suspension polymerization method (hereinafter also referred to as “polymerized toner particles”) have an almost spherical spherical shape, and the charge distribution is relatively uniform. Improvement can be expected.

The following are mentioned as a polymerizable monomer.
Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate, Acrylic esters such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate , Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenolic methacrylate , Dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, and monomers such as acrylamide. These monomers can be used alone or in combination. Among the above-mentioned monomers, styrene is preferably used alone or mixed with other monomers from the viewpoint of toner development characteristics and durability.

  As the polymerization initiator used in the production of the toner by a polymerization method, those having a half-life of 0.5 to 30 hours during the polymerization reaction are preferable. Moreover, when a polymerization reaction is performed using an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 5,000 to 50,000 is obtained. It is easy to give the toner a desired strength and suitable melting characteristics.

  Specific examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1- Carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo-based or diazo-based polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxide Peroxide polymerization initiators such as oxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxypivalate, etc. Can be mentioned.

When the toner is produced by a polymerization method, a crosslinking agent may be added. The addition amount is preferably 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer.
Here, as the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate and ethylene glycol diacrylate. Carboxylic acid ester having two double bonds such as methacrylate, 1,3-butanediol dimethacrylate; divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and having three or more vinyl groups Are used alone or as a mixture of two or more.

In a method for producing a toner by a polymerization method, a polymerizable monomer composition, which is uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, or an ultrasonic disperser by appropriately adding the above-described materials, is used as a dispersant. Suspend in aqueous medium containing. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size all at once.
The polymerization initiator may be added at the same time as other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.
After granulation, stirring may be performed using an ordinary stirrer to such an extent that the particle state is maintained and particle floating and sedimentation are prevented.

In the case of producing a toner, a known surfactant, organic dispersant, or inorganic dispersant can be used as a dispersant. In particular, inorganic dispersants are less likely to produce harmful ultrafine powders, and because of their steric hindrance, dispersion stability is obtained, so that stability is not easily lost even when the reaction temperature is changed, and cleaning is easy and does not adversely affect the toner. Therefore, it can be preferably used. Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, phosphate polyvalent metal salts such as hydroxyapatite, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, calcium sulfate, Examples include inorganic salts such as barium sulfate, and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.
As for these inorganic dispersing agents, it is desirable to use 0.2-20 mass parts with respect to 100 mass parts of polymerizable monomers. Moreover, the said dispersing agent may be used independently and may use multiple types together. Furthermore, you may use together 0.001-0.1 mass part surfactant with respect to 100 mass parts of polymerizable monomers.

  When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles can be generated and used in an aqueous medium. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed under high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At the same time, water-soluble sodium chloride salt is produced as a by-product. However, if water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and ultrafine toner is generated by emulsion polymerization. This is preferable.

  Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

  The weight average particle diameter (D4) of the toner is preferably 3.0 μm or more and 12.0 μm or less, more preferably 4.0 μm or more and 10.0 μm or less. When the weight average particle diameter (D4) is 3.0 μm or more and 12.0 μm or less, good fluidity can be obtained, and development can be performed faithfully to the latent image.

Attention is focused on a toner production method for the purpose of crystallizing a crystalline material, preferably a crystalline polyester resin.
For example, when a toner is produced by a pulverization method, suspension polymerization, or emulsion polymerization, it is preferable to include a step of once raising the temperature to a temperature at which the crystalline polyester resin or wax is melted and then cooling to room temperature. Considering the cooling process, the crystalline polyester resin liquefied by the temperature rise becomes dull as the temperature decreases, and crystallization starts when it reaches the vicinity of the crystallization temperature. When it is further cooled, crystallization proceeds and it is completely solidified at room temperature. According to the study by the present inventors, it has been found that the crystallinity of the crystalline material varies depending on the cooling rate.
Specifically, when cooling at a rate of 5.0 ° C./min or more from a sufficiently high temperature (for example, 100 ° C.) at which crystalline polyester or wax melts to a glass transition temperature (hereinafter referred to as Tg) of toner particles or less. The crystallinity of the contained crystalline material tended to increase. By setting it as the above-mentioned cooling conditions, it becomes easy to control the two-particle force of the toner at 45 ° C. and 80 ° C. within the above-mentioned range.

More specifically, the state where the cooling rate is sufficiently high is the case where the cooling is performed at a rate sufficiently higher than 5.0 ° C./min as described above. The cooling rate is preferably 10.0 ° C./min or more, more preferably 30.0 ° C./min or more, and further preferably 50.0 ° C./min or more. The upper limit of the cooling rate is about 3000 ° C./min or less at which the effect is saturated. The cooling stop temperature is equal to or lower than the Tg of the toner particles, but more preferably when stopped at a temperature lower than Tg−5 ° C., it is easy to maintain the dispersibility of the crystalline material and facilitate the subsequent crystal growth.
Furthermore, after cooling the dispersion to a temperature not higher than Tg of the toner particles with a sufficiently high cooling rate, annealing may be performed in a temperature range of Tg ± 10 ° C. to increase the crystallinity of the crystalline material. This is preferable. More preferably, the dispersion liquid is annealed in a temperature range of Tg ± 5 ° C.
The holding time in the annealing treatment is preferably 30 minutes or more, more preferably 60 minutes or more, and further preferably 100 minutes or more. The upper limit of the holding time is about 24 hours or less from the viewpoint of manufacturing efficiency.

