JP2023171240A - toner - Google Patents

Abstract

To provide a toner which exhibits all of low-temperature fixability, transferability, and scratch resistance at high levels.SOLUTION: A toner is provided, comprising toner particles containing a binder resin, wax, and inorganic fine particles. In a temperature range of 30°C to T1°C, the inorganic fine particles always exhibit a thermal expansion coefficient of -0.1×10-6 (/K) or less as determined from X-ray diffraction, where T1 (°C) represents an outflow start temperature measured using the toner. Content of the wax is in a range of 3.0-20.0 mass%, inclusive, with respect to a mass of a toner particle.SELECTED DRAWING: None

Description

The present invention relates to a toner used in electrophotography, electrostatic recording, and electrostatic printing.

In recent years, as electrophotographic full-color copying machines have become widespread, the demand for high-speed printing and energy saving has further increased. In order to support high-speed printing, technologies are being considered to more quickly melt toner in the fixing process. Furthermore, as an energy-saving measure, a technique for fixing toner at a lower temperature is being considered in order to reduce power consumption in the fixing process.
In order to cope with high-speed printing and improve the low-temperature fixability of toner, there is a method of lowering the glass transition point and softening point of the binder resin of the toner and using a binder resin having sharp melting properties. However, toners with improved low-temperature fixing properties have a problem in that they have low internal cohesive force, and the toner tends to set off when printed sheets rub against each other, resulting in reduced scratch resistance.
In order to solve the above problems, Patent Document 1 proposes increasing the molecular weight of a toner binder to harden the toner fixing material. Further, Patent Document 2 proposes lowering the surface friction coefficient of the toner fixing material by increasing the amount of wax in the toner or making it easier to seep out.

Japanese Patent Application Publication No. 2010-191355 Japanese Patent Application Publication No. 2011-70002

However, while the toner described in Patent Document 1 has improved scratch resistance, it has been found that the toner becomes hard, resulting in deterioration in low-temperature fixability and deterioration in pulverization properties in the melt-kneading pulverization method.
In addition, while the toner described in Patent Document 2 has improved scratch resistance, the increase in wax on the toner surface causes uneven charging on the toner surface and increases the adhesion force between the toners. It was found that the transferability deteriorated.
An object of the present invention is to obtain a toner that exhibits all of low-temperature fixability, transferability, and scratch resistance at high levels.

As a result of extensive studies, the present inventors found that by internally adding a negative thermal expansion material with a thermal expansion coefficient of -0.1×10 ^-6 (/K) or less to toner particles, low-temperature fixing properties can be improved. It has been found that a toner having both transferability and scratch resistance can be obtained.
That is, the present invention provides a toner having toner particles containing a binder resin, wax, and inorganic fine particles,
When the outflow start temperature measured using toner is T1 (°C), the inorganic fine particles always have a thermal expansion coefficient of -0.1× determined by X-ray diffraction in the temperature range of 30°C to T1°C. 10 ^-6 (/K) or less,
The present invention relates to a toner characterized in that the wax content is 3% by mass or more and 20% by mass or less based on the mass of the toner particles.

According to the present invention, it is possible to provide a toner that exhibits all of low-temperature fixability, transferability, and scratch resistance at high levels.

FIG. 2 is a schematic diagram of an apparatus suitable for heat treatment of resin particles that will become toner particles.

In the present invention, the descriptions such as "○○ or more and XX or less" or "○○ to XX" expressing a numerical range mean a numerical range that includes the lower limit and the upper limit, which are the end points, unless otherwise specified.

EMBODIMENT OF THE INVENTION Hereinafter, the form for implementing this invention is demonstrated in detail.

The toner of the present invention is a toner having toner particles containing a binder resin, wax, and inorganic fine particles,
When the outflow start temperature measured using toner is T1 (°C), the inorganic fine particles always have a thermal expansion coefficient of -0.1× determined by X-ray diffraction in the temperature range of 30°C to T1°C. 10 ^-6 (/K) or less,
The content of the wax is 3.0% by mass or more and 20.0% by mass or less based on the mass of the toner particles.

The above-mentioned toner has excellent properties in terms of low-temperature fixability, transferability, and scratch resistance.

The present inventors think about the mechanism as follows.

By internally adding a negative thermal expansion material to toner particles, when heated during fixing, the volume of the negative thermal expansion material contracts and the toner as a whole becomes more crushed. It is believed that the wax, which could not seep out to the surface layer of the toner in the case of toner without the addition of wax, is now able to seep out. It is also believed that when the temperature returns to room temperature after fixing, the volume of the negative thermally expandable material returns, thereby preventing the fixed toner from shrinking and causing the edges of the toner to become angular. Therefore, by increasing the amount of surface wax, the friction coefficient of the image surface decreases, and by suppressing the angle of the toner edge, it reduces catching during rubbing, and as a result, scratch resistance improves. I think it will get better. Furthermore, we believe that by adding a negative thermal expansion material internally rather than externally, it is possible to suppress wax seepage and shrinkage even in image areas where toner particles hardly overlap, such as in halftone images. . In addition, since there is no need to increase the amount of surface wax in the toner before fixing, there is no need to reduce transferability, and there is no need to harden the binder resin, so there is no need to reduce low-temperature fixability. think.

The constituent materials of the toner will be explained below.

[Inorganic fine particles with a thermal expansion coefficient (linear expansion coefficient) of -0.1×10 ^-6 (/K) or less]
When the outflow start temperature measured using toner is T1 (°C), the inorganic fine particles always have a thermal expansion coefficient of -0.1× determined by X-ray diffraction in the temperature range of 30°C or more and T1°C or less. It is necessary that it is 10 ^-6 (/K) or less. Any inorganic fine particles having a thermal expansion coefficient within this range are not particularly limited, and any known material can be used. Within this range, the wax exudation during fixing is promoted, the shrinkage of the toner after fixing is suppressed, and the edge angle is suppressed, thereby improving scratch resistance. Note that the outflow start temperature measured using the toner reflects the outflow start temperature of the binder resin.

From the viewpoint of improving scratch resistance, the thermal expansion coefficient of the inorganic fine particles is preferably −0.2×10 ⁻⁶ (/K) or less, more preferably −1.0×10 ⁻⁶ (/K) or less.

Inorganic fine particles include, for example, zirconium tungstate particles, zirconium tungstate phosphate particles, zirconium phosphate particles, zeolite, crystallized glass, etc. in the range from 30°C to the outflow start temperature of general toner (binder resin). Examples include particles exhibiting negative thermal expansion, and one type or a plurality of types may be used.

Among these, it is preferable to include zirconium tungstate phosphate particles or zirconium phosphate particles, and more preferably zirconium tungstate phosphate particles or zirconium phosphate particles. Zirconium tungstate phosphate particles or zirconium phosphate particles are preferable because they have relatively high negative thermal expansion and can have a sharp distribution depending on the particle size when added internally to the toner.

The number average particle diameter of the inorganic fine particles is preferably 0.1 μm or more and 3.0 μm or less, more preferably 0.5 μm or more and 2.0 μm or less. Moreover, in those particle size distributions, it is preferable that the peak top of the number frequency is within the above particle size range. When the number average particle diameter is within the above range, the wax bleeds out during fixing and does not impede the color.

The content of inorganic fine particles in the toner is preferably 1.0% by volume or more and 10.0% by volume or less based on the toner particles. When the content is 1.0% by volume or more, the wax bleeds out during fixing, and when it is 10.0% by volume or less, the color tone is not inhibited, which is preferable. From the viewpoint of wax bleeding and color, the content is preferably 1.0% by volume or more and 10.0% by volume or less, more preferably 4.0% by volume or more and 8.0% by volume or less.

Although there are no particular limitations on the method for producing inorganic fine particles, a wet method is preferred because it allows a desired particle size to be easily obtained and a uniform crystal structure to be obtained.

When measuring the coefficient of thermal expansion of inorganic fine particles, it is necessary to separate the inorganic fine particles from the toner. Although the method of separation is not limited, the following methods may be mentioned.

The toner is dissolved in toluene heated to 60° C., thoroughly stirred, and then insoluble matter is precipitated using a centrifuge. Discard the supernatant and collect the precipitate, which has been thoroughly washed with toluene.

In addition to the target inorganic fine particles, the sediment contains external additives, pigments, etc., but scanning electron microscopy (SEM) and energy dispersive By identifying the pigment, etc., it is possible to measure the thermal expansion coefficient of a mixture as long as the peaks derived from the crystal do not overlap with each other using an X-ray diffraction device (XRD).

If the peaks of external additives overlap, add a surfactant to sucrose water that is a 1:2 mixture of pure water and sucrose powder, and add about 2 parts by mass of toner to 100 parts by mass of sucrose water. In addition, after stirring thoroughly, the external additives are released using an ultrasonic cleaner and then centrifuged, so that the external additives settle and the toner particles from which the external additives have been released can be collected as a film on the liquid surface. This is redispersed in pure water, filtered and washed, and then dried to obtain toner particles from which external additives have been removed.

[Binder resin]
The toner particles contain a binder resin. There are no particular restrictions on the binder resin, and known polymers commonly used in toners can be appropriately selected depending on the purpose. Although it is preferable to use an amorphous resin as the main binder, a crystalline resin may also be used in combination to improve low-temperature fixability.

The content of the amorphous resin in the binder resin is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and even more preferably 90% by mass or more and 100% by mass or less.

[Amorphous resin]
There are no particular limitations on the amorphous resin, and specifically, the following polymers can be used.

Monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene copolymers, styrene - Acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Styrenic copolymers such as copolymers, styrene-vinyl methyl ketone copolymers, and styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resins, natural resin-modified phenolic resins, natural resin-modified maleic acid resins, acrylics Examples include resins, methacrylic resins, polyvinyl acetate, silicone resins, polyester resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, polyvinyl butyral resins, terpene resins, coumaron-indene resins, and petroleum-based resins.

The binder resin preferably contains a polyester resin, more preferably a polyester resin. Hereinafter, an example in which polyester resin is selected as the binder resin will be described in detail, but the binder resin is not limited to polyester resin.

Preferably, the polyester resin is an amorphous polyester resin. The polyester resin is not particularly limited, but examples include those obtained by polycondensation of an alcohol component and a carboxylic acid component.

Specifically, the alcohol component includes the following.

Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (3.3)-2,2-bis(4-hydroxyphenyl)propane, polyoxyethylene (2. 0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (2.0)-polyoxyethylene(2.0)-2,2-bis(4-hydroxyphenyl)propane, polyoxypropylene (6) Alkylene oxide adducts of bisphenol A such as -2,2-bis(4-hydroxyphenyl)propane, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1 , 4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, poly Tetramethylene glycol, bisphenol A, hydrogenated bisphenol A, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane triol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trihydroxymethyl Benzene and their derivatives. The derivative is not particularly limited as long as a similar resin structure can be obtained by the polycondensation. Examples include derivatives obtained by esterifying the alcohol component.

On the other hand, examples of the carboxylic acid component include the following.

Aromatic dicarboxylic acids or their anhydrides such as phthalic acid, isophthalic acid and terephthalic acid; Alkyl dicarboxylic acids or their anhydrides such as succinic acid, adipic acid, sebacic acid and azelaic acid; Alkyl having 6 to 18 carbon atoms or alkenyl group-substituted succinic acid or its anhydride; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and citraconic acid or their anhydrides; trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides polyhydric carboxylic acids such as carboxylic acids; and derivatives thereof. The derivative is not particularly limited as long as a similar resin structure can be obtained by the polycondensation. Examples include derivatives obtained by converting the carboxylic acid component into methyl ester, ethyl ester, or acid chloride.

A preferred example of the amorphous polyester resin is an alcohol component containing a compound selected from the group consisting of bisphenol and its derivatives represented by the following formula (2), and a divalent or higher carboxylic acid and its derivatives. A resin obtained by condensation polymerization with a carboxylic acid component containing a compound selected from the group (for example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) Can be mentioned.

（式中、Ｒはエチレン基又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつ、ｘ＋ｙの平均値は２以上６以下である。）

(In the formula, R represents an ethylene group or a propylene group, x and y are each an integer of 1 or more, and the average value of x+y is 2 or more and 6 or less.)

