JP2010152208A - Toner and developer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner and developer capable of obtaining a uniform solid image with reduced unevenness in the solid image and at the edge thereof, and greatly reducing a cost per a piece of paper by reducing an amount of toner consumed for image output owing to reduction of toner deposition. <P>SOLUTION: The toner contains at least a binder resin, coloring agent and dispersing agent. The coloring agent contains at least one kind of pigment, and the dispersing agent has a base skeleton compatible with the binder resin and at least one aromatic scaffold. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner and a developer that are used for developing an electrostatic latent image in an electrophotographic copying machine, a laser printer, a facsimile, and the like and are suitable for forming a color image.

  Conventionally, in an image forming apparatus, an electrostatic recording apparatus, or the like, an electrical or magnetic latent image is visualized with toner. For example, in electrophotography, an electrostatic charge image (latent image) is formed on a photoreceptor, and then the latent image is developed with toner to form a toner image. The toner image is usually transferred onto a transfer material such as paper and then fixed by a method such as heating. The toner used for electrostatic image development is generally colored particles in which a colorant, a charge control agent, and other additives are contained in a binder resin. And suspension polymerization. In the pulverization method, a colorant, a charge control agent, an offset preventive agent, and the like are melt-mixed in a thermoplastic resin and uniformly dispersed, and the resulting composition is pulverized and classified to produce a toner. .

  According to the pulverization method, it is possible to produce a toner having excellent characteristics to some extent, but there is a limitation in the selection of the toner material. For example, a toner composition obtained by melt mixing must be capable of being pulverized and classified by an economically usable apparatus. From this demand, the melt-mixed toner composition must be sufficiently brittle. For this reason, when the toner composition is actually pulverized into particles, a wide range of particle size distribution is likely to be formed, and when attempting to obtain a copy image with good resolution and gradation, for example, the particle size The fine powder of 5 μm or less, particularly 3 μm or less and the coarse powder of 20 μm or more must be removed by classification, which has the disadvantage that the yield becomes very low. Further, in the pulverization method, it is difficult to uniformly disperse the colorant, the charge control agent, and the like in the thermoplastic resin. Further, since the colorant added to the toner is exposed on the surface of the obtained toner, there is a problem that the toner surface is not uniformly charged, the toner charge distribution is widened, and the development characteristics are deteriorated. Therefore, because of these problems, the kneading and pulverizing method cannot sufficiently meet the demand for high performance.

  In recent years, in order to overcome these problems in the pulverization method, a toner production method by a suspension polymerization method has been proposed and implemented. A technique for producing a toner for developing an electrostatic latent image by a polymerization method is known. For example, toner particles are obtained by a suspension polymerization method. However, the toner particles obtained by the suspension polymerization method are spherical and have a drawback of poor cleaning properties. In development and transfer with a low image area ratio, there is little transfer residual toner, and cleaning defects do not become a problem. However, untransferred images were formed due to high image area ratios such as photographic images, as well as poor paper feed. Toner may be generated on the photoconductor as untransferred toner, and if accumulated, the image may be soiled.

  In addition, the charging roller that contacts and charges the photosensitive member is contaminated, and the original charging ability cannot be exhibited. Furthermore, since the resin is polymerized at the same time as the preparation of the toner, there are many cases where the materials used in the conventional toner cannot be used. Even those that can be polymerized using conventional materials may not be able to adequately control particle size due to the effects of additives such as resins and colorants. There is a problem that is small. The problem in particular is that polyester resins that have exhibited excellent fixing performance and color suitability by the conventional kneading and grinding method cannot be used basically, so that they can sufficiently cope with downsizing, high speed, colorization, etc. It is a point that cannot be done. For this reason, a method for obtaining irregularly shaped toner particles by associating resin fine particles obtained by an emulsion polymerization method is disclosed (see Patent Document 1).

  However, in the toner particles obtained by the emulsion polymerization method, a large amount of the surfactant remains not only on the surface but also inside the particles even after the water washing step, and the environmental stability of the toner charging is impaired. The amount distribution is widened, resulting in poor soiling of the obtained image. Further, the remaining surfactant contaminates the photoreceptor, the charging roller, the developing roller, etc., and the original charging ability cannot be exhibited. In addition, even in the emulsion polymerization method in which the colorant component is hardly exposed on the toner surface, the colorant easily aggregates, so that it is difficult to add and disperse the colorant uniformly in the toner. Due to the difference, there is a problem that the non-uniformity of charging occurs and the stability when used for a long time is lowered. In the case of color output, a slight deterioration in developability and transferability causes a problem in color balance and gradation. Furthermore, since the colorant in the toner is generally hydrophilic and incompatible with the resin, there is also a problem that the transmitted light is irregularly reflected at the interface and the image density and saturation are deteriorated.

  Patent Document 2 discloses a step of preparing a pigment dispersion by dissolving and / or dispersing a pigment and a pigment dispersant surface-treated with a fatty acid in a first organic solvent solubilizing a binder resin; A step of preparing an oil component by mixing the binder resin and the pigment dispersion in a second organic solvent solubilizing the binder resin, and a step of suspending the oil component in an aqueous medium and atomizing the mixture. A toner obtained by removing the solvent from the resulting suspension is disclosed. However, fatty acids do not have amino groups that control the chargeability of the toner. Furthermore, in particular, in color output machines, an oil-less toner that eliminates the need for an oil supply device for the fixing device and adds a release agent that replaces the oil into the toner has become common sense. Further, since it cannot be atomized as much as a colorant, it is difficult to add and disperse more uniformly, and there is also a problem that charging property, developability and storage stability are hindered if the release agent is poorly dispersed.

  In addition, with recent full-color printers, the demand for image quality is increasing year by year. In Patent Document 3, a synergist (pigment derivative) and a polymer dispersant are used as a pigment, and the pigment is highly dispersed in the toner to achieve high saturation and coloring power. However, since the synergist and the polymer dispersant disperse the pigment using the characteristics of acid-base, a highly polar salt is formed on the pigment surface. Therefore, underwater granulation, which is a normal chemical toner manufacturing method, pigments are unevenly distributed on the toner surface, which can contaminate the photoconductor, charging roller, developing roller, etc., or change the surface condition. As a result, the original charging ability cannot be exhibited.

  In Patent Document 4, an attempt is made to increase the dispersion of the pigment by adjusting the acid value and amine value of the polyester-based dispersant. However, since this also forms an acid-base salt, the surface of the pigment is unevenly distributed. It is not possible to improve.

  Therefore, at present, toners and developers that can sufficiently meet the demand for higher performance have not been provided.

Japanese Patent No. 2537503 JP 2001-66827 A Japanese Patent Laid-Open No. 11-231572 Japanese Patent No. 3661422

  An object of the present invention is to solve various problems in the prior art and achieve the following objects. That is, according to the present invention, a uniform solid image with reduced unevenness in the solid image and at the edge thereof can be obtained, and the toner adhesion amount can be reduced, so that the amount of toner consumed at the time of image output can be reduced. An object of the present invention is to provide a toner and a developer that can significantly reduce the cost per sheet.

Means for solving the problems are as follows. That is,
<1> A toner comprising at least a binder resin, a colorant, and a pigment dispersant,
The colorant contains at least one pigment;
The toner according to claim 1, wherein the pigment dispersant has a base skeleton compatible with the binder resin and at least one aromatic skeleton.
<2> The toner according to <1>, wherein the toner is granulated in an aqueous medium.
<3> The coating film prepared by applying a solution obtained by dissolving 10 g of toner in 40 g of tetrahydrofuran (THF) onto a substrate with a 0.3 mm wire bar has a haze degree of 0.1 to 25. The toner according to any one of <1> to <2>.
<4> The toner according to any one of <1> to <3>, wherein the aromatic skeleton of the pigment dispersant is a naphthalene skeleton.
<5> The toner according to any one of <1> to <4>, wherein a base skeleton of the pigment dispersant is a polyester skeleton.
<6> The base skeleton of the pigment dispersant is represented by the general formula: HO (OCC ₄ H ₈ —COO—C ₆ H ₁₂ —O—) _n H (where n is 5 to 5,000) < The toner according to any one of <1> to <5>.
<7> The toner according to any one of <1> to <6>, wherein the pigment dispersant has a weight average molecular weight (Mw) of 1,000 to 1,000,000.
<8> The toner according to any one of <1> to <7>, wherein a content of the pigment in the toner is 3% by mass to 15% by mass.
<9> The toner according to any one of <1> to <8>, wherein the volume average particle diameter Dv is 2.0 μm to 5.0 μm.
<10> The toner according to any one of <1> to <9>, wherein a ratio (Dv / Dn) of the volume average particle diameter Dv to the number average particle diameter Dn is 1.00 to 1.20.
<11> From the above <1> to <10, in which the toner is adhered on the recording medium so that the adhesion amount is 0.25 mg / cm ² and the reflection density of the fixed monochrome image is 1.2 to 2.5. > The toner according to any one of the above.
<12> A compound having at least an active hydrogen group and a polymer having a site capable of reacting with the compound having an active hydrogen group are dissolved or dispersed in an organic solvent, and the solution or dispersion is crosslinked in an aqueous medium. Or the toner according to any one of <1> to <11>, which is obtained by performing an elongation reaction and removing the solvent from the obtained dispersion.
<13> The toner according to <12>, wherein the polymer having a site capable of reacting with a compound having an active hydrogen group is a modified polyester resin (i) having a reactive substituent.
<14> The toner according to <13>, wherein the reactive substituent of the modified polyester resin (i) is an isocyanate group.
<15> The binder resin contains an unmodified polyester resin (ii) together with the modified polyester resin (i) subjected to crosslinking or elongation reaction, and the mass ratio [(i) / (ii)] is 5/95. The toner according to any one of <12> to <14>, which is ˜30 / 70.
<16> The toner according to any one of <1> to <15>, which is at least one selected from a yellow toner, a magenta toner, and a cyan toner.
<17> A developer comprising the toner according to any one of <1> to <16>.