Holding for 30 minutes or more is preferable because the crystallinity of the crystalline material is easily increased. When the annealing start temperature is lower than the above temperature range, the aqueous medium dispersion may be heated again to keep the temperature within the above temperature range.
Toner particles are obtained by filtering, washing, and drying a dispersion containing toner particles obtained by the above annealing by a known method. The toner particles may be used as toner as they are. The toner may be obtained by mixing inorganic fine particles such as silica fine particles as described above, if necessary, and adhering them to the surface of the toner particles. As for the mixing method, a known method can be used. For example, a Henschel mixer is a device that can be suitably used.
It is also possible to insert a classification step in the manufacturing process (before mixing of the inorganic fine particles) to cut coarse powder and fine powder contained in the toner particles.

Next, an example of an image forming apparatus that can suitably use the toner of the present invention will be specifically described with reference to FIG. In FIG. 1, reference numeral 100 denotes a photosensitive drum, which is provided with a primary charging roller 117, a developing device 140 having a developing sleeve 102, a transfer charging roller 114, a cleaner 116, a register roller 124, and the like. The photosensitive drum 100 is charged to, for example, −600 V by the primary charging roller 117 (applied voltages are, for example, an AC voltage of 1.85 kVpp and a DC voltage of −620 Vdc).
Then, exposure is performed by irradiating the photoreceptor 100 with the laser beam 123 by the laser generator 121, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the photosensitive drum 100 is developed with a one-component toner by the developing device 140 to obtain a toner image, and the toner image is transferred onto the transfer material by the transfer roller 114 in contact with the photoreceptor via the transfer material. Is done. The transfer material on which the toner image is placed is conveyed to the fixing device 126 by the conveying belt 125 or the like and fixed on the transfer material. In addition, toner remaining on a part of the photoconductor is cleaned by a cleaner 116.
Although an image forming apparatus for magnetic one-component jumping development is shown here, it may be used for any method of jumping development or contact development.

It describes about the measuring method of each physical property which concerns on this invention.
<Method of measuring the force Fp (A) between two particles at 45 ° C.>
The two-particle forces Fp (A) and Fp (B) of the toner are measured using an Agrobot manufactured by Hosokawa Micron Corporation in accordance with the instruction manual of the apparatus.
A specific measurement method is as follows.
(1) In the case of magnetic toner In an environment of 45 ° C./50% RH, 10.5 g of toner is filled in a cylindrical cell divided into two upper and lower parts as shown in FIG. 2A and left for 1 hour. Thereafter, by lowering the compression rod at 0.1 mm / sec, a vertical load of 1.6 kN / m ² is applied for 5.0 sec to form a toner compact.
Thereafter, as shown in FIG. 2B, the upper cell is lifted by a spring at a speed of 0.4 mm / sec to pull the toner compact, and the maximum tensile fracture obtained when the toner compact is broken. The force between two particles Fp (A) (nN) is measured based on the force.
Here, the “maximum tensile breaking force”, that is, the force applied when breaking the powder is obtained as a value obtained by subtracting “stress when breaking begins” from “maximum tensile stress” in FIG. .
The cylindrical cell has an inner diameter of 25 mm and a height of 37.5 mm.
(2) In the case of non-magnetic toner The same measurement method is used except that the toner filling amount is changed from 10.5 g to 7.7 g.

<Method for measuring force Fp (B) between two particles at 80 ° C.>
(1) In the case of magnetic toner Under an environment of 80 ° C., 10.5 g of toner is filled in a cylindrical cell divided into upper and lower parts shown in FIG. Thereafter, the compression rod is lowered at 0.1 mm / sec to apply a vertical load of 10.0 kN / m ² for 1.0 sec to form a toner compact.
Thereafter, as shown in FIG. 2B, the upper cell is lifted by a spring at a speed of 0.4 mm / sec to pull the toner compact, and the maximum tensile fracture obtained when the toner compact is broken. The force between two particles Fp (B) (nN) is measured based on the force.
Here, the “maximum tensile breaking force”, that is, the force applied when breaking the powder is obtained as a value obtained by subtracting “stress when breaking begins” from “maximum tensile stress” in FIG. .
The cylindrical cell has an inner diameter of 25 mm and a height of 37.5 mm.
(2) In the case of non-magnetic toner The same measurement method is used except that the toner filling amount is changed from 10.5 g to 7.7 g.

<Isolation of crystalline polyester resin and wax>
Using the toner, the crystalline polyester resin and the wax can be isolated as follows.
First, the toner is dispersed in ethanol, which is a poor solvent for the toner, and the temperature is raised to a temperature exceeding the melting points of the crystalline polyester resin and the wax. At this time, you may pressurize as needed. At this point, the crystalline polyester resin and wax exceeding the melting point are melted. Thereafter, a mixture of the crystalline polyester resin and the wax can be collected from the toner by solid-liquid separation. By separating the mixture for each molecular weight, it is possible to isolate the crystalline polyester resin and the wax.