Furthermore, in the bisphenol and its derivatives represented by the above formula (2), an alcohol component in which R is -CH ₂ -CH(CH ₃ )-, and an aromatic dicarboxylic acid and its derivatives. Examples include resins obtained by condensation polymerization of a carboxylic acid component containing a compound (for example, isophthalic acid, terephthalic acid).

In addition, in the bisphenol and its derivatives represented by the above formula (2), the content of the alcohol component in which R is -CH ₂ -CH(CH ₃ )- is 50 mol % or more or more than 100 mol in total in the alcohol component. % or less, more preferably 90 mol% or more and 100 mol% or less.

Further, the content of the amorphous polyester resin in the amorphous resin is preferably 25% by mass or more and 100% by mass or less, and more preferably 50% by mass or more and 100% by mass or less.

From the viewpoint of charging stability, the acid value of the amorphous polyester is preferably 1 mgKOH/g or more and 10 mgKOH/g or less.

Further, it is preferable that the amorphous polyester contains amorphous polyester A having a low softening point and amorphous polyester B having a high softening point in order to achieve both low-temperature fixability and separability.

The content ratio (A/B) of amorphous polyester A with a low softening point and amorphous polyester B with a high softening point should be 60/40 to 90/10 on a mass basis to improve low-temperature fixability and separability. Preferable from this point of view.

The softening point of the amorphous polyester A having a low softening point is preferably 70° C. or more and 100° C. or less from the viewpoint of achieving both toner storage stability and low-temperature fixability.

The softening point of the high softening point amorphous polyester B is preferably 110° C. or higher and 180° C. or lower from the viewpoint of hot offset resistance.

[wax]
The toner particles contain wax. Examples of wax include the following:

Hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, alkylene copolymers, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax; oxides of hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; Waxes whose main components are fatty acid esters such as carnauba wax; waxes that have been partially or fully deoxidized from fatty acid esters such as deoxidized carnauba wax.

Additionally, the following may be mentioned: Saturated straight chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and parinaric acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, seryl alcohol, Saturated alcohols such as sil alcohol; polyhydric alcohols such as sorbitol; fatty acids such as palmitic acid, stearic acid, behenic acid, and montanic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubil alcohol, seryl alcohol, Esters with alcohols such as sil alcohol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bisstearic acid amide, ethylene biscapric acid amide, ethylene bislauric acid amide, hexamethylene bis stearin Saturated fatty acid bisamides such as acid amide; unsaturated fatty acid amides such as ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N,N' dioleyl adipic acid amide, N, N' dioleyl sebacic acid amide; m - Aromatic bisamides such as xylene bisstearamide and N,N' distearyl isophthalic acid amide; aliphatic metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate (generally used with metal soaps) Waxes made by grafting aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid; Partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; Vegetable oils and fats A methyl ester compound with a hydroxyl group obtained by hydrogenation of

Among these waxes, hydrocarbon waxes such as paraffin wax and Fischer-Tropsch wax, or fatty acid ester waxes such as carnauba wax are preferred from the viewpoint of improving low-temperature fixability, hot offset resistance, and scratch resistance.

The content of the wax is 3.0% by mass or more and 20.0% by mass or less based on the mass of the toner particles (3.0 parts by mass or more and 20.0 parts by mass or less based on 100 parts by mass of toner particles). . When the content of the wax is within this range, the wax oozes out onto the surface of the fixed image, providing scratch resistance, and easily exhibiting the fixing separation property at high temperatures. Wax on the surface is suppressed and uneven charging on the toner surface is suppressed, thereby suppressing adhesion and maintaining transferability.

In addition, from the perspective of achieving both toner storage stability, fixing and separation properties at high temperatures, and scratch resistance, the endothermic curve measured by a differential scanning calorimeter (DSC) when the temperature is increased is 30°C or higher and 200°C or lower. It is preferable that the peak temperature of the maximum endothermic peak of the wax existing in the range of 50°C or more and 110°C or less.

Furthermore, regarding the presence state of wax in the toner particles, in cross-sectional observation of the toner using a transmission electron microscope, the area ratio Ws occupied by wax in the surface layer region from the surface of the toner particle to a depth of 500 nm, and 500 nm. It is preferable that the ratio Wi of the area occupied by the wax in the inner region satisfies the following formula (1) because both scratch resistance and transferability can be achieved.
2.0≧Ws/Wi≧1.0 Formula (1)

The state of wax distribution in the toner is determined by observing the cross section of the toner particles using a transmission electron microscope (TEM), calculating Ws and Wi from the cross-sectional area of the domain formed by the wax, and calculating the average of 100 arbitrarily selected toner particles. Evaluate with value.

In detail, the toner was embedded in a visible light-curable embedding resin (D-800, manufactured by Nissin EM), cut to a thickness of 60 nm using an ultrasonic ultramicrotome (EM5, manufactured by Leica), and then Ru staining is performed using (manufactured by Philgen). Thereafter, observation is performed using a transmission electron microscope (H7500, manufactured by Hitachi) at an accelerating voltage of 120 kV. 100 cross sections of the toner to be observed are selected and photographed within ±2.0 μm from the weight average particle diameter. Image processing software (Photoshop 5.0, manufactured by Adobe) is used on the obtained image to clarify the distinction between the wax domain and the binder resin region. In detail, wax domains can be distinguished as follows. Using image processing software, the captured TEM image is binarized by setting the brightness (gradation level 255) threshold to 160. At this time, the wax of the toner and the photocurable resin D800 become a bright part, and the part other than the wax of the toner becomes a dark part. The outline of the toner can be distinguished by the brightness and darkness of the toner and photocurable resin.

Masking is performed on the cross section of the toner particle, leaving a surface layer region from the toner particle surface (outline of the cross section) to a depth of 500 nm (including the 500 nm boundary). Specifically, a line is drawn from the center of gravity of the toner particle cross section to a point on the contour of the toner particle cross section. On the line, a position 500 nm away from the contour in the direction of the center of gravity is specified. Then, this operation is performed for one rotation around the contour of the toner particle cross section to clarify the surface layer region up to 500 nm from the contour of the toner particle cross section. The area percentage occupied by the wax domain in the area of the obtained surface layer region is calculated, and this is defined as Ws.

[Wax dispersant]
In order to improve the dispersibility of wax in the binder resin, a resin having both a polar part close to the wax component and a part close to the resin polarity may be added as a wax dispersant. Specifically, a styrene acrylic resin graft-modified with a hydrocarbon compound is preferred. More preferred is a resin composition in which a styrene acrylic resin is reacted (grafted) with a polyolefin such as polyethylene. The content of such a wax dispersant (resin composition) is preferably 1.0 parts by mass or more and 15.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

[Colorant]
As the coloring agent, the following may be mentioned.

Examples of the black colorant include carbon black, which is colored black using a yellow colorant, a magenta colorant, and a cyan colorant. Although a pigment may be used alone as a coloring agent, it is more preferable to use a dye and a pigment together to improve the clarity from the viewpoint of the image quality of a full-color image.

Examples of magenta colored pigments include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48:2, 48:3, 48:4, 49, 50, 51, 52, 53, 54, 55, 57:1, 58, 60, 63, 64, 68, 81:1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 146, 147, 150, 163, 184, 202, 206, 207, 209, 238, 269, 282; I. Pigment Violet 19; C. I. Bat Red 1, 2, 10, 13, 15, 23, 29, 35.

Examples of magenta coloring dyes include the following. C. I. Solvent red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; C.I. I. Dispersed Red 9; C. I. Solvent Violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; C. I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Examples of cyan colored pigments include the following. C. I. Pigment Blue 2, 3, 15:2, 15:3, 15:4, 16, 17; C.I. I. Bat Blue 6;C. I. Acid Blue 45, a copper phthalocyanine pigment with 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton.

As the cyan coloring dye, C.I. I. There is Solvent Blue 70.

Examples of yellow colored pigments include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; C. I. Bat yellow 1, 3, 20.

As the yellow coloring dye, C.I. I. There is Solvent Yellow 162.

The amount of the colorant used is preferably 0.1 parts by mass or more and 30 parts by mass or less based on 100 parts by mass of the binder resin.

[Charge control agent]
The toner can also contain a charge control agent if necessary. As the charge control agent, any known charge control agent can be used, but a metal compound of an aromatic carboxylic acid is particularly preferable because it is colorless, can charge the toner quickly, and can stably maintain a constant charge amount.

Examples of negative charge control agents include the following. Salicylic acid metal compounds, naphthoic acid metal compounds, dicarboxylic acid metal compounds, polymeric compounds with sulfonic acid or carboxylic acid in the side chain, polymeric compounds with sulfonic acid salts or sulfonic acid esters in the side chain, carboxylic acid salts Or polymer-type compounds having carboxylic acid esters in their side chains, boron compounds, urea compounds, silicon compounds, calixarene.

Examples of positive charge control agents include quaternary ammonium salts, polymeric compounds having the quaternary ammonium salts in their side chains, guanidine compounds, and imidazole compounds. The charge control agent may be added internally or externally to the toner particles.

The amount of the charge control agent added is preferably 0.2 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin.

[Developer]
Although the toner can be used as a one-component developer, in order to further improve dot reproducibility, it is preferable to mix it with a magnetic carrier and use it as a two-component developer. It is also preferable in that stable images can be obtained over a long period of time.

As the magnetic carrier, the following known ones can be used. Iron powder with oxidized surface or unoxidized iron powder, metal particles such as iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth, etc., alloy particles thereof, oxide particles , a magnetic material-dispersed resin carrier (so-called resin carrier) containing a magnetic material such as ferrite, or a magnetic material and a binder resin that holds the magnetic material in a dispersed state.

When the toner is mixed with a magnetic carrier and used as a two-component developer, the carrier mixing ratio is preferably 2% by mass or more and 15% by mass or less, more preferably 2% by mass or more and 15% by mass or less, as the toner concentration in the two-component developer. Good results are usually obtained when the amount is 4% by mass or more and 13% by mass or less.

[Toner manufacturing method]
It is possible to employ known toner manufacturing methods such as a suspension polymerization method, a kneading and pulverization method, an emulsion aggregation method, and a dissolution/suspension method, and the method is not limited to any one of them.

Specific examples of toner manufacturing methods using the kneading and pulverization method and the emulsion aggregation method will be given below, but the method is not limited thereto.

[Kneading and grinding method]
First, in the raw material mixing step, predetermined amounts of inorganic fine particles, binder resin, wax, and optionally additives such as a wax dispersant are weighed, blended, and mixed as toner raw materials.

Examples of devices used for mixing include Henschel mixer (manufactured by Nippon Coke Co., Ltd.); Super Mixer (manufactured by Kawata Co., Ltd.); Ribocorn (manufactured by Okawara Seisakusho Co., Ltd.); Nauta mixer, Turbulizer, and Cyclomix (manufactured by Hosokawa Micron Co., Ltd.) ); spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); and Loedige mixer (manufactured by Matsubo Co., Ltd.).

Next, the obtained mixture is melted and kneaded to melt the binder resin and disperse inorganic fine particles, wax, etc. therein (melt kneading step).

Examples of devices used for melt-kneading include a TEM extruder (manufactured by Toshiba Machinery Co., Ltd.); a TEX twin-screw kneader (manufactured by Japan Steel Works, Ltd.); a PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); (manufactured by Mitsui Mining Co., Ltd.). A continuous kneading machine such as a single-screw or twin-screw extruder is preferable to a batch-type kneading machine because of its advantages such as continuous production.

Next, the obtained melt-kneaded product is rolled with two rolls or the like and cooled with water or the like.

The resulting cooled material is ground to the desired particle size. First, it is coarsely pulverized using a crusher, hammer mill, feather mill, etc., and then finely pulverized using a Cryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), a Super Rotor (manufactured by Nisshin Engineering Co., Ltd.), etc. to obtain resin particles.

The obtained resin particles may be classified to a desired particle size and used as toner particles. Examples of devices used for classification include Turboplex, Faculty, TSP, and TTSP (manufactured by Hosokawa Micron Corporation); Elbow Jet (manufactured by Nippon Steel Mining Corporation).

