JP5146672B2 - Toner for developing electrostatic image, developer, container containing toner, image forming apparatus, process cartridge, and image forming method - Google Patents

Description

  The present invention relates to an electrostatic charge image developing toner, a developer, a toner-containing container, an image forming apparatus, a process cartridge, and an image forming method.

  Conventionally, in an electrophotographic apparatus, an electrostatic recording apparatus, or the like, an electric 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. Toner used for electrostatic image development is generally colored particles in which a binder, a colorant, a charge control agent, and other additives are contained in a binder resin. There is a suspension polymerization method.

In the pulverization method, a colorant, a charge control agent, an offset preventing 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, a toner having some excellent characteristics can be produced, but there is a limitation in the selection of the toner material. For example, the composition obtained by melt mixing must be capable of being pulverized and classified by economically usable equipment. From this requirement, the melt-mixed composition must be made sufficiently brittle. For this reason, when the above 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, a particle size of 5 μm Hereinafter, in particular, fine powder of 3 μm or less and coarse powder of 20 μm or more must be removed by classification, which has a 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. In addition, 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 charge distribution of the toner is expanded, 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. Development / transfer with a low image area ratio results in a small amount of residual toner, and poor cleaning does not pose a problem. However, images with a high image area ratio, such as photographic images, and untransferred images formed due to poor paper feed, etc. 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, the materials used in conventional toners cannot be used in many cases. Even those that can be polymerized using conventional materials may not be able to adequately control the particle size due to the influence 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, the transmitted light is irregularly reflected at the interface, and the transparency of OHP or the like is hindered. Therefore, if the dispersion of the colorant is poor, there is also a problem that the transparency with OHP deteriorates.

  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 that solubilizes the binder resin. A step of preparing an oily component by mixing the binder resin and the pigment dispersion in a second organic solvent solubilizing the resin, a step of suspending the oily component in an aqueous medium and atomizing 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.

  Patent Document 3 discloses an example in which a polymer dispersant is used as a pigment dispersant. Patent Document 3 discloses a toner that is excellent in offset property, chargeability, and storage stability, and has good color developability and OHP permeability by regulating the acid value and amine value of the polymer dispersant. However, when a toner is prepared by suspending and granulating in an aqueous system, it is not sufficient to define the acid value and amine value of the polymer dispersant. Aggregation of the pigment occurs during the preparation of the toner, and the color developability of the toner. Transparency after fixing becomes worse.

  Patent Document 3 adds a synergist, which is a pigment derivative, as a pigment dispersion aid. The synergist can improve the pigment dispersibility by improving the interaction with the pigment dispersant by introducing a polar group into the pigment. However, when a synergist is used for a so-called chemical toner that makes toner in an aqueous system, there arises a problem that the pigment moves to the toner surface or the pigment escapes to the aqueous phase during toner preparation. Although these reasons are not clear, it is generally considered that the synergist is adsorbed on the surface of the pigment, and the synergist is believed to strengthen the interaction with the pigment dispersant by introducing a polar group into the pigment. . Since the polar group of the synergist is generally considered to have hydrophilicity, it is considered that the pigment is removed from the toner surface or into the aqueous phase during toner preparation. When these phenomena occur, coloring power, saturation, and / or fixing characteristics are deteriorated, and further, the pigment is contaminated by other members.

  Furthermore, in particular, in color output machines, 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 the colorant, it is difficult to add and disperse more uniformly, and if the dispersion of the release agent is poor, there is a problem that charging property, developability, storage property and OHP permeability are inhibited.

  Copper phthalocyanine pigment is one of excellent pigments having a clear blue color tone and excellent fastness properties, and has been conventionally used as one of the three primary colors for process printing. However, in addition to conventional printing methods using printing plates, the use of pigments as colorants is expanding in various image recording methods, including electrophotographic recording methods, ink jet recording methods, and thermal transfer recording methods. In these recording methods, in order to realize better color reproducibility when forming an image, instead of cyan copper phthalocyanine pigment, a pigment having a blue-green color tone and a clear and transparent image using the same are used. There is an increasing demand for recording agents. In addition, there is ISO / Japan Color established by the Japan Printing Society, the Japan Printing Industrial Machinery Manufacturers Association, and the ISO / TC130 National Committee (Non-Patent Document 1). For this, colors using standard ink and standard paper have been established. Cyan color on art paper, which has the widest color reproduction area of standard paper, is usually difficult to reproduce with copper phthalocyanine alone, and is usually mixed with chlorinated copper phthalocyanine pigment.

The blue-green pigment is generally prepared by mixing a copper phthalocyanine pigment and a chlorinated copper phthalocyanine pigment. As an improved type of this mixed pigment, Patent Document 4 describes a solid solution pigment (blue green) obtained from a high chlorinated copper phthalocyanine pigment and a low chlorinated copper phthalocyanine pigment. Patent Document 5 describes a medium chlorinated copper phthalocyanine pigment (blue-green) in which the number of chlorine atoms bonded to copper phthalocyanine is adjusted in the copper phthalocyanine synthesis stage.
However, the chlorinated copper phthalocyanine pigment contains chlorine in the pigment and cannot cope with recent dehalogenation.

Patent Document 6 describes an example in which a chlorinated copper phthalocyanine pigment is not used by mixing copper phthalocyanine and aluminum phthalocyanine.
When applied to an electrostatic charge image developing toner, cyan blue-greening can be achieved, but simply mixing the two pigments deteriorates the saturation, compared to when using copper phthalocyanine pigment alone, The color reproduction area is greatly reduced. In addition, copper phthalocyanine and aluminum phthalocyanine are mixed in the pigment manufacturing process to reduce the saturation, but a sufficient color reproduction range can be obtained even when applied to a method of obtaining toner by aqueous granulation. In addition, sufficient coloring power cannot be obtained.
As described above, an electrophotographic toner that can sufficiently meet the demand for high performance has not yet been obtained.
Japanese Patent No. 2537503 JP 2001-66827 A Japanese Patent No. 3661422 JP-A-5-263006 JP-A-9-68607 JP 2001-89682 A ISO / Japan Color offset sheet printing color standard Japan Color Color Reproduction Printing 2001 Manual (issued by the Japan Printing Society, ISO / TC130 National Committee)

  Accordingly, an object of the present invention is to provide a toner obtained by aqueous granulation using at least a polyester resin as a binder resin and having excellent color reproducibility.

As a result of intensive studies, the present inventors have obtained a toner obtained by aqueous granulation using at least a polyester resin as a binder resin, the polyester resin having bisphenol added with propylene oxide as a constituent monomer, It is a polyester resin having a specific hydroxyl value and oxidation, and it has been found that a toner having excellent color reproducibility can be obtained by using a polymer dispersant having a specific acid value and an amine value. It came to.
That is, the present invention has the following configuration.

(1) In a toner in which an oil phase containing at least a binder resin and a colorant is suspended and granulated in an aqueous medium, the toner has an acid value of 20 mgKOH / g or more and 50 mgKOH / g or less, and an amine value of 1 A polymer dispersant which is a polyester derivative having a polyester derivative of 50 or more, and the binder resin is composed of a diol component and an acid component, and the diol component contains a propylene oxide adduct of bisphenols in an amount of 50 mol% or more. And an electrostatic charge image developing toner comprising a polyester resin having a hydroxyl value of 25 mgKOH / g to 45 mgKOH / g and an acid value of 15 mgKOH / g to 25 mgKOH / g.
(2) The electrostatic image developing toner according to (1), wherein the polymer dispersant is contained in a proportion of 5% by mass to 45% by mass with respect to the colorant.

(3) The electrostatic image developing toner according to (1) or (2), wherein the melting point (A) of the polymer dispersant and the Tg (B) of the binder resin satisfy the following formula: .
B-15 (° C) ≤ A (° C) ≤ B + 30 (° C)
(4) The electrostatic image developing toner according to any one of (1) to (3), wherein the colorant is contained in the toner in a proportion of 3% by mass to 15% by mass. .

(5) The electrostatic image developing toner according to any one of (1) to (4), wherein the colorant is a yellow pigment.
(6) The electrostatic image developing toner according to (5), wherein the yellow pigment contains at least one of Pigment Yellow 74, Pigment Yellow 155, Pigment Yellow 180, and Pigment Yellow 185.

(7) The electrostatic image developing toner according to any one of (1) to (4), wherein the colorant is a magenta pigment.
(8) The electrostatic image developing toner according to (7), wherein the magenta pigment contains at least one of Pigment Red 184, Pigment Red 269, Pigment Red 122, and Pigment Violet 19.
(9) The magenta pigment contains Pigment Red 269 and Pigment Red 122, and the content ratio of Pigment Red 269 and Pigment Red 122 is 80:20 to 95: 5 by mass ratio (8) The toner for developing an electrostatic charge image according to 1.

(10) The above magenta pigment contains Pigment Red 269 and Pigment Violet 19, and the content ratio of Pigment Red 269 and Pigment Violet 19 is 80:20 to 95: 5 in mass ratio. The toner for developing an electrostatic charge image according to 1.
(11) The magenta pigment contains Pigment Red 269 and quinacridone pigment, and the content ratio of Pigment Red 269 and quinacridone pigment is 80:20 to 95: 5 by mass ratio. The quinacridone pigment is Pigment Red 122 and Pigment Violet 19 The toner for developing an electrostatic charge image according to (8), wherein the content ratio of Pigment Red 122 and Pigment Violet 19 is 90:10 to 10:90 by mass ratio.

(12) The electrostatic image developing toner according to any one of (1) to (4), wherein the colorant is a cyan pigment.
(13) The cyan pigment contains at least one of Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, and halogen-free aluminum phthalocyanine, which are copper phthalocyanines. The toner for developing an electrostatic image according to (12), which is characterized in that
(14) The electrostatic image developing toner according to (13), wherein the halogen-free aluminum phthalocyanine is aluminum hydroxide phthalocyanine.
(15) The cyan pigment contains copper phthalocyanine and halogen-free aluminum phthalocyanine, and the content ratio of copper phthalocyanine and halogen-free aluminum phthalocyanine is 50:50 to 90:10 by mass ratio (13) Or the electrostatic charge image developing toner according to (14).

(16) In the toner, an oil phase obtained by dissolving a polymer having a site capable of reacting with an active hydrogen group-containing compound together with the colorant dispersed with the polyester resin and the polymer dispersant in an aqueous medium. It is granulated by cross-linking reaction and / or elongation reaction of a polymer having a site capable of reacting with the active hydrogen group-containing compound in the emulsion dispersion liquid. The toner for developing an electrostatic charge image according to any one of (1) to (15).
(17) A developer used for electrophotographic image formation, wherein the developer includes the electrostatic image developing toner according to any one of (1) to (16). .

(18) In a toner-containing container for storing a developer used for electrophotographic image formation, the toner-containing container is filled with the electrostatic image developing toner according to any one of (1) to (16). A container containing toner.
(19) An electrostatic latent image carrier, a charging device that charges the surface of the electrostatic latent image carrier, an exposure device that exposes the surface of the electrostatic latent image carrier to form an electrostatic latent image, and A developing device that develops an electrostatic latent image with toner to form a visible image, a transfer device that transfers the visible image to a recording medium, and a fixing device that fixes the transferred image transferred to the recording medium And the toner is an electrostatic charge image developing toner according to any one of (1) to (16).

(20) At least integrally supporting an electrostatic latent image carrier and a developing device that develops the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A process cartridge detachable from the main body of the image forming apparatus, wherein the toner is the electrostatic image developing toner according to any one of (1) to (16).
(21) a charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the surface of the electrostatic latent image carrier to form an electrostatic latent image, and the electrostatic latent image using toner. In an image forming method comprising at least a development step of developing to form a visible image, a transfer step of transferring the visible image to a recording medium, and a fixing step of fixing the transferred image transferred to the recording medium. An image forming method, wherein the toner is the electrostatic image developing toner according to any one of (1) to (16).