<Measurement method of calorific values A and B in the temperature-decreasing process of DSC measurement>
TA instrument Q1000 can be used for the measurement by a differential scanning calorimeter (DSC).
The measurement conditions were a heating rate: 10 ° C./min, a measurement temperature range of 20 ° C. to 180 ° C., and measurement was performed in the standard mode. About 2 mg of the sample is precisely weighed and placed in a silver pan, and DSC measurement is performed using an empty silver pan as a reference. In the measurement, the temperature is once raised to 180 ° C. at 10 ° C./min, and subsequently lowered to 20 ° C. at a temperature lowering rate of 10 ° C./min.
The monoester wax alone or the monoester wax extracted from the toner in advance is measured under the above conditions, and the peak top temperature of the maximum exothermic peak is analyzed from the DSC curve obtained by the temperature lowering process to obtain the maximum exothermic peak temperature. Further, a region A having the maximum exothermic peak temperature ± 5 ° C. and a region B having the maximum exothermic peak temperature + 5 to the maximum exothermic peak temperature + 15 ° C. are specified.
Subsequently, the toner is measured under the above conditions, and the heat generation amount of the areas A and B is calculated.

<Measurement of the number average particle diameter (D1) of toner (particles)>
For the number average particle diameter (D1) of the toner (particles), a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) equipped with a 100 μm aperture tube is used. Use to measure.
Measurement is performed with 25,000 effective measurement channels using the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) for setting measurement conditions and analyzing measurement data. Then, the measurement data is analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture tube flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion exchange water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) About 10 mg of toner (particles) is added to the electrolytic aqueous solution little by little in a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) The electrolytic solution (5) in which the toner (particles) is dispersed with a pipette is dropped into the round bottom beaker (1) installed in the sample stand so that the measured concentration becomes about 5%. Adjust to. Measurement is performed until the number of measured particles reaches 50,000.
(7) Analyze the measured data using the dedicated software attached to the device, and set the average diameter on the “Analysis / Number Statistics (Arithmetic Average)” screen when the graph / number% is set with the dedicated software. Average particle size (D1).

<Method for observing toner particle cross-section in transmission electron microscope (TEM) dyed with ruthenium>
Cross-sectional observation of the toner with a transmission electron microscope (TEM) can be performed as follows.
The toner particle cross section is observed by ruthenium staining. Since crystalline polyester and wax have crystallinity, they are dyed with ruthenium rather than an amorphous resin such as a binder resin. Therefore, the contrast becomes clear and observation becomes easy. Because the amount of ruthenium atoms varies depending on the intensity of staining, the strongly stained part has many of these atoms, the electron beam does not pass through, it becomes black on the observation image, and the part that is weakly stained is The electron beam is easily transmitted and becomes white on the observation image.
First, a toner is spread on the cover glass (Matsunami Glass Co., Ltd., square cover glass square No. 1) in a single layer, and an Os film is used as a protective film using an osmium plasma coater (filgen, OPC80T). (5 nm) and naphthalene film (20 nm) are applied. Next, a PTFE tube (Φ1.5 mm × Φ3 mm × 3 mm) is filled with a photocurable resin D800 (JEOL Ltd.), and the cover glass is placed on the tube so that the toner contacts the photocurable resin D800. Put it quietly in the direction. In this state, the resin is cured by irradiating light, and then the cover glass and the tube are removed to form a cylindrical resin in which toner is embedded on the outermost surface.
Using an ultrasonic ultramicrotome (Leica, UC7) at a cutting speed of 0.6 mm / s, the radius of the toner particles from the outermost surface of the cylindrical resin (number average particle diameter (D1) is 4.0 μm is 4.0 μm). 0 μm) is cut to obtain a cross section of the toner particles. Next, cutting was performed to a film thickness of 250 nm to prepare a thin sample having a cross section of the toner particles. By cutting with such a method, the cross section of the toner particle central portion can be obtained.
The resulting flakes sample vacuum electron dyeing apparatus (Filgen Co., VSC4R1H) was used to stain for 15 minutes with RuO ₄ gas 500Pa atmosphere, TEM (JEOL Co., JEM2800) was STEM observation using STEM functions.
An image was acquired with a STEM probe size of 1 nm and an image size of 1024 × 1024 pixels.
Further, the contrast of the detector control panel of the bright-field image was adjusted to 1425, the brightness was adjusted to 3750, the contrast of the image control panel was adjusted to 0.0, the brightness was adjusted to 0.5, and the gamma was acquired to be 1.00.

<Identification of crystalline polyester and release agent domain>
Based on the TEM image of the toner particle cross section, the domain of the crystalline material is identified by the following procedure.
When crystalline materials are available as raw materials, their crystal structures are observed in the same manner as in the above-described method for observing the cross section of toner particles in a transmission electron microscope (TEM) dyed with ruthenium. Obtain an image of the lamella structure. The lamella structure of the domain in the cross section of the toner particle is compared with them, and when the lamellar layer interval has an error of 10% or less, the raw material forming the domain in the cross section of the toner particle can be specified.

<Measurement of number average value (D1) of major axis of domain of crystalline material>
The number average value (D1) of the major axis of the domain of the crystalline material means the number average value obtained from the major axis of the domain of the crystalline material based on the TEM image. Moreover, the micro domain of a crystalline material measures a 1.0 micrometer or less domain. That is, a domain of crystalline material larger than 1.0 μm is present, but it is determined that there is no domain for toner having no domain of 1.0 μm or less.
Based on the TEM image obtained by observing the cross section of the toner particle with the transmission electron microscope (TEM) subjected to the ruthenium dyeing process, the number average value of the major axis of the domain of the crystalline material is measured. At that time, a cross section of 100 toner particles is observed. The observed toner particle cross section exhibits a long diameter R (μm) satisfying a relationship of 0.9 ≦ R / D4 ≦ 1.1 with respect to the weight average particle diameter (D4) of the toner. The major axis of all domains is measured, and the number average value (D1) is calculated.