Further, it is preferable to heat-treat the obtained resin particles to obtain toner particles. That is, it is preferable that the toner particles are subjected to a surface treatment using heat. By performing the heat treatment, the unevenness of the toner particles is alleviated, making it easier to achieve both developability, cleaning performance, and transferability.

Furthermore, if coarse particles are present after the heat treatment, the coarse particles may be removed by classification or sieving, if necessary. The apparatus used for classification includes the above-mentioned apparatus. On the other hand, the devices used for sieving include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sieve, Gyro Shifter (Tokuju Kogyo Co., Ltd.); Turbo Screener (manufactured by Turbo Kogyo Co., Ltd.); High Bolter (manufactured by Toyo Hitech Co., Ltd.) Examples include.

On the other hand, before the heat treatment step, inorganic fine particles or the like may be added to the obtained resin particles as necessary.

Hereinafter, a method of heat-treating resin particles using the heat-treating apparatus shown in FIG. 1 will be specifically illustrated.

The resin particles quantitatively supplied by the raw material quantitative supply means 1 are guided by compressed gas adjusted by the compressed gas flow rate adjustment means 2 to the introduction pipe 3 installed on the vertical line of the raw material supply means. The mixture that has passed through the introduction pipe 3 is uniformly dispersed by a conical protruding member 4 provided at the center of the raw material supply means, and is led to a radially extending supply pipe 5 extending in eight directions into a processing chamber where heat treatment is performed. 6.

At this time, the flow of the resin particles supplied to the processing chamber 6 is regulated by a regulating means 9 provided in the processing chamber 6 for regulating the flow of resin particles. Therefore, the resin particles supplied to the processing chamber 6 are heat-treated while swirling within the processing chamber 6, and then cooled.

Hot air for heat-treating the supplied resin particles is supplied from the hot air supply means 7 and distributed by the distribution member 12, and the hot air is spirally swirled into the processing chamber 6 by the swirling member 13 for swirling the hot air. It will be introduced. As for its configuration, the rotating member 13 for rotating the hot air has a plurality of blades, and the rotation of the hot air can be controlled by the number and angle of the blades.

The temperature of the hot air supplied into the processing chamber 6 at the outlet of the hot air supply means 7 is preferably 100°C or more and 300°C or less, more preferably 130°C or more and 170°C or less. If the temperature at the outlet of the hot air supply means 7 is within the above range, it is possible to uniformly process the particles while preventing the particles from fusing or coalescing due to excessive heating of the resin particles.

Hot air is supplied from hot air supply means 7. Further, the heat-treated resin particles are cooled by the cold air supplied from the cold air supply means 8. The temperature of the cold air supplied from the cold air supply means 8 is preferably -20°C or more and 30°C or less. If the temperature of the cold air is within the above range, the heat-treated resin particles can be efficiently cooled, and fusion and coalescence of the heat-treated resin particles can be prevented without interfering with uniform heat treatment of the resin particles. Can be done. Further, the absolute moisture content of the cold air is preferably 0.5 g/m ³ or more and 15.0 g/m ³ or less.

Next, the cooled heat-treated resin particles are collected by a collection means 10 located at the lower end of the processing chamber 6. Note that a blower (not shown) is provided at the tip of the collecting means 10, and the collecting means 10 is configured to be sucked and transported by the blower (not shown).

Further, the powder particle supply port 14 is provided so that the swirling direction of the supplied resin particles and the swirling direction of the hot air are the same, and the collecting means 10 also maintains the swirling direction of the swirled resin particles. It is provided in the tangential direction on the outer periphery of the processing chamber 6 so as to do so. Furthermore, the cold air supplied from the cold air supply means 8 is configured to be supplied horizontally and tangentially from the outer periphery of the apparatus to the periphery of the processing chamber.

The swirling direction of the resin particles before heat treatment supplied from the powder particle supply port 14, the swirling direction of the cold air supplied from the cold air supply means 8, and the swirling direction of the hot air supplied from the hot air supply means 7 are all the same direction. Therefore, turbulence does not occur in the processing chamber, the swirling flow inside the device is strengthened, a strong centrifugal force is applied to the resin particles before heat treatment, and the dispersibility of the resin particles before heat treatment is further improved, resulting in fewer coalesced particles. , it is possible to obtain heat-treated resin particles with a uniform shape.

The average circularity of the toner is preferably 0.960 or more, more preferably 0.965 or more. When the average circularity of the toner is within the above range, the toner transfer efficiency is improved.

[Emulsification aggregation method]
The emulsion aggregation method involves preparing in advance an aqueous dispersion of fine particles made of toner particle constituent materials that are sufficiently small for the desired particle size, and then agglomerating the fine particles in an aqueous medium until they reach the toner particle size. This method produces toner by fusing the resin with heat.

In other words, the emulsion aggregation method includes a dispersion process to prepare a fine particle dispersion liquid made of the constituent materials of the toner particles, and an aggregation process to agglomerate the fine particles made of the constituent materials of the toner particles and control the particle size until it reaches the particle size of the toner. A toner is manufactured through a fusion step of fusing the resin contained in the obtained aggregated particles, and a subsequent cooling step.

In order to unevenly distribute the wax near the surface of the toner particles, a shelling step containing wax may be added. Examples include a method in which a shelling step is added after the aggregation step, and a method in which a shelling step is added after the cooling step, followed by a fusion step and a cooling step to obtain the toner.

[Dispersion process]
An aqueous dispersion of fine particles of resin such as a binder resin can be prepared by known methods, but is not limited to these methods. Known methods include, for example, an emulsion polymerization method, a self-emulsification method, a phase inversion emulsification method in which a resin is emulsified by adding an aqueous medium to a resin solution dissolved in an organic solvent, or a method that does not use an organic solvent. , a forced emulsification method in which the resin is forcibly emulsified by treatment at high temperature in an aqueous medium.

Specifically, a resin such as a binder resin is dissolved in an organic solvent in which the resin is dissolved, and a surfactant and a basic compound are added. Subsequently, while stirring with a homogenizer or the like, an aqueous medium is slowly added to precipitate resin particles. Thereafter, the solvent is removed by heating or under reduced pressure to prepare an aqueous dispersion of resin particles.

Any organic solvent can be used as long as it can dissolve the resin, but from the viewpoint of suppressing the generation of coarse powder, it is recommended to use an organic solvent that forms a homogeneous phase with water, such as tetrahydrofuran. preferable.

The surfactant used during the emulsification is not particularly limited, but includes anionic surfactants such as sulfate ester salts, sulfonate salts, carboxylate salts, phosphate esters, soaps, etc. Cationic surfactants such as amine salt type and quaternary ammonium salt type; Nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type, and polyhydric alcohol type. The surfactants may be used alone or in combination of two or more.

Examples of the basic compound used during the emulsification include inorganic bases such as sodium hydroxide and potassium hydroxide; organic bases such as ammonia, triethylamine, trimethylamine, dimethylaminoethanol, and diethylaminoethanol. The bases may be used alone or in combination of two or more.

The 50% particle diameter (D50) of the resin fine particles based on volume distribution is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.05 μm or more and 0.4 μm or less.

By adjusting the 50% particle size (D50) based on the volume distribution within the above range, it becomes easy to obtain toner particles having a preferable weight average particle size of 4.0 μm or more and 7.0 μm or less.

Note that a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150, manufactured by Nikkiso) is used to measure the 50% particle size (D50) based on volume distribution.

The aqueous dispersion of inorganic fine particles can be prepared by the following known methods, but is not limited to these methods.

It can be prepared by mixing inorganic fine particles, an aqueous medium, and a dispersant using a known mixer such as a stirrer, an emulsifier, and a disperser. As the dispersant used here, known ones such as surfactants and polymer dispersants can be used.

Although both surfactants and polymeric dispersants can be removed in the cleaning step described below, surfactants are preferred from the viewpoint of cleaning efficiency. Among the surfactants, anionic surfactants and nonionic surfactants are more preferred.

The surfactants include anionic surfactants such as sulfate ester salts, sulfonate salts, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; Examples include nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type, and polyhydric alcohol type surfactants. Among these, nonionic surfactants and anionic surfactants are preferred. Furthermore, a nonionic surfactant and an anionic surfactant may be used in combination. The surfactants may be used alone or in combination of two or more.

Further, the amount of the dispersant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the inorganic fine particles, and from the viewpoint of achieving both dispersion stability and cleaning efficiency, 2 parts by mass or more and 10 parts by mass. It is more preferable that it is below.

The content of inorganic fine particles in the aqueous dispersion of inorganic fine particles is not particularly limited, but is preferably 1% by mass or more and 30% by mass or less based on the total mass of the aqueous dispersion of inorganic fine particles.

In addition, the dispersed particle size of the inorganic fine particles in the aqueous dispersion liquid should be such that the 50% particle size (D50) based on volume distribution is 3.0 μm or less from the viewpoint of dispersibility in the finally obtained toner. preferable. The dispersed particle size of the inorganic fine particles dispersed in the aqueous medium can be determined using a dynamic light scattering particle size distribution meter (Nanotrack UPA-EX150, manufactured by Nikkiso) or a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark). , manufactured by Beckman Coulter, Inc.).

Known mixers such as stirrers, emulsifiers, and dispersion machines used to disperse inorganic fine particles in an aqueous medium include ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint mills. An example is a shaker. These may be used alone or in combination.

The aqueous dispersion of release agent fine particles can be prepared by the following known methods, but is not limited to these methods.

An aqueous dispersion of mold release agent fine particles is prepared by adding the mold release agent to an aqueous medium containing a surfactant, heating it above the melting point of the mold release agent, and using a homogenizer with strong shearing ability (for example, M Technique Co., Ltd.). It can be produced by dispersing it into particles using a "Clearmix W Motion" (manufactured by Manufacturer, Inc.) or a pressure discharge type dispersion machine (for example, "Gorlin Homogenizer", manufactured by Gorin Co., Ltd.) and then cooling it to below the melting point.

The dispersed particle size of the release agent fine particles in the aqueous dispersion is preferably such that the 50% particle size (D50) based on volume distribution is 0.03 μm or more and 1.0 μm or less, and 0.1 μm or more and 0.5 μm or less. It is more preferable that there be. Further, it is preferable that coarse particles of 1 μm or more are not present.

When the dispersed particle size of the release agent fine particles is within the above range, the release agent can be eluted well during fixing, the hot offset temperature can be increased, and the occurrence of filming on the photoreceptor can be prevented. It becomes possible to suppress this.

The dispersed particle size of the release agent fine particles dispersed in the aqueous medium is measured using a dynamic light scattering particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso).

The aqueous dispersion of colorant fine particles used as needed can be prepared by the following known methods, but is not limited to these methods.

It can be prepared by mixing a colorant, an aqueous medium, and a dispersant using a known mixer such as a stirrer, an emulsifier, and a dispersion machine. As the dispersant used here, known ones such as surfactants and polymer dispersants can be used.

Although both surfactants and polymeric dispersants can be removed in the cleaning step described below, surfactants are preferred from the viewpoint of cleaning efficiency. Among the surfactants, anionic surfactants and nonionic surfactants are more preferred.

The surfactants include anionic surfactants such as sulfate ester salts, sulfonate salts, phosphate esters, and soaps; cationic surfactants such as amine salts and quaternary ammonium salts; Examples include nonionic surfactants such as polyethylene glycol type, alkylphenol ethylene oxide adduct type, and polyhydric alcohol type surfactants. Among these, nonionic surfactants and anionic surfactants are preferred. Furthermore, a nonionic surfactant and an anionic surfactant may be used in combination. The surfactants may be used alone or in combination of two or more.

Further, the amount of the dispersant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the colorant, and from the viewpoint of achieving both dispersion stability and cleaning efficiency, 2 parts by mass or more and 10 parts by mass. It is more preferable that it is below.

The content of the colorant in the aqueous dispersion of fine colorant particles is not particularly limited, but is preferably 1% by mass or more and 30% by mass or less based on the total mass of the aqueous dispersion of fine colorant particles.