  As will be well understood from the following detailed and specific description, according to the present invention, the binder resin comprises a diol component and an acid component, and the diol component contains a certain amount of a propylene oxide adduct of bisphenols. In addition, by combining a polymer dispersant that is a polyester resin having a specific hydroxyl value and an acid value and a polyester derivative having a certain acid value and amine value, the dispersibility of specific yellow, magenta, and cyan pigments In addition to improving the stability of pigment dispersion and improving the reproducibility of Japan Color color, not only the efficiency of particle preparation is increased, but also the chargeability deterioration and the storage of toner that are harmful when using a pigment dispersant Sex can be improved. As a result, the selectivity of the resin is wide, and the pigment dispersion system can be prevented from collapsing due to the addition of other additives such as wax, and at the same time, the resin and the coloring in the organic solvent that solubilizes the toner constituent resin. By dispersing the oil phase component in which the agent is dissolved or dispersed in the aqueous medium and granulating the particles, the colorant fine particles are formed by the difference in the affinity between the colorant and the oil phase component and between the colorant and the aqueous medium. An extremely excellent effect is exhibited that the colorant exposure amount on the toner surface is reduced by being uniformly dispersed in the toner particles.

Next, the best mode for carrying out the present invention will be described.
The electrostatic image developing toner of the present invention is a toner in which an oil phase containing at least a binder resin and a colorant is suspended and granulated in an aqueous medium, and the toner has an acid value of 20 mgKOH / g or more and 50 mgKOH. / G or less, a polymer dispersant which is a polyester derivative having an amine value of 1 or more and 50 or less, and the binder resin comprises a diol component and an acid component, and the diol component contains propylene oxide of bisphenols It has a polyester resin containing an adduct of 50 mol% or more, having a hydroxyl value of 25 mgKOH / g to 45 mgKOH / g and an acid value of 15 mgKOH / g to 25 mgKOH / g. The colorant is preferably contained in the oil phase after being dispersed with the polymer dispersant.

The toner of the present invention is excellent by combining a polyester resin containing a specific monomer and a polymer dispersant, which is a polyester derivative having a predetermined acid value and amine value, in dispersing a colorant such as yellow, magenta, and cyan pigment. It is possible to provide toner with sufficient coloring power and sufficient saturation for Japan Color.
When the amine value of the polymer dispersant is too high, the charging characteristics of the toner are adversely affected. It is considered that the amine value-imparting component of the polymer dispersant has an influence on the charging characteristics of the toner, and particularly has a great influence on the negatively chargeable toner. Accordingly, it is necessary to have an amine value more appropriate than the pigment dispersibility and charging characteristics. In the present invention, the amine value of the polymer dispersant is from 1 to 50, preferably from 10 to 35.
As the adjustment of the amine value, adjustment is performed using a diol compound having a primary to tertiary amine. Such compounds include N, N-bis-2-hydroxypropylaniline and N, N′-bishydroxyisopropyl-2-methylpiperazine.

  When the acid value of the polymer dispersant exceeds 50 mgKOH / g, it may be inhibited when a polymer having a site capable of reacting with an active hydrogen group-containing compound described below is reacted. A polymer having a site capable of reacting with an active hydrogen group-containing compound uses a compound having an active hydrogen group as a crosslinking or extending agent. The compound having an active hydrogen group is a basic substance, and when the acid value of the polymer dispersant is high, the crosslinking or elongation agent can bind to the acidic group of the polymer dispersant and react with the active hydrogen group-containing compound. The reaction with the polymer having a site is inhibited. As a result, the toner fixing characteristics, particularly hot offset properties, are deteriorated. Further, when the polymer having a site capable of reacting with the active hydrogen group-containing compound has a low molecular weight component, the storage stability of the toner is deteriorated. On the other hand, when the acid value of the polymer dispersant is lower than 20 mgKOH / g, the compatibility with the binder resin becomes insufficient and the pigment dispersibility in the toner is deteriorated. Therefore, in the present invention, the acid value of the polymer dispersant is from 20 mgKOH / g to 50 mgKOH / g, and preferably from 20 mgKOH / g to 37 mgKOH / g.

  The polymer dispersant is a polyester derivative having a specific acid value and an amine value, and the same monomer as that of the polyester can be used as the skeleton polyester. To have affinity with pigments. A combination with a monomer having an epoxy group is preferred. In this case, it is preferable to use a tertiary amine as a catalyst. Furthermore, as adjustment of an acid value, after completion | finish of reaction with polyester and the monomer which has an epoxy group, a primary amine can be added and an acid value can be adjusted. That is, in order to improve pigment dispersion, it is necessary to increase the acid value to some extent.

Furthermore, it is necessary to optimize the content of the polymer dispersant in the toner in order to satisfy the above-described characteristics. When the content of the polymer dispersant in the toner is low, the pigment dispersibility is deteriorated. When the content of the polymer dispersant is high, the above-described storage stability, charging characteristics, and fixing characteristics are deteriorated.
The content of the polymer dispersant in the toner is preferably 5% by mass or more and 45% by mass or less with respect to the colorant.

  From the viewpoint of dispersibility of the pigment, the polyester resin preferably contains a propylene oxide adduct of bisphenols in an amount of 50 mol% or more based on the diol component used when the polyester resin is polymerized. More preferred is 70 mol% or more, and more preferred is 80 mol% or more. When combined with a polyester resin containing a certain amount of propylene oxide adduct as a diol component and a polymer dispersant which is a polyester derivative having a predetermined acid value and amine value, the pigment dispersibility is excellent, and the color reproducibility of the toner is excellent. improves. The reason for this is not clear, but it is thought that the affinity between the polyester resin and the polymer dispersant is increased and the pigment is stabilized.

Alcohols and acids other than propylene oxide adducts of bisphenols can be arbitrarily selected in consideration of the glass transition point, molecular weight, softening point, etc. of the polyester resin. The hydroxyl value and acid value can be arbitrarily adjusted by adding a trivalent or higher alcohol or acid.
Examples of diol components other than propylene oxide adducts of bisphenols include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol; diethylene glycol Diols having an oxyalkylene group such as triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic Diol added with alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide; bisphenol such as bisphenol A, bisphenol F, bisphenol S Nord acids; the bisphenols include ethylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferred, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbons. The mixture of is particularly preferred.

  In addition, trihydric or higher alcohols can be used. As trihydric or higher alcohols, trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, alkylene oxide adducts of trihydric or higher polyphenols, etc. should be used. Can do. Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like. Specific examples of adducts of trivalent or higher polyphenols with alkylene oxides include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.

Examples of the acid component include polycarboxylic acid. The polycarboxylic acid can be appropriately selected according to the purpose, and dicarboxylic acid, trivalent or higher carboxylic acid, a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, and the like can be used. And a small amount of a trivalent or higher polycarboxylic acid mixture is preferred. These may be used alone or in combination of two or more.
Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid. Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid. The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.

As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.

In the case of using a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, the mass ratio of trivalent or higher carboxylic acid to dicarboxylic acid is preferably 0.01 to 10%, more preferably 0.01 to 1%. preferable.
As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.

  As the colorant, known dyes and pigments can be used. Especially when specific cyan pigments, yellow pigments, and magenta pigments are used, dispersibility and stability of pigment dispersion are improved, and reproducibility of Japan Color. As well as improving the efficiency of the particle production, the deterioration of the charging property and the storage stability of the toner, which are harmful when the pigment dispersant is used, can be improved.

The following thing can be used for the cyan pigment in connection with this invention. As the copper phthalocyanine pigment, Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, and Pigment Blue 15: 4 are preferably used alone or in combination, and are produced by light resistance and aqueous granulation. As for the toner, Pigment Blue 15: 3, which does not escape into the aqueous phase during toner production, is most preferable.
The aluminum phthalocyanine according to the present invention is most preferably halogen-free and aluminum hydroxide phthalocyanine. Halogen-containing aluminum phthalocyanine pigments have good light resistance, but they are not compatible with the recent halogen-free, and by using aluminum hydroxide, light resistance and color reproducibility comparable to those of halogen-containing aluminum phthalocyanines can be obtained. Aluminum hydroxide phthalocyanine is preferred.

It contains copper phthalocyanine and aluminum hydroxide phthalocyanine, and the mass ratio is preferably 50:50 to 90:10.
In particular, by blending so that the mass ratio of the content of copper phthalocyanine and aluminum hydroxide phthalocyanine in the toner satisfies the range of copper phthalocyanine: aluminum hydroxide phthalocyanine = 50: 50 to 90:10 as described above. Various properties of toner are greatly improved, and JapanColor magenta (art paper) can be reproduced on plain paper.

  The copper phthalocyanine pigment and the aluminum phthalocyanine pigment can be mixed and used during the preparation of the toner particles. However, in order to fully bring out the characteristics of the respective pigments, it is desirable to mix them during the pigment production process. Mixing in the pigment production process, particularly solvent salt milling, is a desirable process in order to bring out the characteristics of each pigment and to prevent contamination during pigment production.

  The following can be used as the magenta pigment according to the present invention. Monoazo pigments include CIPigment Red 5, CIPigment Red 31, CIPigment Red 146, CIPigment Red 147, CIPigment Red 150, CIPigment Red 176, CIPigment Red 184, or CIPigment Red 269 (Names described in the 4th edition) are preferably used alone or in combination, and CIPigment Red 184 and Pigment Red 269 are more preferred. Pigment Red 269 is more preferable from the viewpoints of dispersibility in toner particles, toner color tone, chargeability, and the like.

［Ｘ₁、及びＸ₂は、水素原子又はハロゲン原子、或いはアルキル基及びアルコキシ基からなる群より選ばれる置換基を示す。］
上記式で示されるキナクリドン顔料としては、C.I.Pigment Red 122、Pigment Violet 19が挙げられる。これらは単独、もしくは併用して用いることができる。 It is one of the very preferable embodiments that the monoazo pigment according to the present invention is used in combination with a quinacridone pigment represented by the following formula.

[X ₁ and X _{2 each} represents a hydrogen atom or a halogen atom, or a substituent selected from the group consisting of an alkyl group and an alkoxy group. ]
Examples of the quinacridone pigment represented by the above formula include CIPigment Red 122 and Pigment Violet 19. These can be used alone or in combination.

In particular, various properties of the toner as described above can be obtained by blending so that the mass ratio of the content of the monoazo pigment to the quinacridone pigment satisfies the range of quinacridone pigment: monoazo pigment = 20: 80 to 5:95. Is greatly improved, and Japan Color 2001 magenta (art paper) can be reproduced on plain paper.
The mass ratio of the content of the monoazo pigment and the quinacridone pigment in the toner is quinacridone pigment: monoazo pigment = 20: 80 to 5:95, the quinacridone pigment contains Pigment Red 122 and Pigment Violet 19, and Pigment Red 122 And Pigment Violet 19 are more preferably 90:10 to 10:90 in mass ratio. Pigment Red 122 is optimal as a magenta pigment in saturation and hue, but has weak coloring power. Pigment Violet 19 has high coloring power, but its saturation is inferior to Pigment Red 122. Thus, by combining Pigment Red 122 and Pigment Violet 19, excellent coloring power and saturation can be achieved. This is probably because Pigment Red 122 and Pigment Violet 19 are the same quinacridone pigment.

  As the yellow pigment according to the present invention, it is preferable to use Pigment Yellow 74, Pigment Yellow 155, Pigment Yellow 180, and Pigment Yellow 185 alone or in combination.

  Next, a method for producing the electrostatic latent image developing toner of the present invention will be described. The electrostatic latent image developing toner of the present invention is an oil phase in which a polymer having a site capable of reacting with an active hydrogen group-containing compound is dissolved in a solvent together with the colorant dispersed with the polyester resin and the polymer dispersant. Is suspended in an aqueous medium to form an emulsified dispersion, and a polymer having a site capable of reacting with the active hydrogen group-containing compound in the emulsified dispersion is subjected to a crosslinking reaction and / or an extension reaction and granulated. Is preferred. There is no particular limitation as long as the colorant as the toner component is dispersed in advance by the polymer dispersant.

