JP2018112637A - toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that can form an image having high glossiness and excellent in durability and image quality, and is excellent in releasability and low-temperature fixability.SOLUTION: A toner includes toner particles each containing binder resin and wax. On a cross section of the toner observed by a transmission electron microscope, an average aspect ratio of the wax is 15 or more and 200 or less; an average length in a minor axis direction of the wax is 50 nm or more and 300 nm or less; an average length in a major axis direction of the wax is 750 nm or more and 5000 nm or less; a ratio of the wax present in an area within 10% of the distance between a contour and the center of gravity of the cross section is 35 area% or more with respect to an area of the wax present on the cross section; the content of the wax in the toner is 3.0 mass% or more and 20.0 mass% or less.SELECTED DRAWING: None

Description

  The present invention relates to a toner used for forming a toner image by developing an electrostatic latent image formed by a method such as electrophotography, electrostatic recording, or toner jet recording.

In recent years, there has been a demand for higher quality images in printers and copiers. Specifically, improvement in image quality and image durability is required. In order to cope with this, a toner having a high gloss (gloss) and capable of forming a high-quality image, and a toner capable of forming an image resistant to rubbing and scratching are preferable. In order to obtain a toner excellent in these characteristics, studies have been made to improve the gloss and image strength of the image by using wax.
Wax is added to suppress the offset phenomenon during fixing. Here, the offset phenomenon indicates an image detrimental effect in which a part of an image adheres to the fixing member due to adhesion between the toner and the fixing member. At the same time, since the image covers the wax, an image having higher gloss and durability can be obtained.
In addition, in order to cope with energy saving of printers and copiers, a toner having excellent low-temperature fixability is also demanded. In order to obtain the effect of wax even at low temperature fixing, it is important to use wax more effectively than before. On the other hand, if the wax is eluted on the paper side, it may cause a decrease in low-temperature fixability.

With respect to these problems, Patent Documents 1 and 2 propose a toner in which wax is disposed in the vicinity of the surface of the toner.
Similarly, Patent Document 3 proposes a toner in which wax is present in the form of islands in the vicinity of the surface of the toner.
Patent Documents 4 to 6 propose toners in which the shape such as the aspect ratio of the wax is controlled to be present in the toner in an elongated state.

JP2015-148724A Japanese Patent Laid-Open No. 2006-61966 JP 2007-192952 A JP, 2015-172722, A Japanese Patent Laying-Open No. 2015-194699 JP, 2006-057591, A

The toners described in Patent Documents 1 and 2 do not disclose the exudation of wax on the paper side. Also, the shape of the wax is not described, and the effect for improving the strength and gloss of the image is unclear and there is room for improvement.
Further, in the toner described in Patent Document 3, since the wax is present in an island shape, it is not disclosed to uniformly cover the image surface.
In Patent Documents 4 to 6, the wax is efficiently used by allowing the wax to be present in the toner in an elongated state. However, there is no detailed description relating to the arrangement state, and the effects described later are disclosed. It hasn't been done yet.
Further, the above-mentioned patent documents are not studied with a focus on image strength and high gloss. Therefore, further improvement is required for the strength of the image and the high gloss.
The present invention provides a toner that solves the conventional problems.
That is, the present invention provides a toner having high glossiness, capable of forming an image excellent in durability and image quality, and excellent in releasability and low-temperature fixability.

The present invention is a toner having toner particles containing a binder resin and a wax,
In the cross section of the toner observed with a transmission electron microscope,
The average aspect ratio of the wax is 15 or more and 200 or less,
The average length in the minor axis direction of the wax is 50 nm or more and 300 nm or less,
The average length in the major axis direction of the wax is 750 nm or more and 5000 nm or less,
The ratio of the wax existing in a region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section is 35 area% or more with respect to the area of the wax existing in the cross section. ,
The toner has a wax content of 3.0% by mass or more and 20.0% by mass or less.

  According to the present invention, it is possible to provide a toner having high glossiness, capable of forming an image excellent in durability and image quality, and excellent in releasability and low-temperature fixability.

Figure showing an example of a toner cross section observed with a transmission electron microscope (drawing substitute photo) Another view showing an example of a cross section of a toner observed with a transmission electron microscope (drawing substitute photograph) Schematic diagram showing the state of the fixed image of the present invention and the prior art The figure which shows the relationship between the area | region within 10% of the distance of the outline in the cross section of a toner, a surface layer, and the outline and the gravity center of a cross section.

In the present invention, the description of “XX or more and XX or less” or “XX to XX” representing a numerical range means a numerical range including a lower limit and an upper limit as endpoints unless otherwise specified.
The inventors of the present invention have come to the present invention as a result of studying the presence of wax in the toner in order to sufficiently cover the image surface with wax even at a low fixing temperature.
The present invention is a toner having toner particles containing a binder resin and a wax,
In the cross section of the toner observed with a transmission electron microscope,
The average aspect ratio of the wax is 15 or more and 200 or less,
The average length in the minor axis direction of the wax is 50 nm or more and 300 nm or less,
The average length in the major axis direction of the wax is 750 nm or more and 5000 nm or less,
The ratio of the wax existing in a region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section is 35 area% or more with respect to the area of the wax existing in the cross section. ,
The toner has a wax content of 3.0% by mass or more and 20.0% by mass or less.

The average aspect ratio of the wax is 15 or more and 200 or less, and the ratio of the wax existing in the region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the toner cross section is the wax area existing in the cross section. On the other hand, it is 35 area% or more.
By satisfying these, the wax oozes uniformly on the toner surface even at a low fixing temperature, and the image surface is uniformly covered with the wax. As a result, an image having high glossiness and excellent durability can be obtained. The reason is considered as follows.

The average aspect ratio of the wax is 15 or more and 200 or less, and preferably 15 or more and 80 or less. This means that the wax exists in the toner in a plate-like or linear state.
Further, the ratio of the wax present in the region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the toner cross section is 35% by area or more with respect to the area of the wax present in the cross section. % Or more and 70 area% or less is preferable.
This means that a lot of wax is present near the surface of the toner. Satisfying these conditions means that plate-like or linear wax is present in the vicinity of the surface of the toner along the outline of the toner.

Specific examples of the cross section of the toner observed with a transmission electron microscope are shown in FIGS.
With such an existing state, it is considered that the wax oozes uniformly on the toner surface even at a low fixing temperature, and as a result, the image surface is uniformly covered with the wax.
In the prior art, there is no example in which the state of the wax in the toner is controlled in consideration of the state of the wax coating on the image surface in detail.
If the average aspect ratio of the wax is less than 15, the shape of the wax is close to a granular domain, so that the portion covered by the wax at the time of fixing and the portion not covered by the microscopically exist, Is hard to be uniformly covered with wax.
In addition, when the ratio of the wax existing in the region within 10% of the distance between the contour and the center of gravity of the cross section is less than 35% by area, the wax does not sufficiently ooze out at a low fixing temperature, so that the image surface is It is hard to be covered enough with wax.
In such a state, as a result, an image with high glossiness cannot be obtained, or the image is weak against rubbing and scratching.
A schematic diagram showing the difference between the above state and the state of the prior art is shown in FIG.

  As described above, it is preferable that the ratio of the wax existing in the region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the toner cross section is 70 area% or less. When it is 70 area% or less, the amount of the wax that has exuded becomes appropriate, and it becomes difficult to exude to the paper side. As a result, the low-temperature fixability is improved. The ratio of the wax is more preferably 35 area% or more and 60 area% or less.