<Measurement of 25% ratio of domains of crystalline material>
The 25% rate is the ratio (number%) of fine domains of the crystalline material existing in a region within 25% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section of the toner particle.
The method of calculating the 25% rate is as follows. The observed toner particle cross section exhibits a long diameter R (μm) satisfying a relationship of 0.9 ≦ R / D4 ≦ 1.1 with respect to the weight average particle diameter (D4) of the toner.
Based on the image obtained by the TEM observation described above, the contour (edge detection) of the cross section of the toner particle is clarified using image processing software. Next, the center of gravity of the cross section of the toner particles is obtained. A line is drawn from the center of gravity to a point on the contour of the toner particle cross section. On the line, the position of 25% of the distance between the outline and the center of gravity of the cross section is specified from the outline.
Then, this operation is performed once for the contour of the toner particle cross section, and a boundary line of 25% of the distance between the contour and the center of gravity of the cross section is clearly shown from the contour of the toner particle cross section. (Figure 3). Based on the TEM image showing the 25% boundary line, the number of micro domains (hereinafter referred to as C) of the crystalline material in the cross section of one toner particle is measured. Further, the number of fine domains (hereinafter referred to as B) of the crystalline material existing in a region within 25% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section of the toner particle in the cross section of one toner particle. Measure. The 25% rate of the crystalline material domain is calculated according to the following equation.
The micro domain of the crystalline material existing on the 25% boundary line is measured as “D”.
25% rate = {“D” / “C”} × 100 (%)
This is performed for a cross section of 100 toner particles, and the arithmetic average value is set to a 25% ratio.

<Method for measuring molecular weight of crystalline resin>
The molecular weight of a crystalline resin such as a crystalline polyester resin is measured by gel permeation chromatography (GPC) as follows. The measurement method will be described below by taking crystalline polyester as an example.
First, the crystalline polyester is dissolved in tetrahydrofuran (THF) at room temperature. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Equipment: High-speed GPC equipment “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: LF-604 double eluent: THF
Flow rate: 0.6 ml / min
Oven temperature: 40 ° C
Sample injection amount: 0.020 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation), and a molecular weight calibration curve is used.

<Measurement of particle size distribution and aspect ratio of silica fine particles on toner particle surface>
The number average particle size of the primary particles of silica fine particles was measured by taking a photograph of the surface of the toner particles magnified 100,000 times with FE-SEM S-4800 (manufactured by Hitachi, Ltd.), and using the enlarged photo, The particle size of the silica fine particles is measured, and the particle size distribution is obtained from the dispersion diameter of each silica fine particle. The particle diameter of the silica fine particle is counted as the absolute maximum length when the shape is spherical, and the major axis is counted as the particle diameter when it has a major axis and a minor axis.
Further, the aspect ratio is obtained by averaging the ratio of the major axis and minor axis of the silica fine particles on the toner particle surface.

<Measurement of melting point>
Melting | fusing point of crystalline resin, wax, etc. can be calculated | required as the peak top temperature of an endothermic peak at the time of measuring by DSC. Measurement can be performed using Q1000 manufactured by TA Instruments. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, and an empty pan is set for control and measured.

<Method for Measuring Glass Transition Temperature Tg (° C.) of Toner, Colored Particle, and Resin>
The glass transition temperature Tg (° C.) of the toner, the colored particles and the resin can be measured using Q1000 manufactured by TA Instruments. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of a sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure at / min.
In this temperature raising process, a specific heat change is obtained in the range of 40 ° C. or more and 100 ° C. or less. At this time, the temperature at the point where the straight line equidistant from the straight line extending the base line before and after the specific heat change and the curve of the stepwise change part of the glass transition intersects the glass transition temperature. Tg (° C.).

  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. In addition, the part in the following mixing | blending is a mass reference | standard unless there is particular notice.

<Production of crystalline polyesters 1 to 3>
The alcohol monomers and carboxylic acid monomers 1 and 2 were as shown in Table 1, and the reaction time and temperature, and the amount of monomer added were adjusted so as to have desired physical properties to obtain crystalline polyesters 1 to 3. The physical properties are shown in Table 1. Crystalline polyesters 1 to 3 had a clear endothermic peak in differential scanning calorimetry (DSC).

<Manufacture of magnetic iron oxide>
4.0 mol in 50 liters of iron sulfate first aqueous solution containing 2.0 mol / L Fe ²⁺
/ L sodium hydroxide aqueous solution (55 liters) was mixed and stirred to obtain a ferrous salt aqueous solution containing ferrous hydroxide colloid. This aqueous solution was kept at 85 ° C., and an oxidation reaction was performed while blowing air at 20 L / min to obtain a slurry containing core particles.
The obtained slurry was filtered and washed with a filter press, and then the core particles were dispersed again in water and reslurried. To this reslurry liquid, sodium silicate that is 0.20% by mass in terms of silicon per 100 parts of the core particles is added, the pH of the slurry liquid is adjusted to 6.0, and the magnetic oxidation having a silicon-rich surface is performed by stirring. Iron particles were obtained. The obtained slurry was filtered and washed with a filter press, and further reslurried with ion-exchanged water. To this reslurry liquid (solid content 50 g / L), 500 parts (10% by mass with respect to magnetic iron oxide) of ion exchange resin SK110 (manufactured by Mitsubishi Chemical) was added, and ion exchange was performed by stirring for 2 hours. Thereafter, the ion exchange resin was removed by filtration through a mesh, filtered and washed with a filter press, dried and crushed to obtain magnetic iron oxide having a number average diameter of 0.23 μm.