In addition, from the viewpoint of the dispersibility of the colorant in the final toner, the dispersed particle size of the colorant fine particles in the aqueous dispersion is 50% particle size (D50) based on volume distribution of 0.5 μm or less. It is preferable that Further, for the same reason, it is preferable that the 90% particle diameter (D90) based on volume distribution is 2 μm or less. The dispersed particle size of the colorant fine particles dispersed in the aqueous medium is measured using a dynamic light scattering particle size distribution analyzer (Nanotrack UPA-EX150, manufactured by Nikkiso).

Known mixers such as stirrers, emulsifiers, and dispersers used to disperse colorants in aqueous media include ultrasonic homogenizers, jet mills, pressure homogenizers, colloid mills, ball mills, sand mills, and paint mills. An example is a shaker. These may be used alone or in combination.

[Agglomeration process]
In the aggregation step, a liquid mixture is prepared by mixing an aqueous dispersion of binder resin particles, an aqueous dispersion of inorganic particles, an aqueous dispersion of release agent particles, and, if necessary, an aqueous dispersion of colorant particles. . Next, the fine particles contained in the prepared liquid mixture are aggregated to form aggregates having a desired particle size. At this time, it is preferable to form agglomerated particles in which the resin fine particles, colorant fine particles, and mold release agent fine particles are aggregated by adding and mixing a flocculant and applying heating and/or mechanical power as necessary. .

As the flocculant, it is preferable to use a flocculant containing a divalent or higher valent metal ion.

A flocculant containing metal ions with a valence of two or more has a high cohesive force, and when added in a small amount, the acidic polar group of the resin fine particles, aqueous dispersion of resin fine particles, aqueous dispersion of inorganic fine particles, mold release agent fine particles The ionic surfactant contained in the aqueous dispersion of and the aqueous dispersion of fine colorant particles can be ionically neutralized. As a result, the resin fine particles, inorganic fine particles, mold release agent fine particles, and colorant fine particles are aggregated due to the effects of salting out and ionic crosslinking.

Examples of the flocculant containing a divalent or higher valence metal ion include a divalent or higher valence metal salt or a polymer of a metal salt. Specifically, divalent inorganic metal salts such as calcium chloride, calcium nitrate, magnesium chloride, magnesium sulfate, and zinc chloride, iron(III) chloride, iron(III) sulfate, aluminum sulfate, and aluminum chloride. Examples include, but are not limited to, trivalent metal salts, and inorganic metal salt polymers such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. These may be used alone or in combination of two or more.

The flocculant may be added in the form of either a dry powder or an aqueous solution dissolved in an aqueous medium, but in order to cause uniform flocculation, it is preferably added in the form of an aqueous solution.

Further, the addition and mixing of the flocculant is preferably performed at a temperature equal to or lower than the glass transition temperature of the resin contained in the mixed liquid. By mixing under this temperature condition, aggregation progresses uniformly. The flocculant can be mixed into the liquid mixture using a known mixing device such as a homogenizer or a mixer.

The average particle size of the aggregated particles formed in the aggregation step is not particularly limited, but it is usually preferably controlled to be approximately the same as the average particle size of the toner to be finally obtained. The particle size of the aggregated particles can be easily controlled by appropriately adjusting the temperature, solid content concentration, flocculant concentration, and stirring conditions.

[Fusion process]
In the fusion step, first, an aggregation stopper is added to the dispersion containing the aggregated particles obtained in the aggregation step under stirring similar to the aggregation step. As an aggregation stopper, it is a basic compound that shifts the equilibrium of the acidic polar groups of the resin fine particles to the dissociation side and stabilizes the aggregated particles; Examples include chelating agents that stabilize aggregated particles by dissociating and forming coordination bonds with metal ions. Among these, chelating agents having a greater effect of stopping aggregation are preferred.

After the dispersion state of the aggregated particles in the dispersion becomes stable due to the action of the aggregation stopper, the agglomerated particles are heated to a temperature higher than the glass transition temperature of the binder resin to fuse the aggregated particles.

The chelating agent is not particularly limited as long as it is a known water-soluble chelating agent. Specifically, oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, and their sodium salts; iminodiaic acid (IDA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA); The sodium salt of

The chelating agent coordinates with the metal ion of the flocculant present in the dispersion of aggregated particles, thereby changing the environment in the dispersion from an electrostatically unstable state that is prone to agglomeration to an electrostatically unstable state. It is possible to change the state to a state that is stable and difficult to cause further aggregation. Thereby, further aggregation of the aggregated particles in the dispersion liquid can be suppressed and the aggregated particles can be stabilized.

The chelating agent is preferably an organic metal salt having a trivalent or higher carboxylic acid, since it is effective even when added in a small amount, and toner particles with a sharp particle size distribution can be obtained.

Further, from the viewpoint of achieving both stabilization from the agglomerated state and cleaning efficiency, the amount of the chelating agent added is preferably 1 part by mass or more and 30 parts by mass or less, and 2.5 parts by mass or more, based on 100 parts by mass of the resin particles. More preferably, it is at least 15 parts by mass and at most 15 parts by mass.

When a desired degree of circularity is obtained through the fusion step, particles having irregular shapes other than spherical shapes can be obtained by cooling the particles to a temperature below the glass transition temperature of the binder resin.

[Shelling process]
The shelling step is a step of attaching desired resin fine particles or resin fine particles and mold release agent fine particles to particles after the aggregation step or particles after the fusion step, which will become core particles, to cover the core particles. Here, the binder resin and the mold release agent are mixed and used as a shell, but after the mold release agent is formed into a shell, the binder resin may be further formed into a shell.

[When adding a shelling process after the agglomeration process]
An aqueous dispersion prepared by mixing an aqueous dispersion of a binder resin and a release agent is added to the aggregated particles formed in the aggregation step. The method of addition is not particularly limited, and it may be added all at once or in portions. In addition, if the flocculant is insufficient, the flocculant may be added additionally, either before, during or after adding the aqueous dispersion of the binder resin and mold release agent, or it may be added multiple times. It's okay.

After shelling, core-shelled particles are obtained by performing the fusion step.

[When adding shelling process after fusion process]
An aqueous dispersion of a binder resin and a release agent is added to the particles obtained in the fusion step. The addition may be made after cooling. The method of addition is not particularly limited, and it may be added all at once or in portions.

Thereafter, a flocculant is added as needed, and the binder resin and release agent are attached to the fused particles. Core-shell particles are obtained by further performing a fusion step.

Next, toner particles can be obtained by washing, filtering, drying, etc. the fused particles.

The obtained toner particles may be used as a toner as they are. If necessary, fine inorganic particles such as silica, alumina, titania, and calcium carbonate, and fine resin particles such as vinyl resin, polyester resin, and silicone resin are added to the toner particles by applying shearing force in a dry state. You may. These inorganic fine particles and resin fine particles function as external additives such as fluidity aids and cleaning aids.

Methods for measuring various physical properties of toner and raw materials will be described below.

[Method for measuring outflow start temperature T1]
Measurement is performed using a constant force extrusion type capillary rheometer "Flow Characteristic Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, a constant load is applied from the top of the measurement sample by a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve can be obtained that shows the relationship between temperature and temperature. The outflow start temperature T1 is specified from the obtained flow curve.

In addition, in the examples described later, the softening points of the resin and toner are also described, but this is the "melting temperature in the 1/2 method" described in the manual attached to the "Flow Tester CFT-500D". It is about.

The measurement sample was obtained by compression molding approximately 1.0 g of toner at approximately 10 MPa for approximately 60 seconds using a tablet molding and compressing machine (for example, NT-100H, manufactured by NP A System Co., Ltd.) in an environment of 25° C. A cylinder with a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Heating method Starting temperature: 40℃
Achieved temperature: 200℃
Measurement interval: 1.0℃
Temperature increase rate: 4.0℃/min
Piston cross-sectional area: 1.000cm ²
Test load (piston load): 10.0kgf (0.9807MPa)
Preheating time: 300 seconds Die hole diameter: 1.0mm
Die length: 1.0mm

[Method for measuring the thermal expansion coefficient (linear expansion coefficient) of inorganic fine particles]
The thermal expansion coefficient of inorganic fine particles is calculated as follows.

The lattice constant of inorganic fine particles is measured using the following apparatus under the following conditions.
・Measuring device: MiniFlex600 (product name, manufactured by Rigaku Co., Ltd.)
Sample medium temperature attachment Hot plate/X-ray source: Cu-Kα ray/slit system: DS=SS=1.25°, RS=0.3mm
・Detector: Scintillation counter ・Scan method: 2θ-θ continuous scan ・Measurement range (2θ): 5-60°
・Step width (2θ): 0.02°
・Scan speed: 1°/min
・Measurement temperature: 30℃/50℃/70℃/100℃
Measured 10 minutes after reaching the target temperature

Based on the graph obtained and the inorganic material database, the lattice constants of the a-axis, b-axis, and c-axis at each temperature are determined, and the change in volumetric expansion is converted into linear expansion to determine the coefficient of thermal expansion.

[Method for measuring number average particle diameter of inorganic fine particles]
The number average particle diameter of inorganic fine particles is determined by an image of inorganic fine particles separated from toner (if toner contains pigment, a mixture with pigment) taken with a scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). Calculated from. Incidentally, the inorganic fine particles can be separated by the method described above. The image shooting conditions for S-4800 are as follows.

(1) Sample Preparation A conductive paste is applied thinly to a sample stand (aluminum sample stand 15 mm x 6 mm), and inorganic fine particles separated from toner are sprayed onto it. Further, air is blown to remove excess inorganic fine particles from the sample stage and thoroughly dry it. Set the sample stage in the sample holder, and adjust the height of the sample stage to 36 mm using the sample height gauge.

(2) Setting S-4800 observation conditions Calculation of the number average particle diameter is performed using images obtained by backscattered electron image observation of the S-4800. Pour liquid nitrogen into the anti-contamination trap attached to the S-4800 housing until it overflows, and leave it for 30 minutes. Start up the "PC-SEM" of the S-4800 and perform flushing (cleaning of the FE chip, which is the electron source). Click the acceleration voltage display area of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Check that the flushing strength is 2 and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.

Click the acceleration voltage display area to open the HV setting dialog, and set the acceleration voltage to [1.1 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select the SE detector to [Upper (U)] and [+BSE], and select [ in the selection box to the right of [+BSE]. L. A. 100] to set the mode for observation using a backscattered electron image. Similarly, in the [Basics] tab of the operation panel, set the probe current of the electron optical system condition block to [Normal], the focus mode to [UHR], and the WD to [4.5 mm]. Press the [ON] button on the acceleration voltage display section of the control panel to apply acceleration voltage.

(3) Focus adjustment Rotate the focus knob [COARSE] on the operation panel and adjust the aperture alignment when the image is in focus to a certain extent. Click [Align] on the control panel to display the alignment dialog and select [Beam]. Rotate the STIGMA/ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA/ALIGNMENT knobs (X, Y) one by one to stop or minimize the image movement. Close the aperture dialog and use autofocus to focus. Then, set the magnification to 80,000 (80k) times, adjust the focus using the focus knob and STIGMA/ALIGNMENT knob in the same way as above, and focus again using autofocus. Repeat this operation again to focus. If the angle of inclination of the observation surface is large, the measurement accuracy of the number average particle diameter tends to decrease, so when adjusting the focus, select a device that allows the entire observation surface to be brought into focus at the same time, so that there is as little surface inclination as possible. Select and analyze.

(4) Image saving Adjust the brightness in ABC mode, take a photo with a size of 640 x 480 pixels, and save it. The following analysis will be performed using this image file. In order to calculate the number average particle size by measuring the particle size of at least 500 inorganic fine particles, in order to obtain the required number of inorganic fine particles, images are taken at multiple locations so as not to photograph the same inorganic fine particles.

(5) Image analysis Measure the particle size of at least 500 inorganic fine particles, and use the obtained results to determine the number average particle size. In the present invention, image analysis software Image-Pro Plus ver. 5.0, the number average particle diameter is calculated by binarizing the image obtained by the method described above.

If the inorganic fine particles separated from the toner contain pigments, etc., perform elemental analysis using an energy dispersive X-ray spectrometer (EDS) and distinguish them based on particle size and shape, and exclude particles other than the inorganic fine particles to be measured. After that, perform the measurement.