On the other hand, a small part of the wax is compatible with the binder resin and does not bleed out. For this reason, when the average length of the wax in the minor axis direction is 50 nm or more, the above-described effect can be obtained because the amount of the wax that does not dissolve in the binder resin and oozes out to the outside can be secured sufficiently.
Further, when the thickness is 300 nm or less, the wax is sufficiently melted even at a low fixing temperature, and a state in which the wax remains undissolved can be obtained.
The average length in the minor axis direction of the wax is preferably 50 nm or more and 200 nm or less.

  When the average length in the major axis direction of the wax is 750 nm or more, the wax can be present so as to uniformly surround the contour of the cross section of the toner, and thus the above effect can be obtained. The average length of the wax in the major axis direction is more preferably 1500 nm or more. Further, the average length of the wax in the major axis direction is 5000 nm or less and preferably 4000 nm or less from the viewpoint of inclusion in the toner.

A specific method for realizing the shape and presence state of the wax is not particularly limited, and a conventionally known production method can be used.
Examples thereof include suspension polymerization, dissolution suspension, emulsion aggregation, pulverization, and spray drying. In view of production stability and simplicity, it is preferable to use a suspension polymerization method.
More preferably, a suspension polymerization method is adopted, and the melting point of the wax and the temperature of the production process are controlled to crystallize the wax before phase separation. Specifically, it is as shown below.
In the suspension polymerization method, a granulation step of forming particles of a polymerizable monomer composition containing a polymerizable monomer capable of forming a binder resin and a wax in an aqueous medium, and contained in the particles. The toner particles are manufactured through a polymerization step of polymerizing the polymerizable monomer.
At this time, the wax is uniformly dissolved in the polymerizable monomer, but after the polymerizable monomer forms the binder resin through the polymerization step, the binder resin and the wax are phase-separated.
That is, in the polymerization step, the binder resin, the polymerizable monomer (hereinafter also referred to as a binder phase) and the wax gradually form a phase separation structure. In the process of forming the phase separation structure, before the wax and the binder phase undergo phase separation, the wax is crystallized to obtain a toner having the shape and presence state of the wax.

More specifically, in the granulation step, the temperature above the melting point of the wax in the polymerizable monomer is maintained, and in the polymerization step, the polymerization temperature gradually falls below the melting point of the wax in the binder phase. Set conditions. At this time, since the polymerizable monomer serves as a solvent for the wax, the melting point of the wax in the polymerizable monomer is lower than the melting point of the wax alone. Furthermore, as the polymerizable monomer forms a binder resin in the polymerization process, the polymerizable monomer that acts as a solvent decreases, so the melting point of the wax in the polymerizable monomer gradually increases. Shows the behavior. Using this phenomenon, the above temperature conditions may be set.
According to this production method, a toner that is excellent in production stability and in which the wax is difficult to be exposed on the toner surface can be produced.
In the above production method, the shape and presence state of the wax can be controlled by the melting point of the wax, the type of wax, and the like. It can also be controlled by the amount of the wax dispersant described later.
Specifically, in the suspension polymerization method and the dissolution suspension method, the higher the polymerization rate and the solvent removal rate, the less the wax moves, and therefore the wax tends to stay inside. On the other hand, the higher the melting point of the wax, the higher the average aspect ratio and the shorter the average length in the minor axis direction. In other words, the toner cross section tends to be observed in an elongated state.
Further, as the amount of the wax dispersant increases, the wax stays inside and tends to be observed in an elongated state in the toner cross section.
The shape and presence state of the wax described above are specified using a cross section of the toner observed with a transmission electron microscope (TEM). Details will be described later.

Moreover, when using a suspension polymerization method, you may use the polymerization initiator for carrying out the polymerization reaction of a polymerizable monomer. The addition amount of the polymerization initiator is preferably 2.0 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer.
Various polymerization initiators such as peroxide polymerization initiators and azo polymerization initiators can be used.

The wax content in the toner is 3.0% by mass or more and 20.0% by mass or less, and preferably 5.0% by mass or more and 10.0% by mass or less.
When the content of the wax is 3.0% by mass or more, the above effect can be obtained because the wax can sufficiently cover the image surface. On the other hand, when the wax content is 20.0% by mass or less, the amount of the wax that exudes excessively can be suppressed, and thus the above effect can be obtained while suppressing the exudation of the wax to the paper side. The content of the wax can be controlled by the amount charged when the toner is produced. A method for measuring the wax content will be described later.

In the cross section of the toner, a surface layer is preferably present inside the outline of the cross section.
FIG. 4 shows the relationship between the contour of the cross section when the surface layer exists, the surface layer, and the area within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section (in FIG. 4, 20 is the cross section of the toner, 21 is the surface layer, 22 is the contour, and 23 is within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section).
The surface layer is also included in a region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section. When the surface layer is present, it is preferable that the cross section of the toner is present as a multilayered structure in the order of the outermost surface layer, a layer containing wax and a binder resin.
As the toner is multi-layered, the surface layer plays a role of holding the charge, and the wax plays a role of appropriately releasing the obtained charge, so that a toner that is charged more quickly can be obtained and a high-quality image can be obtained. Can be obtained.
The thickness of the surface layer is preferably 10 nm or more and 100 nm or less, and more preferably 15 nm or more and 80 nm or less.
When the thickness of the surface layer is in the above range, the influence on the charging property of the wax existing inside the surface layer can be appropriately controlled, and thus a toner having more excellent charging property can be obtained.
The thickness of the surface layer can be controlled by the amount of the material forming the surface layer. The thickness of the surface layer is calculated using a cross section of the toner observed with a transmission electron microscope (TEM). Details thereof will be described later.

As the material used for the surface layer, conventionally known resins can be used. For example, polyester resin; styrene acrylic resin; polyamide resin; furan resin; epoxy resin; xylene resin;
The surface layer preferably contains a polyester resin. Furthermore, the acid value of the polyester resin is preferably 4.0 mgKOH / g or more and 20.0 mgKOH / g or less, and more preferably 4.0 mgKOH / g or more and 16.0 mgKOH / g or less.
When the acid value of the polyester resin is within the above range, a rapid charge can be achieved while obtaining a sufficient charge amount, and a higher quality image can be obtained.
The acid value can be controlled by the type, amount, and ratio of monomers used when the polyester resin is synthesized. A method for measuring the acid value will be described later.
The amount of the material used for the surface layer is preferably 1.0 part by mass or more and 15.0 parts by mass or less, and 3.0 parts by mass or more and 10.0 parts by mass with respect to 100 parts by mass of the binder resin. The following is more preferable.

The polyester resin may be prepared by a conventional method. Specific examples include dibasic acids and derivatives thereof (carboxylic acid halides, esters, acid anhydrides) and dihydric alcohols, and tribasic or higher polybasic acids and derivatives thereof (carboxylic acid halogens) as necessary. Compound, ester, acid anhydride), monobasic acid, trihydric or higher alcohol, monohydric alcohol and the like.
Examples of the dibasic acid include maleic acid, fumaric acid, itaconic acid, succinic acid, malonic acid, succinic acid, dodecyl succinic acid, dodecenyl succinic acid, adipic acid, azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid, etc. Aliphatic dibasic acids such as: phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, tetrabromophthalic acid, tetrachlorophthalic acid, het acid, hymic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, etc. Aromatic dibasic acid; and the like.
Examples of the dibasic acid derivative include carboxylic acid halides, esterified products, and acid anhydrides of the above aliphatic dibasic acids and aromatic dibasic acids.
On the other hand, examples of the divalent alcohol include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and diethylene glycol. , Acyclic aliphatic diols such as dipropylene glycol, triethylene glycol and neopentyl glycol; bisphenols such as bisphenol A and bisphenol F; ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc. An alkylene oxide adduct of bisphenol A; aralkylene glycols such as xylylene glycol;

Examples of the tribasic or higher polybasic acid and its anhydride include trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, and the like.
Especially, as polyester resin contained in a surface layer, it is preferable that the ratio C / O ratio of a carbon atom and an oxygen atom is 4.70 or less. When the C / O ratio is in the above range, it means that the polarity of the polyester resin is high and the phase separation from the wax is high. Therefore, the effect of the surface layer can be obtained more suitably. The C / O ratio can be controlled by the type and ratio of raw materials used when producing the polyester resin. A method for calculating the C / O ratio will be described later.