<Manufacture of silane compounds>
30 parts of iso-butyltrimethoxysilane was added dropwise to 70 parts of ion exchange water with stirring. Thereafter, this aqueous solution was kept at pH 5.5 and a temperature of 55 ° C., and hydrolyzed by dispersing for 120 minutes at a peripheral speed of 0.46 m / s using a disper blade. Thereafter, the pH of the aqueous solution was adjusted to 7.0 and cooled to 10 ° C. to stop the hydrolysis reaction. Thus, an aqueous solution containing a silane compound was obtained.

<Manufacture of magnetic body 1>
100 parts of magnetic iron oxide was put into a high-speed mixer (LFS-2 type manufactured by Fukae Pautech Co., Ltd.), and 8.0 parts of an aqueous solution containing a silane compound was dropped over 2 minutes while stirring at a rotational speed of 2000 rpm. Thereafter, the mixture was mixed and stirred for 5 minutes. Next, in order to enhance the fixing property of the silane compound, after drying at 40 ° C. for 1 hour to reduce moisture, the mixture was dried at 110 ° C. for 3 hours to proceed the condensation reaction of the silane compound. Then, it pulverized and obtained the magnetic body 1 through the sieve of 100 micrometers of openings.

<Manufacture of toner 1>
After adding 450 parts of 0.1 mol / L-Na ₃ PO ₄ aqueous solution to 720 parts of ion-exchanged water and heating to 60 ° C., 67.7 parts of 1.0 mol / L-CaCl ₂ aqueous solution was added. An aqueous medium containing a dispersion stabilizer was obtained.
・ Styrene 76.0 parts ・ N-butyl acrylate 24.0 parts ・ Divinylbenzene 0.2 part ・ Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1.5 parts ・ Magnetic substance 1 90.0 parts Amorphous saturated polyester resin 3.0 parts (amorphous saturated polyester resin obtained by condensation reaction of bisphenol A ethylene oxide (2 mol) adduct and terephthalic acid; Mw = 9500, acid value = 2.2 mgKOH / G, glass transition temperature = 68 ° C.)
About the said prescription, it was uniformly disperse-mixed using the attritor (made by Nippon Coke Industries Co., Ltd.), and the monomer composition was obtained. This monomer composition was heated to 63 ° C., 20 parts of behenyl stearate (melting point 68 ° C., weight average molecular weight 590) and 2 parts of crystalline polyester 1 were mixed and dissolved therein.
The aqueous medium of the above monomer composition was charged in, 60 ° C., T. under N ₂ atmosphere K. The mixture was stirred at 12000 rpm for 10 minutes with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) and granulated. Thereafter, 8.0 parts of a polymerization initiator t-butyl peroxypivalate was added while stirring with a paddle stirring blade, and the temperature was raised to 70 ° C. and reacted for 4 hours. After completion of the reaction, the suspension was heated to 100 ° C. and held for 2 hours.
Thereafter, as a cooling step, 0 ° C. water is added to the suspension, and the suspension is cooled from 100 ° C. to 40 ° C. at a rate of 100 ° C./min. The temperature was raised again and held for 120 minutes. Then, it cooled by naturally cooling to room temperature at 25 degreeC. The cooling rate at that time was 2 ° C./min.
Thereafter, hydrochloric acid was added to the suspension and thoroughly washed to dissolve the dispersion stabilizer, followed by filtration and drying to obtain toner particles 1. The production conditions of the toner particles 1 are shown in Table 2.

<Production of toner particles 2 to 21 and comparative toner particles 1 to 5>
In the production of toner particles 1, toner particles 2 to 21 and comparative toner particles 1 to 5 were produced in the same manner except that the materials and production conditions were changed as shown in Table 2.