[Method for measuring number average particle diameter (D1) and weight average particle diameter (D4) of toner particles]
The number average particle diameter (D1) and weight average particle diameter (D4) of the toner particles were measured using a precise particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman) using a pore electrical resistance method equipped with a 100 μm aperture tube.・The effective measurement channel can be determined using the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data. Measurements are made using several 25,000 channels, and the measurement data is analyzed and calculated.

The electrolytic aqueous solution used in the measurement can be one prepared by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, such as "ISOTON II" (manufactured by Beckman Coulter, Inc.). .

Note that before performing 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 control mode to 50,000 particles, set the number of measurements to 1, and set the Kd value to "standard particle 10.0 μm" (Beckman・Set the value obtained by using the product (manufactured by Coulter Co., Ltd.). By pressing the threshold/noise level measurement button, the threshold and noise level are automatically set. Also, set the current to 1,600 μA, the gain to 2, the electrolyte to ISOTON II, and check the aperture tube flush after measurement.

On the "Pulse to particle size conversion setting screen" of the dedicated software, set the bin interval to logarithmic particle size, the particle size bin to 256 particle size bins, and the particle size range to 2 μm or more and 60 μm or less.

The specific measurement method is as follows.
(1) Approximately 200 mL of the electrolyte aqueous solution is placed in a 250 mL glass round bottom beaker exclusively for Multisizer 3, set on a sample stand, and stirred counterclockwise at 24 rotations/second with a stirrer rod. Then, use the dedicated software's ``Aperture Tube Flush'' function to remove dirt and air bubbles from inside the aperture tube.
(2) Place about 30 mL of the electrolytic aqueous solution in a 100 mL glass flat-bottomed beaker, and add about 0.3 mL of the following diluent as a dispersant.
- Diluent: "Contaminon N" (10% by mass aqueous solution of pH 7 neutral detergent for cleaning precision measuring instruments consisting of nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd.) ) diluted to 3 times the mass with ion-exchanged water (3) The following ultrasonic disperser has two built-in oscillators with an oscillation frequency of 50 kHz with their phases shifted by 180 degrees, and has an electrical output of 120 W. A predetermined amount of ion-exchanged water is placed in a water tank, and approximately 2 mL of the contaminon N is added to the water tank.
・Ultrasonic dispersion system: "Ultrasonic Dispersion System Tetora150" (manufactured by Nikkaki Bios Co., Ltd.)
(4) Set the beaker of (2) above in the beaker fixing hole of the ultrasonic disperser, and operate the ultrasonic disperser. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) While the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion treatment is continued for another 60 seconds. In addition, in the ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 15° C. or higher and 40° C. or lower.
(6) Using a pipette, drop the electrolytic aqueous solution of (5) in which toner is dispersed into the round-bottomed beaker of (1) placed in the sample stand, and adjust the measured concentration to approximately 5%. . The measurement is then continued until the number of particles to be measured reaches 50,000.
(7) Analyze the measurement data using the dedicated software attached to the device to calculate the number average particle diameter (D1) and weight average particle diameter (D4). In addition, when setting the graph/volume% in the dedicated software, the "average diameter" on the analysis/number statistics (arithmetic mean) screen is the number average particle diameter (D1), and the analysis/volume statistics (arithmetic mean) The "average diameter" on the screen is the weight average particle diameter (D4).

[Method of measuring average circularity]
The average circularity of toner particles is measured using a flow type particle image analyzer "FPIA-3000" (manufactured by Sysmex Corporation) under measurement and analysis conditions during calibration work.

The specific measurement method is as follows. First, approximately 20 mL of ion-exchanged water from which impure solid matter has been removed is placed in a glass container. This contains "Contaminon N" as a dispersant (a 10% by mass aqueous solution of a pH 7 neutral detergent for cleaning precision measuring instruments consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, Wako Pure Chemical Industries, Ltd. Add approximately 0.2 mL of a diluted solution obtained by diluting (manufactured by )) with ion-exchanged water to approximately 3 times the mass. Furthermore, approximately 0.02 g of the measurement sample is added and dispersed for 2 minutes using an ultrasonic disperser to obtain a dispersion liquid for measurement. At that time, the temperature of the dispersion liquid is appropriately cooled to a temperature of 10° C. or higher and 40° C. or lower. As the ultrasonic disperser, a tabletop ultrasonic cleaner disperser ("VS-150" (manufactured by Vervo Crea Co., Ltd.)) with an oscillation frequency of 50 kHz and an electrical output of 150 W was used, and a predetermined amount of water was used in the water tank. of ion-exchanged water, and add about 2 mL of the contaminon N to this water tank.

For the measurement, the flow-type particle image analyzer equipped with a standard objective lens (10x magnification) was used, and a particle sheath "PSE-900A" (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image analyzer, and 3,000 toner particles are measured in HPF measurement mode and total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analyzed particle diameter is limited to an equivalent circle diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is determined.

In the measurement, automatic focus adjustment is performed using standard latex particles ("RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific, diluted with ion-exchanged water) before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of the measurement.

In the examples of the present application, a flow type particle image analyzer was used, which was calibrated by Sysmex Corporation and had a calibration certificate issued by Sysmex Corporation. The measurements were carried out under the same measurement and analysis conditions as when the calibration certificate was obtained, except that the analyzed particle diameter was limited to an equivalent circle diameter of 1.985 μm or more and less than 39.69 μm.

[Method for measuring the softening point of resin]
The softening point of the resin is measured using a constant load extrusion type capillary rheometer "Flow Characteristic Evaluation Device Flow Tester CFT-500D" (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, a constant load is applied from the top of the measurement sample by a piston, the temperature of the measurement sample filled in the cylinder is raised and melted, and the molten measurement sample is pushed out from the die at the bottom of the cylinder. A flow curve can be obtained that shows the relationship between temperature and temperature.

In the present invention, the "melting temperature in the 1/2 method" described in the manual attached to the "Flow Tester CFT-500D" is defined as the softening point. Note that the melting temperature in the 1/2 method is calculated as follows. First, find 1/2 of the difference between the piston descent amount Smax at the time when the outflow ends and the piston descent amount Smin at the time the outflow starts (this is set as X. X = (Smax - Smin) / 2). The temperature at which the amount of descent of the piston becomes the sum of X and Smin in the flow curve is the melting temperature in the 1/2 method.

The measurement sample was obtained by compression molding about 1.0 g of resin at about 10 MPa for about 60 seconds using a tablet molding and compression machine (for example, NT-100H, manufactured by NP Systems, Inc.) in an environment of 25 ° C. A cylinder with a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Heating method Starting temperature: 40℃
Achieved temperature: 200℃
Measurement interval: 1.0℃
Temperature increase rate: 4.0℃/min
Piston cross-sectional area: 1.000cm ²
Test load (piston load): 10.0kgf (0.9807MPa)
Preheating time: 300 seconds Die hole diameter: 1.0mm
Die length: 1.0mm

[Measurement of wax peak temperature and calorific value]
The peak temperature and calorific value of the wax are measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments). The temperature correction of the device detection part uses the melting points of indium and zinc, and the heat of fusion of indium is used to correct the amount of heat.

Specifically, approximately 5 mg of a sample (toner) is accurately weighed, placed in an aluminum pan, and using an empty aluminum pan as a reference, the measurement is performed according to the following procedure.

Heating from 20°C to 180°C at a temperature increase rate of 10°C/min (Step I), followed by cooling to 20°C at a cooling rate of 10°C/min (Step II), followed again by a heating rate of 10°C A heating step (step III) is performed from 20° C. to 180° C./min.

The peak temperature (℃) of the peak derived from wax observed in Step II is T2w, the calorific value (J/g) is H2w, the peak temperature (℃) derived from crystalline polyester is T2c, the calorific value (J/g) ) is set as H2c. Furthermore, the temperature at which the DSC curve exhibits the maximum endothermic peak observed in step III is defined as the peak temperature of the maximum endothermic peak of the wax.

[Calculation method of inorganic fine particle content (volume %)]
is calculated using the number average particle diameter of the inorganic fine particles obtained by the above measurement method and the number average particle diameter of the toner. Specifically, the value is the value obtained by dividing "the cube of the number average particle diameter of inorganic fine particles" by "the cube of the number average particle diameter of toner" multiplied by 100.

[Configuration included in the embodiment of the present invention]
The disclosure of this embodiment includes the following configurations.
(Structure 1) A toner having toner particles containing a binder resin, wax, and inorganic fine particles,
When the outflow start temperature measured using toner is T1 (°C), the inorganic fine particles always have a thermal expansion coefficient of -0.1× determined by X-ray diffraction in the temperature range of 30°C to T1°C. 10 ^-6 (/K) or less,
A toner characterized in that the content of the wax is 3.0% by mass or more and 20.0% by mass or less based on the mass of the toner particles.
(Structure 2) In cross-sectional observation of the toner particles using a transmission electron microscope, the ratio Ws of the area occupied by wax in the surface layer region from the surface of the toner particle to a depth of 500 nm, and the area occupied by wax in the region inner than 500 nm. The toner according to configuration 1, wherein the ratio of the area ratio Wi satisfies the following formula (1).
2.0≧Ws/Wi≧1.0 Formula (1)
(Structure 3) The toner according to Structure 1 or 2, wherein the inorganic fine particles have a number average particle diameter of 0.1 μm or more and 3.0 μm or less.
(Structure 4) The toner according to Structure 1 or 2, wherein the inorganic fine particles have a number average particle diameter of 0.5 μm or more and 2.0 μm or less.
(Structure 5) The toner according to any one of Structures 1 to 4, wherein the content of inorganic fine particles in the toner particles is 1.0% by volume or more and 10.0% by volume or less.
(Arrangement 6) The toner according to any one of Arrangements 1 to 5, wherein the inorganic fine particles are zirconium phosphate having negative thermal expansion.

The present invention will be explained below with reference to production examples and examples. The present invention is not limited to these. In addition, the parts in the following formulations indicate parts by mass unless otherwise specified.

(Production example of inorganic fine particles A)
・Oxalic acid dihydrate 3.1 parts ・Zirconium oxychloride octahydrate 15.3 parts ・Pure water 73.2 parts Stir the beaker containing the above pure water with a three-one motor, and weigh out the above other ingredients. A solution was prepared by adding . Next, 8.4 parts of an 85% by mass phosphoric acid aqueous solution was added while stirring. Next, the pH was adjusted to 2.2 using an aqueous sodium hydroxide solution adjusted to 20% by mass, and then stirred at 98° C. for 10 hours. Thereafter, the obtained precipitate was filtered and washed, and dried in a dryer at 120° C. for 24 hours to obtain zirconium phosphate (Zr ₂ (PO ₄ ) ₃ ). The obtained zirconium phosphate was crushed with a coffee mill, and the number average particle diameter measured was 4.0 μm. Next, classification was performed using an inertial classification type elbow jet (manufactured by Nippon Steel Mining Co., Ltd.) to obtain a desired particle size. Table 1 shows the physical properties of the obtained inorganic fine particles A.

(Production example of inorganic fine particles B)
- 15.0 parts of tungsten trioxide (number average particle size 1.0 μm) - 2.5 parts of 40% by mass polycarboxylic acid ammonium salt - 82.5 parts of pure water The above materials were weighed in a beaker. Next, the mixture was stirred at 27° C. for 1 hour using a three-one motor to obtain a slurry. Next, 20.6 parts of zirconium hydroxide and 15.0 parts of an 85% by mass phosphoric acid aqueous solution were added to the slurry, and the mixture was further stirred for 4 hours to cause a reaction.

After the reaction, the product was dried in a dryer at 200°C for 24 hours or more, and then fired in a kiln at 950°C for 2 hours to obtain zirconium phosphoric acid tungstate (Zr ₂ (WO ₄ ) (PO ₄ ) ₂ ). The obtained zirconium tungstate phosphate was crushed in a coffee mill, and the physical properties of the obtained inorganic fine particles B are shown in Table 1.