In the measurement of the toner using a differential scanning calorimeter (DSC), the endothermic amount derived from the wax obtained at the first temperature rise is defined as H1 (J / g), and the absorption derived from the wax obtained at the second temperature rise. When the amount of heat is H2 (J / g), the ratio of H2 to H1 (H2 / H1) is preferably 0.80 or more and 1.00 or less.
That (H2 / H1) is 0.80 or more means that the wax and the binder resin are hardly compatible even when the wax and the binder resin are heated. Therefore, by being in the above range, the wax easily exudes to the outside of the toner, and a more excellent wax effect can be obtained. The value of (H2 / H1) is more preferably 0.90 or more.
The (H2 / H1) can be controlled by the types of wax and binder resin. The method for measuring (H2 / H1) will be described later.

The binder resin is not particularly limited, and known resins used for toners as described below can be used. The binder resin refers to a resin having a content ratio in the total resin constituting the toner of 50% by mass or more.
Polyester resin; styrene acrylic resin; polyamide resin; furan resin; epoxy resin; xylene resin; These can be used alone or in combination of two or more.
Among these, a styrene acrylic resin is preferable from the viewpoint of phase separation from the wax.
Examples of the polymerizable monomer capable of forming the styrene acrylic resin include styrene monomers such as styrene, α-methylstyrene and divinylbenzene; methyl acrylate, butyl acrylate, methyl methacrylate, 2-methacrylic acid 2- Unsaturated carboxylic esters such as hydroxyethyl, t-butyl methacrylate, 2-ethylhexyl methacrylate; unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as maleic acid; maleic anhydride Unsaturated carboxylic acid anhydrides such as nitrile vinyl monomers such as acrylonitrile; halogen-containing vinyl monomers such as vinyl chloride; nitro vinyl monomers such as nitrostyrene; . These can be used alone or in combination of two or more.
When the toner binder resin is a styrene acrylic resin, the content thereof is preferably 70% by mass or more, and more preferably 80% by mass or more based on the total amount of the resin constituting the toner.
In addition, the manufacturing method of the said binder resin is not specifically limited, A well-known method can be used.

The wax is not particularly limited, and known waxes used for the following toners can be used.
Monohydric alcohol and aliphatic monocarboxylic acid ester, such as behenyl behenate, stearyl stearate, palmityl palmitate, or monovalent carboxylic acid and aliphatic monoalcohol ester; dibehenyl sebacate, dihexane hexanediol Esters of dihydric alcohols and aliphatic monocarboxylic acids such as nates, or esters of divalent carboxylic acids and aliphatic monoalcohols; Trivalent alcohols and aliphatic monocarboxylic acids such as glycerin tribehenate Or an ester of a trivalent carboxylic acid and an aliphatic monoalcohol; an ester of a tetravalent alcohol and an aliphatic monocarboxylic acid such as pentaerythritol tetrastearate or pentaerythritol tetrapalmitate, or a tetravalent S of carboxylic acid and aliphatic monoalcohol An ester of a hexavalent alcohol and an aliphatic monocarboxylic acid, such as dipentaerythritol hexastearate or dipentaerythritol hexapalmitate, or an ester of a hexavalent carboxylic acid and an aliphatic monoalcohol; Esters of polyhydric alcohols and aliphatic monocarboxylic acids such as nates, or esters of polyhydric carboxylic acids and aliphatic monoalcohols; natural ester waxes such as carnauba wax and rice wax; paraffin wax, microcrystalline wax, petrolatum Petroleum-based waxes and their derivatives; Hydrocarbon waxes and their derivatives by Fischer-Tropsch process; Polyolefin waxes and their derivatives such as polyethylene wax and polypropylene wax; Higher aliphatic alcohols Le; stearic acid, fatty acids such as palmitic acid; acid amide waxes.
Among these, hydrocarbon waxes having high phase separation from the binder resin, ester waxes of alcohols having 4 to 6 valences and aliphatic monocarboxylic acids, or carboxylic acids having 4 to 6 valences and aliphatics. Monoalcohol ester waxes are preferred.
Since these waxes have a high phase separation property with the binder resin and a low viscosity, a good release property can be obtained at the time of fixing. Among these, hydrocarbon wax is more preferable.
Hydrocarbon wax covers the image surface in the form of a wax when it oozes out on the image surface, so that the glossiness is further increased and an image resistant to rubbing and scratching can be obtained.
The melting point of the wax is preferably 60 ° C. or higher and 120 ° C. or lower, and more preferably 70 ° C. or higher and 100 ° C. or lower.
When the melting point of the wax satisfies the above range, even when fixed at a low temperature, it melts sufficiently and exhibits its effect, and it can suppress the seepage to the paper side. It is done.
The melting point of a hydrocarbon wax can be controlled by the molecular weight and degree of branching of the wax. An ester wax can be controlled by the molecular structure. A method for measuring the melting point will be described later.

The toner particles may contain a wax dispersant.
The wax dispersant is not particularly limited as long as it has affinity for both the binder resin and the wax.
As described above, the wax dispersant has an affinity for both the binder resin and the wax, and thus acts as a wax dispersion stabilizer. By adding the wax dispersant, the wax in the toner can be made thinner and more elongated. As a result, the above effect on the wax can be obtained more strongly.
The content of the wax dispersant is preferably 5.0 parts by mass or more and 100.0 parts by mass or less with respect to 100 parts by mass of the wax.
The wax dispersant preferably contains a reaction product of the binder resin and a hydrocarbon or an alkyl (meth) acrylate from the viewpoint of affinity for both the binder resin and the wax.
For example, when the binder resin is a styrene acrylic resin, it is preferably a reaction product of a styrene acrylic resin and a hydrocarbon or alkyl (meth) acrylate.
Here, the alkyl (meth) acrylate means an alkyl acrylate or an alkyl methacrylate.
Examples of the hydrocarbon or alkyl (meth) acrylate include hydrocarbons such as polyethylene, polypropylene, and polyolefin; long-chain alkyl acrylates such as polybehenyl acrylate, polystearyl acrylate, and polylauryl acrylate; polybehenyl methacrylate, poly Long chain alkyl methacrylates such as stearyl methacrylate and polylauryl methacrylate can be mentioned.