  According to the present invention, conventional problems can be solved, and a uniform solid image with reduced unevenness in the solid image and at the edge thereof can be obtained. Therefore, it is possible to provide a toner and a developer that can reduce the amount of toner to be produced and can significantly reduce the cost per sheet.

  The toner of the present invention contains a binder resin, at least one pigment as a colorant, and a pigment dispersant, and further contains other components as necessary.

<Pigment dispersant>
The pigment dispersant has a base skeleton compatible with the binder resin and at least one aromatic skeleton, the base skeleton is a polyester-based skeleton, and the aromatic skeleton is at a molecular intermediate site or terminal. A polyester resin having a distributed structure is preferable.
Specific examples include polyester resins obtained by polycondensation of the following A component, B component, and C component.

-A component-
As said A component, the aromatic compound shown by following General formula (1) is mentioned.
XY ... General formula (1)
However, in said general formula (1), X represents an aryl group. Examples of the aryl group include a benzene ring, a naphthalene ring, an anthracene ring, a tetracene ring, a pentacene ring, a hexacene ring, and a heptacene ring.
Y represents an organic group represented by the following general formula (2), an organic group represented by the following general formula (3), an organic group represented by the following general formula (4), or an organic group represented by the following general formula (5). Represents a group.
-CO ₂ Z ¹ ··· general formula (2)
-R ¹ CO ^₂ Z ₂ ··· general formula (3)
-R ² OH ··· general formula (4)
_{^{-O (R 3 O) m H}} ··· formula (5)
However, the general formula (2) ~ (5), Z 1 and ^{Z 2} are both hydrogen atom, or an alkyl group having 1 to 12 carbon atoms. R ¹ and R ² each represent a residue obtained by removing one hydrogen atom from each chain end of an aliphatic hydrocarbon compound having 1 to 12 carbon atoms. R ³ represents a residue obtained by removing one hydrogen atom from each chain end of an aliphatic hydrocarbon compound having 2 to 4 carbon atoms. m is an integer of 1-3.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tertiary butyl group, a pentyl group, an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an isoheptyl group, and an octyl group. , Isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, cyclopentyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, and the like.

The aromatic compound is an unsaturated cyclic compound in which the number of electrons contained in the π-electron system on the ring is 4n + 2 (where n = 0, 1, 2, 3,...). Such a conjugated unsaturated ring structure is called an aromatic ring, and this rule is called the Hückel rule.
The π electrons on the aromatic ring are delocalized and distributed over the ring. At this time, the π electron system is not limited to π electrons derived from a double bond. Further, there is no need for a 6-membered ring, and many 5-membered aromatic compounds are known. For example, the cyclopentadienyl anion is considered to exhibit aromaticity because the anion electrons are involved in the π-electron system, or in thiophene, the sulfur lone pair is involved in the π-electron system. For this reason, thiophene oxidizes sulfur atoms, and when SO is used, it loses aromaticity and exhibits reactivity as a diene.
The shielding effect derived from non-localized electrons may be referred to as a ring current because it acts as if a circular current exists, but it does not mean that electrons actually circulate. As the above-mentioned term “delocalization” indicates, π electrons do not exist even in specific places, and spread as a cloud as a whole.

By having such an aromatic skeleton, a π electron cloud expressing the aromatic contained in the organic pigment and a π electron cloud possessed by the aromatic skeleton of the pigment dispersant form a bond by π-π interaction. It can be adsorbed on the pigment surface without generating polarity, and the dispersibility of the pigment can be maintained due to steric hindrance by the polyester-based skeleton serving as the base skeleton.
The π-π interaction is a dispersion force (London dispersion force) acting between aromatic rings of organic compound molecules. Since the two aromatic rings tend to stabilize in an arrangement where coins are stacked, stacking interactions occur, allowing the pigment dispersant to be adsorbed on the pigment surface.
Aromatic compounds have a strong planar structure and abundantly delocalized electrons due to the π-electron system, so the London dispersion force is particularly strong. Therefore, it increases as π electrons increase.
The aromatic skeleton having such a π-π interaction is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a benzene ring, naphthalene ring, anthracene ring, tetracene ring, pentacene ring, hexacene ring And heptacene ring. Among these, a naphthalene ring is particularly preferable because it is industrially mass-productive and advantageous in terms of cost, and satisfies the object pigment adsorbing property of the present invention.
Examples of the compound having an aromatic skeleton include a compound having a benzene ring, a compound having a naphthalene ring, a compound having an anthracene ring, a compound having a tetracene ring, a compound having a pentacene ring, a compound having a hexacene ring, and a heptacene ring. And the like. Specific examples include dimethyl 2,6-naphthalenedisulfonate, 2-naphthalenecarboxylic acid, benzoic acid, 4,5-dihydroxy-9,10-dioxo-9,10-dihydroanthracene-2-carboxylic acid, and the like. It is done.

-B component-
Examples of the component B include polyvalent carboxylic acids.
Examples of the polyvalent carboxylic acid include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, or anhydrides thereof, alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, or anhydrides thereof, and maleic acid. Unsaturated dibasic acids such as acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid, etc., maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc. Basic acid anhydride, trimet acid, pyrometic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarbo Ci-2-methyl-2-methylenecarboxypropane, tetrakis (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acids, their anhydrides, partial lower alkyl esters, etc. Can be mentioned.
These may be used individually by 1 type and may use 2 or more types together.

-C component-
Examples of the component C include polyhydric alcohols.
The polyhydric alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol , Diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, bisphenol A, ethylene oxide, propylene oxide, etc. And a dihydric alcohol obtained by adding a cyclic ether. These may be used individually by 1 type and may use 2 or more types together.
In order to crosslink the polyester resin, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol 1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. It is preferable to use a trivalent or higher alcohol together.

Among these, the base skeleton of the pigment dispersant is represented by the general formula: HO (OCC ₄ H ₈ —COO—C ₆ H ₁₂ —O—) _n H (where n is 5 to 5,000). Those are particularly preferred.
In addition, as a substance (pigment derivative, synergist) having the same skeleton as the pigment as the colorant, a polyester chain may be added to a substance having a structure similar to the pigment.

-Method for synthesizing pigment dispersant-
The method for synthesizing the pigment dispersant is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a raw material (for example, the above-mentioned A) is placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe. Component, B component, and C component), and can be synthesized by reacting them at an appropriate time under normal pressure and at a polymerizable temperature.

The pigment dispersant preferably has a weight average molecular weight (Mw) of 1,000 to 1,000,000.
Here, the weight average molecular weight (Mw) can be measured, for example, by gel permeation chromatography (GPC).
The addition amount of the pigment dispersant is preferably 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the pigment. If the addition amount is too small, the effect is small and the pigment can be sufficiently dispersed and cannot be stabilized. If it is too large, the binder resin is plasticized or the charging characteristics deteriorate, and the quality is reduced. It may be disadvantageous in terms of cost and cost.

  In the present invention, the pigment is finely dispersed in the conventional pigment dispersion. Thus, in order to reduce the pigment dispersion diameter, it is necessary to use a specific pigment dispersant. As a requirement for the pigment dispersant, a coating film is prepared on a transparent film with a 0.3 mm wire bar by dissolving 10 g of toner in 40 g of tetrahydrofuran (THF), and the haze degree of the coating film is determined. A pigment dispersant having an ability of 0.1 to 25 is preferred. Thereby, compared with the past, a pigment dispersion diameter becomes small and transparency improves.

In the toner of the present invention, it is preferable that the pigment as the colorant is uniformly dispersed or dissolved in the toner. In addition, although a dye can also be used as a coloring agent, a pigment is used from the point which is excellent in light resistance.
When a pigment is used as the colorant, it is preferable that the pigment is uniformly dispersed and stabilized in the toner by the pigment dispersant. In this case, the dispersed particle diameter of the pigment can be measured by, for example, a laser scattering / diffraction method, a laser Doppler method, a centrifugal sedimentation method, an ultrasonic attenuation method, or the like.
The laser scattering / diffraction method requires large dilution, and parameter setting becomes difficult. The laser Doppler method can measure at a relatively low dilution, but requires dilution. The centrifugal sedimentation method takes a long time to measure. The ultrasonic attenuation method has many parameters necessary for measurement, and is set for each material type.
As described above, the conventional methods for measuring the dispersed particle size have the problems that it is troublesome and requires large dilution, takes time, and it is difficult to accurately measure the dispersed particle size. there were.