  In the present invention, it is preferable to prepare a colorant dispersion in which a colorant is dispersed in advance with a polymer dispersant before mixing the oil phase, and mix this with a binder resin or the like. In preparing the colorant dispersion, first, a polymer dispersant is attached to the colorant. The colorant is attached using a normal stirring device. Specifically, for example, a coloring material and a polymer dispersant are charged into a suitable container equipped with granular media such as an attritor, a ball mill, a sand mill, and a vibration mill, and the container is placed in a preferable temperature range, for example, 20 ° C. to 160 ° C. The granular media can be used in the following temperature range, and steel such as stainless steel and carbon steel, alumina, zirconia, silica and the like are preferably used. With these stirring devices, the aggregation of the colorant is released, and the colorant is dispersed until the average particle size of the colorant is about 0.5 μm or less, preferably about 0.3 μm or less, and a polymer is applied with a stirring load. A dispersant is attached to the colorant. This is diluted with a solvent to obtain a colorant dispersion.

  In the present invention, it is preferable to disperse again by high-speed shearing or the like so that the colorant does not aggregate when the colorant dispersion and the binder resin are mixed. Dispersion can be performed by a disperser equipped with a high-speed blade rotating type or a forced interval passing type high-speed shearing mechanism such as various homomixers, homogenizers, colloid mills, ultra turraxes, and Claire mills. When adjusting the oil phase liquid, it is preferable to disperse the colorant in the oil phase liquid to 1 μm or less, preferably 0.5 μm or less, and more preferably about 0.3 μm or less.

The weight average molecular weight of the binder resin contained in the oil phase is preferably 1000 to 30000, and more preferably 1500 to 15000. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered. For this reason, it is preferable that content of the component whose weight average molecular weight is less than 1000 is 8-28 mass%. On the other hand, if the weight average molecular weight exceeds 30000, the low-temperature fixability may be lowered.
The glass transition temperature of the binder resin is usually 30 to 70 ° C, more preferably 35 to 60 ° C, and still more preferably 35 to 55 ° C. When the glass transition temperature is less than 30 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 70 ° C., the low-temperature fixability may be lowered.

The hydroxyl value of the binder resin is preferably 25 mgKOH / g or more and 45 mgKOH / g or less, and more preferably 30 to 40 mgKOH / g. When the hydroxyl value is less than 25 mgKOH / g, it may be difficult to achieve both pigment dispersibility and a glass transition point of the binder resin and a weight average molecular weight. When the hydroxyl value is greater than 45 mgKOH / g, the pigment dispersibility deteriorates.
The acid value of the binder resin is preferably 15 mgKOH / g or more and 25 mgKOH / g or less, and more preferably 15 to 23 mgKOH / g. Particles are easily formed when the oil phase, which is a toner material solution, is dispersed in an aqueous medium. Furthermore, the pigment dispersibility is excellent.

The amount of the polymeric dispersant used is preferably 5% by mass or more and 45% by mass or less based on the pigment. From the viewpoint of pigment dispersion, it is preferably 10% by mass or more and 45% by mass or less, and from the viewpoint of toner charging characteristics and high temperature storage stability, more preferably 10% by mass or more and 35% by mass.
The melting point of the polymer dispersant is preferably not less than Tg (° C.) of the binder resin used in the toner from the viewpoint of storage stability when the toner is left at high temperature, but considering the pigment dispersibility, Tg-15 of the binder resin. (C) to Tg + 30 (C) is preferred. More preferable is Tg ± 0 (° C.) or higher and Tg + 30 (° C.) or lower.

  The aqueous medium can be appropriately selected from known ones. Specific examples include water, water-miscible solvents, and mixtures thereof. Among these, water is particularly preferable. Examples of the water-miscible solvent include alcohol, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. Examples of the alcohol include methanol, isopropanol, and ethylene glycol. Examples of lower ketones include acetone and methyl ethyl ketone. These may be used alone or in combination of two or more.

In the present invention, it is preferable that an oil phase containing a toner material containing at least a binder resin and a colorant is dissolved or dispersed in a solvent. The solvent preferably contains an organic solvent. The organic solvent is preferably removed when forming the toner base particles or after forming the toner base particles.
The organic solvent can be appropriately selected according to the purpose, but since the removal is easy, the boiling point is preferably less than 150 ° C. Specifically, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, And methyl isobutyl ketone. Of these, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is particularly preferable. These may be used alone or in combination of two or more.

  The amount of the organic solvent used can be appropriately selected according to the purpose, but is preferably 40 to 300 parts by mass, more preferably 60 to 140 parts by mass, and more preferably 80 to 140 parts by mass with respect to 100 parts by mass of the toner material. 120 parts by mass is more preferable.

  The toner material can be appropriately selected according to the purpose, but usually contains at least a binder resin and a colorant, and a polymer having a reactive hydrogen group-containing compound and a reactive hydrogen group-containing compound. It is preferable to further contain other components such as a mold release agent and a charge control agent as necessary.

  The mixing ratio of the colorant and the organic solvent in the oil phase containing the toner material can be appropriately selected according to the purpose, and is preferably 5:95 to 50:50. When the blending amount of the colorant is less than this range, the amount of the organic solvent is increased during the production of the toner, and the toner production efficiency may be lowered. When the blending amount is larger than this range, the dispersion of the pigment becomes insufficient. There is.

The content of the colorant in the toner can be appropriately selected according to the purpose, but is usually 3 to 15% by mass, and preferably 5 to 12% by mass. When the content of the colorant is less than 3% by mass, the coloring power of the toner decreases. When the content of the colorant exceeds 15% by mass, the pigment is poorly dispersed in the toner. May be reduced.
The content of the colorant in the toner can be determined by fluorescent X-rays when the colorant contains a unique metal element. In this case, as in a normal quantitative analysis, a certain amount of colorant is mixed in the toner constituents, and this can be determined as a calibration curve. In the case of a colorant having no intrinsic metal element, the same means as in ordinary quantitative analysis can be used. For example, the toner can be dissolved in a solvent in which the colorant can be dissolved, and quantification can be performed by high performance liquid chromatography. Further, in this case, quantitative determination is possible by preparing a calibration curve by mixing a certain amount of colorant in toner constituents in advance.

When emulsifying or dispersing the toner material in the aqueous medium using the oil phase containing the toner material, the oil phase containing the toner material is preferably dispersed in the aqueous medium while stirring.
A known disperser or the like can be appropriately used for the dispersion. Specific examples of the disperser include a low speed shear disperser, a high speed shear disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic disperser. Especially, since the particle diameter of a dispersion (oil droplet) can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C. and more preferably 40 to 98 ° C. under pressure. In general, the dispersion is easier when the dispersion temperature is higher.

The method for forming the toner base particles can be appropriately selected from known methods. Specific examples include a method of forming toner base particles using a dissolution suspension method and the like, and a method of forming toner base particles while producing a binder resin. A method of forming toner base particles while producing a resin is preferred. Here, the binder resin is a base material having adhesion to a recording medium such as paper.
A method of forming toner base particles while producing a binder resin is a method in which a toner material contains a compound having an active hydrogen group and a polymer having a site capable of reacting with the active hydrogen group-containing compound in an aqueous medium. In this method, toner particles are formed while a binder resin is formed by reacting a compound having an active hydrogen group with a polymer having a site capable of reacting with the active hydrogen group-containing compound.
The toner thus obtained may further contain other components such as a release agent and a charge control agent that are appropriately selected as necessary.

As the polymer having a site capable of reacting with an active hydrogen group-containing compound, a modified polyester resin capable of reacting with a compound having an active hydrogen group is preferably used.
The modified polyester resin capable of reacting with a compound having an active hydrogen group is preferably a polyester having an isocyanate group as a polymer having reactivity with the active hydrogen group. In addition, you may form a urethane bond by adding alcohol when making the isocyanate group containing polyester resin and the compound which has an active hydrogen group react. The molar ratio of the urethane bond to the urea bond thus formed (to distinguish it from the urethane bond of the polyester prepolymer having an isocyanate group) is preferably from 0 to 9, and preferably from 1/4 to 4. Is more preferable, and 2/3 to 7/3 is particularly preferable. If this ratio is greater than 9, the hot offset resistance may decrease.

The compound having an active hydrogen group acts as an elongation agent, a crosslinking agent or the like when a polymer having a site capable of reacting with the active hydrogen group-containing compound undergoes an elongation reaction, a crosslinking reaction, or the like in an aqueous medium.
Specific examples of the active hydrogen group include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), amino group, carboxyl group, mercapto group and the like. In addition, an active hydrogen group may be individual, and 2 or more types of mixtures may be sufficient as it.

The compound having an active hydrogen group can be appropriately selected depending on the purpose, but when the polymer having a site capable of reacting with the active hydrogen group-containing compound is a polyester prepolymer having an isocyanate group, the polyester prepolymer is used. Amines are preferred because they can be made to have a high molecular weight by a polymer, elongation reaction, crosslinking reaction or the like.
The amines can be appropriately selected depending on the purpose, and specific examples include diamines, trivalent or higher amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Diamines and mixtures of diamines and small amounts of trivalent or higher amines are preferred. These may be used alone or in combination of two or more.

  Examples of diamines include aromatic diamines, alicyclic diamines, and aliphatic diamines. Specific examples of the aromatic diamine include phenylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, and the like. Specific examples of the alicyclic diamine include 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, diaminocyclohexane, isophorone diamine and the like. Specific examples of the aliphatic diamine include ethylene diamine, tetramethylene diamine, hexamethylene diamine and the like. Specific examples of the trivalent or higher amine include diethylenetriamine and triethylenetetramine. Specific examples of amino alcohols include ethanolamine and hydroxyethylaniline. Specific examples of amino mercaptans include aminoethyl mercaptan and aminopropyl mercaptan. Specific examples of amino acids include aminopropionic acid and aminocaproic acid. Specific examples of those in which the amino group is blocked include ketimine compounds and oxazolidone compounds obtained by blocking the amino group with ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone.

  In addition, a reaction terminator can be used to stop the elongation reaction, the cross-linking reaction, and the like of the compound having an active hydrogen group and a polymer having a site capable of reacting with the active hydrogen group-containing compound. When a reaction terminator is used, the molecular weight and the like of the adhesive substrate can be controlled within a desired range. Specific examples of the reaction terminator include monoamines such as diethylamine, dibutylamine, butylamine and laurylamine, and ketimine compounds in which these amino groups are blocked.

  The ratio of the equivalent of the isocyanate group of the polyester prepolymer to the equivalent of the amino group of the amine is preferably 1/3 to 3, more preferably 1/2 to 2, and particularly preferably 2/3 to 1.5. . If this ratio is less than 1/3, the low-temperature fixability may be lowered. If it exceeds 3, the molecular weight of the urea-modified polyester resin may be lowered, and the hot offset resistance may be lowered.

The polymer having a site capable of reacting with the active hydrogen group-containing compound (hereinafter sometimes referred to as “prepolymer”) can be appropriately selected from known resins and the like, such as polyol resin, polyacrylic resin, polyester Examples thereof include resins, epoxy resins and derivatives thereof. Among them, it is preferable to use a polyester resin in terms of high fluidity and transparency at the time of melting. These may be used alone or in combination of two or more.
Sites capable of reacting with the active hydrogen group-containing compound of the prepolymer include isocyanate groups, epoxy groups, carboxyl groups, chemical structural formulas —COCl
In particular, an isocyanate group is preferable. The prepolymer may have one of such functional groups or two or more kinds.

As a prepolymer, the molecular weight of the polymer component can be easily adjusted, and oil-less low-temperature fixing characteristics in dry toners, in particular, good releasability and fixability even in the absence of a release oil application mechanism to a fixing heating medium. Since it can ensure, it is preferable to use the polyester resin which has an isocyanate group etc. which can produce | generate a urea bond.
The polyester prepolymer containing an isocyanate group can be appropriately selected depending on the purpose. Specific examples include a reaction product of a polyester resin having an active hydrogen group obtained by polycondensation of a polyol and a polycarboxylic acid, and a polyisocyanate.

The polyol can be appropriately selected according to the purpose, and a diol, a trihydric or higher alcohol, a mixture of a diol and a trihydric or higher alcohol, etc. can be used, but the diol or the diol and a small amount of a trihydric or higher alcohol. Is preferred. These may be used alone or in combination of two or more.
Specific examples of the diol include alkylene glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol; diethylene glycol, triethylene glycol, dipropylene Diols having an oxyalkylene group such as glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; alicyclic diols including ethylene oxide and propylene oxide , With addition of alkylene oxide such as butylene oxide; bisphenols such as bisphenol A, bisphenol F and bisphenol S; bisphenols with ethyleneoxy , Propylene oxide, alkylene oxide adducts of bisphenols such as those obtained by adding alkylene oxides such as butylene oxide. In addition, it is preferable that carbon number of alkylene glycol is 2-12. Among these, alkylene glycols having 2 to 12 carbon atoms or alkylene oxide adducts of bisphenols are preferred, alkylene oxide adducts of bisphenols or alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbons. The mixture of is particularly preferred.