<Production of Comparative Toner Particle 6>
(Manufacture of binder resin)
Let the molar ratio of the raw material monomer which concerns on manufacture of polyester be the following.
BPA-PO: BPA-EO: TPA: TMA = 50: 45: 70: 12
Here, BPA-PO: bisphenol A propylene oxide 2.2 mol adduct, BPA-EO: bisphenol A ethylene oxide 2.2 mol adduct, TPA: terephthalic acid, TMA: trimellitic anhydride are shown, respectively.
Among the raw material monomers shown above, raw material monomers other than TMA and 0.1% by mass of tetrabutyl titanate as a catalyst are placed in a flask equipped with a dehydrating tube, a stirring blade, a nitrogen introducing tube, etc., and subjected to condensation polymerization at 220 ° C. for 10 hours. I let you. Further, TMA was added and reacted at 210 ° C. until a desired acid value was reached, thereby obtaining an amorphous polyester resin (glass transition temperature Tg: 55 ° C., acid value: 17 mgKOH / g, weight average molecular weight: 9000). .
(Manufacture of toner)
Amorphous polyester resin 100.0 parts Crystalline polyester 1 2.0 parts Monoazo dye iron complex (T-77 manufactured by Hodogaya Chemical Co., Ltd.) 1.5 parts Magnetic substance 10.0 parts Stearic acid 20.0 parts of behenyl The above raw materials were premixed with an FM mixer (Nihon Coke Industries, Ltd.). Subsequently, the set temperature was adjusted so that the direct temperature in the vicinity of the outlet of the kneaded material was 140 ° C. by a twin-screw kneading extruder (PCM-30: manufactured by Ikegai Iron Works Co., Ltd.) set at a rotation speed of 200 rpm, and melt kneading. did.
The obtained melt-kneaded product was cooled, and the cooled melt-kneaded product was coarsely pulverized with a cutter mill. Subsequently, the obtained coarsely pulverized product was finely pulverized using a turbo mill T-250 (manufactured by Turbo Kogyo Co., Ltd.), classified using a multi-division classifier utilizing the Coanda effect, and the number average particle diameter (D1 Comparative toner particles 6 having a diameter of 6.6 μm were obtained.

<Production of Comparative Toner Particles 7>
(Preparation of amorphous polyester resin dispersion)
A compound having the following composition and 0.12 part of dibutyltin oxide as a catalyst are charged into a heat-dried three-necked flask, and the pressure in the container is reduced by a depressurization operation. The mixture was refluxed at 180 ° C. for 6 hours. Thereafter, the mixture was stirred for 5 hours while gradually raising the temperature to 200 ° C. by vacuum distillation, and when it became viscous, the molecular weight was measured by GPC. When the weight average molecular weight reached 13700, vacuum distillation was performed. It stopped and air-cooled and the amorphous polyester resin 2 was produced.
Bisphenol A propylene oxide adduct (average added mole number 2): 140 parts Bisphenol A ethylene oxide adduct (average added mole number 2): 60 parts Dimethyl isophthalate: 40 parts Terephthalic acid: 70 parts Next, amorphous polyester Resin 2 was transferred to “Cavitron CD1010” (manufactured by Eurotech) at a rate of 100 g / min in the molten state. On the other hand, dilute aqueous ammonia prepared by diluting reagent aqueous ammonia with ion-exchanged water to a concentration of 0.37% by mass was put into a separately prepared aqueous medium tank and heated to 120 ° C. with a heat exchanger.
The heated diluted ammonia water was transferred to Cavitron CD1010 simultaneously with the amorphous polyester resin. The transfer speed is 0.1 liter per minute. In this state, by operating the Cavitron CD1010 with the rotor rotating frequency set to 60 Hz and the pressure set to 4.9 × 10 ⁵ Pa, an amorphous polyester resin having a volume-based median diameter of 0.28 μm. 2 dispersion was prepared. Thereafter, the water content of the dispersion was adjusted so that the resin concentration was 20% by mass.

(Preparation of dispersion of crystalline polyester containing wax)
20 parts of crystalline polyester 1 was put into a heat-dried three-necked flask and refluxed at 180 ° C. for 5 hours by mechanical stirring. Thereafter, the temperature was raised to 200 ° C. under reduced pressure distillation, 200 parts of behenyl stearate was added as a wax, and the crystalline polyester 1 was transferred to the Cavitron CD1010 at a rate of 100 g / min in a molten state.
Further, diluted aqueous ammonia prepared by diluting reagent aqueous ammonia with ion-exchanged water to a concentration of 0.37% by mass was put into a separately prepared aqueous medium tank and heated to 120 ° C. with a heat exchanger. The heated diluted ammonia water was transferred to the Cavitron CD1010 at a rate of 0.1 liter per minute simultaneously with the melt of the crystalline polyester resin 1. In this state, the rotation frequency of the rotor was set to 60 Hz and the pressure was set to 4.9 × 10 ⁵ Pa, and the Cavitron CD1010 was operated to prepare a dispersion liquid of the crystalline polyester resin 1 containing the wax.
Further, the volume-based median diameter of the crystalline polyester resin 1 encapsulating the wax was 0.26 μm. The water content of the dispersion was adjusted so that the resin particle concentration was 20% by mass.

(Preparation of colorant dispersion)
Carbon black (CB): 50 parts Ionic surfactant (sodium n-dodecylbenzenesulfonate): 8 parts Ion exchange water: 250 parts After a dispersion treatment for 10 minutes, the mixture was treated with an ultrasonic disperser for 20 minutes to prepare a colorant dispersion in which colorant particles having a volume-based median diameter of 180 nm were dispersed.