In contrast, the toner of the present invention employs a haze degree as a measure of transparency that correlates with the dispersed particle diameter, and when the haze degree falls within a certain numerical range, the dispersion degree of the pigment in the target toner is determined. Can be satisfied.
The haze degree is preferably from 0.1 to 25, and more preferably from 0.1 to 20. When the haze degree is less than 0.1, the hiding power is lost and the coloring power is lowered. When the haze degree exceeds 25, dispersion may be insufficient and coloring power and saturation may be lowered.
Here, the haze degree is obtained by applying a solution obtained by dissolving 10 g of toner in 40 g of tetrahydrofuran (THF) onto a substrate with a 0.3 mm wire bar to prepare a coating film. For example, it can be determined by measuring with a TM double beam type automatic haze computer (manufactured by Suga Test Instruments Co., Ltd.).
A transparent film is suitable as the substrate, and examples thereof include a PET film, a PP film, and a PE film.

Further, in the present invention, the reflection density (ID) of the fixed monochrome image obtained by adhering the toner to the recording medium so that the adhering amount is 0.25 mg / cm ² is 1.2 to 2.5. It is preferable that 1.3 to 2.0 is more preferable. As a result, the amount of toner required can be reduced, reducing the environmental burden by reducing the amount of raw materials, reducing the cost by reducing the amount of pigment used as a high-cost material, and reducing the image thickness. Unevenness in the (solid image) or the edge thereof is reduced, and a uniform solid image is obtained. A uniform solid image can also be obtained by uniform dispersion of the pigment.
The reflection density (ID) is an optical reflection density and may also be called an image density.
If the reflection density is less than 1.2, the image may not be able to reproduce the original image due to insufficient coloring power. If the reflection density exceeds 2.5, the amount of pigment will be too high, resulting in high costs and color reproduction. Sexuality may worsen.
There is no restriction | limiting in particular as said recording medium, According to the objective, it can select suitably, For example, in addition to paper media, such as an art paper, a coated paper, a plain paper, an OHP sheet etc. are mentioned.
There is no restriction | limiting in particular as said fixing, According to the objective, it can select suitably, For example, oilless fixing is suitable.

<Colorant>
There is no restriction | limiting in particular as said coloring agent, According to the objective, it can select suitably, For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium Yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG) , Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sa Red Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian , Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Maracay Toledo lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, ritbon, etc. In addition, you may use together well-known dye with the said pigment. These may be used individually by 1 type and may use 2 or more types together.

The content of the colorant in the toner is preferably 3% by mass to 15% by mass, and more preferably 4% by mass to 8.5% by mass. Thus, by reducing the amount of the relatively expensive pigment, the cost of the entire toner can be reduced.
The toner adhesion amount of this time 0.25 mg / cm ^2, the reflection density 1.2 to 2.5 of fixing the monochrome image is obtained. However, the toner particle diameter at this time is 2.0 μm to 5.0 μm in terms of volume average particle diameter Dv. The reason why a reflection density of 1.2 to 2.5 can be obtained with a low toner adhesion amount of 0.25 mg / cm ² is that the particle size is controlled to be small, and the fine dispersion of colorants, particularly pigments, is improved. By letting The color development of the pigment changes due to a change in light absorption probability due to a change in the number of pigment particles, a change in light transmittance due to a change in the pigment aggregate particle diameter, and a change in light scattering degree on the pigment surface. That is, by reducing the pigment particle diameter, pigment scattering is reduced and the light absorption probability is improved. Further, since the transparency is improved, the light transmittance is improved and the scattered light is also reduced, so that the high reflection density and the color reproduction range can be expanded.

<Binder resin>
There is no restriction | limiting in particular as said binder resin, According to the objective, it can select suitably, For example, styrenes, such as styrene, parachlorostyrene, (alpha) -methylstyrene; Methyl acrylate, ethyl acrylate, acrylic acid n -Esters having an unsaturated bond such as propyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate; acrylonitrile, methacrylo Nitriles having an unsaturated bond such as nitrile; Vinyl ethers such as vinyl methyl ether and vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl ethyl ketone and vinyl isopropenyl ketone; Ethylene, propylene, butadiene and the like Polymers or copolymers with monomers of olefins and the like, or mixtures thereof, and the like.
Further, non-vinyl condensation resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, and polyether resins; a mixture of these condensation resins with the vinyl resins, or vinyl in the presence of these polymers. Examples thereof include a graft polymer obtained by polymerizing a monomer. Among these, a polyester resin is particularly preferable in terms of excellent low-temperature fixability and color reproducibility.

As the polyester resin, modified polyester resin (i) or unmodified polyester resin (ii) can be used. These may be used singly, but the modified polyester resin (i) and the unmodified polyester resin (ii) are used for improving the low-temperature fixability and the gloss when used in a full-color apparatus. It is preferable to use together.
Hereinafter, the modified polyester resin (i) and the unmodified polyester resin will be described in detail.

The modified polyester resin includes a functional group contained in a monomer unit of acid or alcohol and a bonding group other than an ester bond in the polyester resin, or a resin component having a different configuration in the polyester resin is a covalent bond, an ion It means the state of being connected by bonding or the like. For example, the polyester terminal is reacted with something other than an ester bond, specifically, a functional group such as an isocyanate group that reacts with an acid group or a hydroxyl group is introduced into the terminal, and further reacted with an active hydrogen compound, and the terminal is Those that have been modified or extended are also included. Moreover, as long as it is a compound in which a plurality of active hydrogen groups are present, those in which polyester ends are bonded to each other are included (urea-modified polyester, urethane-modified polyester, etc.). Furthermore, a reactive group such as a double bond is introduced into the polyester main chain, and radical polymerization is caused therefrom to introduce a carbon-carbon bond graft component into the side chain, or the double bonds are bridged together. (Styrene modified polyester, acrylic modified polyester, etc.).
In addition, a resin component having a different structure is copolymerized in the main chain of the polyester, or reacted with a carboxyl group or a hydroxyl group at the terminal, for example, a silicone having a terminal modified with a carboxyl group, a hydroxyl group, an epoxy group, or a mercapto group Also included are those copolymerized with resins (silicone-modified polyesters, etc.).

  Examples of the polyester resin (i) modified with a urea bond include a reaction product of a modified polyester (A) having an isocyanate group and an amine (B). The modified polyester resin (A) having an isocyanate group is a polycondensate of a polyol (1) and a polycarboxylic acid (2), and a polyester obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), etc. Is mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are particularly preferable.

Examples of the polyol (1) include diol (1-1), trivalent or higher polyol (1-2), (1-1) alone or (1-1) and a small amount of (1-2). Mixtures are preferred.
Examples of the diol (1-1) include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (Diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); Bisphenols (bisphenol A) Bisphenol F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the alicyclic diol; bis Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among these, alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are preferable, and the combination of alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms is particularly preferable.

  Examples of the trivalent or higher polyol (1-2) include 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); (Trisphenol PA, phenol novolak, cresol novolac, etc.); alkylene oxide adducts of the above-mentioned trihydric or higher polyphenols.

Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2), (2-1) alone and (2-1) and a small amount of ( The mixture of 2-2) is preferable.
Examples of the dicarboxylic acid (2-1) include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, Terephthalic acid, naphthalenedicarboxylic acid, etc.). Among these, alkenylene dicarboxylic acid having 4 to 20 carbon atoms and aromatic dicarboxylic acid having 8 to 20 carbon atoms are particularly preferable.
Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) and the polycarboxylic acid (2) is preferably 2/1 to 1/1 as an equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1 is more preferable, and 1.3 / 1 to 1.02 / 1 is still more preferable.

Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.) Aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; Those blocked with caprolactam or the like, or a combination of two or more of these may be mentioned.
The ratio of the polyisocyanate (3) is preferably 5/1 to 1/1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester resin having a hydroxyl group. / 1 to 1.2 / 1 is more preferable, and 2.5 / 1 to 1.5 / 1 is still more preferable. When the [NCO] / [OH] exceeds 5, the low-temperature fixability may be deteriorated. When the molar ratio of [NCO] is less than 1, the urea content in the modified polyester resin is lowered and the hot offset resistance is reduced. May get worse.

The content of the polyisocyanate (3) component in the modified polyester resin (A) having an isocyanate group at the terminal is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass. A mass% to 20 mass% is more preferable. When the content is less than 0.5% by mass, the hot offset resistance deteriorates and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. When the content exceeds 40% by mass, low-temperature fixability is obtained. May get worse.
The number of isocyanate groups contained per molecule in the modified polyester resin (A) having an isocyanate group at the end is preferably 1 or more, more preferably 1.5 to 3 on average, and 1.8 to 2.5 on average. Is more preferable. When the number of isocyanate groups is less than 1 per molecule, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be deteriorated.

Examples of the amines (B) include diamines (B1), trivalent or higher polyamines (B2), amino alcohols (B3), amino mercaptans (B4), amino acids (B5), and amino groups blocked from B1 to B5. (B6) etc. are mentioned.
Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diamines). Cyclohexane, isophoronediamine, etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.
Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
In addition, as the thing (B6) which blocked the amino group of B1-B5, the ketimine compound and oxazolidine compound which are obtained from amines and ketones (Acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) of said (B1)-(B5) Etc. Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted by using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
The ratio of the amines (B) is equivalent to the equivalent ratio [NCO] / [NHx of the isocyanate group [NCO] in the modified polyester resin (A) having an isocyanate group and the amino group [NHx] in the amine (B). ] Is preferably 1/2 to 2/1, more preferably 1.5 / 1 to 1 / 1.5, and still more preferably 1.2 / 1 to 1 / 1.2. When the [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester resin (i) is lowered, and the hot offset resistance may be deteriorated.