Examples of trihydric or higher alcohols include trihydric or higher aliphatic alcohols, trihydric or higher polyphenols, and alkylene oxide adducts of trihydric or higher polyphenols. Specific examples of the trihydric or higher aliphatic alcohol include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and the like. Specific examples of the trihydric or higher polyphenols include trisphenol PA, phenol novolak, cresol novolak and the like. Specific examples of adducts of trivalent or higher polyphenols with alkylene oxides include those obtained by adding alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide to trihydric or higher polyphenols.
When a diol and a trihydric or higher alcohol are mixed and used, the mass ratio of the trihydric or higher alcohol to the diol is preferably 0.01 to 10%, and more preferably 0.01 to 1%.

  The polycarboxylic acid can be appropriately selected according to the purpose, and dicarboxylic acid, trivalent or higher carboxylic acid, a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, and the like can be used. And a small amount of a trivalent or higher polycarboxylic acid mixture is preferred. These may be used alone or in combination of two or more.

  Specific examples of the dicarboxylic acid include divalent alkanoic acid, divalent alkenoic acid, and aromatic dicarboxylic acid. Specific examples of the divalent alkanoic acid include succinic acid, adipic acid, sebacic acid and the like. The number of carbon atoms of the divalent alkenoic acid is preferably 4 to 20, and specific examples include maleic acid and fumaric acid. The aromatic dicarboxylic acid preferably has 8 to 20 carbon atoms, and specific examples thereof include phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid. Among these, a divalent alkenoic acid having 4 to 20 carbon atoms or an aromatic dicarboxylic acid having 8 to 20 carbon atoms is preferable.

As the trivalent or higher carboxylic acid, trivalent or higher aromatic carboxylic acid or the like can be used. The carbon number of the trivalent or higher aromatic carboxylic acid is preferably 9 to 20, and specific examples thereof include trimellitic acid and pyromellitic acid.
As the polycarboxylic acid, an acid anhydride or lower alkyl ester of any of dicarboxylic acid, trivalent or higher carboxylic acid, and a mixture of dicarboxylic acid and trivalent or higher carboxylic acid can be used. Specific examples of the lower alkyl ester include methyl ester, ethyl ester, isopropyl ester and the like.
In the case of using a mixture of dicarboxylic acid and trivalent or higher carboxylic acid, the mass ratio of trivalent or higher carboxylic acid to dicarboxylic acid is preferably 0.01 to 10%, more preferably 0.01 to 1%. preferable.

  As for the mixing ratio at the time of polycondensation of the polyol and the polycarboxylic acid, the equivalent ratio of the hydroxyl group of the polyol to the carboxyl group of the polycarboxylic acid is usually preferably 1 to 2, more preferably 1 to 1.5, 1.02-1.3 is particularly preferred.

  The content of the structural unit derived from the polyol in the polyester prepolymer having an isocyanate group is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and particularly preferably 2 to 20% by mass. When the content is less than 0.5% by mass, the hot offset resistance is lowered, and it may be difficult to achieve both the heat-resistant storage stability and the low-temperature fixability of the toner, and exceeds 40% by mass. In this case, the low-temperature fixability may be lowered.

  The polyisocyanate can be appropriately selected depending on the purpose, but it is blocked with an aliphatic diisocyanate, an alicyclic diisocyanate, an aromatic diisocyanate, an araliphatic diisocyanate, an isocyanurate, or the like, blocked with a phenol derivative, oxime, caprolactam, or the like. And the like.

  Specific examples of the aliphatic diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetra And methyl hexane diisocyanate. Specific examples of the alicyclic diisocyanate include isophorone diisocyanate and cyclohexylmethane diisocyanate. Specific examples of the aromatic diisocyanate include tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanatodiphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl. 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like. Specific examples of the araliphatic diisocyanate include α, α, α ′, α′-tetramethylxylylene diisocyanate. Specific examples of the isocyanurates include tris (isocyanatoalkyl) isocyanurate, tris (isocyanatocycloalkyl) isocyanurate, and the like. These may be used alone or in combination of two or more.

  When the polyisocyanate and the polyester resin having a hydroxyl group are reacted, the equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyester resin is usually preferably 1 to 5, more preferably 1.2 to 4, more preferably 1 .5-3 are particularly preferred. When the equivalent ratio exceeds 5, the low-temperature fixability may decrease, and when it is less than 1, the offset resistance may decrease.

  The content of the structural unit derived from polyisocyanate in the polyester prepolymer containing an isocyanate group is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass, and further 2 to 20% by mass. preferable. When this content is less than 0.5% by mass, the hot offset resistance may be lowered, and when it exceeds 40% by mass, the low-temperature fixability may be lowered.

  The average number of isocyanate groups that the polyester prepolymer has per molecule is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4. When the average number is less than 1, the molecular weight of the urea-modified polyester resin is lowered, and the hot offset resistance may be lowered.

  1000-30000 are preferable and, as for the weight average molecular weight of the polymer which has a site | part which can react with an active hydrogen group containing compound, 1500-15000 are more preferable. When the weight average molecular weight is less than 1000, the heat resistant storage stability may be lowered, and when it exceeds 30000, the low temperature fixability may be lowered. In addition, a weight average molecular weight is obtained by measuring tetrahydrofuran soluble part using a gel permeation chromatography (GPC).

The GPC measurement can be performed as follows, for example. First, the column is stabilized in a 40 ° C. heat chamber. At this temperature, tetrahydrofuran is used as a column solvent at a flow rate of 1 ml per minute, and 50 to 200 μl of a tetrahydrofuran solution adjusted to a sample concentration of 0.05 to 0.6 mass% is injected and measured. In measuring the molecular weight, the molecular weight is calculated from the relationship between the logarithmic value of the calibration curve prepared from several kinds of standard samples and the number of counts. As a standard sample for preparing a calibration curve, the molecular weight is 6 × 10 ² , 2.1 × 10 ² , 4 × 10 ² , 1.75 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ and 4.48 × 10 ⁶ monodisperse polystyrene (manufactured by Pressure Chemical or Toyo Soda Industry Co., Ltd.) can be used. At this time, it is preferable to use about 10 kinds of standard samples. A refractive index detector can be used as the detector.

  The diol component in the oil phase contains propylene oxide adducts of bisphenols in an amount of 50 mol% or more, and the mass ratio of the polyester prepolymer having an isocyanate group to the polyester resin having a specific hydroxyl value and an acid value is 5/95. -25/75 is preferable, and 10 / 90-25 / 75 is more preferable. When the mass ratio is less than 5/95, the hot offset resistance may be lowered, and when it exceeds 25/75, the low-temperature fixability and the glossiness of the image may be lowered.

Therefore, as a specific example of the adhesive substrate contained in the toner, a polyester prepolymer obtained by reacting a polycondensate of bisphenol A propylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate is uread with isophorone diamine. A polyester prepolymer prepared by reacting a polycondensate of bisphenol A propylene oxide 2 mol adduct and isophthalic acid with isophorone diisocyanate with isophorone diamine. Mixture of uread product with bisphenol A propylene oxide 2 mol adduct and terephthalic acid polycondensate; bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide A polyester prepolymer obtained by reacting a polycondensate of idophthalic acid and a polycondensate of terephthalic acid with isophorone diisocyanate and urealated with isophorone diamine, and a bisphenol A ethylene oxide 2 mole adduct / bisphenol A propylene oxide 2 mole adduct ( Bisphenol A propylene oxide 2 mol adduct mixture ratio is 50 mol% or more) and polycondensate of terephthalic acid; polycondensation of bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct and terephthalic acid A polyester prepolymer obtained by reacting a product with isophorone diisocyanate and uread with isophorone diamine, and a polycondensate of bisphenol A propylene oxide 2 mol adduct and terephthalic acid Compound: Polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2-mole adduct and terephthalic acid with isophorone diisocyanate, ureated with hexamethylenediamine, bisphenol A propylene oxide 2-mole adduct, and terephthalate Mixture with acid polycondensate; bisphenol A ethylene oxide 2 mol adduct and polyester prepolymer obtained by reacting terephthalic acid polycondensate with isophorone diisocyanate and urethanized with hexamethylenediamine, and bisphenol A ethylene oxide 2 Mole adduct / bisphenol A propylene oxide 2 mol adduct (mixing ratio of bisphenol A propylene oxide 2 mol adduct is 50 mol% or more) and polycondensate of terephthalic acid A polyester prepolymer obtained by reacting a polycondensate of bisphenol A ethylene oxide 2 mol adduct and terephthalic acid with isophorone diisocyanate with urea and ethylenediamine, a polycondensate of bisphenol A propylene oxide 2 mol adduct and terephthalic acid A mixture of bisphenol A ethylene oxide 2-mole adduct and a polycondensate of isophthalic acid with diphenylmethane diisocyanate, urealated with hexamethylenediamine, bisphenol A propylene oxide 2-mole adduct and isophthalic acid Mixtures with acid polycondensates; bisphenol A ethylene oxide 2-mole adduct / bisphenol A propylene oxide 2-mole adduct and terephthalic acid / dodecenyl A polyester prepolymer obtained by reacting a polycondensate of an acid anhydride with diphenylmethane diisocyanate and uread with hexamethylenediamine, and a bisphenol A ethylene oxide 2 mol adduct / bisphenol A propylene oxide 2 mol adduct (bisphenol A propylene oxide). 2 mol adduct mixture ratio is 50 mol% or more) and a mixture of terephthalic acid polycondensate; a polyester prepolymer obtained by reacting bisphenol A ethylene oxide 2 mol adduct and isophthalic acid polycondensate with toluene diisocyanate. Mixture of urealated with methylenediamine and bisphenol A propylene oxide 2 mol adduct and isophthalic acid polycondensate: bisphenol A ethylene oxide 2 mol adduct / bisph A polyester prepolymer obtained by reacting a 2-mole adduct of diol A propylene oxide, a polycondensate of terephthalic acid and trimellitic acid with isophorone diisocyanate, and urethanized with a ketimine compound whose amino group is blocked with ketones, and bisphenol A ethylene A mixture of oxide 2 mol adduct / bisphenol A propylene oxide 3 mol adduct (bisphenol A propylene oxide 3 mol adduct mixture ratio is 50 mol% or more) and polycondensate of terephthalic acid, adipic acid, trimellitic acid, etc. Can be mentioned.

In the present invention, the toner may further contain a release agent, a charge control agent, resin fine particles, inorganic fine particles, a fluidity improver, a cleaning property improver, a magnetic material, a metal soap, and the like.
The release agent can be appropriately selected from known ones according to the purpose, and waxes having a carbonyl group, polyolefin waxes, long-chain hydrocarbons, and the like can be used. Waxes having a carbonyl group are preferred. These may be used alone or in combination of two or more.

  Specific examples of the wax having a carbonyl group include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerol tribehenate, 1,18- An ester having a plurality of alkanoic acid residues such as octadecandiol diol stearate; an ester having a plurality of alkanol residues such as tristearyl trimellitic acid and distearyl maleate; a plurality of alkanoic acid residues such as dibehenyl amide Amides; amides having a plurality of monoamine residues such as trimellitic acid tristearyl amide; dialkyl ketones such as distearyl ketone and the like, and esters having a plurality of alkanoic acid residues are particularly preferred. Specific examples of the polyolefin wax include polyethylene wax and polypropylene wax. Specific examples of the long chain hydrocarbon include paraffin wax and sazol wax.