The toner particles may contain a colorant. Examples of the colorant include a black colorant, a yellow colorant, a magenta colorant, and a cyan colorant.
Examples of the black colorant include carbon black.
Yellow colorants include monoazo compounds; disazo compounds; condensed azo compounds; isoindolinone compounds; isoindoline compounds; benzimidazolone compounds; anthraquinone compounds; azo metal complexes; methine compounds; Pigments. Specifically, C.I. I. Pigment yellow 74, 93, 95, 109, 111, 128, 155, 174, 180, 185, and the like.
The magenta colorant includes monoazo compounds; condensed azo compounds; diketopyrrolopyrrole compounds; anthraquinone compounds; quinacridone compounds; basic dye lake compounds; naphthol compounds: benzimidazolone compounds; thioindigo compounds; Pigments. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 144, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.
Examples of the colorant for cyan include cyan pigments represented by copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds; basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.
In addition to the pigment, various dyes conventionally known as colorants can also be used.
The content of the colorant is preferably 1.0 part by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner particles may contain a known material such as a charge control agent, a charge control resin, a plasticizer, and a pigment dispersant as necessary.
Further, the toner particles may be made into toner by mixing an external additive, if necessary, and adhering it to the surface.
Examples of the external additive include inorganic fine particles selected from silica fine particles, alumina fine particles, and titania fine particles, or composite oxides thereof. Examples of the composite oxide include silica aluminum fine particles and strontium titanate fine particles. These inorganic fine particles are preferably used after the surface is hydrophobized.
In addition, the toner further includes other additives such as lubricant powders such as Teflon (registered trademark) powder, zinc stearate powder, and polyvinylidene fluoride powder, cerium oxide powder, and the like within a range that does not substantially adversely affect the toner. It can also be used as an abrasive such as silicon carbide powder, or an anti-caking agent. These additives can also be used after hydrophobizing the surface.
The addition amount of the external additive is preferably 0.01 parts by mass or more and 8.0 parts by mass or less, more preferably 0.1 parts by mass or more and 4.0 parts by mass with respect to 100 parts by mass of the toner particles. It is as follows.

In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the toner, the peak molecular weight (Mp) is preferably 5000 or more and 35000 or less, and preferably 8000 or more and 30000 or less. Is more preferable.
The lower the peak molecular weight (Mp), the higher the compatibility between the binder resin and the wax, and the more difficult it is for the wax to seep out of the toner during fixing.
On the other hand, as the peak molecular weight (Mp) is larger, the binder resin is less likely to be softened.
Therefore, by controlling the peak molecular weight (Mp) within the above range, it is possible to obtain a more excellent wax exudation state at the time of fixing.
The peak molecular weight (Mp) can be controlled by the temperature at which the toner and the binder resin used for the toner are synthesized and the amount of the polymerization initiator. A method for measuring the molecular weight distribution of the toner will be described later.

The weight average particle diameter (D4) of the toner is preferably 4.0 μm or more and 9.0 μm or less. When D4 is in the above range, the wax is not unevenly distributed between the toners, and the charged amount is sufficiently included.
In the toner, the ratio (D4 / D1) of the weight average particle diameter (D4) to the number average particle diameter (D1) is preferably 1.00 or more and 1.35 or less.
When (D4 / D1) is 1.35 or less, the wax is included between the toners without unevenness. The weight average particle size (D4) and number average particle size (D1) of the toner can be controlled by the production conditions. A method for measuring the weight average particle size (D4) and the number average particle size (D1) of the toner will be described later.

  The toner can be used as it is as a one-component developer or as a two-component developer mixed with a magnetic carrier.

Hereinafter, methods for measuring physical properties of toner and raw materials will be described.
<The ratio of the wax existing in the area within 10% of the distance between the average aspect ratio of the wax, the average length in the minor axis direction, the average length in the major axis direction, and the contour of the cross section of the toner and the center of gravity of the cross section (Hereinafter, also referred to as “abundance ratio within 10%”) and measurement method of surface layer thickness>
The cross section of the toner observed with a transmission electron microscope is prepared as follows.
Hereinafter, a procedure for producing a cross section of the ruthenium-dyed toner will be described.
First, a toner is spread on a cover glass (Matsunami Glass Co., Ltd., square cover glass; square No. 1) in a single layer, and an osmium plasma coater (filgen, OPC80T) is used as a protective film for the toner. A film (5 nm) and a naphthalene film (20 nm) are applied.
Next, a PTFE tube (Φ1.5 mm × Φ3 mm × 3 mm) is filled with a photocurable resin D800 (JEOL Ltd.), and a cover glass is placed on the tube so that the toner is in contact with the photocurable resin D800. Put it quietly. In this state, the resin is cured by irradiating light, and then the cover glass and the tube are removed to form a cylindrical resin in which toner is embedded on the outermost surface.
Using an ultrasonic ultramicrotome (Leica, UC7), the cutting radius is 0.6 mm / s, and the radius of the toner from the outermost surface of the cylindrical resin (for example, 4 when the weight average particle diameter (D4) is 8.0 μm is 4). Is cut by a length of 0.0 μm), and a cross section of the toner central portion is taken out.
Next, it cuts so that it may become a film thickness of 100 nm, and the thin piece sample of the cross section of a toner is produced. By cutting with such a method, a cross section of the toner central portion can be obtained.
The obtained flake sample was dyed for 15 minutes in a 500 Pa atmosphere of ruthenium tetroxide (RuO ₄ ) gas using a vacuum electron staining apparatus (filgen, VSC4R1H), and a transmission electron microscope (TEM) (JEM2800 manufactured by JEOL Ltd.) was used. A TEM image of the toner is produced under the conditions of the acceleration voltage of 200 kV.
An image is acquired with a TEM probe size of 1 nm and an image size of 1024 × 1024 pixels.
In the obtained TEM image, the amorphous part of the toner is strongly dyed by ruthenium tetroxide. As a result, the wax can be observed as contrast. Specifically, the wax portion is observed to be white with respect to the binder resin portion (see FIGS. 1 and 2).
Further, the binder resin and the surface layer are observed as different contrasts in the TEM image of the toner. Although the difference in brightness differs depending on the material, in the present invention, a portion observed as a portion having a contrast different from that of the binder resin is defined as a surface layer.
As for the toner to be observed, photographing is performed by selecting ten toners within ± 1.0 μm from the weight average particle diameter (D4). The observation magnification is 20000 times.
For various measurements shown below, commercially available image analysis software, for example, WinROOF (manufactured by Mitani Corporation) is used.

(1) The average length of the wax in the short axis direction, the average length in the long axis direction The measurable length of the wax in the short axis direction and the long axis in the TEM images of ten randomly selected toners Measure the total length of the direction and find the arithmetic average value.
The length of the wax in the minor axis direction corresponds to the thickness of the wax domain. The thickest part in each wax domain is measured as the length in the minor axis direction. Further, the length in the major axis direction corresponds to the length of the wax domain. Since each wax domain may be curved, the length when each wax domain is a straight line is measured as the length in the major axis direction. Moreover, when branching on the way, the branched part is measured as another domain.

(2) Average aspect ratio of wax The aspect ratio is (average length in major axis direction / average length in minor axis direction).
The “average length in the major axis direction” and the “average length in the minor axis direction” obtained in (1) above are determined by substituting them into the above.

(3) The proportion of wax present in the region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the toner cross section (existence ratio within 10%)
In the TEM image of the toner, a line is drawn from the center of gravity to a point on the contour of the toner cross section. On the line, the position of 10% of the distance between the contour and the center of gravity of the cross section is specified from the contour.
Then, this operation is performed for one round with respect to the outline of the toner cross section, and a boundary line of 10% of the distance between the outline and the center of gravity of the cross section is clearly shown from the outline of the toner cross section.
Based on the TEM image in which the 10% boundary line is clearly defined, the outline of the wax from the cross section of one toner (hereinafter referred to as A) and the outline of the cross section of the toner in the cross section of one toner The area (hereinafter referred to as B) of the wax existing in a region within 10% of the distance between the center of gravity and the center of gravity of the cross section is measured.
Next, the existing ratio within 10% in the cross section of one toner is calculated by the following formula.
Presence ratio within 10% in cross section of one toner = {“B” / “A”} × 100 (%)
This is performed for the cross section of 10 toners, and the arithmetic average value is set to an existing ratio (area%) within 10% in the cross section of the toner.

(4) Surface Layer Thickness In a TEM image of 10 randomly selected toners, the surface layer thickness is measured for each toner at four points. Specifically, two straight lines perpendicular to the approximate center of the toner cross section are drawn, and the thickness of the surface layer at four points on the two lines intersecting the surface layer is measured. The thickness of the surface layer is the distance from the contour of the cross section of the toner to the interface between the binder resin and the surface layer. The average value of all the measured values is taken as the thickness of the surface layer of the toner.