In the present invention, the modified polyester resin (i) may contain a urethane bond together with a urea bond. The molar ratio between the urea bond content and the urethane bond content is preferably 100/0 to 10/90, more preferably 80/20 to 20/80, and still more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance may be deteriorated.
The modified polyester resin (i) is produced by a one-shot method or a prepolymer method. The mass average molecular weight of the modified polyester (i) is preferably 10,000 or more, more preferably 20,000 to 10,000,000, and still more preferably 30,000 to 1,000,000. When the mass average molecular weight is less than 10,000, the hot offset resistance may be deteriorated. Further, the number average molecular weight of the modified polyester resin (i) is not particularly limited when the unmodified polyester resin (ii) described later is used, and the number average that is easily obtained to obtain the mass average molecular weight. Molecular weight is sufficient. (I) When used alone, the number average molecular weight is preferably 20,000 or less, more preferably 1,000 to 10,000, and still more preferably 2,000 to 8,000. When the number average molecular weight exceeds 20,000, low temperature fixability and gloss when used in a full color apparatus may be deteriorated.

In the present invention, not only the modified polyester resin (i) is used alone, but also the unmodified polyester resin (ii) can be contained as a toner binder component together with the (i). Use of the unmodified polyester resin (ii) in combination improves low-temperature fixability and gloss when used in a full-color device, and is more preferable than single use. Examples of the unmodified polyester resin (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i), and preferred one (i) It is the same. Further, (ii) is not limited to unmodified polyester, but may be modified with, for example, a urea bond or a urethane bond. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions.
When the unmodified polyester resin (ii) is contained, the mass ratio of (i) to (ii) is preferably 5/95 to 30/70, more preferably 5/95 to 25/75, and 7/93. ~ 20/80 is more preferred. When the mass ratio of (i) is less than 5%, hot offset resistance is deteriorated, and it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

-Release agent-
The release agent is not particularly limited, and known ones can be used, for example, polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl Examples thereof include a group-containing wax. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecanediol distearate, etc.); polyalkanol esters (trimellitic acid tristearyl, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); polyalkylamides (trimellitic acid tristearylamide, etc.) And dialkyl ketones (such as distearyl ketone). Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

The melting point of the wax is preferably 40 ° C to 160 ° C, more preferably 50 ° C to 120 ° C, and still more preferably 60 ° C to 90 ° C. If the melting point is less than 40 ° C., the wax may adversely affect the heat resistant storage stability. If the melting point exceeds 160 ° C., a cold offset tends to occur during fixing at a low temperature. The melt viscosity of the wax is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point. The wax having a melt viscosity exceeding 1,000 cps is poor in improving hot offset resistance and low temperature fixability.
The content of the wax in the toner is preferably 40% by mass or less, and more preferably 3% by mass to 30% by mass.

-Charge control agent-
The toner of the present invention may contain a charge control agent as necessary. The charge control agent is not particularly limited and known ones can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, Quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, metal salts of salicylic acid and salicylic acid derivatives, and the like. Specifically, Bontron 03 of nigrosine dye, Bontron P-51 of quaternary ammonium salt, Bontron S-34 of metal-containing azo dye, E-82 of oxynaphthoic acid metal complex, E of salicylic acid metal complex -84, phenolic condensate E-89 (both manufactured by Orient Chemical Co., Ltd.); quaternary ammonium salt molybdenum complex TP-302, TP-415 (both manufactured by Hodogaya Chemical Co., Ltd.) Quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (all manufactured by Hoechst); LRA-901, boron Complex LR-147 (Nippon Carlit Co., Ltd.); Nin, perylene, quinacridone, azo pigments, sulfonate group, a carboxyl group, and the like and polymeric compounds having a functional group such as a quaternary ammonium salt.

The content of the charge control agent is determined by the toner production method including the type of the binder resin, the presence or absence of additives used as necessary, and the dispersion method. Although it is not, 0.1 mass-10 mass parts are preferable with respect to 100 mass parts of said binder resin, and 0.2 mass part-5 mass parts are more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be lowered.
These charge control agents and release agents can be melt-kneaded together with the masterbatch and resin, and may be added when dissolved or dispersed in an organic solvent.

-External additive-
The external additive used for assisting the fluidity, developability and chargeability of the toner is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, inorganic fine particles Is preferred.
The primary particle size of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. In addition, the specific surface area by BET method is ^{20m 2} / ^g~500m 2 / g are preferred.
The addition amount of the inorganic fine particles is preferably 0.01% by mass to 5% by mass, and more preferably 0.01% by mass to 2.0% by mass with respect to the toner.

The inorganic fine particles are not particularly limited and can be appropriately selected depending on the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, Tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, Etc.
Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, etc. are mentioned.

The fluidity improver can be surface-treated to increase hydrophobicity and prevent deterioration of fluidity and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, and a fluoride can be used. Examples thereof include silane coupling agents having an alkyl group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils.
The cleaning improver is added to the toner to remove the developer after transfer remaining on the electrostatic latent image carrier or the intermediate transfer member. For example, fatty acid such as zinc stearate, calcium stearate, stearic acid Metal salts; polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.
There is no restriction | limiting in particular as said magnetic material, According to the objective, it can select suitably from well-known things, For example, iron powder, a magnetite, a ferrite, etc. are mentioned. Among these, white is preferable in terms of color tone.

<Toner production method>
The method for producing the toner is not particularly limited and can be appropriately selected according to the purpose from conventionally known toner production methods. For example, a kneading / pulverizing method, a polymerization method, a dissolution suspension method, The spray granulation method etc. are mentioned. Among these, the polymerization method is particularly preferable. The polymerization method includes dissolving or dispersing a toner material containing at least a compound having an active hydrogen group, a polymer having a site capable of reacting with the compound having an active hydrogen group, and a pigment in an organic solvent, A method of reacting the dispersion in an aqueous medium and removing the organic solvent from the obtained dispersion is preferred.

Hereinafter, when urea-modified polyester is used, the toner binder can be produced by the following method.
First, the polyol (1) and the polycarboxylic acid (2) are heated to 150 ° C. to 280 ° C. in the presence of an esterification catalyst such as tetrabutoxy titanate or dibutyltin oxide, and water generated while reducing the pressure as necessary is stored. To obtain a polyester having a hydroxyl group. Subsequently, this is made to react with polyisocyanate (3) at 40 to 140 degreeC, and the modified polyester (A) which has an isocyanate group is obtained. Further, (A) is reacted with amines (B) at 0 ° C. to 140 ° C. to obtain a polyester modified with a urea bond. When reacting the polyisocyanate (3) and reacting (A) and (B), a solvent may be used if necessary.

  Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (ii) not modified with urea bond is used in combination, (ii) is produced in the same manner as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do. The dry toner can be produced by the following method, but is not limited thereto.

As an aqueous medium used in the present invention, water alone may be used, but a solvent miscible with water may be used in combination. Examples of solvents miscible with water include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
The toner particles may be formed by reacting a dispersion composed of a modified polyester (A) having a substituent capable of reacting in an aqueous medium with (B), or using a modified polyester (i) produced in advance. Good. As a method for stably forming a dispersion composed of the modified polyester (i) and the modified polyester (A) having a reactive substituent in the aqueous medium, the modified polyester (i) and the reactive substitution can be performed in the aqueous medium. Examples thereof include a method of adding a composition of a toner material composed of a modified polyester (A) having a group and dispersing the composition by shearing force. Modified polyester (A) having a reactive substituent and other toner composition (hereinafter also referred to as toner material), pigment, pigment master batch, release agent, charge control agent, unmodified polyester resin, etc. May be mixed when the dispersion is formed in the aqueous medium, but it is more preferable to mix the toner material in advance and then add and disperse the mixture in the aqueous medium.

The dispersion method is not particularly limited, and known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 μm to 20 μm, a high-speed shearing method is preferable. When a high-speed shearing disperser is used, the number of rotations is not particularly limited, but is preferably 1,000 to 30,000 rpm, and more preferably 5,000 to 20,000 rpm.
Although there is no limitation in particular as said dispersion | distribution time, in the case of a batch system, 0.1 minute-5 minutes are preferable normally. As the temperature during dispersion, a higher temperature is preferable in that the dispersion of the modified polyester (i) or the modified polyester (A) having a reactive substituent has a low viscosity and is easily dispersed.
The amount of the aqueous medium used relative to 100 parts by mass of the toner composition containing the modified polyester resin (i) and the modified polyester resin (A) having a reactive substituent is preferably 50 parts by mass to 2,000 parts by mass. Mass parts to 1,000 parts by mass are more preferable. When the amount used is less than 50 parts by mass, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle size may not be obtained. When the amount exceeds 2,000 parts by mass, it is not economical.

Moreover, a dispersing agent can also be used as needed. The use of a dispersant is preferable in that the particle size distribution becomes sharp and the dispersion is stable.
Dispersants used to emulsify and disperse the oily phase in which the toner material is dispersed in a liquid containing water include anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, and phosphate esters, Amine salt types such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N -Archi -N, amphoteric surfactants of tines such as downy N- dimethyl ammonium.