The melting point of the release agent is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. When the melting point is less than 40 ° C., the wax may adversely affect the heat resistant storage stability, and when it exceeds 160 ° C., cold offset may occur during fixing at a low temperature.
The melt viscosity of the release agent is preferably 5 to 1000 cps and more preferably 10 to 100 cps at a temperature 20 ° C. higher than the melting point of the wax. If the melt viscosity is less than 5 cps, the releasability may be lowered, and if it exceeds 1000 cps, the effect of improving the hot offset resistance and the low-temperature fixability may not be obtained.
The content of the release agent in the toner is preferably 0 to 40% by mass, and more preferably 3 to 30% by mass. When the content exceeds 40% by mass, the fluidity of the toner may be lowered.

  The charge control agent can be appropriately selected from known ones according to the purpose. However, since a color tone may change when a colored material is used, it is preferable to use a colorless or nearly white material. Specifically, triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts including fluorine-modified quaternary ammonium salts, alkylamides, phosphorus alone or compounds thereof, tungsten alone Or a compound thereof, a fluorosurfactant, a metal salt of salicylic acid, a metal salt of a salicylic acid derivative, and the like. These may be used alone or in combination of two or more.

  Commercially available products may be used as the charge control agent. Examples of commercially available products include quaternary ammonium salt Bontron P-51, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, and phenol. Condensate E-89 (above, Orient Chemical Industry Co., Ltd.), quaternary ammonium salt molybdenum complex TP-302, TP-415 (above, Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit), Quinacridone, azo pigments, other sulfonic acid groups, carboxyl groups, quaternary ammonia Examples thereof include polymers having a functional group such as a salt.

The charge control agent may be dissolved or dispersed after being melt-kneaded with the master batch, dissolved or dispersed in a solvent together with each component of the toner, or may be fixed on the surface of the toner after the toner is produced. Good.
The content of the charge control agent in the toner varies depending on the type of the binder resin, the presence or absence of the additive, the dispersion method, etc., and cannot be generally specified, but is 0.1 to 10 mass relative to the binder resin. % Is preferable, and 0.2 to 5% by mass is more preferable. If the content is less than 0.1% by mass, the charge controllability may not be obtained. If the content exceeds 10% by mass, the chargeability of the toner becomes too large and the electrostatic attraction with the developing roller increases. However, the fluidity of the developer and the image density may be reduced.

  The resin particle is not particularly limited as long as it is a resin that can form an aqueous dispersion in an aqueous medium, and can be appropriately selected from known resins according to the purpose, and may be a thermoplastic resin. A thermosetting resin may be used. Specific examples include vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, polycarbonate resins, and the like. Among these, one or more resins selected from the group consisting of vinyl resins, polyurethane resins, epoxy resins, and polyester resins are preferable because an aqueous dispersion of fine spherical resin particles is easily obtained. These may be used alone or in combination of two or more.

  The vinyl resin is a resin obtained by homopolymerizing or copolymerizing a vinyl monomer. Specifically, a styrene- (meth) acrylic acid ester copolymer, a styrene-butadiene copolymer, (meth) Acrylic acid-acrylic acid ester polymer, styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.

  Moreover, as the resin particles, a copolymer obtained by polymerizing a monomer having a plurality of unsaturated groups can also be used. The monomer having a plurality of unsaturated groups can be appropriately selected according to the purpose. Specifically, sodium salt eleminol RS-30 of methacrylic acid ethylene oxide adduct sulfate (manufactured by Sanyo Chemical Industries), divinylbenzene 1,6-hexanediol diacrylate and the like.

  The resin particles can be obtained by polymerization using a known method, but are preferably used as an aqueous dispersion of resin particles. As a method for preparing an aqueous dispersion of resin particles, in the case of a vinyl resin, an aqueous dispersion of resin particles is obtained by polymerizing a vinyl monomer using a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, or a dispersion polymerization method. In the case of polyaddition or condensation resins such as polyester resins, polyurethane resins, and epoxy resins, a precursor such as a monomer or oligomer or a solution thereof is dispersed in an aqueous medium in the presence of an appropriate dispersant. After that, heating or adding a curing agent to cure, a method for producing an aqueous dispersion of resin particles, a precursor such as a monomer or oligomer, or an appropriate emulsifier is dissolved in the solution, and then water is added. Method of phase inversion emulsification: Resin is pulverized and classified using a mechanical pulverizer or jet pulverizer to obtain resin particles, which are then dispersed in water in the presence of an appropriate dispersant. After obtaining resin particles by spraying a resin solution in the form of a mist, the resin particles are dispersed in water in the presence of an appropriate dispersant, a poor solvent is added to the resin solution, or the solvent is heated. By cooling the dissolved resin solution, the resin particles are precipitated, and after removing the solvent to obtain resin particles, a method of dispersing the resin particles in water in the presence of an appropriate dispersant, a resin solution, Disperse in an aqueous medium in the presence of an appropriate dispersant, then remove the solvent by heating, reduced pressure, etc., dissolve an appropriate emulsifier in the resin solution, and then add water to emulsify the phase. Methods and the like.

  The inorganic particles can be appropriately selected from known ones according to the purpose. Specifically, 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. These may be used alone or in combination of two or more.

The primary particle diameter of the inorganic particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic particle is 20-500 m < ² > / g.
The content of inorganic particles in the toner is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 5.0% by mass.

  When surface treatment is performed using a fluidity improver, the hydrophobicity of the toner surface is improved, and deterioration of fluidity and charging characteristics can be suppressed even under high humidity. Specific examples of fluidity improvers include silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, and modified silicone oils. Etc.

  When the cleaning property improving agent is added to the toner, the transferred developer remaining on the photoreceptor or the primary transfer medium is easily removed. Specific examples of the cleaning improver include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, resin particles obtained using soap-free emulsion polymerization such as polymethyl methacrylate particles and polystyrene particles. . The resin particles preferably have a narrow particle size distribution, and preferably have a volume average particle diameter of 0.01 to 1 μm.

  The magnetic material can be appropriately selected from known materials according to the purpose, and examples thereof include iron powder, magnetite, and ferrite. Among them, a white magnetic material is preferable in terms of color tone.

As an example of a toner production method, a method for forming toner base particles while producing an adhesive substrate will be described below. In such a method, preparation of an aqueous medium phase, preparation of an oil phase containing a toner material, emulsification or dispersion of the toner material, formation of an adhesive substrate, removal of the solvent, heavy weight having reactivity with active hydrogen groups. Synthesis of a compound, synthesis of a compound having an active hydrogen group, and the like are performed.
The aqueous medium can be prepared by dispersing the resin particles in the aqueous medium. The addition amount of the resin particles in the aqueous medium is preferably 0.5 to 10% by mass.

The oil phase containing the toner material is prepared in a solvent by a compound having an active hydrogen group, a polymer having a site capable of reacting with the active hydrogen group-containing compound, a colorant dispersed with a polymer dispersant, a release agent. It can be carried out by dissolving or dispersing a toner material such as an agent, a charge control agent and the polyester resin.
In the toner material, components other than the polymer having a site capable of reacting with the active hydrogen group-containing compound, the colorant, and the polyester resin are added and mixed in the aqueous medium when the resin particles are dispersed in the aqueous medium. Alternatively, the oil phase containing the toner material may be added to the aqueous medium when it is added to the aqueous medium.
The emulsification or dispersion of the toner material can be performed by dispersing an oil phase containing the toner material in an aqueous medium. Then, when the toner material is emulsified or dispersed, an adhesive base material is obtained by subjecting a polymer having a site capable of reacting with the active hydrogen group-containing compound and the active hydrogen group-containing compound to an extension reaction and / or a crosslinking reaction. Generate.

  Adhesive substrates such as urea-modified polyester-based resins contain, for example, an oil phase containing a polymer having reactivity with active hydrogen groups such as polyester prepolymers having isocyanate groups, and active hydrogen groups such as amines. The oil phase containing the toner material may have an active hydrogen group in advance. The oil phase may be emulsified or dispersed in an aqueous medium together with the compound to be produced, and then both may be subjected to an extension reaction and / or a crosslinking reaction in the aqueous medium. The oil phase containing the toner material may be emulsified or dispersed in an aqueous medium by emulsifying or dispersing it in an aqueous medium to which a compound is added, and subjecting both to an extension reaction and / or a crosslinking reaction in the aqueous medium. Then, a compound having an active hydrogen group is added, and an extension reaction and / or a cross-linking reaction are performed in the aqueous medium from the particle interface. It may be. When both are subjected to an extension reaction and / or a crosslinking reaction from the particle interface, a urea-modified polyester resin is preferentially formed on the surface of the toner to be produced, and a concentration gradient of the urea-modified polyester resin can be provided in the toner.

  The reaction conditions for producing the adhesive substrate can be appropriately selected according to the combination of the polymer having a site capable of reacting with the active hydrogen group-containing compound and the compound having an active hydrogen group. The reaction time is preferably 10 minutes to 40 hours, more preferably 2 hours to 24 hours. The reaction temperature is preferably 0 to 150 ° C, more preferably 40 to 98 ° C.

  As a method for stably forming a dispersion containing a polymer having a site capable of reacting with an active hydrogen group-containing compound such as a polyester prepolymer having an isocyanate group in an aqueous medium, active hydrogen is added in the aqueous medium phase. An oil phase prepared by dissolving or dispersing a toner material such as a polymer having a site capable of reacting with a group-containing compound, a colorant, a release agent, a charge control agent and the polyester resin in a solvent is added, and shear force is applied. The method of making it disperse | distribute etc. is mentioned.

Dispersion can be performed using a known disperser, and examples of the disperser include a low-speed shear disperser, a high-speed shear disperser, a friction disperser, a high-pressure jet disperser, and an ultrasonic disperser. Although mentioned, since the particle diameter of a dispersion can be controlled to 2-20 micrometers, a high-speed shearing disperser is preferable.
When a high-speed shearing disperser is used, conditions such as the number of rotations, dispersion time, dispersion temperature and the like can be appropriately selected according to the purpose. The rotation speed is preferably 1000 to 30000 rpm, more preferably 5000 to 20000 rpm. In the case of a batch system, the dispersion time is preferably 0.1 to 5 minutes, and the dispersion temperature is preferably 0 to 150 ° C., more preferably 40 to 98 ° C. under pressure. The dispersion temperature is generally easier to disperse when the temperature is higher.

  The amount of the aqueous medium used when emulsifying or dispersing the toner material is preferably 50 to 2000 parts by mass, more preferably 100 to 1000 parts by mass with respect to 100 parts by mass of the toner material. If the amount used is less than 50 parts by mass, the dispersion state of the toner material may be deteriorated, and toner base particles having a predetermined particle diameter may not be obtained. May be.

In the step of emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoints of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution.
The dispersant can be appropriately selected according to the purpose, and examples thereof include surfactants, sparingly water-soluble inorganic compound dispersants, and polymeric protective colloids, and surfactants are preferred. These may be used alone or in combination of two or more.

As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and the like can be used.
Examples of the anionic surfactant include alkylbenzene sulfonate, α-olefin sulfonate, phosphate ester, and the like, and those having a fluoroalkyl group are preferably used. As an anionic surfactant having a fluoroalkyl group, a fluoroalkylcarboxylic acid having 2 to 10 carbon atoms or a metal salt thereof, disodium perfluorooctanesulfonylglutamate, 3- [ω-fluoroalkyl (C6-C11) oxy ] Sodium 1-alkyl (C3-C4) sulfonate, sodium 3- [ω-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) carboxylic acid or Its metal salt, perfluoroalkylcarboxylic acid (C7 to C13) or its metal salt, perfluoroalkyl (C4 to C12) sulfonic acid or its metal salt, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2 -Hydroxyethyl) perfluorooctance Examples include sulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, and the like. Commercially available surfactants having a fluoroalkyl group include Surflon S-111, S-112, S-113 (manufactured by Asahi Glass Co., Ltd.), Fluorard FC-93, FC-95, FC-98, FC-129. (Above, manufactured by Sumitomo 3M), Unidyne DS-101, DS-102 (above, manufactured by Daikin Industries, Ltd.), MegaFuck F-110, F-120, F-113, F-191, F-812, F- 833 (above, manufactured by Dainippon Ink, Inc.), Xtop EF-102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (above, manufactured by Tochem Products), Footage 100, 150 (above, manufactured by Neos).