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. The acid value in the present invention is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 mL of ethyl alcohol (95% by volume), and ion exchanged water is added to make 100 mL to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 mL of water, and ethyl alcohol (95% by volume) is added to make 1 L. In order to avoid contact with carbon dioxide, etc., it is placed in an alkali-resistant container and allowed to stand for 3 days, followed by filtration to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution is that 25 mL of 0.1 mol / L hydrochloric acid is placed in an Erlenmeyer flask, a few drops of phenolphthalein solution is added, titrated with potassium hydroxide solution, and the amount of potassium hydroxide solution required for neutralization. Ask from. As 0.1 mol / L hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the pulverized sample is precisely weighed into a 200 mL Erlenmeyer flask, and 100 mL of a mixed solution of toluene: ethanol (2: 1) is added and dissolved over 5 hours. Next, a few drops of phenolphthalein solution is added as an indicator and titrated with a potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as described above, except that no sample is used (that is, only a mixed solution of toluene: ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (mL) of potassium hydroxide solution in blank test, C: addition amount (mL) of potassium hydroxide solution in final test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement method of molecular weight distribution>
The molecular weight distribution [weight average molecular weight (Mw), number average molecular weight (Mn), peak molecular weight (Mp)] of the toner or resin is measured by gel permeation chromatography (GPC) as follows.
First, a sample is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. In addition, a sample solution is prepared so that the density | concentration of the component soluble in THF may be 0.8 mass%. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 mL
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 "manufactured by Tosoh Corporation) are used.

<Measurement Method of Wax Content, H2, H1, Glass Transition Temperature (Tg), and Melting Point>
The wax content, H2, H1, glass transition temperature (Tg), and melting point are measured using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments) according to ASTM D3418-82.
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 1 mg of a sample is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference.
First, the temperature is increased from 0 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C./min, and the endothermic amount of the endothermic peak derived from the wax observed at this time is defined as H1 (J / g).
After maintaining at 150 ° C. for 15 minutes, the temperature is decreased from 150 ° C. to 0 ° C. at a temperature decrease rate of 10 ° C./min.
Further, after being held at 0 ° C. for 10 minutes, the temperature is raised for the second time from 0 ° C. to 150 ° C. at a rate of temperature increase of 10 ° C./min. / G).
The endothermic amount is calculated from the area surrounded by the differential scanning calorific value curve showing the endothermic peak obtained by the temperature rise and the base line of the differential scanning calorific value curve in the temperature region where the endothermic peak appears.

In addition, the above measurement is carried out in the same manner with the wax alone, and the peak temperature of the endothermic peak in the second temperature rising process is defined as the melting point (° C.) of the wax, and the endothermic amount is defined as Hw (J / g).
Here, the content (% by mass) of the wax is obtained by the following calculation formula.
Wax content (% by mass) = 100 × H1 / Hw

The glass transition temperature (Tg) of the toner or resin is measured using the above-described measuring apparatus, and the temperature rise rate is 1 ° C./min and the amplitude temperature range is ± 0.318 ° C./min. Modulation measurement is performed with min setting. In this temperature raising process, a specific heat change is obtained in the temperature range of 20 ° C to 140 ° C.
The glass transition temperature is the curve of the stepwise change portion of the glass transition and the straight line that is equidistant from the extended straight line of each baseline before and after the specific heat change of the obtained specific heat change curve. Is the temperature (° C) at the point where.

<Method for measuring particle size distribution of toner particles>
The particle size distribution of the toner particles is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with an aperture tube of 100 μm is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion exchange water so that the concentration becomes 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Place 200 mL of electrolytic solution in a glass 250 mL round bottom beaker for exclusive use of Multisizer 3, set on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) 30 mL of electrolytic aqueous solution is put into a glass 100 mL flat bottom beaker. Among them, “Contaminone N” (a non-ionic surfactant, an anionic surfactant, and a 10% by weight aqueous solution of a neutral detergent for cleaning precision measuring instruments having a pH of 7 comprising an organic builder, Wako Pure Chemical Industries, Ltd. 0.3 ml of a diluted solution obtained by diluting the product (manufactured) with ion exchange water about 3 times by mass.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) having an electrical output of 120 W is prepared. Put 3.3 L of ion exchange water in the water tank of the ultrasonic disperser, and add 2 mL of Contaminone N into this water tank. (4) The beaker of the above (2) is set in the beaker fixing hole of the ultrasonic disperser and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker is maximized.
(5) In the state where the electrolytic aqueous solution in the beaker of the above (4) is irradiated with ultrasonic waves, the toner particles are added to the electrolytic aqueous solution little by little so as to be 10 mg, and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of the above (1) installed in the sample stand, the electrolytic aqueous solution of the above (5) in which toner is dispersed using a pipette is dropped to prepare a measurement concentration of 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated.

<Calculation method of C / O ratio>
The C / O ratio can be calculated by calculation.
The C / O ratio is determined by counting the number of carbon atoms and oxygen atoms in the structure. The C / O ratio of the polyester resin is determined from the structure of the monomer constituting the polyester resin and the molar ratio introduced.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% are based on mass unless otherwise specified.

<Example of production of polyester resin 1>
In a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device, 100.0 mol part of terephthalic acid, 65.0 mol part of propylene oxide 2 mol adduct of bisphenol A, 35.0 mol part of ethylene glycol Then, 100.0 parts of the mixture mixed at the above ratio was added and heated to a temperature of 130 ° C. with stirring. Thereafter, 0.52 part of di (2-ethylhexanoic acid) tin was added as an esterification catalyst, and the temperature was raised to 200 ° C., followed by condensation polymerization until the desired molecular weight was reached.
Furthermore, 3.0 parts of trimellitic anhydride was added to obtain polyester resin 1.
The obtained polyester resin 1 had a weight average molecular weight (Mw) of 12000, a glass transition temperature (Tg) of 70 ° C., and an acid value of 8.2 mgKOH / g.

<Examples of production of polyester resins 2-7>
As shown in Table 1, polyester resins 2 to 7 were obtained in the same manner as in the production example of polyester resin 1 except that the types and mol ratios of the acid component and the alcohol component were changed.
Moreover, in the manufacture example of each polyester resin, reaction temperature and time were adjusted so that it might become a desired molecular weight. The physical properties of the obtained polyester resins 1 to 7 are shown in Table 2.

表１において、ＢＰＡ−ＰＯ２ｍｏｌ付加物は、ビスフェノールＡのプロピレンオキサイド２ｍｏｌ付加物を、ＢＰＡ−ＥＯ２ｍｏｌ付加物は、ビスフェノールＡのエチレンオキサイド２ｍｏｌ付加物を表す。

In Table 1, BPA-PO 2 mol adduct represents bisphenol A propylene oxide 2 mol adduct, and BPA-EO 2 mol adduct represents bisphenol A ethylene oxide 2 mol adduct.

<Production example of styrene acrylic resin>
After putting 300 parts of xylene (boiling point 144 ° C.) into an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, the inside of the device was sufficiently replaced with nitrogen while stirring. The temperature was raised to reflux.
Under this reflux, styrene 91.2 parts, methyl methacrylate 2.5 parts, methacrylic acid 3.0 parts, 2-hydroxyethyl methacrylate 3.8 parts, di-tert-butyl peroxide (polymerization initiator) 2.0 After adding a part of the mixed solution, the polymerization was carried out at a reaction pressure of 0.150 MPa and a polymerization temperature of 170 ° C. for 5 hours. Then, the solvent removal process was performed under reduced pressure for 3 hours, xylene was removed and pulverized to obtain a styrene acrylic resin (indicated as StAc in Table 4).
The weight average molecular weight (Mw) of the styrene acrylic resin was 15000, the glass transition temperature (Tg) was 90 ° C., and the acid value was 20 mgKOH / g.