Further, by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group include a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [omega-fluoroalkyl (6 to 11 carbon atoms). ) Oxy] -1-alkyl (3 to 4 carbon atoms) sodium sulfonate, 3- [omega-fluoroalkanoyl (6 to 8 carbon atoms) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (carbon 11-20) Carboxylic acid or metal salt thereof, perfluoroalkyl carboxylic acid (carbon number 7-13) or metal salt thereof, perfluoroalkyl (carbon number 4-12) sulfonic acid or metal salt thereof, perfluorooctane sulfone Acid diethanolamide, N-propyl-N- (2hydroxyethyl Perfluorooctanesulfonamide, perfluoroalkyl (carbon number 6-10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (carbon number 6-10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (carbon number 6-6) 16) Ethyl phosphate ester and the like.
Examples of commercially available products include Surflon S-111, S-112, and S-113 (all manufactured by Asahi Glass Co., Ltd.); Fluorard FC-93, FC-95, FC-98, and FC-129 (manufactured by Sumitomo 3M Corporation). Unidyne DS-101, DS-102 (manufactured by Daikin Industries, Ltd.); Megafac F-110, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Chemical Co., Ltd.) Xttop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204, (manufactured by Tochem Products Co., Ltd.); ), Etc.

In addition, as the cationic surfactant, aliphatic quaternary ammonium salts such as aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, and perfluoroalkyl (carbon number 6 to 10) sulfonamidopropyltrimethylammonium salt. Benzalkonium salt, benzethonium chloride salt, pyridinium salt, imidazolinium salt and the like.
Commercially available products include, for example, Surflon S-121 (manufactured by Asahi Glass Co., Ltd.), Florard FC-135 (manufactured by Sumitomo 3M Co., Ltd.), Unidyne DS-202 (manufactured by Daikin Industries, Ltd.); Megafuck F-150, F-824 (Dainippon Ink & Chemicals Co., Ltd.); Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.), and the like.

Examples of the inorganic compound dispersant that is hardly soluble in water include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. Examples of the polymeric protective colloid include acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; Containing (meth) acrylic monomer (for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, methacryl Γ-hydroxypropyl acid, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate Tacric acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc.); Vinyl alcohol or ethers with vinyl alcohol (for example, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc.); Contains vinyl alcohol and carboxyl group Esters of compounds (eg, pinyl acetate, vinyl propionate, vinyl butyrate, etc.); acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride, methacrylic acid chloride; pinylviridine, vinyl Homopolymers or copolymers such as those having a nitrogen atom such as pyrrolidone, vinylimidazole, ethyleneimine or the heterocyclic ring thereof; polyoxyethylene, polyoxypropylene, Reoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl Examples thereof include polyoxyethylenes such as phenyl esters; celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. It is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner particles, and to evaporate and remove the aqueous dispersant together. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. A spray dryer, belt dryer, rotary kiln, etc. can sufficiently achieve the desired quality in a short time.
In addition, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. In addition, it can be removed by an operation such as enzymatic degradation. When a dispersant is used, the dispersant may remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

Further, in order to lower the viscosity of the toner material, a solvent in which the modified polyester resin (i) and the modified polyester resin (A) having a reactive substituent can be used may be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. This solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal.
Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Among these, aromatic solvents such as toluene and xylene, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are particularly preferable. These may be used individually by 1 type and may use 2 or more types together.
300 mass parts or less are preferable, as for the usage-amount of the solvent with respect to 100 mass parts of modified polyester (A) which has a reactive substituent, 100 mass parts or less are more preferable, and 25 mass parts-70 mass parts are still more preferable. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.

In the case of a urea-modified polyester, the elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the modified polyester (A) having a reactive substituent and the amines (B). Minutes to 40 hours are preferable, and 2 hours to 24 hours are more preferable. The reaction temperature is preferably 0 ° C to 150 ° C, more preferably 40 ° C to 98 ° C. Moreover, a well-known catalyst can be used as needed, Specifically, a dibutyltin laurate, a dioctyltin laurate, etc. are mentioned.
In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. It is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner particles, and to evaporate and remove the aqueous dispersant together. As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. A spray dryer, belt dryer, rotary kiln, etc. can sufficiently achieve the desired quality in a short time.
When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution. In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Although classification operation may be performed after obtaining as powder after drying, it is preferable in terms of efficiency to be performed in a liquid. The obtained unnecessary fine particles or coarse particles can be returned to the kneading step and used for forming particles. At that time, fine particles or coarse particles may be wet. The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation.
By mixing the obtained toner powder after drying with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder. By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture into a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) was remodeled to reduce pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
According to such a production method, it is possible to obtain a toner that is excellent in powder flowability and transferability, and that provides a high-quality image with a small particle diameter. Furthermore, it is excellent in low-temperature fixability and hot offset resistance, and does not cause filming or spent. Thus, toners that satisfy various required characteristics, including pulverized toners, have not been obtained conventionally.

-Physical properties of toner-
The volume average particle diameter (Dv) of the toner of the present invention is preferably 2.0 μm to 5.0 μm. When the volume average particle size exceeds 5.0 μm, it is difficult to obtain a high-quality image when the amount of adhesion is low, and when it is less than 2.0 μm, transferability and cleaning properties are reduced. Filming, spent to the carrier, etc. are likely to occur.

  Further, the ratio (Dv / Dn) of the volume average particle diameter (Dv) to the number average particle diameter (Dn) of the toner is preferably from 1.00 to 1.20, more preferably from 1.00 to 1.15. In the two-component developer, even if the toner balance for a long period of time is performed, the fluctuation of the toner particle diameter in the developer is reduced, and good and stable developability can be obtained even with long-term stirring in the developing device. Even when used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle size is reduced, and the toner filming on the developing roller and the toner layer are made thin. The toner is not fused to a member such as a blade, and good and stable developability and an image can be obtained even when the developing device is used (stirred) for a long time.

  Here, the volume average particle diameter (Dv) and the number average particle diameter (Dn) of the toner are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) at an aperture diameter of 100 μm, and analysis software is used. It can be measured by analyzing with (Beckman Coulter Multisizer 3 Version 3.51).

The toner has a peak molecular weight of preferably 1,000 to 30,000, more preferably 1,500 to 10,000, and still more preferably 2,000 to 8,000. When the peak molecular weight is less than 1,000, the heat resistant storage stability may be deteriorated, and when it exceeds 30,000, the low temperature fixability may be deteriorated.
Here, the peak molecular weight of the toner in the present invention is specifically determined by the following procedure.
-Measurement of peak molecular weight of toner-
Gel permeation chromatography (GPC) measuring device: GPC-8220 GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperHZM-H 15 cm triple (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: THF
・ Flow rate: 0.35 ml / min
-Sample: 0.4 ml of 0.15% sample was injected-Sample pretreatment: Toner was dissolved in tetrahydrofuran THF (containing stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15% by mass, and then 0.2 μm filter was used. Filter and use the filtrate as a sample. 100 μl of the THF sample solution is injected and measured.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd STANDARD Std. No. S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

The hydroxyl value of the toner is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, and still more preferably 20 mgKOH / g to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
The acid value of the toner is preferably 1 mgKOH / g to 40 mgKOH / g, more preferably 5 mgKOH / g to 30 mgKOH / g, and still more preferably 15 mgKOH / g to 28 mgKOH / g. By giving an acid value, it tends to be negatively charged, and the affinity with paper at the time of fixing is increased, and the fixing power is increased.
Here, the acid value (AV) and the hydroxyl value (OHV) in the toner are specifically determined by the following procedure.
・ Measuring device: potentiometric automatic titrator DL-53 Titrator (Metler Toledo)
-Electrode used: DG113-SC (manufactured by METTLER TOLEDO)
・ Analysis software: LabX Light Version1.00.000
-Calibration of apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
・ Measurement temperature: 23 ℃
The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH ₃ ONa
Concentration [mol / L] 0.1
Sensor DG115
Unit of measurement mV
Predispensing to volume
Volume [mL] 1.0
Wait time [s] 0
Titrant addition Dynamic
dE (set) [mV] 8.0
dV (min) [mL] 0.03
dV (max) [mL] 0.5
Measure mode Equilibrium controlled
dE [mV] 0.5
dt [s] 1.0
t (min) [s] 2.0
t (max) [s] 20.0
Recognition
Threshold 100.0
Steepest jump only No
Range No
Tendency None
Termination
At maximum volume [mL] 10.0
At potential No
At slope No
After number EQPs Yes
n = 1
comb. Termination conditions No
Evaluation
Procedure Standard
Potential 1 No
Potential 2 No
Stop for reevaluation No
-Method of measuring acid value-
The acid value can be measured under the following conditions based on the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of toner (0.3 g for ethyl acetate-soluble component) is added to 120 ml of toluene and dissolved by stirring for about 10 hours at room temperature (23 ° C.). Furthermore, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, and specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample weight (where N is a factor of N / 10 KOH)

-Measurement method of hydroxyl value-
The hydroxyl value can be measured under the following conditions based on the measurement method described in JIS K0070-1966.
Weigh accurately 0.5 g of sample into a 100 ml volumetric flask and add 5 ml of acetylating reagent correctly. Then, it is immersed in a bath at 100 ° C. ± 5 ° C. and heated. After 1-2 hours, the flask is removed from the bath, allowed to cool, water is added and shaken to decompose acetic anhydride. Next, in order to complete the decomposition, the flask is again heated in a bath for 10 minutes or more and allowed to cool, and then the wall of the flask is thoroughly washed with an organic solvent. This solution is subjected to potentiometric titration with an N / 2 potassium hydroxide ethyl alcohol solution using the electrode to determine the hydroxyl value.