  As cationic surfactants, amine salt type surfactants such as alkylamine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts And quaternary ammonium salt type surfactants such as alkylisoquinolinium salts and benzethonium chloride. Among them, aliphatic primary, secondary or tertiary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salts, benzalkonium salts, benzethonium chloride, Examples include pyridinium salts and imidazolinium salts. Commercially available cationic surfactants include Surflon S-121 (Asahi Glass Co., Ltd.); Fluorad FC-135 (Sumitomo 3M Co.); -824 (manufactured by Dainippon Ink Co., Ltd.); Xtop EF-132 (manufactured by Tochem Products);

Examples of nonionic surfactants include fatty acid amide derivatives and polyhydric alcohol derivatives.
Specific examples of the amphoteric surfactant include alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine, N-alkyl-N, N-dimethylammonium betaine and the like.

  Specific examples of the hardly water-soluble inorganic compound dispersant include tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, and hydroxyapatite.

  Polymeric protective colloids include monomers having carboxyl groups, alkyl (meth) acrylates having hydroxyl groups, vinyl ethers, vinyl carboxylates, amide monomers, acid chloride monomers, monomers having nitrogen atoms or heterocyclic rings thereof, and the like. Examples thereof include homopolymers or copolymers obtained by polymerization, polyoxyethylene resins, and celluloses. In addition, the homopolymer or copolymer obtained by polymerizing the above monomers includes those having a structural unit derived from vinyl alcohol.

  Specific examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride and the like. Specific examples of the (meth) acrylic monomer containing a hydroxyl group include β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, and γ-acrylate. -Hydroxypropyl, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc. Is mentioned. Specific examples of vinyl ether include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like. Specific examples of vinyl carboxylate include vinyl acetate, vinyl propionate, vinyl butyrate and the like. Specific examples of the amide monomer include acrylamide, methacrylamide, diacetone acrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like. Specific examples of the acid chloride monomer include acrylic acid chloride and methacrylic acid chloride. Specific examples of the monomer having a nitrogen atom or a heterocyclic ring thereof include vinyl pyridine, vinyl pyrrolidone, vinyl imidazole, and ethyleneimine. Specific examples of the polyoxyethylene resin include polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, Examples include polyoxyethylene lauryl phenyl ether, polyoxyethylene phenyl stearate, and polyoxyethylene pelargonate phenyl. Specific examples of celluloses include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and the like.

  Specific examples of the dispersant include acids such as calcium phosphate salts and those that are soluble in alkali. When calcium phosphate is used as the dispersant, the calcium phosphate salt can be removed by dissolving the calcium salt with hydrochloric acid or the like and washing it with water or decomposing with an enzyme.

  A catalyst can be used for the elongation reaction and / or the crosslinking reaction in producing the adhesive substrate. Specific examples of the catalyst include dibutyltin laurate and dioctyltin laurate.

As a method for removing the organic solvent from the dispersion liquid such as an emulsified slurry, the temperature of the entire reaction system is gradually raised to evaporate the organic solvent in the oil droplets, and the dispersion liquid is sprayed in a dry atmosphere to obtain the oil. Examples include a method of removing the organic solvent in the droplets.
When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. Classification may be performed by removing fine particle portions by a cyclone, decanter, centrifugation, or the like in the liquid, or classification may be performed after drying.

The obtained toner base particles may be mixed with particles such as a release agent and a charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent particles such as a release agent from detaching from the surface of the toner base particles.
As a method of applying mechanical impact force, a method of applying impact force to a mixture using a blade rotating at a high speed, throwing the mixture into a high-speed air current, and accelerating the particles or particles to an appropriate collision plate The method of making it collide etc. is mentioned. As an apparatus used in this method, an Ong mill (manufactured by Hosokawa Micron Corporation), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are lowered, and a hybridization system (manufactured by Nara Machinery Co., Ltd.) Kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.

  Since the toner of the present invention has a smooth surface, it has excellent properties such as transferability and chargeability, and can form a high-quality image. Further, when the toner of the present invention contains an adhesive substrate obtained by reacting a compound having an active hydrogen group with a polymer having reactivity to the active hydrogen group in an aqueous medium, the transferability and fixability are improved. Further excellent properties such as Therefore, the toner of the present invention can be used in various fields and can be suitably used for image formation by electrophotography.

  The volume average particle diameter of the toner of the present invention is preferably 3 to 8 μm, and more preferably 4 to 7 μm. When the volume average particle diameter is less than 3 μm, in the two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the case of a one-component developer, toner filming on the developing roller and toner fusion to a member such as a blade for thinning the toner may occur. When the volume average particle diameter exceeds 8 μm, it becomes difficult to obtain a high-resolution and high-quality image, and when the toner in the developer is balanced, the fluctuation of the toner particle diameter may increase. .

  The ratio of the volume average particle diameter to the number average particle diameter of the toner of the present invention is preferably 1.00 to 1.25, and more preferably 1.05 to 1.25. As a result, in the two-component developer, even if the toner balance for a long period of time is performed, the toner particle diameter in the developer is little changed, and good and stable developability can be obtained even in the case of long-term stirring in the developing device. . In the case of a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is reduced, and the toner filming on the developing roller and the toner on a member such as a blade for thinning the toner Therefore, even when the developing device is used (stirred) for a long time, good and stable developability can be obtained, so that a high-quality image can be obtained. When this ratio exceeds 1.25, it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle diameter may increase. is there.

  The ratio of the volume average particle diameter to the volume average particle diameter and the number average particle diameter can be measured as follows using a particle size measuring device Multisizer III (manufactured by Beckman Coulter, Inc.). First, 0.1 to 5 ml of a surfactant such as an alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of an electrolyte aqueous solution such as an approximately 1% by mass sodium chloride aqueous solution. Next, about 2 to 20 mg of a measurement sample is added. The aqueous electrolyte solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and then the volume and number of toners are measured using a 100 μm aperture to determine the volume distribution and number distribution. calculate. From the obtained distribution, the volume average particle diameter and the number average particle diameter of the toner can be obtained.

The penetration of the toner of the present invention is preferably 15 mm or more, and more preferably 20 to 30 mm. When the penetration is less than 15 mm, the heat resistant storage stability is deteriorated. The penetration can be measured by a penetration test (JIS K2235-1991).
Specifically, the toner is filled in a 50 ml glass container and left in a thermostat at 50 ° C. for 20 hours, and then the toner is cooled to room temperature and a penetration test is performed. In addition, it has shown that heat resistance preservability is excellent, so that the value of penetration is large.

  The toner of the present invention preferably has a low fixing minimum temperature and a high offset non-occurrence temperature from the viewpoint of achieving both low-temperature fixability and offset resistance. For this purpose, it is preferable that the lower limit fixing temperature is less than 140 ° C. and the temperature at which no offset occurs is 200 ° C. or more. Here, the lower limit fixing temperature is the lower limit of the fixing temperature at which the residual ratio of the image density after a copy test using an image forming apparatus and rubbing the obtained image with a pad is 70% or more. The offset non-occurrence temperature can be obtained by measuring a temperature at which no offset occurs using an image forming apparatus adjusted to be developed with a predetermined amount of toner.

The thermal characteristics of the toner, also called flow tester characteristics, are evaluated as a softening temperature, an outflow start temperature, a 1/2 method softening point, and the like. These thermal characteristics can be measured by an appropriately selected method, and can be measured using an elevated flow tester CFT500 type (manufactured by Shimadzu Corporation).
The softening temperature of the toner of the present invention is preferably 30 ° C. or higher, and more preferably 50 to 90 ° C. When the softening temperature is less than 30 ° C., the heat resistant storage stability may be deteriorated.
The outflow start temperature of the toner of the present invention is preferably 60 ° C. or higher, and more preferably 80 to 120 ° C. When the outflow start temperature is less than 60 ° C., at least one of heat resistant storage stability and offset resistance may be deteriorated.

The 1/2 method softening point of the toner of the present invention is preferably 90 ° C. or higher, more preferably 100 to 170 ° C. When the 1/2 method softening point is less than 90 ° C., the offset resistance may be deteriorated.
The glass transition temperature of the toner of the present invention is preferably 40 to 70 ° C, more preferably 45 to 65 ° C. When the glass transition temperature is less than 40 ° C., the heat-resistant storage stability of the toner may deteriorate, and when it exceeds 70 ° C., the low-temperature fixability may not be sufficient. The glass transition temperature can be measured using a differential scanning calorimeter DSC-60 (manufactured by Shimadzu Corporation) or the like.

The density of an image formed using the toner of the present invention is preferably 1.35 or more, more preferably 1.40 or more, and further preferably 1.45 or more. When the image density is less than 1.35, the image density is low, and in particular, the visibility of characters may be deteriorated. The image density was developed on Ricoh full color PPC paper TYPE6000 <70W> A4T (manufactured by Ricoh) using a tandem color electrophotographic apparatus imagio Neo C285 (manufactured by Ricoh) with a fixing roller surface temperature of 160 ± 2 ° C. A solid image in which the adhesion amount of the agent is 0.30 ± 0.05 mg / cm ² is formed, and the image density at any five positions in the obtained solid image is measured using a color difference meter 938 Spectrodentitometer (measurement light source CIE manufactured by X-Rite). It can obtain | require by measuring using -D50 and measurement mode Status A density) and calculating the average value.

  The color of the toner of the present invention can be appropriately selected according to the purpose, and can be one or more selected from the group consisting of black toner, cyan toner, magenta toner, and yellow toner. It can be obtained by appropriately selecting a colorant.

  The developer of the present invention contains the toner of the present invention, and may further contain other components appropriately selected such as a carrier. For this reason, it is excellent in transferability, chargeability, etc., and a high quality image can be formed stably. The developer may be a one-component developer or a two-component developer. However, when used in a high-speed printer or the like that supports an increase in information processing speed in recent years, the lifetime is shortened. A two-component developer is preferred because it improves.

When the developer of the present invention is used as a one-component developer, even if the balance of the toner is performed, the fluctuation of the toner particle diameter is small, the filming of the toner on the developing roller, the blade for thinning the toner, etc. Therefore, good and stable developability and images can be obtained even with long-term stirring in the developing device.
When the developer of the present invention is used as a two-component developer, there is little fluctuation in the particle diameter of the toner even if the toner balance is maintained over a long period of time, and good and stable developability even with long-term agitation in the developing device. An image is obtained.

The carrier can be appropriately selected according to the purpose, but a carrier having a core material and a resin layer covering the core material is preferable.
The material of the core material can be appropriately selected from known materials, and examples thereof include 50 to 90 emu / g manganese-strontium-based material, manganese-magnesium-based material, and the like. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 to 120 emu / g. In addition, it is preferable to use a low-magnetization material such as 30-80 emu / g of copper-zinc system because it can reduce the impact of the developer in a spiked state on the photoconductor and is advantageous for high image quality. . These may be used alone or in combination of two or more.

  The volume average particle diameter of the core material is preferably 10 to 150 μm, and more preferably 40 to 100 μm. If the volume average particle size is less than 10 μm, fine particles are increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. If it exceeds 150 μm, the specific surface area is decreased, and In the case of a full color with many solid portions, the reproduction of the solid portions may be deteriorated.

  The material of the resin layer can be appropriately selected from known resins according to the purpose, but amino resin, polyvinyl resin, polystyrene resin, polyhalogenated olefin, polyester resin, polycarbonate resin, polyethylene , Polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, polyhexafluoropropylene, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Examples include fluoroterpolymers such as copolymers of monomers having no fluoro group, silicone resins, and the like. These may be used alone or in combination of two or more.

  Specific examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Specific examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Specific examples of the polystyrene resin include polystyrene and styrene-acrylic copolymer. Specific examples of the polyhalogenated olefin include polyvinyl chloride. Specific examples of the polyester resin include polyethylene terephthalate and polybutylene terephthalate.

The resin layer may contain conductive powder or the like as necessary. Specific examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of the conductive powder is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control the electric resistance.
The resin layer can be formed by preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying and drying the coating solution on the surface of the core using a known coating method, followed by baking. it can. As a coating method, a dip coating method, a spray method, a brush coating method, or the like can be used. The solvent can be appropriately selected depending on the purpose, and examples thereof include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and butyl cellosolve. The baking may be an external heating method or an internal heating method, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, a method using a microwave, or the like. Is mentioned.