<Production example of styrene acrylic resin fine particle dispersion>
After adding 320 parts of styrene, 80 parts of n-butyl acrylate, 1.4 parts of 1,10-decanediol diacrylate, and 3.0 parts of dodecanethiol to the container, they were mixed and dissolved.
To this, a solution prepared by dissolving 8.0 parts of an anionic surfactant (Dowfax, manufactured by Dow Chemical Co., Ltd.) in 800 parts of ion-exchanged water was added, dispersed and emulsified, and slowly mixed and stirred for 10 minutes. Further, 50 parts of ion-exchanged water in which 4.0 parts of ammonium persulfate was dissolved was added.
Next, after replacing the nitrogen in the container, the solution in the container was heated with an oil bath to 65 ° C. while stirring, and emulsion polymerization was continued for 5 hours to obtain a dispersion of styrene acrylic resin fine particles. It was. The volume average particle diameter of particles in the dispersion of styrene acrylic resin fine particles was 80 nm, the solid content was 32%, the glass transition temperature (Tg) was 65 ° C., and the weight average molecular weight (Mw) was 50,000.

<Production Example of Wax Dispersant>
In a reaction vessel equipped with a stirrer, a thermometer, a nitrogen introduction tube, and a decompression device, 600 parts of xylene and 240 parts of polyethylene wax (melting point 77 ° C., average molecular weight 489) were sufficiently dissolved and subjected to nitrogen substitution. . After raising the temperature to 175 ° C., a mixed solution of 1685 parts of styrene, 475 parts of n-butyl acrylate, 78.0 parts of di-t-butyl peroxide, and 455 parts of xylene was added dropwise over 3 hours. Furthermore, it superposed | polymerized by hold | maintaining for 30 minutes at this temperature. Next, the solvent was removed to obtain a wax dispersant.
The weight average molecular weight (Mw) of the wax dispersant was 10,000, and the glass transition temperature (Tg) was 65 ° C.

  Table 3 shows the types and melting points of the waxes used.

<Production Example of Toner 1>
・ Styrene 60.0 parts ・ Coloring agent 6.0 parts (CI Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.)
The above material was put into an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.) and further dispersed at 220 rpm for 5 hours using zirconia particles having a diameter of 1.7 mm to obtain a pigment dispersion.
-Styrene 18.0 parts-N-butyl acrylate 22.0 parts-Polyester resin 1 5.0 parts-Wax 1 6.0 parts-Wax dispersant 0.5 parts The above materials were mixed and added to the pigment dispersion. . The resulting mixture was kept at 70 ° C. K. Using a homomixer (made by Tokushu Kika Kogyo Co., Ltd.), the mixture was stirred at 500 rpm, and uniformly dissolved and dispersed to prepare a polymerizable monomer composition.
On the other hand, 850.0 parts of 0.10 mol / L-Na ₃ PO ₄ aqueous solution and 8.0 parts of 10% hydrochloric acid were added to a container equipped with a high-speed stirring device CLEARMIX (M Technique Co., Ltd.), and the number of rotations was adjusted. It adjusted to 15000 rpm and heated to 70 degreeC. To this, 68.0 parts of a 1.0 mol / L-CaCl ₂ aqueous solution was added to prepare an aqueous medium containing a calcium phosphate compound.
After introducing the polymerizable monomer composition into an aqueous medium, 7.0 parts of t-butyl peroxypivalate as a polymerization initiator is added, and the mixture is prepared for 10 minutes while maintaining the rotation speed of 15000 rotations / minute. Granulated (granulation process).
Thereafter, the high-speed stirring device was changed to a stirring device equipped with a propeller stirring blade, and a polymerization reaction was carried out at 70 ° C. for 10 hours while refluxing (polymerization step).
After completion of the polymerization reaction, the obtained slurry was cooled, a part was extracted, and the particle size distribution was measured.
Furthermore, hydrochloric acid was added to the slurry to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. Thereafter, it was washed with a water amount three times that of the slurry, filtered, dried, and classified to obtain toner particles.
Thereafter, 100.0 parts of the toner particles are treated with dimethyl silicone oil (20% by mass) as an external additive, and hydrophobized silica fine particles (triboelectrically charged to the same polarity (negative polarity) as the toner particles) ( Number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ^{2 /} g) 2.0 parts are added, and using Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.), mixed for 15 minutes at 3000 rpm toner 1 was obtained.

<Production Examples of Toner 2 to 20 and 26 to 27>
As shown in Table 4, the type and addition amount of wax, the amount of wax dispersant, the type and addition amount of polyester resin, the type and addition amount of polymerization initiator, the temperature of the granulation step, and the temperature of the polymerization step are changed. Except that, Toner 2 to 20 and 26 to 27 were obtained in the same manner as in Toner 1 Production Example.
However, in the production of the toners 12, 13, and 18, some conditions were further changed as described below.
In the production example of the toner 12, the 0.10 mol / L-Na ₃ PO ₄ aqueous solution is changed to a 0.12 mol / L-Na ₃ PO ₄ aqueous solution, and the addition amount of the 1.0 mol / L-CaCl ₂ aqueous solution is changed to 81. Changed to 6 parts.
In the production example of toner _{13, 0.10mol / L-Na 3} PO 4 aqueous solution was changed to 0.08mol / _L-Na 3 PO ₄ aqueous solution, 1.0mol / L-CaCl ₂ aqueous solution added amount of 54. Changed to 4 parts.
In the production example of the toner 18, the production was performed without adding 10% hydrochloric acid.

表４中の重合開始剤１（種類：Ｎｏ．１）はｔ−ブチルパーオキシピバレート（半減期温度５８℃）であり、重合開始剤２（種類：Ｎｏ．２）は３−ヒドロキシ−１，１−ジメチルブチルパーオキシネオデカノエート（半減期温度３７℃）である。

The polymerization initiator 1 (type: No. 1) in Table 4 is t-butyl peroxypivalate (half-life temperature 58 ° C.), and the polymerization initiator 2 (type: No. 2) is 3-hydroxy-1 , 1-dimethylbutylperoxyneodecanoate (half-life temperature 37 ° C.).