The glass transition temperature of the toner is preferably 40 ° C to 70 ° C, more preferably 45 ° C to 60 ° C. If the glass transition temperature is less than 40 ° C, the heat-resistant storage stability may be insufficient, and if it exceeds 70 ° C, the low-temperature fixability may be adversely affected.
Here, the glass transition temperature (Tg) is specifically determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
〔Measurement condition〕
・ Sample container: Aluminum sample pan (with lid)
-Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10 mg)
・ Atmosphere: Nitrogen (flow rate 50ml / min)
・ Temperature conditions ・ Starting temperature: 20 ℃
・ Raising rate: 10 ° C / min
・ End temperature: 150 ℃
-Holding time: None-Temperature drop: 10 ° C / min
・ End temperature: 20 ℃
-Holding time: None-Temperature rising rate: 10 ° C / min
・ End temperature: 150 ℃
The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method is to specify a range of ± 5 ° C centering on the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and use the peak analysis function of the analysis software to determine the peak temperature. Ask. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the glass transition temperature (Tg) of the toner.

  The coloration of the toner is not particularly limited and may be appropriately selected according to the purpose, and may be at least one selected from black toner, cyan toner, magenta toner, and yellow toner. Can be obtained by appropriately selecting the type of the colorant, and is preferably a color toner.

(Developer)
The toner of the present invention may be used as a one-component developer (magnetic or non-magnetic) composed only of toner, or may be used as a two-component developer together with a carrier.
When used as the two-component developer, the toner is used by mixing with a magnetic carrier. The content ratio of the carrier and the toner in the developer is preferably 1 part by mass to 10 parts by mass of the toner with respect to 100 parts by mass of the carrier.

Examples of the magnetic carrier include iron powder, ferrite powder, magnetite powder having a particle size of about 20 μm to 200 μm, and a coated carrier obtained by coating the surface of the magnetic carrier with a resin. Among these, a coated carrier is particularly preferable.
Examples of the coating resin in the coated carrier include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, epoxy resin, polyvinyl resin, polyvinylidene resin, acrylic resin, polymethyl methacrylate resin, polyacrylonitrile. Resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl butyral resin, polystyrene resin, styrene-acrylic copolymer resin, polyvinyl chloride resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride Resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, Copolymers of vinylidene fluoride and vinyl fluoride, fluoro terpolymers such as of tetrafluoroethylene and vinylidene fluoride and non-fluoride monomers including, and a silicone resin.
Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle size is larger than 1 μm, it becomes difficult to control the electric resistance.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Synthesis Example 1)
-Synthesis of pigment dispersant-
Into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, the raw materials shown in Table 1 below were charged and reacted at 230 ° C. under normal pressure for 5 hours to obtain pigment dispersants (1) to (5). Was synthesized.
About the obtained pigment dispersants (1) to (5), the acid value and the weight average molecular weight by GPC were measured as follows. The results are shown in Table 1.

<Acid value>
The acid value was measured using a potentiometric automatic titrator with 5 g of sample dissolved in a mixed solvent of 30 mL of xylene and 30 mL of methanol and a 01N potassium hydroxide methanol solution as a titrant.

<Weight average molecular weight (Mw)>
The weight average molecular weight was determined by the GPC method using tetrahydrofuran as a solvent and polystyrene having a known molecular weight as a standard.

Example 1
<Preparation of Toner 1>
--Preparation of fine particle dispersion 1-
In a reaction vessel in which a stir bar and a thermometer are set, 683 parts by mass of water, 11 parts by mass of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries Ltd.), 83 parts by mass of styrene Part, 83 parts by weight of methacrylic acid, 110 parts by weight of butyl acrylate, and 1 part by weight of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the temperature in the system to 75 ° C. and reacted for 5 hours. Further, 30 parts by mass of a 1% by mass ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours to give a vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt). An aqueous dispersion [fine particle dispersion 1] was obtained.
The volume average particle size of the obtained [fine particle dispersion 1] measured by a particle size distribution analyzer (LA-920, manufactured by Horiba Seisakusho) was 105 nm. A portion of [Fine Particle Dispersion 1] was dried to isolate the resin component. The glass transition temperature (Tg) of the resin was 59 ° C., and the weight average molecular weight (Mw) was 150,000.

--Synthesis of polyester resin (1)-
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 229 parts by mass of bisphenol A ethylene oxide 2-mole adduct, 529 parts by mass of bisphenol A propylene oxide 3-mole adduct, 208 parts by mass of terephthalic acid, adipic acid 46 parts by mass and 2 parts by mass of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 8 hours, further reacted at 5 to 15 mmHg under reduced pressure, and then 30 masses of trimellitic anhydride in the reaction vessel. The polyester resin (1) was obtained by putting a part and making it react at 180 degreeC under a normal pressure for 2 hours. The polyester resin (1) had a weight average molecular weight (Mw) of 6,700, a glass transition temperature (Tg) of 43 ° C., and an acid value of 20 mgKOH / g.

-Preparation of aqueous phase-
990 parts by mass of water, 183 parts by mass of the fine particle dispersion, 37 parts by mass of an aqueous solution of 48.5% by mass of sodium dodecyl diphenyl ether disulfonate (“Eleminol MON-7” manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts by mass of ethyl acetate The parts were mixed and stirred to obtain a milky white liquid (aqueous phase).

--Synthesis of low molecular weight polyester--
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, A low molecular weight polyester was synthesized by charging 22 parts by weight of merit acid and 2 parts by weight of dibutyltin oxide and reacting at 230 ° C. for 5 hours under normal pressure.
The obtained low molecular weight polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., and an acid value of 0.5 mgKOH / g. The hydroxyl value was 51 mgKOH / g.

--Synthesis of modified polyester having a reactive substituent--
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 410 parts by mass of the low molecular weight polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate were charged and reacted at 100 ° C. for 5 hours. Then, a modified polyester having a reactive substituent (polymer capable of reacting with the active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained modified polyester having a reactive substituent was 1.53% by mass.

-Preparation of master batch-
1200 parts by weight of water and C.I. I. 270 parts by mass of PB15: 3 (Toyo Ink Manufacturing Co., Ltd., 7351), 54 parts by mass of the dispersant (1), and 1200 parts by mass of the polyester resin (1) were mixed with a Henschel mixer (Mitsui Mining Co., Ltd.). did. The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

-Preparation of organic solvent phase-
In a reaction vessel in which a stir bar and a thermometer were set, 378 parts by mass of the polyester resin (1), 110 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at ℃ for 30 hours, it was cooled to 30 ℃ over 1 hour to obtain a raw material solution.
1324 parts by mass of the obtained raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), the liquid feeding speed was 1 kg / hr, the disk peripheral speed was 6 m / sec, and 0.5 mm zirconia. The carnauba wax was dispersed by dispersing for 9 hours under the condition of 80% by volume of beads.
Next, 1324 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion, and 500 parts by mass of the master batch and 500 parts by mass of ethyl acetate were charged and mixed for 1 hour. Next, the mixed liquid was kept at 25 ° C., and an organic solvent phase (pigment / wax dispersion) was prepared by passing 4 passes at a flow rate of 1 kg / min with an Ebara milder (combination of G, M, and S from the inlet side).
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.

--Emulsification and dispersion--
Into a reaction vessel, 749 parts by mass of the organic solvent phase, 115 parts by mass of the modified polyester having a reactive substituent, and 2.9 parts by mass of isophoronediamine (manufactured by Wako Pure Chemical Industries, Ltd.) compound are charged, and a homomixer is prepared. After mixing for 1 minute at 5,000 rpm using TK Homomixer MKII (made by Tokushu Kika Kogyo Co., Ltd.), 1200 parts by mass of the aqueous phase was added to the reaction vessel, and the rotation speed was 9 with the homomixer. Mix for 3 minutes at 1,000 rpm. Thereafter, the mixture was stirred with a stirrer for 20 minutes to prepare an emulsified slurry.
Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and the solvent was removed at 25 ° C. After removing the organic solvent, aging was performed at 45 ° C. for 15 hours to obtain a dispersed slurry.

-Washing process-
After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts by mass of ion-exchanged water was added to the filter cake, mixed with a homomixer (rotation speed: 8,000 rpm for 10 minutes), and then filtered. 100 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a homomixer (10 minutes at a rotation speed of 8,000 rpm), and then filtered under reduced pressure. 100 mass parts of 10 mass% sodium hydroxide aqueous solution was added to the filter cake obtained here, it mixed with the homomixer (10 minutes at the rotation speed of 8,000 rpm), and then filtered. 100 mass parts of 10 mass% hydrochloric acid was added to the filter cake obtained here, it mixed with the homomixer (10 minutes at the rotation speed of 8,000 rpm), and then filtered. 300 parts by mass of ion-exchanged water was added to the obtained filter cake, mixed with a homomixer (10 minutes at a rotation speed of 8,000 rpm), and then filtered twice to obtain a final filter cake. The final filter cake obtained here was dried at 45 ° C. for 48 hours with a circulating drier and sieved with a mesh having a mesh size of 75 μm, whereby toner base particles of Example 1 were obtained.