The content of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. If the content is less than 0.01% by mass, a uniform resin layer may not be formed on the surface of the core material. If the content exceeds 5.0% by mass, the resin layer is thick, so May occur, and the uniformity of the carrier may be reduced.
The content of the carrier in the two-component developer is preferably 90 to 98% by mass, and more preferably 93 to 97% by mass.
The developer of the present invention can be used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

The toner-containing container of the present invention has the toner of the present invention. The toner-containing container of the present invention includes the case of having the developer of the present invention.
The container of the toner container can be appropriately selected from known containers, and those having a container body and a cap are preferably used.
The size, shape, structure, material and the like of the container body can be appropriately selected according to the purpose. The shape is preferably cylindrical or the like, and preferably has spiral irregularities formed on the inner peripheral surface, and part or all of the spiral portion has a bellows function. By rotating such a container main body, the toner as the contents can be transferred to the discharge port side.
The material of the container body is preferably a material with good dimensional accuracy, and examples thereof include resins such as polyester resin, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyacrylic acid, polycarbonate resin, ABS resin, and polyacetal resin.
The toner-containing container of the present invention can be easily stored and transported, has excellent handleability, and can be removably attached to a process cartridge, an image forming apparatus or the like to supply toner.

The process cartridge of the present invention has a developing means having the developer of the present invention and an electrostatic latent image carrier (hereinafter also referred to as an image carrier), and further has other means appropriately selected as necessary. May be. As a result, the electrostatic latent image carried on the image carrier can be developed using the developer to form a visible image.
The developing means preferably includes the toner-containing container of the present invention and a developer carrier for carrying and transporting the developer, and further includes a layer thickness regulating member for regulating the thickness of the toner layer to be carried. May be.
The process cartridge of the present invention can be detachably attached to the image forming apparatus main body.

The image forming method of the present invention forms an image using the developer of the present invention. For this reason, high image quality can be obtained efficiently.
The image forming method of the present invention preferably includes an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step. If necessary, a static elimination step, a cleaning step, a recycling step, a control step, etc. You may have a process further.
An image forming apparatus for forming an image using the developer of the present invention includes an image carrier, an electrostatic latent image forming unit, a developing unit having the developer of the present invention, a transfer unit, and a fixing unit. Preferably, it may further include means such as a static elimination means, a cleaning means, a recycling means, and a control means as necessary.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on the image carrier. The material, shape, structure, size and the like of the image carrier can be appropriately selected from known ones. Examples of the material include inorganic substances such as amorphous silicon and selenium, and organic substances such as polysilane and phthalopolymethine. Amorphous silicon is preferable because of its long life. Further, the shape is preferably a drum shape. The electrostatic latent image can be formed by uniformly charging the surface of the image carrier and then exposing it imagewise, and can be performed by an electrostatic latent image forming unit. The electrostatic latent image forming unit preferably includes a charger that is a charging unit that uniformly charges the surface of the image carrier and an exposure unit that is an exposure unit that exposes the surface of the image carrier.

  Charging can be performed by applying a voltage to the surface of the image carrier using a charger. The charger can be appropriately selected according to the purpose, but a known contact charger equipped with a conductive or semiconductive roll, brush, film, rubber blade, etc., or corona discharge such as corotron or scorotron is used. Non-contact chargers and the like.

  The exposure can be performed by exposing the surface of the image carrier using an exposure device. The exposure device can be appropriately selected according to the purpose, but various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used. It should be noted that an optical back side system in which exposure is performed from the back side of the image carrier may be adopted.

  The development step is a step of forming a visible image by developing the electrostatic latent image using the developer of the present invention. The visible image can be formed using a developing unit. The developing means can be appropriately selected from known ones, and preferably has a developing device that accommodates the developer of the present invention and can apply the developer to the electrostatic latent image in a contact or non-contact manner. As the developing device, it is preferable to use a developing device provided with the toner container of the present invention. The developing device may be a dry development system or a wet development system. Further, it may be a single color developer or a multicolor developer. Specifically, a stirrer for charging the developer by friction stirring and a developer having a rotatable magnet roller can be used. The developer accommodated in the developing device is the developer of the present invention, but may be a one-component developer or a two-component developer.

  In a developing device having a two-component developer, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the image carrier, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with toner, and a visible image is formed with toner on the surface of the image carrier.

  The transfer step is a step of transferring a visible image to a recording medium. The intermediate transfer member is used to primarily transfer the visible image onto the intermediate transfer member, and then the secondary transfer of the visible image onto the recording medium. It is preferable. At this time, the toner used is usually two or more colors, and it is preferable to use a full-color toner. For this reason, it is more preferable to have a primary transfer process in which a visible image is transferred onto an intermediate transfer member to form a composite transfer image, and a secondary transfer process in which the composite transfer image is transferred onto a recording medium.

  The transfer can be performed by charging the image carrier using a transfer unit. The transfer means preferably has a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. The intermediate transfer member can be appropriately selected from known transfer members according to the purpose, and a transfer belt or the like can be used.

  The transfer means preferably has a transfer device that peels and charges the visible image formed on the image carrier to the recording medium side. There may be one transfer means or a plurality of transfer means. Specific examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device. The recording medium can be appropriately selected from known recording media, and recording paper or the like can be used.

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing unit, and may be fixed each time the toner of each color is transferred to the recording medium, or each color toner is laminated. You may fix at once in the state. The fixing unit can be appropriately selected according to the purpose, but a known heating and pressing unit can be used. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt. The heating in the heating and pressurizing means is usually preferably 80 ° C to 200 ° C. A known optical fixing device may be used together with or instead of the fixing unit depending on the purpose.

  The neutralization step is a step of neutralizing by applying a neutralization bias to the image carrier, and can be performed using a neutralization unit. The neutralization means can be appropriately selected from known neutralizers, and a neutralization lamp or the like can be used.

  The cleaning step is a step of removing toner remaining on the image carrier, and can be performed using a cleaning unit. The cleaning means can be appropriately selected from known cleaners, and a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web cleaner, or the like can be used.

The recycling process is a process in which the toner removed in the cleaning process is recycled by the developing unit, and can be performed using the recycling unit. The recycling means can be appropriately selected according to the purpose, and a known conveying means or the like can be used.
The control means is a process for controlling each process, and can be performed using the control means. The control means can be appropriately selected according to the purpose, and devices such as a sequencer and a computer can be used.

  Examples of the present invention will be described below, but the present invention is not limited to the following examples. In the examples, “part” and “%” in each example are based on mass, and “mol” means molar ratio.

(Synthesis Example 1)
In a 4-neck 500 ml separable flask equipped with a stirrer, dropping funnel, reflux condenser, gas inlet tube, thermometer, 4 parts of bisphenol A propylene oxide 3 mol adduct, 10 parts of dimethylolbutanoic acid, N, N -44 parts of bis (2-hydroxypropyl) aniline and 60 parts of methyl ethyl ketone were charged, the inside of the flask was replaced with dry nitrogen, and the temperature was raised to 80 ° C while stirring. Under stirring, 62 parts of isophorone diisocyanate was added dropwise over 10 minutes and allowed to react for 6 hours. The reaction product was cooled to 65 ° C., 319 parts of water and 11 parts of 25% ammonia water were added, the temperature was raised, and 60 parts of methyl ethyl ketone as a solvent and 330 parts of alkaline water were removed. A polymer dispersant A having an acid value of 31 mgKOH / g and an amine value of 25 was obtained.

Here, the acid value (AV), hydroxyl value (OHV), and amine value in the present invention 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 Version 1.00.000
Calibration of the apparatus: Use a mixed solvent of 120 ml of toluene and 30 ml of ethanol.
Measurement temperature: 23 ° C

The measurement conditions are as follows.
Stir
Speed [%] 25
Time [s] 15
EQP titration
Titrant / Sensor
Titrant CH3ONa
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

(Measurement method of acid value)
Measurement is performed under the following conditions in accordance with the measurement method described in JIS K0070-1992.
Sample preparation: 0.5 g of sample is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but 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 mass (where N is a factor of N / 10 KOH)

(Measurement method of hydroxyl value)
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. Furthermore, 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 OH value (according to JISK0070-1966).

(Method for measuring amine value)
Sample preparation: 0.5 g of sample is added to 120 ml of toluene and dissolved by stirring at room temperature (23 ° C.) for about 10 hours. Further, 30 ml of ethanol is added to prepare a sample solution.
The measurement can be calculated by the apparatus described above, but specifically, the calculation is performed as follows.
Titration is performed with a pre-standardized N / 10 hydrochloric acid-alcohol solution, and the amine value is determined from the consumption of hydrochloric acid-alcohol solution.

(Measurement of softening point Tm and glass transition point Tg)
The softening point Tm in the present invention is determined by a peak top indicating the maximum endotherm of the DSC curve in differential scanning calorimetry (DSC). The glass transition point Tg in the present invention is determined at the peak top of the DSC differential curve.
The measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.

Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50 ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

  The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method of the softening point Tm specifies a range of ± 5 ° C. around the point showing the maximum peak of the DSC curve of the second temperature increase, and obtains the peak temperature using the peak analysis function of the analysis software. 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 indicated here corresponds to the Tm of the wax. The glass transition point Tg analysis method designates a range of ± 5 ° C. around the point showing the maximum peak of the DrDSC curve which is the DSC differential curve of the second temperature increase. Next, the DSC curve temperature is obtained by using the tangential intersection 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 point Tg.

(Synthesis Examples 2 to 7)
Polymeric dispersants B to G were obtained in the same manner as in Synthesis Example 1 except that the number of raw material parts in Synthesis Example 1 was changed to the number of raw material parts shown in Table 1.

(Polymerization example 1)
A polyhydric alcohol having the raw material composition shown in Table 2, a divalent carboxylic acid, and 2 parts of dibutyltin oxide were charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe. Reacted for hours. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, the amount of trimellitic anhydride shown in Table 2 was added to the reaction vessel, and the reaction was allowed to proceed at 180 ° C. for a predetermined time under normal pressure. A polyester resin as a resin was synthesized. The obtained polyester resin property values are shown in Table 2. In addition, the quantity of the raw material in Table 2 shows a mass part.

(Measurement of molecular weight)
Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel SuperHZM-H 15cm triple (made by Tosoh Corporation)
Temperature: 40 ° C
Solvent: THF
Flow rate: 0.35 ml / min
Sample: Pretreatment of 0.15% sample injected into 0.4 ml sample: Sample was dissolved in tetrahydrofuran THF (made by Wako Pure Chemical Industries, Ltd.) at 0.15 wt% and filtered through a 0.2 μm filter. Used 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. NoS-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.

Example 1
(Example of preparation of pigment dispersion)
In a container in which a stir bar was set, 250 parts of polyester resin 1, 100 parts of polymer dispersant A, and 1625 parts of ethyl acetate were charged and stirred until polyester resin 1 was dissolved. Next, 150 parts of copper phthalocyanine pigment (Pigment Blue 15: 3, manufactured by Sanyo Color Co., Ltd.) and 100 parts of aluminum hydroxide phthalocyanine pigment (manufactured by Sanyo Color Co., Ltd.) are added to the container, and the mixture is stirred for 1 hour to prepare a pigment mixed solution. Got.
The obtained pigment mixed solution was filled with 80% by volume of 0.3 mm zirconia beads using an ultra visco mill (made by Imex Co., Ltd.), a liquid feed speed of 1 kg / hour, and a disk peripheral speed of 8 m / second. The pigment dispersion A was obtained after 5 passes under the conditions.

(Example of preparing raw material solution)
378 parts of polyester resin 1, 110 parts of carnauba wax, 22 parts of salicylic acid metal complex E-84 (manufactured by Orient Chemical Co., Ltd.) and 947 parts of ethyl acetate were charged into a reaction vessel equipped with a stirring bar and a thermometer. The temperature was raised to 80 ° C. and held at 80 ° C. for 5 hours, and then cooled to 30 ° C. over 1 hour to obtain a raw material solution.
The obtained raw material solution is transferred to a reaction vessel and filled with 80% by volume of 0.5 mm zirconia beads using an ultra visco mill (manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hour and a disk peripheral speed of Carnauba wax was dispersed by 3 passes under the condition of 6 m / sec to obtain a wax dispersion.
Next, a wax dispersion and 290 parts of a pigment dispersion were added to 1324 parts of a 65% by weight ethyl acetate solution of polyester resin 1, and T.P. K. The mixture was stirred for 30 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a toner material dispersion.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propylene oxide 2-mole adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride And 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester resin was synthesize | combined.
The obtained intermediate polyester resin had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.
Next, 410 parts of the intermediate polyester resin, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Was synthesized. The free isocyanate content of the obtained prepolymer was 1.53% by mass.