<Production Example of Toner 21 (Dissolution Suspension Method)>
(Preparation of masterbatch)
40 parts of C.I. I. Pigment Blue 15: 3 (manufactured by Dainichi Seika Co., Ltd.), 60 parts of polyester resin 6 and 30 parts of water were mixed with a Henschel mixer to obtain a mixture in which water was soaked into the pigment aggregate. This was kneaded for 60 minutes with two rolls with the roll surface temperature set at 130 ° C. and pulverized to obtain a master batch.
(Preparation of pigment / wax dispersion)
970 parts of polyester resin 6, 181 parts of wax 2, and 1450 parts of ethyl acetate / methyl ethyl ketone mixed solution (60/40 [vol%]) were charged in a container equipped with a stir bar and a thermometer and stirred at 80 ° C. And kept at 80 ° C. for 5 hours.
Next, 500 parts of the master batch and 330 parts of ethyl acetate / methyl ethyl ketone mixed solution (60/40 [volume%]) were charged into the container and mixed for 1 hour to obtain a raw material solution.
1500 parts of the raw material solution is transferred to a container, put into an attritor (manufactured by Mitsui Miike Chemical Co., Ltd.), and further dispersed at 220 rpm for 5 hours using 1.7 mm diameter zirconia particles to obtain a pigment / wax dispersion. Got. An ethyl acetate / methyl ethyl ketone mixed solution (60/40 [volume%]) was added to adjust the solid content concentration of the pigment / wax dispersion to 50%. Furthermore, the raw material solution was heated to 80 ° C.
(Preparation of aqueous phase)
850.0 parts of 0.10 mol / L-Na ₃ PO ₄ aqueous solution and 8.0 parts of 10% hydrochloric acid are added to a container equipped with a high-speed agitator CLEARMIX (M Technique Co., Ltd.), and the rotational speed is 15000 rpm. Adjust and warm to 80 ° C. Here was added 1.0mol / L-CaCl ₂ aqueous solution 68.0 parts, was to prepare an aqueous phase comprising calcium phosphate compounds.
(Granulation / solvent removal)
200.0 parts of the pigment / wax dispersion was put into the aqueous phase, and granulated for 10 minutes using the high-speed agitator while maintaining the temperature at 80 ° C. and 15000 rpm. Then, it changed to the stirring apparatus provided with the propeller stirring blade from the high-speed stirring apparatus, and solvent removal was performed at 80 degreeC for 5 hours, and the slurry was obtained.
(Particle adhesion process)
A dispersion of styrene acrylic resin fine particles was added to the obtained slurry so that the solid content ratio was 1: 0.03, and the mixture was heated to 65 ° C.
(Washing / drying / external addition)
Hydrochloric acid was added to the slurry to adjust the pH to 1.4, and the calcium phosphate salt was dissolved by stirring for 1 hour. Thereafter, it was washed with a water amount three times that of the slurry, filtered, dried, and classified to obtain toner particles.
Thereafter, 100.0 parts of the toner particles are treated with dimethyl silicone oil (20% by mass) as an external additive, and hydrophobized silica fine particles (triboelectrically charged to the same polarity (negative polarity) as the toner particles) ( Number average particle diameter of primary particles: 10 nm, BET specific surface area: 170 m ^{2 /} g) 2.0 parts are added, and using Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.), mixed for 15 minutes at 3000 rpm toner 21 was obtained.

<Example of production of toner 22 (dissolution suspension method)>
In the production example of toner 21, a toner 22 was obtained in the same manner as in the production example of toner 21 except that the ethyl acetate / methyl ethyl ketone mixed solution was changed to toluene.

<Example of Toner 23 Production (Crushing Method)>
-Polyester resin 6 70.0 parts-Styrene acrylic resin 30.0 parts-Colorant 8.0 parts (CI Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.)
-Wax 1 5.0 parts-Wax dispersant 0.5 parts After pre-mixing the above materials with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), using PCM-30 (Ikegai Iron Works Co., Ltd.), at the discharge port The temperature was set such that the melt temperature was 180 ° C., and melt kneading was performed.
The obtained kneaded product was cooled, coarsely pulverized to 1 mm or less with a hammer mill (manufactured by Hosokawa Micron Corporation), and then finely pulverized using a turbo mill T250 (manufactured by Turbo Industry Co., Ltd.) as a pulverizer.
The obtained finely pulverized product was classified using a multi-division classifier (manufactured by Nippon Steel Mining Co., Ltd .: EJ-L-3 type) using the Coanda effect. Thereafter, an external additive was added in the same manner as in the production example of toner 1 to obtain toner 23.

<Production Example of Toner 24 (Emulsion Aggregation Method)>
(Preparation of polyester resin dispersion)
-Polyester resin 7 144.0 parts-Isopropyl acrylamide 16.0 parts-Ethyl acetate 233.0 parts-Sodium hydroxide aqueous solution (0.3 mol / L) 0.1 part The said material is put into a 1000 mL separable flask, 70 The mixture was heated at 0 ° C. and stirred with a three-one motor to prepare a resin mixture. While further stirring this resin mixture, 373 parts of ion-exchanged water was gradually added to effect phase inversion emulsification and solvent removal to obtain a polyester resin dispersion (solid content concentration: 30%). The volume average particle size of the resin particles in the dispersion was 160 nm.
(Preparation of wax dispersion)
・ Wax 1 180.0 parts ・ Anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 4.5 parts ・ Ion-exchanged water 410.0 parts Heated to 110 ° C. and homogenizer (IKA) Manufactured by Ultra Turrax T50), the concentration is adjusted with ion-exchanged water, and wax particles having a volume average particle size of 200 nm are dispersed. The wax dispersion (the solid content concentration of the wax particles is 30). 0.0%) was prepared.
(Preparation of colorant dispersion)
In a stainless steel container, 280.0 parts of ion-exchanged water and 33.0 parts of an anionic surfactant are added, and after sufficiently dissolving the surfactant,
Colorant 250.0 parts (CI Pigment Blue 15: 3, manufactured by Dainichi Seika Co., Ltd.)
-Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen SC) 33.0 parts-Ion-exchanged water 750.0 parts All the above components were added and sufficiently stirred. Then, after dispersing for 20 minutes at 6000 rpm using a homogenizer (manufactured by IKA, Ultra Tarrax T50), using a high-pressure impact disperser ultimateizer (manufactured by Sugino Machine Co., Ltd., HJP30006), the pressure is 240 MPa. Dispersed. The volume average particle size of the particles in this colorant dispersion was 150 nm.
(Manufacture of toner)
・ Ion-exchanged water 215.0 parts ・ Polyester resin dispersion 228.0 parts ・ Colorant dispersion (solid content 20%) 20.0 parts ・ Anionic surfactant 2.8 parts (Daiichi Kogyo Seiyaku Co., Ltd.) : Neogen RK, solid content concentration 20%)
The material was placed in a reaction vessel equipped with a thermometer, a pH meter, and a stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. Thereafter, a 0.3 mol / L nitric acid aqueous solution was added to adjust the pH to 3.0.
Further, an aqueous solution in which 0.7 part of polyaluminum chloride was dissolved in 7.0 parts of ion-exchanged water was added while being dispersed with a homogenizer (manufactured by IKA Japan: Ultra Turrax T50), and the mixture was stirred up to 50 ° C. The temperature rose. Then, it stirred until the volume average particle diameter became 5.0 micrometers.
Further, 30.0 parts of a polyester resin dispersion and 15.0 parts of a wax dispersion were additionally added. After 30 minutes, 47.0 parts of a polyester resin dispersion was further added, and the wax dispersion and the polyester resin were adhered to the surface of the aggregated particles.
Subsequently, 20 parts of 10% NTA (nitrilotriacetic acid) metal salt aqueous solution (Cyrest 70: manufactured by Crest Co., Ltd.) was added, and then the pH was adjusted to 9.0 using a 1 mol / L sodium hydroxide aqueous solution. Thereafter, the temperature was raised to 90 ° C., held at 90 ° C. for 3 hours, cooled to 30 ° C., and filtered to obtain coarse toner particles. This was further redispersed with ion-exchanged water, filtered, and washed, and then vacuum dried in an oven at 40 ° C. for 5 hours to obtain toner particles. Thereafter, an external additive was added in the same manner as in the production example of toner 1 to obtain toner 24.

<Production Example of Toner 25>
In the production example of the toner 24, a toner 25 was obtained in the same manner as in the production example of the toner 24 except that the wax 1 was changed to the wax 6.

  With respect to the obtained toners 1 to 27, each physical property was measured by using the method described above. The results are summarized in Table 5.

表５中の、「Ｎ．Ｃ．」は、計測不能を意味する。

“NC” in Table 5 means that measurement is impossible.

<Examples 1-20 and Comparative Examples 1-7>
The resulting toners 1 to 27 were evaluated for performance according to the following methods. The results are shown in Table 6.