-External additive treatment-
To 100 parts by mass of the obtained toner base particles, 1 part by mass of “Silica R972” (manufactured by Nippon Aerosil Co., Ltd.) was added as an external additive and mixed for 1 minute in a sample mill to prepare toner 1.

  The obtained toner 1 was spherical when the shape of the toner was confirmed with an optical microscope, and the pigment dispersion state inside the toner was confirmed with a transmission electron microscope (TEM). It was confirmed that the particles were uniformly dispersed in.

(Example 2)
<Preparation of Toner 2>
In Example 1, Toner 2 was produced in the same manner as in Example 1 except that the preparation of the master batch was changed as follows.
-Preparation of master batch-
1,200 parts by weight of water, C.I. I. PR269 (Dainippon Ink & Chemicals, Inc., 1022M) 405 parts by mass, pigment dispersant (2) 81 parts by mass, and polyester resin (1) 1,200 parts by mass Henschel mixer (Mitsui Mining Co., Ltd.) Mixed. The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

  The obtained toner 2 was spherical when the shape of the toner was confirmed with an optical microscope, and the pigment dispersion state inside the toner was confirmed with a transmission electron microscope. It was confirmed that they were distributed.

(Example 3)
<Preparation of Toner 3>
In Example 1, Toner 3 was produced in the same manner as Example 1 except that the preparation of the master batch was changed as follows.
-Preparation of master batch-
1200 parts by weight of water and C.I. I. 540 parts by mass of PY155 (manufactured by Clariant Japan, Yellow 4G-PT VP2669), 108 parts by mass of the pigment dispersant (3), and 1200 parts by mass of the polyester resin (1) were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). did. The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron) to prepare a master batch.

  The obtained toner 3 was spherical when the shape of the toner was confirmed with an optical microscope, and the pigment dispersion state inside the toner was confirmed with a transmission electron microscope. It was confirmed that they were distributed.

Example 4
<Preparation of Toner 4>
In Example 1, the toner 4 was produced in the same manner as in Example 1 except that the preparation of the master batch was changed to the preparation of the pigment dispersion as follows and the preparation of the organic solvent phase was changed as follows. did.
-Preparation of pigment dispersion-
7,000 parts by mass of ethyl acetate, C.I. I. 1,500 parts by mass of PB15: 3 (Dainippon Ink Chemical Co., Ltd., Fastgen Blue GCTF), 300 parts by mass of the pigment dispersant (1), and 1,500 parts by mass of the polyester resin (1), The mixture was filled using a bead mill (Shinmaru Enterprises, Horizontal Wet Disperser Dynomill) at a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% by volume of 0.5 mm zirconia beads. After dispersing for 6 hours, a pigment dispersion was prepared.

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stirring bar and a thermometer, 378 parts by mass of the polyester resin (1), 110 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at ℃ for 30 hours, it was cooled to 30 ℃ over 1 hour to obtain a raw material solution.
1,324 parts by mass of the resulting raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, The carnauba wax was dispersed by dispersing for 9 hours under the condition that 80% by volume of 5 mm zirconia beads were filled.
Next, 940 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion, and 1,667 parts by mass of the pigment dispersion and 250 parts by mass of ethyl acetate were charged and mixed for 1 hour. Next, the mixed liquid was kept at 25 ° C., and passed through an ebara milder (a combination of G, M, and S from the inlet side) at a flow rate of 1 kg / min for 4 passes to prepare an organic solvent phase (pigment / wax dispersion).
The solid content concentration of the obtained organic solvent phase (130 ° C., 30 minutes) was 50% by mass.

  The obtained toner 4 was spherical when the shape of the toner was confirmed with an optical microscope. Further, when the pigment dispersion state inside the toner was confirmed with a transmission electron microscope, the surface was not unevenly distributed as shown in FIG. 1, and it was confirmed that the pigment was uniformly dispersed inside the toner.

(Example 5)
<Preparation of Toner 5>
In Example 4, Toner 5 was produced in the same manner as in Example 4 except that the preparation of the pigment dispersion and the preparation of the organic solvent phase were changed as follows.
-Preparation of pigment dispersion-
7,000 parts by mass of ethyl acetate, C.I. I. PR269 (Dainippon Ink & Chemicals, Inc., 1022 KB) 1,500 parts by mass, the pigment dispersant (2) 300 parts by mass, and the polyester resin (1) 150 parts by mass were mixed, and the mixture was mixed with a bead mill (synth A pigment dispersion was prepared by dispersing for 6 hours using a horizontal wet disperser (Dynomill, manufactured by Marenter Prizes).

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stirring bar and a thermometer, 378 parts by mass of the polyester resin (1), 110 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at ℃ for 30 hours, it was cooled to 30 ℃ over 1 hour to obtain a raw material solution.
1,324 parts by mass of the resulting raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, The carnauba wax was dispersed by dispersing for 9 hours under the condition that 80% by volume of 5 mm zirconia beads were filled.
Next, 1074 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion, and 2,500 parts by mass of the pigment dispersion was charged and mixed for 1 hour. Next, the mixed liquid was kept at 25 ° C., and passed through an ebara milder (a combination of G, M, and S from the inlet side) at a flow rate of 1 kg / min for 4 passes to prepare an organic solvent phase (pigment / wax dispersion).
The solid content concentration of the organic solvent phase obtained (130 ° C., 30 minutes) was 45% by mass.

  The obtained toner 5 was spherical when the shape of the toner was confirmed with an optical microscope, and the state of pigment dispersion inside the toner was confirmed with a transmission electron microscope. It was confirmed that they were distributed.

(Example 6)
<Preparation of Toner 6>
In Example 4, Toner 6 was produced in the same manner as in Example 4 except that the preparation of the pigment dispersion and the preparation of the organic solvent phase were changed as follows.
-Preparation of pigment dispersion-
7,000 parts by mass of ethyl acetate, C.I. I. 1,500 parts by mass of PY74 (manufactured by Sanyo Dye Co., Ltd., 7416), 300 parts by mass of the pigment dispersant (3), and 1,500 parts by mass of the polyester resin (1) are mixed, and the mixture is mixed with a bead mill (Shinmaru A pigment dispersion was prepared by dispersing for 6 hours using a horizontal wet disperser manufactured by Enterprises Co., Ltd.).

-Preparation of organic solvent phase-
In a reaction vessel equipped with a stirring bar and a thermometer, 378 parts by mass of the polyester resin (1), 110 parts by mass of carnauba wax, and 947 parts by mass of ethyl acetate were charged, and the temperature was raised to 80 ° C. with stirring. After maintaining at ℃ for 30 hours, it was cooled to 30 ℃ over 1 hour to obtain a raw material solution.
1,324 parts by mass of the resulting raw material solution was transferred to a reaction vessel, and using a bead mill (“Ultra Visco Mill”, manufactured by Imex Co., Ltd.), a liquid feed speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, The carnauba wax was dispersed by dispersing for 9 hours under the condition that 80% by volume of 5 mm zirconia beads were filled.
Next, 1074 parts by mass of a 65% by mass ethyl acetate solution of the low molecular weight polyester was added to the dispersion, and 3,333 parts by mass of the pigment dispersion was charged and mixed for 1 hour. Next, the mixed liquid was kept at 25 ° C. and passed 4 times with an Ebara milder (combination of G, M, and S from the inlet side) at a flow rate of 1 kg / min to prepare an organic solvent phase (pigment / wax dispersion).
The solid content concentration of the organic solvent phase obtained (130 ° C., 30 minutes) was 43% by mass.

  The obtained toner 6 was spherical when the shape of the toner was confirmed with an optical microscope, and the pigment dispersion state inside the toner was confirmed with a transmission electron microscope. It was confirmed that they were distributed.

(Example 7)
<Preparation of Toner 7>
In Example 4, Toner 7 was produced in the same manner as in Example 4 except that the preparation of the pigment dispersion was changed as follows.
-Preparation of pigment dispersion-
7,000 parts by mass of ethyl acetate, C.I. I. PB15: 3 (Dainippon Ink Chemical Co., Ltd., Fastgen Blue GCTF) 1,500 parts by mass, the pigment dispersant (4) 300 parts by mass, and the polyester resin (1) 1,500 parts by mass, The mixture was filled using a bead mill (Shinmaru Enterprises, Horizontal Wet Disperser Dynomill) at a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% by volume of 0.5 mm zirconia beads. A pigment dispersion was prepared by dispersing for 6 hours.

  The obtained toner 7 was spherical when the shape of the toner was confirmed with an optical microscope, and the pigment dispersion state inside the toner was confirmed with a transmission electron microscope. It was confirmed that they were distributed.

(Example 8)
<Preparation of Toner 8>
In Example 4, Toner 8 was produced in the same manner as in Example 4 except that the preparation of the pigment dispersion was changed as follows.
-Preparation of pigment dispersion-
7,000 parts by mass of ethyl acetate, C.I. I. PB15: 3 (Dainippon Ink Chemical Co., Ltd., Fastgen Blue GCTF) 1,500 parts by mass, the pigment dispersant (5) 300 parts by mass, and the polyester resin (1) 1,500 parts by mass, The mixture was filled using a bead mill (Shinmaru Enterprises, Horizontal Wet Disperser Dynomill) at a liquid feed rate of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 80% by volume of 0.5 mm zirconia beads. A pigment dispersion was prepared by dispersing for 6 hours.