In a reaction vessel equipped with a stir bar and a thermometer, 170 parts of isophoronediamine and 75 parts of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound. The amine value of the obtained ketimine compound was 418 mgKOH / g.
In a reaction vessel, 749 parts of a dispersion of toner material, 115 parts of a prepolymer and 2.9 parts of a ketimine compound are charged and mixed at 5,000 rpm for 1 minute using a TK homomixer (manufactured by Tokushu Kika). A mixture was obtained.

In a reaction vessel equipped with a stirring bar and a thermometer, 683 parts of water, 11 parts of reactive emulsifier (sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct), Eleminol RS-30 (manufactured by Sanyo Chemical Industries), styrene 83 Parts, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were stirred at 400 rpm for 15 minutes to obtain an emulsion. The emulsion was heated, heated to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by mass ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.
990 parts of water, 83 parts of resin particle dispersion, 37 parts of 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate, Eleminol MON-7 (manufactured by Sanyo Chemical Industries), 1% by weight aqueous solution of sodium carboxymethylcellulose polymer dispersant 135 parts of BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to obtain an aqueous medium.

To 1200 parts of the aqueous medium, 867 parts of the oil phase mixed liquid was added and mixed for 20 minutes at 13000 rpm using a TK homomixer to prepare a dispersion (emulsified slurry).
Next, the emulsified slurry was charged into a reaction vessel in which a stirrer and a thermometer were set, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 4 hours to obtain a dispersed slurry.

After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered.
To the obtained filter cake, 10% by mass hydrochloric acid was added to adjust the pH to 2.8, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration.
Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake.
The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner mother particles.
To 100 parts of the obtained toner base particles, 1.0 part of hydrophobic silica as an external additive and 0.5 part of hydrophobized titanium oxide are added and mixed using a Henschel mixer (Mitsui Mining Co., Ltd.). Toner 1 was manufactured.
The content of the colorant in the toner was 10% by mass.

(Examples 2 to 6)
Toners 2 to 6 were produced in the same manner as in Example 1 except that the polyester resin 1 was changed to the polyester resin shown in Table 3.
(Example 7)
Example 1 except that 150 parts of copper phthalocyanine pigment was changed to 225 parts of magenta pigment Pigment Red 269 (manufactured by Dainichi Seika), and 100 parts of aluminum phthalocyanine was changed to 25 parts of magenta pigment Pigment Red 122 (manufactured by Ciba Japan). In the same manner, Toner 7 was produced.
(Example 8)
Toner 8 was produced in the same manner as in Example 1 except that 150 parts of copper phthalocyanine pigment and 100 parts of aluminum phthalocyanine were changed to 250 parts of yellow pigment Pigment Yellow 74 (manufactured by Toyo Ink).

Example 9
A toner 9 was obtained in the same manner as in Example 1 except that the polymer dispersant A was changed to the polymer dispersant B.
(Example 10)
A toner 10 was produced in the same manner as in Example 1 except that the polymer dispersant A was changed from 100 parts to 12.5 parts.
(Examples 11 and 12)
Toner 11 and toner 12 were produced in the same manner as in Example 1 except that the polymer dispersant A was changed to the polymer dispersant shown in Table 3.

(Comparative Examples 1-7)
Toners 13 to 19 were produced in the same manner as in Example 1 except that the polyester resin 1 was changed to the polyester resin shown in Table 3.
(Comparative Examples 8-9)
Toners 20 to 21 were produced in the same manner as in Example 1 except that the polymer dispersant A was changed to the polymer dispersant shown in Table 3.
(Comparative Example 10)
Toner 22 was prepared in the same manner as in Example 1 except that Polymer Dispersant A was changed to PB711 (manufactured by Ajinomoto Fine Techno Co., Ltd.) (acid value: − (below detection limit, amine value: 45 mgKOH / g). Manufactured.
(Comparative Example 11)
Comparative Example 1 except that 150 parts of copper phthalocyanine pigment was changed to 225 parts of magenta pigment Pigment Red 269 (manufactured by Dainichi Seika), and 100 parts of aluminum phthalocyanine was changed to 25 parts of magenta pigment Pigment Red 122 (manufactured by Ciba Japan). In the same manner, toner 23 was produced.
(Comparative Example 12)
Toner 24 was produced in the same manner as in Comparative Example 1, except that 150 parts of copper phthalocyanine pigment and 100 parts of aluminum phthalocyanine were changed to 250 parts of yellow pigment Pigment Yellow 74 (manufactured by Toyo Ink Co., Ltd.).

The obtained toner was used for evaluation as follows.
(Color characteristic evaluation)
The toner fixed image was prepared as follows. The evaluation was conducted with the surface temperature of the imagio Neo C285 fixing roller manufactured by Ricoh at 160 ± 2 ° C. Ricoh full color PPC paper TYPE6000 <70W> A4T (manufactured by Ricoh) was used as the paper used for creating the fixed image.
The fixed image obtained in this manner was evaluated for color reproducibility (color value). For evaluation of color reproducibility, CIE L ^* , a ^* , and b ^* of the fixed image were measured. Specifically, based on ISO / CD13655, measurement was performed using a color difference meter 938 Spectrodentometer (measurement light source CIE-D50) manufactured by X-Rite.
From this, the saturation by the L ^* a ^* b ^* color system was determined by the following formula (1) (JIS Z8729), and at the same time, the coloring power (measurement mode Status A density) was evaluated.
Formula (1) C ^* _ab = [(a ^* ) ² + (b ^* ) ² ] ^1/2
(Coloring power evaluation)
The coloring power of the toner was measured by measuring the image density of the fixed image using a color difference meter 938 Spectrodentitometer (measuring light source CIE-D50) manufactured by X-Rite.

(Comprehensive evaluation)
The overall evaluation was based on the following criteria.
Judgment criteria A: The coloring power is 1.35 or more and
Saturation is cyan: 63 or more, magenta: 75 or more, yellow: 91 or more ○: coloring power is 1.35 or more
Saturation is cyan: 60 to less than 63, magenta: 70 to less than 75,
Yellow: 85 or more and less than 91 x: coloring power less than 1.35 and
Saturation less than cyan 60, magenta less than 70, yellow less than 85

  From this, it can be seen that the toners of the examples are excellent in saturation, coloring power, and hue difference. Further, since the toners of Comparative Examples 1 to 5 have insufficient pigment dispersibility, the color characteristics of the toner are deteriorated. Since Comparative Example 6 has a low acid value of the polyester resin, and Comparative Example 7 has a high acid value of the polyester resin, a toner could not be produced. As a result, it was impossible to evaluate the color characteristics of the toner.

Claims (21)

  In a toner in which an oil phase containing at least a binder resin and a colorant is suspended and granulated in an aqueous medium, the toner has an acid value of 20 mgKOH / g to 50 mgKOH / g and an amine value of 1 to 50. The binder resin is composed of a diol component and an acid component, the diol component contains a propylene oxide adduct of bisphenols in an amount of 50 mol% or more, and a hydroxyl group. An electrostatic charge image developing toner comprising a polyester resin having a value of 25 mgKOH / g or more and 45 mgKOH / g or less and an acid value of 15 mgKOH / g or more and 25 mgKOH / g or less.   2. The electrostatic image developing toner according to claim 1, wherein the polymer dispersant is contained in a proportion of 5% by mass or more and 45% by mass or less with respect to the colorant. The electrostatic charge image developing toner according to claim 1, wherein a melting point (A) of the polymer dispersant and a Tg (B) of the binder resin satisfy the following formula.
B-15 (° C) ≤ A (° C) ≤ B + 30 (° C)   The electrostatic image developing toner according to claim 1, wherein the colorant is contained in the toner at a ratio of 3% by mass or more and 15% by mass or less.   The electrostatic image developing toner according to claim 1, wherein the colorant is a yellow pigment.   6. The electrostatic image developing toner according to claim 5, wherein the yellow pigment contains at least one of pigment yellow 74, pigment yellow 155, pigment yellow 180, and pigment yellow 185.   The electrostatic charge image developing toner according to claim 1, wherein the colorant is a magenta pigment.   8. The electrostatic image developing toner according to claim 7, wherein the magenta pigment contains at least one of Pigment Red 184, Pigment Red 269, Pigment Red 122, and Pigment Violet 19.   The static ink according to claim 8, wherein the magenta pigment contains Pigment Red 269 and Pigment Red 122, and the content ratio of Pigment Red 269 and Pigment Red 122 is 80:20 to 95: 5 by mass ratio. Toner for charge image development.   The static ink according to claim 8, wherein the magenta pigment contains Pigment Red 269 and Pigment Violet 19, and the content ratio of Pigment Red 269 and Pigment Violet 19 is 80:20 to 95: 5 by mass ratio. Toner for charge image development.   The magenta pigment contains Pigment Red 269 and quinacridone pigment, the content ratio of Pigment Red 269 and quinacridone pigment is 80:20 to 95: 5 by mass, and the quinacridone pigment contains Pigment Red 122 and Pigment Violet 19. The electrostatic charge image developing toner according to claim 8, wherein the content ratio of Pigment Red 122 and Pigment Violet 19 is 90:10 to 10:90 in terms of mass ratio.   The electrostatic image developing toner according to claim 1, wherein the colorant is a cyan pigment.   The cyan pigment contains at least one of Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, and halogen-free aluminum phthalocyanine, which are copper phthalocyanines. The toner for developing an electrostatic charge image according to claim 12.   14. The electrostatic image developing toner according to claim 13, wherein the halogen-free aluminum phthalocyanine is aluminum hydroxide phthalocyanine.   The cyan pigment contains copper phthalocyanine and halogen-free aluminum phthalocyanine, and the content ratio of copper phthalocyanine and halogen-free aluminum phthalocyanine is 50:50 to 90:10 in mass ratio. The toner for developing an electrostatic image according to the description.   In the toner, an oil phase obtained by dissolving a polymer having a site capable of reacting with an active hydrogen group-containing compound together with the colorant dispersed with the polyester resin and the polymer dispersant in a solvent is suspended in an aqueous medium. 2. An emulsion dispersion, which is granulated by a crosslinking reaction and / or elongation reaction of a polymer having a site capable of reacting with the active hydrogen group-containing compound in the emulsion dispersion. The toner for developing an electrostatic charge image according to any one of -15.   The developer used for electrophotographic image formation, wherein the developer has the electrostatic image developing toner according to claim 1.   A toner-containing container for storing a developer used for electrophotographic image formation, wherein the toner-containing container is filled with the electrostatic image developing toner according to any one of claims 1 to 16. Toner containing container.   An electrostatic latent image carrier, a charging device for charging the surface of the electrostatic latent image carrier, an exposure device for exposing the surface of the electrostatic latent image carrier to form an electrostatic latent image, and the electrostatic latent image At least a developing device that develops an image using toner to form a visible image, a transfer device that transfers the visible image to a recording medium, and a fixing device that fixes the transferred image transferred to the recording medium 17. The image forming apparatus according to claim 1, wherein the toner is the electrostatic image developing toner according to claim 1.   At least an electrostatic latent image carrier and a developing device that develops the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image are integrally formed to form an image. 17. A process cartridge that can be attached to and detached from an apparatus main body, wherein the toner is the electrostatic image developing toner according to any one of claims 1 to 16.   A charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the surface of the electrostatic latent image carrier to form an electrostatic latent image, and developing the electrostatic latent image with toner. In the image forming method, comprising: a developing step for forming a visible image; a transferring step for transferring the visible image to a recording medium; and a fixing step for fixing the transferred image transferred to the recording medium. An image forming method comprising the electrostatic image developing toner according to claim 1.