[Low temperature fixability]
Evaluation of the low-temperature fixability is performed by evaluating a minimum fixing temperature at which no visible image defect occurs in a fixed image.
The visible image defects that occur during low-temperature fixing are mainly cold offset that occurs when the toner does not melt, and blister that occurs when the toner is not sufficiently melted and the adhesion between the fixing roller and the toner is high. It is mentioned in.
Note that a blister is a blister-like image defect in which a part of a fixed image is peeled off by a fixing roller in a fixing process, and is visually recognized as a fine white spot as a fixed image.
As for the occurrence temperature of these image defects, the cold offset occurs at a lower temperature, and when the fixing temperature is raised, it becomes a blister occurrence region, and when the fixing temperature is further raised, a good image without image defects can be obtained. . Evaluation was performed as follows.
A color laser printer (HP Color LaserJet 3525dn, manufactured by HP) with the fixing unit removed was prepared, and the toner was taken out from the cyan cartridge and filled with the toner to be evaluated instead.
Next, an unfixed toner image having a length of 2.0 cm and a width of 15.0 cm (toner applied amount: 0.9 mg / cm ² ) using a filled toner on an image receiving paper (Canon office planner; 64 g / m ² ). ) Was formed at a portion 1.0 cm from the upper end with respect to the paper passing direction.
Next, the removed fixing unit was remodeled so that the fixing temperature and the process speed could be adjusted, and a fixing test of an unfixed image was performed using this.
First, in a room temperature and normal humidity environment (23 ° C., 60% RH), the process speed is set to 230 mm / s, the initial temperature is set to 155 ° C., and the set temperature is sequentially raised by 5 ° C. The image was fixed. The obtained fixed image was evaluated for low-temperature fixability based on the following criteria, with a fixing temperature at which no cold offset occurred and no white spots derived from blisters were within two as the minimum fixing temperature.
A: Minimum fixing temperature is 160 ° C. or lower B: Minimum fixing temperature is 165 ° C. or 170 ° C.
C: Minimum fixing temperature is 175 ° C. or 180 ° C.
D: The minimum fixing temperature is 185 ° C. or 190 ° C.

[Releasability]
In the fixing test, the releasability was evaluated according to the following evaluation criteria.
High temperature offset (HO) is a phenomenon in which a part of toner is fused to a fixing roller at high temperature fixing, and a toner having lower releasability is more likely to be generated at a lower fixing temperature.
The evaluation criteria are as follows.
Maximum temperature at which high temperature offset does not occur
A: Minimum fixing temperature plus 50 ° C or higher B: Minimum fixing temperature plus 40 ° C or higher and lower than 50 ° C C: Minimum fixing temperature plus 30 ° C or higher and lower than 40 ° C D: Minimum fixing temperature plus 20 ° C or higher and 30 ° C or higher Is less than

[Glossiness of image]
In the above fixing test, for a fixed image at a set temperature 10 ° C. higher than the minimum fixing temperature, an image is used under a condition of a light incident angle of 75 ° using a handy gloss meter PG-3D (manufactured by Nippon Denshoku Industries Co., Ltd.). The glossiness (gloss) was measured and evaluated according to the following criteria.
A: Glossiness of image part is 25 or more B: Glossiness of image part is 20 or more and less than 25 C: Glossiness of image part is 15 or more and less than 20 D: Glossiness of image part is 10 or more Less than 15

[Image strength; abrasion resistance]
In the fixing test, for a fixed image at a set temperature 10 ° C. higher than the minimum fixing temperature, the fixed image density and the image density after the fixed image was rubbed five times with sylbon paper applied with a load of 50 g / cm ² were used. Measurement was performed to determine the concentration reduction rate.
For the measurement of the density, an “X-Rite color reflection densitometer X-Rite 404A” was used.
The obtained concentration reduction rate was evaluated according to the following criteria.
A: Concentration reduction rate is less than 3.0% B: Concentration reduction rate is 3.0% or more and less than 7.0% C: Concentration reduction rate is 7.0% or more and less than 10.0% D : Concentration reduction rate is 10.0% or more and less than 15.0% E: Concentration reduction rate is 15.0% or more

[image quality]
Image quality was evaluated by evaluating the ghost phenomenon as follows.
A commercially available color laser printer (HP Color LaserJet 3525dn, manufactured by HP) was modified and evaluated so as to operate even when only one color process cartridge was installed.
The toner contained in the cyan cartridge mounted on the color laser printer was taken out, the interior was cleaned by air blow, and the toner to be evaluated (200 g) was filled instead. Under a normal temperature and humidity environment (23 ° C., 60% RH), a Canon office planner (64 g / m ² ) was used as an image receiving paper, and 2000 sheets of a 1% printing rate chart were continuously printed.
Thereafter, after 300 solid white images were printed out, a ghost determination image was output. A ghost determination image is a halftone of 15 mm × 15 mm solid images arranged in a horizontal row at 15 mm intervals at a position 5 mm from the top edge of the transfer paper, and the bottom of the solid image is a toner applied amount of 0.20 mg / cm ² . It is an image.
The difference in reflection density measured by the Macbeth densitometer between the place where the solid black image was formed in the first round (black printing part) and the place where it was not (non-image part) in the halftone part of the image. Calculated as follows.
“Reflection density difference” = (reflection density of an image of a non-image portion on the first rotation of the developing roller) − (reflection density of an image of a black printing portion on the first rotation of the developing roller)
It is evaluated that the smaller the reflection density difference is, the less ghost occurs.
The reflection density difference was evaluated according to the following criteria.
A: 0.00 or more and less than 0.03 B: 0.03 or more and less than 0.06 C: 0.06 or more and less than 0.10 D: 0.10 or more and less than 0.15 E: 0.15 or more

  20: cross section of toner, 21: surface layer, 22: contour, 23: within 10% of the distance between the contour and the center of gravity of the cross section

Claims (10)

A toner having toner particles containing a binder resin and a wax,
In the cross section of the toner observed with a transmission electron microscope,
The average aspect ratio of the wax is 15 or more and 200 or less,
The average length in the minor axis direction of the wax is 50 nm or more and 300 nm or less,
The average length in the major axis direction of the wax is 750 nm or more and 5000 nm or less,
The ratio of the wax existing in a region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section is 35 area% or more with respect to the area of the wax existing in the cross section. ,
A toner, wherein a content of the wax in the toner is 3.0% by mass or more and 20.0% by mass or less.   The toner according to claim 1, wherein a surface layer is present inside a contour of the cross section in the cross section of the toner.   The toner according to claim 2, wherein the surface layer has a thickness of 10 nm to 100 nm. The surface layer contains a polyester resin,
The toner according to claim 2, wherein the acid value of the polyester resin is 4.0 mgKOH / g or more and 20.0 mgKOH / g or less.   The ratio of the wax present in the region within 10% of the distance between the contour and the center of gravity of the cross section from the contour of the cross section is 35 area% or more and 70 area with respect to the area of the wax present in the cross section. The toner according to claim 1, wherein the toner is at most%. In the measurement using the differential scanning calorimeter of the toner,
The endothermic amount derived from the wax obtained at the first temperature increase is H1 (J / g),
When the endothermic amount derived from the wax obtained at the second temperature increase is H2 (J / g),
The toner according to claim 1, wherein a ratio (H2 / H1) of H2 to H1 is 0.80 or more.   The toner according to claim 1, wherein the wax contains a hydrocarbon wax.   The toner according to claim 1, wherein the toner particles contain a wax dispersant.   The toner according to claim 1, wherein the toner particles contain a reaction product of a binder resin and a hydrocarbon or an alkyl (meth) acrylate.   The toner according to claim 1, wherein the wax has a melting point of 60 ° C. or higher and 120 ° C. or lower.

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