(Production example of inorganic fine particles C to G)
After obtaining zirconium phosphate particles with a number average particle diameter of 4.0 μm in the same manner as inorganic fine particles A, inorganic fine particles C to G were obtained in the same manner as inorganic fine particles A, except that the edge of the elbow jet classification was adjusted. Table 1 shows the physical properties of the obtained inorganic fine particles C to G.

(Example of manufacturing inorganic fine particles H)
Neoceram N-0 manufactured by Nippon Electric Glass Co., Ltd. was pulverized with a hammer to a diameter of about 100 mm or less, and then coarsely pulverized with a hammer mill to a diameter of 1 mm or less to obtain a coarsely pulverized product. The obtained coarse material was pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain inorganic fine particles H having a number average particle diameter of 1.5 μm. Table 1 shows the physical properties of the obtained inorganic fine particles H.

(Production example of inorganic fine particles I)
Inorganic fine particles H were melted at 1600° C. and then cooled in a plate-like state to obtain a glass plate. Next, it was heated from 600°C to 930°C at a rate of 1°C/min, maintained for 30 minutes, and then slowly cooled to 600°C at a rate of 1°C/min, and then rapidly cooled to room temperature to obtain crystallized glass. Thereafter, it was crushed in the same manner as inorganic fine particles H to obtain inorganic fine particles I having a number average particle diameter of 1.5 μm. Table 1 shows the physical properties of the obtained inorganic fine particles I.

※表１における熱膨張係数を求める際のＴ１は、後述の実施例におけるトナーを用いて測定される流出開始温度の８５℃である。また、表１中における熱膨張係数は、無機微粒子Ａ～Ｇについては、３０℃～８５℃における最大値であり、無機微粒子ＨおよびＩについては、３０℃～８５℃における最小値である。

*T1 when determining the thermal expansion coefficient in Table 1 is 85° C., which is the outflow start temperature measured using the toner in the examples described later. Further, the thermal expansion coefficients in Table 1 are the maximum values at 30°C to 85°C for inorganic fine particles A to G, and the minimum values at 30°C to 85°C for inorganic fine particles H and I.

(Production example of amorphous polyester resin A)
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 73.3 parts (100.0 mol% based on the total number of moles of polyhydric alcohol)
・Terephthalic acid: 22.4 parts (82.0 mol% based on the total number of moles of polycarboxylic acids)
・Adipic acid: 4.3 parts (18.0 mol% based on the total number of moles of polycarboxylic acids)
- Titanium tetrabutoxide (esterification catalyst): 0.5 part The above materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 4 hours while stirring at a temperature of 200° C., to obtain amorphous polyester resin A. The resulting amorphous polyester resin A had an outflow start temperature of 80°C and a softening point of 95°C.

(Production example of amorphous polyester resin B)
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 72.4 parts (100.0 mol% based on the total number of moles of polyhydric alcohol)
・Terephthalic acid: 22.4 parts (80.0 mol% based on the total number of moles of polycarboxylic acids)
・Adipic acid: 3.4 parts (14.0 mol% based on the total number of moles of polycarboxylic acids)
- Titanium tetrabutoxide (esterification catalyst): 0.5 part The above materials were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the mixture was reacted for 2 hours while stirring at a temperature of 200°C. Further, the pressure inside the reaction tank was lowered to 8.3 kPa and maintained for 1 hour, then cooled to 180° C. and returned to atmospheric pressure (first reaction step).

- Trimellitic anhydride: 2.1 parts (6.0 mol% based on the total number of moles of polycarboxylic acids)
・Tert-butylcatechol (polymerization inhibitor): 0.1 part After that, the above materials were added, the pressure inside the reaction tank was lowered to 8.3 kPa, and the reaction was carried out for 15 hours while maintaining the temperature at 160°C, and ASTM D36- After confirming that the softening point measured according to No. 86 reached a temperature of 140° C., the temperature was lowered to stop the reaction (second reaction step), and amorphous polyester resin B was obtained. The resulting amorphous polyester resin B had an outflow start temperature of 100°C and a softening point of 143°C.

(Production example of amorphous polyester resin C)
・Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 73.9 parts (60.0 mol% based on the total number of moles of polyhydric alcohol)
・Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 29.4 parts (40.0 mol% based on the total number of moles of polyhydric alcohol)
・Terephthalic acid: 24.0 parts (95.5 mol% based on the total number of moles of polycarboxylic acids)
- Stearic acid: 2.7 parts (4.5 mol% based on the total number of moles of polycarboxylic acids)
- Titanium tetrabutoxide (esterification catalyst): 0.5 part The above materials other than stearic acid were weighed into a reaction tank equipped with a cooling tube, a stirrer, a nitrogen introduction tube, and a thermocouple. Next, after purging the inside of the flask with nitrogen gas, the temperature was gradually raised while stirring, and the reaction was carried out for 5 hours while stirring at a temperature of 200°C. After that, stearic acid was added and reacted for 2 hours, and the amorphous Polyester resin C was obtained. The resulting amorphous polyester resin C had an outflow start temperature of 84°C and a softening point of 104°C.

(Production example of resin composition 1)
- 18 parts of low density polyethylene (Mw 1400, Mn 850, maximum endothermic peak by DSC is 100°C) - 66 parts of styrene - 13.5 parts of n-butyl acrylate - 2.5 parts of acrylonitrile were charged into an autoclave, and the system was replaced with N2. The temperature was raised and maintained at 180°C while stirring. Next, 50 parts of a 2% by mass xylene solution of t-butyl hydroperoxide was continuously dropped into the system for 5 hours, and after cooling, the solvent was separated and removed, and the vinyl resin component reacted with the low density polyethylene. Resin composition 1 was obtained. When the molecular weight of Resin Composition 1 was measured, it was found that the weight average molecular weight (Mw) was 7,100 and the number average molecular weight (Mn) was 3,000. Further, the transmittance at a wavelength of 600 nm measured at a temperature of 25° C. in a dispersion in a 45% by volume methanol aqueous solution was 69%.

[Production example of toner 1]
・Amorphous polyester resin A 50.0 parts ・Amorphous polyester resin B 21.0 parts ・Inorganic fine particles A 10.0 parts ・Fischer-Tropsch wax (peak temperature of maximum endothermic peak 90°C) 10.0 parts ・Resin Composition 1 3.6 parts C.I. I. Pigment Blue 15:3 5.0 parts 3,5-di-t-butylsalicylic acid aluminum compound 0.4 parts The raw materials shown in the above recipe were mixed in a Henschel mixer (Model FM-75, manufactured by Nippon Coke Kogyo Co., Ltd.). After mixing at a rotation speed of 20 s ^-1 and a rotation time of 5 minutes, the mixture was kneaded using a twin-screw kneader (PCM-30 model, manufactured by Ikegai Co., Ltd.) set at a temperature of 125°C. The obtained kneaded product was cooled and coarsely ground to a diameter of 1 mm or less using a hammer mill to obtain a coarsely ground product. The obtained coarse material was pulverized using a mechanical pulverizer (T-250, manufactured by Freund Turbo Co., Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron Co., Ltd.) were such that classification was performed at a classification rotor rotation speed of 50.0 s ^-1 .

Next, heat treatment was performed using the heat treatment apparatus shown in FIG. 1 to obtain toner particles 1. The operating conditions are: feed rate of 5 kg/hr, hot air temperature of 180°C, hot air flow rate of 6 m ³ /min, cold air temperature of -5°C, cold air flow rate of 4 m ³ /min, blower air volume of 20 m ³ /min, and injection air. The flow rate was 1 m ³ /min.

To 100 parts of toner particles 1, 1.0 part of hydrophobic silica (BET: 200 m ² /g) and 1.0 part of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (BET: 80 m ² /g) were added. Toner 1 was obtained by mixing with a Henschel mixer (model FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. Table 3 shows the physical properties of the obtained Toner 1.

[Production examples of toners 2 to 10 and 15 to 21]
Toners 2 to 10 and 15 to 21 were obtained in the same manner as in the production example of Toner 1, except that the raw materials were changed as shown in Table 2. Table 3 shows the physical properties of the obtained toner.

[Example of manufacturing toner 11]
・Manufacture of resin particle dispersion:
Tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) 200 parts Amorphous polyester resin A 66 parts Amorphous polyester resin B 28 parts Resin composition 1 4.7 parts 3,5-di-t-butylsalicylic acid aluminum compound 0.5 parts Anion Surfactant (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK) 0.8 parts After mixing the above, the mixture was stirred for 12 hours to dissolve and disperse the resin and other components.

Next, 2.7 parts of N,N-dimethylaminoethanol was added, and a T. K. Stirring was performed at 4000 rpm using Robomix (manufactured by Primix Co., Ltd.).

Further, 360 parts of ion-exchanged water was added to the above mixed solution at a rate of 1 g/min to precipitate resin particles. Thereafter, tetrahydrofuran was removed using an evaporator to obtain a resin fine particle dispersion. The number average particle size of the resin particles in the obtained resin particle dispersion was 0.11 μm, and the solid content concentration was 21.7% by mass.
・Manufacture of inorganic fine particle dispersion:
Inorganic fine particles A 100 parts Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd.: Neogen RK) 10 parts Ion exchange water 390 parts After putting the above into a mixing container equipped with a stirring device, Clear Mix W Motion (M Technique Co., Ltd.) The dispersion treatment was carried out for 20 minutes by circulating the solution. The conditions for the distributed processing were as follows.

・Rotor outer diameter 3cm
・Clearance 0.3mm
・Rotor rotation speed 19000r/min
・Screen rotation speed 19000r/min
The number average particle diameter of the inorganic fine particles A in the obtained inorganic fine particle dispersion was 1.5 μm, and the solid content concentration was 22.0% by mass.
・Manufacture of colorant dispersion:
C. I. Pigment Blue 15:3 100 parts Anionic surfactant 10 parts Ion-exchanged water 890 parts The above ingredients were mixed and dissolved, and then dispersed using a high-pressure impact disperser.

The number average particle diameter of the colorant particles in the obtained colorant dispersion was 0.16 μm, and the solid content concentration was 11.0% by mass.
・Manufacture of wax dispersion:
Fischer-Tropsch wax (peak temperature of maximum endothermic peak is 90°C) 100 parts anionic surfactant 10 parts ion-exchanged water 390 parts Heat the above to 95°C and disperse using a homogenizer, then use a pressure discharge type Gorlin homogenizer. A wax dispersion was obtained. The number average particle diameter of wax particles in the obtained wax dispersion was 0.21 μm, and the solid content concentration was 22.0% by mass.

(Coagulation fusion process)
Resin fine particle dispersion liquid 345 parts Inorganic fine particle dispersion liquid 50 parts Colorant dispersion liquid 50 parts Wax dispersion liquid 50 parts Ion exchange water 400 parts After putting each of the above materials into a round stainless steel flask and mixing, 98 parts of An aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to ion-exchanged water, and dispersed for 10 minutes at 5000 rpm using a homogenizer (Ultra Turrax T50, manufactured by IKA).

Thereafter, the mixed liquid was heated to 58° C. using a stirring blade in a heating water bath while appropriately controlling the rotation speed so that the mixed liquid was stirred. The mixture was maintained at 58° C. for 1 hour to obtain aggregated particles having a weight average particle size of about 7.0 μm.

An aqueous solution prepared by dissolving 20 parts of trisodium citrate in 380 parts of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85°C.

After holding at 85° C. for 2 hours, an aqueous dispersion of toner particles having a weight average particle diameter of about 6.9 μm and an average circularity of 0.966 was obtained.

Thereafter, the toner particle aqueous dispersion is cooled to 25°C, filtered and solid-liquid separated, and the filtered material is thoroughly washed with ion-exchanged water and dried using a vacuum dryer to reduce the weight average particle size. Toner particles 11 of 6.8 μm were obtained.

To 100 parts of toner particles 11, 1.0 part of hydrophobic silica (BET: 200 m ² /g) and 1.0 part of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (BET: 80 m ² /g) were added. Toner 11 was obtained by mixing with a Henschel mixer (model FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. Table 3 shows the physical properties of the obtained toner 11.

[Manufacture example of toner 12]
Toner 12 was produced using the various dispersions prepared in the production example of Toner 11 in the following manner.