(Production of toner)
Amorphous polyester resin 2 dispersion: 560 parts Wax-containing crystalline polyester 1 dispersion: 340 parts Colorant dispersion: 80 parts The above ingredients are charged into a round stainless steel flask and 300 parts of ions The temperature was adjusted to 20 ° C. with stirring with exchange water. Thereafter, the mixture was sufficiently mixed and dispersed with an Ultra Turrax T50 to prepare a dispersion. Next, 0.1 part of polyaluminum chloride was added to the dispersion, and the dispersion treatment was continued with an ultra turrax T50. After the dispersion treatment, the flask was put into a heating oil bath, and the flask was heated to 45 ° C. while stirring. After maintaining the flask at 45 ° C. for 60 minutes, 200 parts of a dispersion of amorphous polyester resin 2 was slowly added to the dispersion.
The pH in the system was adjusted to 8 with a 0.5 mol / liter aqueous sodium hydroxide solution. Thereafter, the stainless steel flask was sealed and heated to 90 ° C. while stirring was continued with a magnetic seal. Further, the pH in the system was adjusted to 7 using 0.5 mol / liter of nitric acid and held for 30 minutes. The reaction was continued.
After completion of the reaction, a multi-tube heat exchanger was used (coolant was 5 ° C. cold water), and the flow rate of cold water was adjusted to 25 ° C./min and cooled to 30 ° C. After cooling, it was filtered and thoroughly washed with ion-exchanged water, and then subjected to solid-liquid separation by Nutsche suction filtration. Further, the separated particles were redispersed in 3 liters of ion exchange water at 43 ° C., and washed by stirring for 15 minutes at 300 rpm.
This operation was repeated 5 times, and when the pH of the filtrate was 6.6 and the electric conductivity was 12 μS / cm, No. was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours, and classification was performed using a multi-division classifier utilizing the Coanda effect, to obtain comparative toner particles 7 having a number average particle diameter (D1) of 6.6 μm.

<Toner production 1>
100 parts of toner particles 1, 0.2 parts of hydrophobic silica fine particles with a primary particle number average diameter of 8 nm, and 0.5 parts of hydrophobic silica fine particles with a primary particle number average diameter of 50 nm are mixed with FM mixer (manufactured by Nippon Coke Industries, Ltd.). ) To obtain toner 1. Table 4 shows the physical properties.

<Production of Toners 2 to 25 and Comparative Toners 1 to 7>
Toner 1 was produced in the same manner except that the formulation was changed as shown in Table 3, and toners 2 to 26 and comparative toners 1 to 7 were produced. Table 4 shows the physical properties.

表中、「ピーク値」は、トナー粒子表面のシリカ微粒子の個数基準の粒径分布における３０〜９０ｎｍの範囲にあるピーク値（ｎｍ）を示す。また、シリカの平均径は、一次粒子の個数平均径である。

In the table, “peak value” indicates a peak value (nm) in the range of 30 to 90 nm in the particle size distribution of the number of silica particles on the toner particle surface. The average diameter of silica is the number average diameter of primary particles.

<Example 1>
The machine used for evaluation in this example is a main body that has been modified so that the process speed of a commercially available magnetic one-component printer HP LaserJet Enterprise M609dn (manufactured by Hewlett-Packard: process speed 377 mm / s) is 400 mm / s. The following evaluation was carried out using toner 1.
The process cartridge used for evaluation in this example is 37X Extra High Yield Black Original LaserJet Toner.
Cartridge (manufactured by Hewlett-Packard Company). Product toner was extracted from the inside of a predetermined process cartridge, cleaned by air blow, and then filled with 950 g of toner obtained in the example (700 g of non-magnetic toner) so as to have a high density. Using this, the toner 1 was evaluated. The evaluation results are shown in Table 5.

(Evaluation of toner scattering in high temperature and high humidity environment)
The thickness of the seal members located at both ends of the process cartridge was increased by about 20%. By doing so, since the rubbing and pressure between the carrier and the seal member increase, the evaluation becomes stricter.
The developing device filled with the toner is left in a high temperature and high humidity environment (32.5 ° C., 85% RH) for 48 hours.
A horizontal line with a printing rate of 1% was output as a durable image. After printing 10,000 sheets and 20,000 sheets by intermittently passing two sheets, the developing device was taken out from the main body, and the state of toner scattering inside and outside the developing device and the main body was visually observed and evaluated according to the following criteria. Moreover, Vitality (the product made from Xerox, basic weight 75g / cm < ² >, letter) was used for the evaluation paper.
The toner scattering after durability was evaluated. The process cartridge is removed from the apparatus, A4 paper is placed around the developer carrier, and the developer carrier is rotated at the same peripheral speed as the main body for 10 minutes. The mass of the toner dropped on the paper was measured and evaluated according to the following criteria.
A: Less than 3 mg B: 3 mg or more and less than 6 mg C: 6 mg or more and less than 10 mg D: 10 mg or more

(Evaluation of paper discharge adhesion in high temperature and high humidity environment)
The developing device filled with the toner is left in a high temperature and high humidity environment (32.5 ° C., 85% RH) for 48 hours. The evaluation machine used in the same evaluation as described above was used, and evaluation was performed using A4 color laser copy paper (manufactured by Canon, 60 g / m ² ) as evaluation paper. Since the evaluation paper is relatively thin and the toner is easily melted, image sticking is likely to occur, and strict evaluation is possible.
100 solid black images were continuously printed on both sides. The bundle of paper discharged from the paper discharge unit was left in the stacking unit for 30 minutes or more and cooled to room temperature. Thereafter, the paper was divided into one sheet, and the sticking of the image was evaluated based on the number of white spots in the solid black image. The smaller the number of white spots in the solid black image, the better. When the solid black image is stuck on the upper layer paper, the solid black image is whitened by peeling off the paper bundle, and the number of the spots increases as the sticking is increased. The ranking was as follows according to the number obtained.
A: No missing B: Number of missing 1-4 C: Number of missing 5-14 D: Number of missing 15 or more

