JP2013061544A - Electrophotographic full-color toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a full-color toner having good pigment dispersibility, which is a toner obtained by water-based granulation using at least a polyester resin as a binder resin, and to provide a production method of the toner and a toner master batch for the toner and the method.SOLUTION: The full-color electrophotographic toner is obtained by suspending and granulating an oil phase of a toner material containing at least a binder resin and/or its precursor, a coloring material and a release agent in an aqueous medium. The coloring material is prepared into a master batch by preliminarily dispersing the coloring material in a master batch resin. At least two types of resins having different viscosities are used as the master batch resin. A resin R1 having the highest viscosity has a storage modulus G1' of 8.0×10E4 to 5.0×10E5 at 90°C; and a resin R2 having the lowest viscosity has a storage modulus G2' of 2.0×10E4 to 7.0×10E4 at 90°C.

Description

The present invention relates to a full-color toner for electrophotography, a production method thereof, and a colorant masterbatch for them.
The present invention relates to an electrophotographic toner, and more specifically, a full-color electrophotographic toner used in an image forming apparatus using a so-called electrophotographic method, such as an electrostatic copying machine or a laser beam printer, and a method for producing the toner And a colorant masterbatch therefor.

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 release agent, the pigment, 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.
According to the polymerization method, the conventional pulverization process and kneading process can be omitted, energy saving, shortening of production time, improvement of process yield, etc. contribute greatly to cost reduction. At the same time, it is easy to make the particle size distribution sharper than that of the pulverization method, and the contribution to high image quality is great, so the polymerization method is a highly promising method. In addition, in order to increase the image quality of a full-color image as in printing in electrophotography, it is necessary that each toner has a wide color reproducibility. In order to achieve the above object without any problems, a colorant having excellent transparency, light resistance and heat resistance is highly dispersed in the toner.

Master batch technology is mainly used for high dispersion of the colorant. As a technique for increasing pigment dispersibility in a master batch, for example, a master batch in which a colorant is highly dispersed can be obtained by dispersing a pigment together with wax. In addition, a master batch in which a colorant is highly dispersed is obtained by, for example, melt-kneading with a plasticizer (Japanese Patent Laid-Open No. 2002-070466 of Patent Document 2). ). In addition, as a melt-kneading condition at the time of master batch production, a master batch in which a colorant is highly dispersed can be obtained by supplying materials to be supplied in stages (Japanese Patent Laid-Open No. 2008-156790). . Furthermore, it is said that a master batch in which a colorant is highly dispersed can be obtained by using two types of waxes as a dispersant and optimizing the melt-kneading temperature (Japanese Patent Application Laid-Open No. 2009-092864).
However, in any case, it is not considered that the pigment is unevenly distributed on the toner surface in the toner obtained by suspending and granulating the oil phase in an aqueous medium.

  The object of the present invention has been made in view of the above. That is, an object of the present invention is a toner obtained by water-based granulation using at least a polyester resin as a binder resin, a full-color toner having good pigment dispersibility, a method for producing the toner, and a toner for the same It is to provide a master batch for toner.