  The obtained toner 8 was spherical when the shape of the toner was confirmed with an optical microscope, and the pigment dispersion state inside the toner was confirmed with a transmission electron microscope. It was confirmed that they were distributed.

(Comparative Example 1)
<Preparation of Toner 9>
In Example 1, a toner 9 was produced in the same manner as in Example 1 except that the preparation of the master batch was changed as follows.
-Preparation of master batch-
1,200 parts by weight of water, C.I. I. 270 parts by mass of PB15: 3 (Dainippon Ink Chemical Co., Ltd., Fastgen Blue GCTF), 54 parts by mass of “Disparon DA-705” (manufactured by Enomoto Kasei Co., Ltd.), a polyester dispersant, Synergist (manufactured by Abyssia) 8.1 parts by mass of Solsper 5000) and 1,200 parts by mass of the polyester resin (1) were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

  With respect to the obtained toner 9, the shape of the toner was confirmed with an optical microscope. Further, when the pigment dispersion state inside the toner was confirmed with a transmission electron microscope, the pigment was unevenly distributed as shown in FIG.

(Comparative Example 2)
<Preparation of Toner 10>
In Example 1, Toner 10 was produced in the same manner as in Example 1 except that the preparation of the master batch was changed as follows.
-Preparation of master batch-
1,200 parts by weight of water, C.I. I. PR269 (manufactured by Dainippon Ink & Chemicals, Inc., 1022M), 405 parts by mass, 81 parts by mass of “EFKA4080” (manufactured by Ciba Specialty Chemicals) which is a polyurethane-based dispersant, and 1,200 parts by mass of the polyester resin (1) It mixed with the Henschel mixer (made by Mitsui Mining Co., Ltd.). The mixture was kneaded for 30 minutes at 150 ° C. with two rolls, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

  The obtained toner 10 was confirmed to have an uneven dimple shape when the shape of the toner was confirmed with an optical microscope. When the pigment dispersion state inside the toner was confirmed with a transmission electron microscope, the pigment was unevenly distributed on the surface.

(Comparative Example 3)
<Preparation of Toner 11>
In Example 1, Toner 11 was produced in the same manner as in Example 1 except that the preparation of the master batch was changed as follows.
-Preparation of master batch-
1,200 parts by weight of water, C.I. I. 540 parts by mass of PY155 (manufactured by Clariant Japan, Yellow 4G-PT VP2669), 108 parts by mass of “Ajisper 821” (manufactured by Ajinomoto Fine Techno Co., Ltd.), a polyester dispersant, synergist (EFKA6750, manufactured by Ciba Specialty Chemicals) 16 parts by mass and 1,200 parts by mass of the polyester resin (1) were mixed with a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.). The mixture was kneaded with two rolls at 150 ° C. for 30 minutes, rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

  The obtained toner 11 was confirmed to have an uneven dimple shape when the toner shape was confirmed with an optical microscope, and when the pigment dispersion state inside the toner was confirmed with a transmission electron microscope, the pigment was unevenly distributed on the surface.

  Next, for each of the obtained toners, the volume average particle diameter (Dv), number average particle diameter (Dn), ratio (Dv / Dn), and haze degree of the coating film were measured as follows. The results are shown in Table 2.

<Volume average particle diameter (Dv), number average particle diameter (Dn), and ratio (Dv / Dn)>
The volume average particle diameter (Dv) and the number average particle diameter (Dn) of each toner are measured with a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.) with an aperture diameter of 100 μm, and analysis software (Beckman Coulter). Analysis was performed using Multisizer 3 Version 3.51).
Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. The mixture was stirred with a micropartel, and then 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important to adjust the concentration to 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

<Haze degree of coating film>
A solution obtained by dissolving 10 g of each obtained toner in 40 g of tetrahydrofuran (THF) was coated on a PET film with a 0.3 mm wire bar to prepare a coating film. The haze degree of the coating film was determined by the TM double beam method. It measured with the automatic haze computer (made by Suga Test Instruments Co., Ltd.).

-Production of developer-
With respect to 2.5 parts by mass of the obtained toners 1 to 11, 97.5 parts by mass of a silicone ferrite carrier (core particle diameter: 45 μm) as a carrier was stirred with a tumbler mixer (manufactured by Shinmaru Enterprises). Each developer was prepared.

  Next, the reflection density, saturation, resolution, and cleaning properties were evaluated using the obtained developers as follows. The results are shown in Table 2.

<Measurement of reflection density (ID)>
Using an image forming apparatus (Imagio Neo450, manufactured by Ricoh Co., Ltd.), a solid image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper <135> manufactured by NBS Ricoh Co., Ltd.) are solid images, 0.25 Adjustment is made so that toner of ± 0.02 mg / cm ² is developed, adjustment is made so that the temperature of the fixing belt is variable, and after outputting a solid image, the image is X-Rite (manufactured by X-Rite). Was used to measure the reflection density (ID) of the image.

<Saturation>
The saturation of each developer is calculated as Saturation = (a ^{* 2} + b ^{* 2} ) ^1/2 based on a ^* b ^* measured by X-rite (manufactured by X-Rite) simultaneously with the image density ID. And asked.

<Resolution>
The resolution of each developer was evaluated according to the following criteria by outputting an N2 image of JIS / JIS-SCID using an image forming apparatus (manufactured by Ricoh Co., Ltd., imagio Neo450).
〔Evaluation criteria〕
○: The image can be clearly seen up to the image details. Δ: Slightly inferior ×: The image details are crushed

<Cleanability>
With regard to cleaning performance, an image forming apparatus (Imagio Neo450, manufactured by Ricoh Co., Ltd.) was used to output a 95% chart with an image area ratio of 95%. (Made by 3M Co., Ltd.) and transferred to white paper, measured with a Macbeth reflection densitometer RD514, and evaluated based on the following evaluation criteria.
〔Evaluation criteria〕
○: Less than 0.010 Δ: 0.011 or more and less than 0.020 ×: 0.020 or more

  From the results shown in Table 2, the toners of Examples 1 to 8 have better chargeability than the toners of Comparative Examples 1 to 3, improved spent, excellent cleaning properties, and high-definition and high-quality images. Can do.

  The toner and developer of the present invention can be widely used in, for example, laser printers, direct digital plate-making machines, full-color copiers using direct or indirect electrophotographic multicolor image development systems, full-color laser printers, full-color plain paper fax machines, and the like. .

1 is a transmission electron microscope (TEM) photograph of the toner produced in Example 4. FIG. FIG. 2 is a transmission electron microscope (TEM) photograph of the toner produced in Comparative Example 1.

Claims (17)

A toner comprising at least a binder resin, a colorant, and a pigment dispersant,
The colorant contains at least one pigment;
The toner, wherein the pigment dispersant has a base skeleton compatible with the binder resin and at least one aromatic skeleton.   The toner according to claim 1, which is granulated in an aqueous medium.   The haze degree of a coating film produced by applying a solution obtained by dissolving 10 g of toner in 40 g of tetrahydrofuran (THF) onto a substrate with a 0.3 mm wire bar is 0.1 to 25. The toner according to any one of 2 above.   The toner according to claim 1, wherein the aromatic skeleton of the pigment dispersant is a naphthalene skeleton.   The toner according to claim 1, wherein the base skeleton of the pigment dispersant is a polyester skeleton. Base skeleton of the pigment dispersing agent has the general _{formula: HO (OCC 4 H 8 -COO} -C 6 H 12 -O-) n H ( where, n is 5 to 5,000) from claim 1, which is represented by the 5 The toner according to any one of the above.   The toner according to claim 1, wherein the pigment dispersant has a weight average molecular weight (Mw) of 1,000 to 1,000,000.   The toner according to claim 1, wherein a content of the pigment in the toner is 3% by mass to 15% by mass.   The toner according to claim 1, wherein the volume average particle diameter Dv is 2.0 μm to 5.0 μm.   The toner according to any one of claims 1 to 9, wherein a ratio (Dv / Dn) of the volume average particle diameter Dv to the number average particle diameter Dn is 1.00 to 1.20. 11. The reflection density of a fixed monochromatic image obtained by adhering toner on a recording medium so that the adhering amount is 0.25 mg / cm ² is 1.2 to 2.5. Toner.   A compound having at least an active hydrogen group and a polymer having a site capable of reacting with the compound having an active hydrogen group are dissolved or dispersed in an organic solvent, and the solution or dispersion is subjected to a crosslinking or extension reaction in an aqueous medium. The toner according to claim 1, wherein the toner is obtained by removing the solvent from the obtained dispersion.   The toner according to claim 12, wherein the polymer having a site capable of reacting with a compound having an active hydrogen group is a modified polyester resin (i) having a reactive substituent.   The toner according to claim 13, wherein the reactive substituent of the modified polyester resin (i) is an isocyanate group.   The binder resin contains the unmodified polyester resin (ii) together with the modified polyester resin (i) subjected to crosslinking or elongation reaction, and the mass ratio [(i) / (ii)] is 5/95 to 30 / The toner according to claim 12, wherein the toner is 70.   The toner according to claim 1, wherein the toner is at least one selected from yellow toner, magenta toner, and cyan toner.   A developer comprising the toner according to claim 1.