(Coagulation fusion process)
Resin fine particle dispersion liquid 245 parts Inorganic fine particle dispersion liquid 50 parts Colorant dispersion liquid 50 parts Wax dispersion liquid 25 parts Ion exchange water 400 parts After putting each of the above materials into a round stainless steel flask and mixing, 98 parts of An aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to ion-exchanged water, and dispersed for 10 minutes at 5000 rpm using a homogenizer (Ultra Turrax T50, manufactured by IKA).

Thereafter, the mixed liquid was heated to 58° C. using a stirring blade in a heating water bath while appropriately controlling the rotation speed so that the mixed liquid was stirred. The mixture was maintained at 50° C. for 1 hour to obtain aggregated particles having a weight average particle size of about 5.2 μm.

An aqueous solution prepared by dissolving 20 parts of trisodium citrate in 380 parts of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85°C.

After holding at 85° C. for 2 hours, fused particles (core particles) having a weight average particle diameter of about 6.5 μm and an average circularity of 0.966 were obtained.

The obtained aqueous dispersion of toner particles was cooled to 25°C while stirring, and 40 parts of a dispersion prepared by stirring and mixing 100 parts of a resin fine particle dispersion and 25 parts of a wax dispersion in advance were added, and the mixture was heated to 25°C. Stirring was performed for 10 minutes under these conditions. Furthermore, a 2% by mass calcium chloride aqueous solution was slowly added dropwise. In this state, a small amount of the liquid was extracted from time to time, passed through a 2 μm microfilter, and stirring was continued at 25° C. until the filtrate became transparent.

After confirming that the filtrate had become transparent, 40 parts of the remaining dispersion was added again and stirring was continued. After confirming that the filtrate had become transparent again, 45 parts of the remaining dispersion liquid was added again, and stirring was continued. After confirming that the filtrate had become transparent, it was heated to 85° C. while adjusting the rotation speed as appropriate. At that time, the particle size was checked from time to time, and when the particle size became large, a 5% by mass aqueous solution of sodium ethylenediaminetetraacetate was added to prevent the progress of aggregation.

After holding at 85° C. for 1 hour, a toner particle dispersion (core-shell particle dispersion) having a number-based median diameter of about 6.8 μm and an average circularity of 0.968 was obtained.

Thereafter, the toner particle aqueous dispersion is cooled to 25°C, filtered and solid-liquid separated, and the filtered material is thoroughly washed with ion-exchanged water and dried using a vacuum dryer to reduce the weight average particle size. Toner particles 12 of 6.7 μm were obtained.

To 100 parts of toner particles 12, 1.0 part of hydrophobic silica (BET: 200 m ² /g) and 1.0 part of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (BET: 80 m ² /g) were added. Toner 12 was obtained by mixing with a Henschel mixer (model FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. Table 3 shows the physical properties of the obtained toner 12.

[Manufacture example of toner 13]
Toner 13 was produced using the various dispersions prepared in the production example of Toner 11 in the following manner.

(Coagulation fusion process)
Resin and compound composite dispersion liquid 245 parts Inorganic fine particle dispersion liquid 50 parts Colorant dispersion liquid 50 parts Wax dispersion liquid 39 parts Ion exchange water 400 parts After putting each of the above materials into a round stainless steel flask and mixing, 98 parts An aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 1 part of ion-exchanged water, and dispersed for 10 minutes at 5000 rpm using a homogenizer (Ultra Turrax T50, manufactured by IKA).

Thereafter, the mixed liquid was heated to 58° C. using a stirring blade in a heating water bath while appropriately controlling the rotation speed so that the mixed liquid was stirred. The mixture was maintained at 50° C. for 1 hour to obtain aggregated particles having a weight average particle size of about 5.2 μm.

An aqueous solution prepared by dissolving 20 parts of trisodium citrate in 380 parts of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85°C.

After holding at 85° C. for 2 hours, fused particles (core particles) having a weight average particle diameter of about 6.6 μm and an average circularity of 0.966 were obtained.

The obtained aqueous dispersion of toner particles was cooled to 25° C. while stirring, and 40 parts of a dispersion prepared by stirring and mixing 100 parts of a resin/compound composite dispersion and 11 parts of a wax dispersion were added first. Stirring was performed for 10 minutes at 25°C. Furthermore, a 2% by mass calcium chloride aqueous solution was slowly added dropwise. In this state, a small amount of the liquid was extracted from time to time, passed through a 2 μm microfilter, and stirring was continued at 25° C. until the filtrate became transparent.

After confirming that the filtrate had become transparent, 40 parts of the remaining dispersion was added again and stirring was continued. After confirming that the filtrate had become transparent again, 45 parts of the remaining dispersion liquid was added again, and stirring was continued. After confirming that the filtrate had become transparent, it was heated to 85° C. while adjusting the rotation speed as appropriate. At that time, the particle size was checked from time to time, and when the particle size became large, a 5% by mass aqueous solution of sodium ethylenediaminetetraacetate was added to prevent the progress of aggregation.

After holding at 85° C. for 1 hour, a toner particle dispersion (core-shell particle dispersion) having a number-based median diameter of about 6.8 μm and an average circularity of 0.968 was obtained.

Thereafter, the toner particle aqueous dispersion is cooled to 25°C, filtered and solid-liquid separated, and the filtered material is thoroughly washed with ion-exchanged water and dried using a vacuum dryer to reduce the weight average particle size. Toner particles 13 of 6.7 μm were obtained.

To 100 parts of toner particles 13, 1.0 part of hydrophobic silica (BET: 200 m ² /g) and 1.0 part of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (BET: 80 m ² /g) were added. Toner 13 was obtained by mixing with a Henschel mixer (model FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. Table 3 shows the physical properties of the obtained toner 13.

[Example of manufacturing toner 14]
Toner 14 was produced using the various dispersions prepared in the production example of Toner 11 in the following manner.

(Coagulation fusion process)
Resin and compound composite dispersion liquid 245 parts Inorganic fine particle dispersion liquid 50 parts Colorant dispersion liquid 50 parts Wax dispersion liquid 23 parts Ion exchange water 400 parts After putting each of the above materials into a round stainless steel flask and mixing, here is 98 parts. An aqueous solution in which 2 parts of magnesium sulfate was dissolved was added to 1 part of ion-exchanged water, and dispersed for 10 minutes at 5000 rpm using a homogenizer (Ultra Turrax T50, manufactured by IKA).

Thereafter, the mixed liquid was heated to 58° C. using a stirring blade in a heating water bath while appropriately controlling the rotation speed so that the mixed liquid was stirred. The mixture was maintained at 50° C. for 1 hour to obtain aggregated particles having a weight average particle size of about 5.2 μm.

An aqueous solution prepared by dissolving 20 parts of trisodium citrate in 380 parts of ion-exchanged water was added to the dispersion containing the aggregated particles, and then heated to 85°C.

After holding at 85° C. for 2 hours, fused particles (core particles) having a weight average particle diameter of about 6.5 μm and an average circularity of 0.966 were obtained.

The obtained aqueous dispersion of toner particles was cooled to 25° C. while stirring, and 40 parts of a dispersion prepared by stirring and mixing 100 parts of a resin/compound composite dispersion and 27 parts of a wax dispersion were first added. Stirring was performed for 10 minutes at 25°C. Furthermore, a 2% by mass calcium chloride aqueous solution was slowly added dropwise. In this state, a small amount of the liquid was extracted from time to time, passed through a 2 μm microfilter, and stirring was continued at 25° C. until the filtrate became transparent.

After confirming that the filtrate had become transparent, 40 parts of the remaining dispersion was added again and stirring was continued. After confirming that the filtrate had become transparent again, 45 parts of the remaining dispersion liquid was added again, and stirring was continued. After confirming that the filtrate had become transparent, it was heated to 85° C. while adjusting the rotation speed as appropriate. At that time, the particle size was checked from time to time, and when the particle size became large, a 5% by mass aqueous solution of sodium ethylenediaminetetraacetate was added to prevent the progress of aggregation.

After holding at 85° C. for 1 hour, a toner particle dispersion (core-shell particle dispersion) having a number-based median diameter of about 6.9 μm and an average circularity of 0.968 was obtained.

Thereafter, the toner particle aqueous dispersion is cooled to 25°C, filtered and solid-liquid separated, and the filtered material is thoroughly washed with ion-exchanged water and dried using a vacuum dryer to reduce the weight average particle size. Toner particles 14 of 6.8 μm were obtained.

To 100 parts of toner particles 14, 1.0 part of hydrophobic silica (BET: 200 m ² /g) and 1.0 part of titanium oxide fine particles surface-treated with isobutyltrimethoxysilane (BET: 80 m ² /g) were added. Toner 14 was obtained by mixing with a Henschel mixer (model FM-75, manufactured by Mitsui Mining Co., Ltd.) at a rotation speed of 30 s ^-1 and a rotation time of 10 min. Table 3 shows the physical properties of the obtained toner 14.

In the table, "wax" is Fischer-Tropsch wax, "resin composition" is resin composition 1, and "pigment" is C.I. I. Pigment Blue 15:3, "compound" refers to aluminum 3,5-di-t-butylsalicylate compound. "Parts by mass" of each component of the toner particles indicates the amount per 100 parts by mass of the toner particles.

[Example of manufacturing carrier]
(Production example of magnetic core particle 1)
・Process 1 (weighing/mixing process):
Fe ₂ O ₃ 62.7 parts MnCO ₃ 29.5 parts Mg(OH) ₂ 6.8 parts SrCO ₃ 1.0 parts The ferrite raw materials were weighed so that the above materials had the above composition ratios. Thereafter, the mixture was ground and mixed for 5 hours using a dry vibration mill using stainless steel beads with a diameter of 1/8 inch.
・Process 2 (temporary firing process):
The obtained pulverized material was made into pellets of approximately 1 mm square using a roller compactor. Coarse powder was removed from the pellets using a vibrating sieve with an opening of 3 mm, then fine powder was removed using a vibrating sieve with an opening of 0.5 mm, and then the pellets were heated in a nitrogen atmosphere (oxygen concentration 0. 01% by volume) at a temperature of 1000° C. for 4 hours to produce calcined ferrite. The composition of the obtained calcined ferrite is as follows.
(MnO)a(MgO)b( _SrO )c( _Fe2O3 )d
In the above formula, a=0.257, b=0.117, c=0.007, d=0.393
・Process 3 (pulverization process):
After crushing to about 0.3 mm with a crusher, 30 parts of water was added to 100 parts of calcined ferrite using zirconia beads having a diameter of 1/8 inch, and the mixture was crushed with a wet ball mill for 1 hour. The slurry was ground for 4 hours in a wet ball mill using alumina beads with a diameter of 1/16 inch to obtain a ferrite slurry (finely ground product of calcined ferrite).
・Process 4 (granulation process):
To the ferrite slurry, 1.0 parts of ammonium polycarboxylate as a dispersant and 2.0 parts of polyvinyl alcohol as a binder were added to 100 parts of calcined ferrite, and the mixture was made into spherical particles using a spray dryer (manufacturer: Okawara Kakoki). Granulated. After adjusting the particle size of the obtained particles, they were heated at 650° C. for 2 hours using a rotary kiln to remove the organic components of the dispersant and binder.
・Process 5 (firing process):
In order to control the firing atmosphere, the temperature was raised from room temperature to 1300°C in 2 hours in an electric furnace under a nitrogen atmosphere (oxygen concentration 1.00% by volume), and then fired at a temperature of 1150°C for 4 hours. Thereafter, the temperature was lowered to 60° C. over a period of 4 hours, the temperature was returned to the atmosphere from the nitrogen atmosphere, and the sample was taken out at a temperature of 40° C. or lower.
・Process 6 (sorting process):
After crushing the agglomerated particles, the low-magnetic particles are cut by magnetic separation, and coarse particles are removed by sieving with a sieve with an opening of 250 μm. Magnetic core particles 1 were obtained.