(Evaluation of motor (density unevenness))
Using the above-mentioned modified machine, the mottle (density unevenness) was evaluated using a solid image. The image density was measured with a color reflection densitometer (manufactured by X-RITE 404 X-Rite). Concentrations at a total of five locations in the vicinity of the four corners and the central portion in the development area were measured and evaluated from the maximum density and minimum density as follows.
Using the above process cartridge, a solid image was output on evaluation paper (FOX RIVER BOND paper [110 g / m ² ]). Since the evaluation paper has relatively large surface irregularities, the mottle can be evaluated more strictly. The evaluation criteria are shown below.
A: The image density difference (maximum density−minimum density) is less than 0.03.
B: Image density difference (maximum density−minimum density) is 0.03 or more and less than 0.05.
C: The image density difference (maximum density−minimum density) is 0.05 or more and less than 0.10.
D: The image density difference (maximum density−minimum density) is 0.10 or more and less than 0.15.
E: Image density difference (maximum density-minimum density) is 0.15 or more.

(Evaluation of tailing in normal temperature and high humidity environment)
The developing device filled with the toner is left for 48 hours in a normal temperature and high humidity environment (23 ° C./85% RH). By evaluating in the above environment, the adsorptivity of moisture to the paper is increased, and the evaluation becomes more severe in tailing.
Using the process cartridge and the evaluation paper (FOX RIVER BOND paper [110 g / m ² ]), a horizontal line image in which 4 dot lines were arranged in a 20 dot space on the evaluation paper was output. After printing 2000 sheets with two intermittent sheets, the number of fixing tails when 50 sheets are passed is visually evaluated. The evaluation criteria are shown below.
A: Fixation tailing has not occurred.
B: The occurrence of fixing tailing is 1 to 5 sheets.
C: The occurrence of fixing tailing is 6 to 10 sheets.
D: 11 or more fixing tails are generated.

(Evaluation of electrostatic offset resistance in low temperature and low humidity environment)
The developing device filled with the toner is left in a low temperature and low humidity environment (15 ° C., 10% RH) for 48 hours. By evaluating in a low temperature and low humidity environment, the chargeability tends to increase, and the antistatic offset resistance is evaluated more severely.
After printing 10,000 sheets of horizontal line images with a printing rate of 1% on intermittent paper, 100 sheets are printed continuously using an electrostatic offset test chart in which the first half of the image is a solid black image and the second half is a white background The electrostatic offset resistance was visually evaluated. In addition, the evaluation criteria of the electrostatic offset resistance are determined as follows.
A: Image disorder is not seen at all.
B: Image disturbance is faintly seen on a white background.
C: Image disturbance is seen on the white background.
D: Image disturbance is clearly seen on the white background.

<Examples 2 to 26>
The toner was changed as shown in Table 4, and image output evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

<Comparative Examples 1-7>
The toner was changed as shown in Table 4, and image output evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 5.

1: distance from the surface of the toner to the center point of the toner, 2: a domain of the crystalline material, 3: a region having a depth of 25% with respect to the particle size of the toner cross section from the surface of the toner,
100: photosensitive drum (image carrier, charged member), 102: developing sleeve (toner carrier), 114: transfer charging roller (transfer member), 116: cleaner, 117: primary charging roller (contact charging member), 121 : Laser generator (latent image forming means, exposure device), 124: register roller, 125: transport belt, 126: fixing device, 140: developing device, 141: stirring member

Claims (8)

A toner having toner particles containing a binder resin, a crystalline resin, a wax and a colorant,
The two-particle force Fp (A) at 45 ° C. of the toner measured by the following method is 80 nN or less,
A toner having a two-particle force Fp (B) at 80 ° C. of 290 nN or more.
[Fp (A) is calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 1.6 kN / m ² at 45 ° C. and the toner compact is broken. Is the force between two particles,
The Fp (B) is calculated from the maximum tensile breaking force when a toner compact is formed by applying a load of 10.0 kN / m ² at 80 ° C. and the toner compact is broken. It is the force between two particles. ]   The toner according to claim 1, wherein the crystalline resin contains a crystalline polyester resin.   The toner according to claim 1, wherein the wax contains a monoester wax. In the DSC curve obtained in the process of increasing the temperature to 180 ° C. and then decreasing the temperature by differential scanning calorimetry of the toner,
The calorific value in the region of the maximum exothermic peak temperature ± 5 ° C of the monoester wax obtained by the measurement under the same conditions is A, and the calorific value in the region of the maximum exothermic peak temperature + 5 ° C or more and the maximum exothermic peak temperature + 15 ° C or less. The toner according to claim 3, wherein B / A is 0.5 or more and 4.0 or less, where B is B.   The toner according to claim 3 or 4, wherein a content of the monoester wax is 10.0 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the binder resin.   The toner according to claim 3, wherein a mass ratio of the crystalline resin to the monoester wax (crystalline resin / monoester wax) is 0.05 or more and 0.33 or less. Silica fine particles are contained on the surface of the toner particles,
The toner according to claim 1, which has a peak in a range of 30 nm to 90 nm in a particle size distribution based on the number of the silica fine particles on the surface of the toner particles observed with a scanning electron microscope. The interparticle force Fp (A) is 10 nN or more and 80 nN or less,
The toner according to claim 1, wherein the interparticle force Fp (B) is 290 nN or more and 500 nN or less.

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