(Preparation of coating resin 1)
Cyclohexyl methacrylate monomer 26.8% by mass
Methyl methacrylate monomer 0.2% by mass
Methyl methacrylate macromonomer 8.4% by mass
(Macromonomer with a weight average molecular weight of 5000 having a methacryloyl group at one end)
Toluene 31.3% by mass
Methyl ethyl ketone 31.3% by mass
Azobisisobutyronitrile 2.0% by mass
Of the above materials, cyclohexyl methacrylate, methyl methacrylate, methyl methacrylate macromonomer, toluene, and methyl ethyl ketone were added to a four-neck separable flask equipped with a reflux condenser, thermometer, nitrogen inlet tube, and stirring device, and nitrogen gas was added. was introduced to create a sufficient nitrogen atmosphere, the mixture was heated to 80° C., azobisisobutyronitrile was added, and the mixture was refluxed for 5 hours for polymerization. Hexane was injected into the obtained reaction product to precipitate the copolymer, and the precipitate was filtered off and dried under vacuum to obtain coated resin 1. 1:30 parts of the obtained coating resin was dissolved in 40 parts of toluene and 30 parts of methyl ethyl ketone to obtain a polymer solution 1 (solid content 30% by mass).

(Preparation of coating resin solution 1)
Polymer solution 1 (resin solid content concentration 30% by mass) 33.3% by mass
Toluene 66.4% by mass
Carbon black (Regal330; manufactured by Cabot) 0.3% by mass
(Primary particle size 25 nm, nitrogen adsorption specific surface area 94 m ² /g, DBP oil absorption 75 mL/100 g)
was dispersed in a paint shaker for 1 hour using zirconia beads with a diameter of 0.5 mm. The obtained dispersion liquid was filtered through a 5.0 μm membrane filter to obtain coating resin solution 1.

[Manufacturing example of magnetic carrier 1]
(Resin coating process):
Coating resin solution 1 was put into a vacuum degassing type kneader maintained at room temperature in an amount of 2.5 parts as a resin component per 1:100 parts of magnetic core particles. After the addition, the mixture was stirred at a rotational speed of 30 rpm for 15 minutes, and after a certain amount of the solvent (80% by mass) had evaporated, the temperature was raised to 80° C. while mixing under reduced pressure, and the toluene was distilled off over 2 hours, followed by cooling. The obtained magnetic carrier was separated into low-magnetic products by magnetic separation, passed through a sieve with an opening of 70 μm, and then classified with an air classifier to obtain a magnetic carrier with a 50% particle size (D50) of 38.2 μm based on volume distribution. I got 1.

[Example of manufacturing two-component developer 1]
To 92.0 parts of magnetic carrier 1, 8.0 parts of toner 1 was added and mixed using a V-type mixer (V-20, manufactured by Seishin Enterprises) to obtain two-component developer 1.

[Production examples of two-component developers 2 to 21]
Two-component developers 2 to 21 were produced in the same manner as in the production example of two-component developer 1, except that the toner was changed as shown in Table 4.

[Examples 1 to 17]
The following evaluations were performed using toners 1 to 17 (two-component developers 1 to 17).

[Comparative Examples 1 to 4]
The following evaluations were performed using Toners 18 to 21 (two-component developers 18 to 21).

[Toner characteristics evaluation]
Evaluations described below were conducted using two-component developers 1 to 21. The results are shown in Table 5.

<Abrasion resistance>
Evaluation was carried out using a Canon full-color copying machine imagePress C10000VP as an image forming apparatus, and two-component developers 1 to 21 were put into the developing device of the cyan station.

The evaluation environment was a normal temperature and normal humidity environment (23° C./50% RH), and OK Top Coat+ (128.0 g/m ² ) was used as the evaluation paper.

The evaluation image was a 10 cm ² halftone image with a reflection density of 0.15.

Evaluation of scratch resistance was determined by the following method.

First, a load of 0.2 kgf/cm ² was applied to the area on which the halftone image was printed, and the fixed image was rubbed (10 times back and forth) with the white coated paper described above.

The average reflectance Ds (%) of the white background portion of the coated paper was measured using a reflectometer (REFLECTOMETER MODEL TC-6DS: manufactured by Tokyo Denshoku).

Next, the average reflectance Dr (%) of the rubbed portion of the coated paper used for rubbing was measured. Then, the reflectance decrease width (%) was calculated using the following formula. The obtained reflectance reduction width was evaluated according to the following evaluation criteria. A score of C or higher was judged to be good.
Fog (%) = Ds (%) - Dr (%)
(Evaluation criteria)
A: Less than 2.0% B: 2.0% or more, less than 5.0% C: 5.0% or more, less than 8.0% D: 8.0% or more

<Evaluation method of low temperature fixability>
A Canon full-color copying machine imagePress C10000VP was used as an image forming apparatus, two-component developers 1 to 21 were put into the developing device of the cyan station, and low-temperature fixability was evaluated.

The unfixed image was output by a modified copying machine from which the fixing unit was removed.

The fixing test was conducted using a fixing unit that was removed from the copying machine and modified so that the fixing temperature could be adjusted. The specific evaluation method is as follows.
Paper: OK Top128 (128g/m ² )
Toner loading amount: 1.20mg/cm ²
Fixing test environment: Low temperature and low humidity environment (15℃/10%RH)
After producing the unfixed image, the process speed was set to 450 mm/sec, the fixing temperature was set to 130° C., and fixing was performed. The image density reduction rate of the obtained image was measured, and this was used as an evaluation index of low-temperature fixability. The image density reduction rate was determined by first measuring the image density at the center using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite). Next, a load of 4.9 kPa (50 g/cm ² ) was applied to the area where the image density was measured, and the fixed image was rubbed (back and forth 5 times) with Silbon paper, and the image density was measured again. Then, the reduction rate (%) of image density before and after rubbing was measured. A score of D or higher was judged to be good.
(Evaluation criteria)
A: Concentration decrease rate less than 1.0% B: Concentration decrease rate 1.0% or more and less than 5.0% C: Concentration decrease rate 5.0% or more and less than 10.0% D: Concentration decrease rate 10.0% or more Less than 15.0% E: Concentration decrease rate 15.0% or more

<Evaluation method of fixing separability>
Using the above-mentioned modified copying machine, an unfixed image of 2 cm x 20 cm was created on the long end in the sheet feeding direction with a 2.0 mm margin at the top end and a toner coverage of 0.08 mg/cm ² .

Next, the fixing temperature of the unfixed image was raised from 140° C. in 5° C. increments using a modified fixing machine at a process speed of 450 mm/sec, and the highest fixing temperature at which no separation failure occurred was evaluated as fixing separability. The test environment was a normal temperature and low humidity environment (23° C./5% RH).

A4 size CS-064 paper (manufactured by Canon Inc., 64 g/m ² ) was used as the transfer material for the fixed image. The evaluation criteria are as follows. A score of D or higher was judged to be good.
(Evaluation criteria)
A: 190°C or more B: 180°C or more and less than 190°C C: 170°C or more and less than 180°C D: 160°C or more and less than 170°C E: Less than 160°C

<Evaluation method of coloring power>
As an image forming apparatus, a modified Canon full-color copying machine imageRUNNER ADVANCE C5255 was used, and two-component developers 1 to 21 were placed in the developing device of the cyan station for evaluation.

The evaluation environment was a normal temperature and humidity environment (23°C, 50% RH), and the evaluation paper was plain copy paper GFC-081 (A4, basis weight 81.4 g/m ² sold by Canon Marketing Japan Inc.). Using.

First, in this evaluation environment, the relationship between image density and the amount of toner on paper was investigated by varying the amount of toner on paper.

Next, the image density of the FFH image (solid area) was adjusted to 1.40, and the amount of toner applied when the image density became 1.40 was determined.

The FFH image is a value in which 256 gradations are expressed in hexadecimal notation, with 00H being the 1st gradation (white area) and FFH being the 256th gradation (solid area).

Image density was measured using an X-Rite color reflection densitometer (500 series: manufactured by X-Rite).

The coloring power of the toner was evaluated based on the applied toner amount (mg/cm ² ) according to the following criteria. A score of C or higher was judged to be good.
(Evaluation criteria)
A: Less than 0.35 mg/cm ² B: 0.35 mg/cm ² or more and less than 0.50 mg/cm ² C: 0.50 mg/cm ^{2 or} more and less than 0.65 mg/cm ² D: 0.65 mg/cm ² or more

<Evaluation of transferability>
Transferability was evaluated using two-component developers 1 to 21.
Paper: GF-C081 (81.0g/m ² ) (Canon Marketing Japan Inc.)
Amount of toner applied in solid image: 0.35mg/cm ²
Primary transfer current: 30μA
Test environment: normal temperature and humidity environment (temperature 23℃/humidity 50%RH)
Process speed: 377mm/sec
The two-component developer to be evaluated was placed in a cyan developer of an image forming apparatus (a commercially available full-color digital copying machine (CLC1100, manufactured by Canon Inc.)), and the evaluation described below was performed.

The toner remaining on the photoreceptor after the primary transfer and the toner before the primary transfer were each taped with transparent polyester adhesive tape and peeled off. The peeled adhesive tape was pasted on paper, and its density was measured using a spectral densitometer 500 series (X-Rite).

Transfer efficiency was defined as (density before primary transfer - density of transfer residue)/density before primary transfer x 100, and evaluation was performed based on the following evaluation criteria. A score of C or higher was judged to be good.
A: Transfer efficiency of 90% or more B: Transfer efficiency of 85% or more and less than 90% C: Transfer efficiency of 80% or more and less than 85% D: Transfer efficiency of less than 80%

The toner of Comparative Example 1 was rated D in scratch resistance. Since the inorganic fine particles I have a thermal expansion coefficient of 0.0 (10 ^-6 /K) and have no negative thermal expansion, it is thought that the bleeding of the wax during fixing cannot be promoted and the friction coefficient of the image surface becomes high. For this reason, it is thought that it had no effect on scratch resistance.

The toner of Comparative Example 2 was rated E in fixing and separability. This is thought to be due to the fact that since the amount of wax in the toner particles was small at 2.0 parts, the amount of wax that seeped out onto the image surface during fixing was reduced. For this reason, it is thought that the fixing separation property was not effective.

The toner of Comparative Example 3 was rated D in transferability. This is considered to be because the amount of wax occupying the surface of the toner particles increased as the amount of wax was large at 22.0 parts in the toner particles, causing uneven charging and increasing the adhesion force. For this reason, it is thought that it had no effect on transferability.

The toner of Comparative Example 4 was rated E in low temperature fixability. It is thought that the temperature required for fixing was higher because inorganic fine particles with negative thermal expansion were not added internally, and the viscosity of the amorphous resin was increased to improve scratch resistance. . Therefore, it did not show any effect on low-temperature fixability.

1 Raw material quantitative supply means, 2 Compressed gas adjustment means, 3 Introducing pipe, 4 Protruding member, 5 Supply pipe, 6 Processing chamber, 7 Hot air supply means, 8 Cold air supply means, 9 Regulation means, 10 Recovery means, 11 Hot air supply Means outlet, 12 distribution member, 13 rotating member, 14 powder particle supply port

Claims (6)

A toner having toner particles containing a binder resin, wax, and inorganic fine particles,
When the outflow start temperature measured using toner is T1 (°C), the inorganic fine particles always have a thermal expansion coefficient of -0.1× determined by X-ray diffraction in the temperature range of 30°C to T1°C. 10 ^-6 (/K) or less,
A toner characterized in that the content of the wax is 3.0% by mass or more and 20.0% by mass or less based on the mass of the toner particles. In cross-sectional observation of the toner particles using a transmission electron microscope, the ratio Ws of the area occupied by wax in the surface layer region from the surface of the toner particle to a depth of 500 nm, and the ratio Wi of the area occupied by wax in the region inner than 500 nm. 2. The toner according to claim 1, wherein the ratio satisfies the following formula (1).
2.0≧Ws/Wi≧1.0 Formula (1) The toner according to claim 1, wherein the inorganic fine particles have a number average particle diameter of 0.1 μm or more and 3.0 μm or less. The toner according to claim 1, wherein the inorganic fine particles have a number average particle diameter of 0.5 μm or more and 2.0 μm or less. The toner according to claim 1, wherein the content of inorganic fine particles in the toner particles is 1.0% by volume or more and 10.0% by volume or less. The toner according to claim 1, wherein the inorganic fine particles are zirconium phosphate having negative thermal expansion.

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