The above object is achieved by the present invention including the “electrophotographic full color toner”, the “method for producing the toner”, and the “colorant masterbatch for toner” for them described in the following items (1) to (10). Is done.
(1) In a full-color electrophotographic toner obtained by suspending and granulating an oil phase of a toner material containing at least a binder resin and / or its precursor, a colorant and a release agent in an aqueous medium, The colorant is a masterbatch that is preliminarily dispersed in a masterbatch resin, and two or more types of resins having different viscosities are used as the masterbatch resin, and the storage elasticity at 90 ° C. of the resin R1 having the highest viscosity. The modulus G1 ′ is 8.0 × 10E4 to 5.0 × 10E5, and the storage modulus G2 ′ at 90 ° C. of the resin R2 having the lowest viscosity is 2.0 × 10E4 to 7.0 × 10E4. Full-color electrophotographic toner characterized by
(2) “The ratio R1 / R2 of the resin R1 having the highest viscosity and the resin R2 having the lowest viscosity is 50/50 to 10/90,” Full-color electrophotographic toner ".
(3) “The master batch is obtained by kneading the resin R2 having the lowest viscosity and a colorant, and then kneading the obtained material and the resin R1. The full-color electrophotographic toner according to (1) or (2) above.
(4) “The full-color electrophotographic toner according to any one of (1) to (3) above, wherein the masterbatch comprises a pigment dispersant.”
(5) “Full-color electrophotographic toner according to (4) above, wherein the pigment dispersant has a melting point of 60 ° C. to 80 ° C.”.
(6) The above-mentioned masterbatch is characterized in that a masterbatch resin, a release agent, and a presscake pigment after pigment washing as a colorant are preliminarily dispersed. The full-color electrophotographic toner according to any one of items 1) to (5).
(7) The item (1) to (6), wherein the master batch is prepared by previously melting and mixing a binder resin, a release agent, and a colorant in an open type melt kneader. The full-color electrophotographic toner according to any one of Items 1 to 3.
(8) The above (1) to (7), wherein the pigment of the magenta toner is a combination of pigments represented by CI Pigment Red 269 and CI Pigment Red 122 The full-color toner according to any one of the items.
(9) “The full-color toner according to any one of (1) to (7) above, wherein the cyan toner pigment is a pigment represented by CI pigment blue 15”.
(10) The full-color toner according to any one of (1) to (7), wherein the yellow toner pigment is a pigment represented by CI Pigment Yellow 185.
The present invention also includes “electrophotographic full color toner”, “electrophotographic full color toner production method”, and “toner masterbatch therefor” described in the following items (11) to (33).
(11) “Full-color electrophotographic toner according to any one of (4) to (10) above, wherein the pigment dispersant is an ester wax”.
(12) “Coloring for producing a full-color electrophotographic toner having a step of suspending and granulating an oil phase comprising at least a binder resin and / or its precursor, a colorant and a release agent in an aqueous medium. The master batch is obtained by previously dispersing the colorant in a master batch resin, and two or more resins having different viscosities are used as the master batch resin. The storage modulus G1 ′ at 90 ° C. of the higher resin R1 is 8.0 × 10E4 to 5.0 × 10E5, and the storage modulus G2 ′ at 90 ° C. of the resin R2 having the lowest viscosity is 2.0. A master batch for full-color electrophotographic toner, characterized in that it is from × 10E4 to 7.0 × 10E4 ”.
(13) “The ratio R1 / R2 of the resin R1 having the highest viscosity and the resin R2 having the lowest viscosity is 50/50 to 10/90,” Master Badge".
(14) The above (12), wherein the resin R2 having the lowest viscosity and the colorant are kneaded and then the obtained material and the resin R1 are kneaded. Or a master batch according to item (13).
(15) “The masterbatch according to any one of (12) to (14) above, wherein a pigment dispersant is used”.
(16) “The masterbatch according to (15), wherein the pigment dispersant is an ester wax”.
(17) “The masterbatch according to (15) or (16) above, wherein the melting point of the pigment dispersant is 60 ° C. to 80 ° C.”.
(18) The above (13) to (17), wherein the masterbatch resin, the release agent, and the press cake pigment after washing the pigment as a colorant are preliminarily dispersed. ) Masterbatch according to any one of items.
(19) In any one of (13) to (18) above, the binder resin, the release agent, and the colorant are melt-mixed in advance using an open-type melt kneader. Masterbatch ".
(20) The above (13) to (19), wherein the pigment of the magenta toner is a combination of pigments represented by CI Pigment Red 269 and CI Pigment Red 122 The master batch according to any one of the items.
(21) “The masterbatch according to any one of (13) to (19) above, wherein the pigment of the cyan toner is a pigment represented by CI Pigment Blue 15”.
(22) The master batch according to any one of (13) to (19) above, wherein the yellow toner pigment is a pigment represented by CI Pigment Yellow 185.
(23) “A method for producing a toner for full-color electrophotography, comprising suspending and granulating an oil phase comprising at least a binder resin and / or a precursor thereof, a colorant and a release agent in an aqueous medium. The masterbatch resin is preliminarily dispersed in the masterbatch resin, two or more resins having different viscosities are used as the masterbatch resin, and the resin R1 having the highest viscosity at 90 ° C. The storage elastic modulus G1 ′ is 8.0 × 10E4 to 5.0 × 10E5, and the storage elastic modulus G2 ′ at 90 ° C. of the resin R2 having the lowest viscosity is 2.0 × 10E4 to 7.0 × 10E4. A method for producing a toner for full-color electrophotography characterized by being ".
(24) The item (23), wherein the ratio R1 / R2 of the resin R1 having the highest viscosity and the resin R2 having the lowest viscosity of the masterbatch is 50/50 to 10/90. The manufacturing method of the toner for full-color electrophotography as described in 1. ".
(25) “In the manufacturing process of the master batch, the resin R2 having the lowest viscosity and the colorant are kneaded, and the material obtained in the first stage and the resin R1 are kneaded. The method for producing a full-color electrophotographic toner according to item (23) or (24), further comprising a second step.
(26) The full-color electrophotographic toner according to any one of items (23) to (25), wherein a pigment dispersant is used in the manufacturing process of the master batch.
(27) “The method for producing a full-color electrophotographic toner according to item (26), wherein the pigment dispersant is an ester wax”.
(28) “The method for producing a full-color electrophotographic toner according to item (26) or (27) above, wherein the pigment dispersant has a melting point of 60 ° C. to 80 ° C.”.
(29) "The masterbatch manufacturing step in which the colorant is dispersed in advance in the masterbatch resin is a step in which the masterbatch resin, the colorant, and the release agent are dispersed in advance, and the step is performed as a colorant. The method for producing a full-color electrophotographic toner according to any one of (23) to (28), wherein the presscake pigment after the pigment washing is used.
(30) The full-color electrophotographic toner according to (29), wherein an open-type melt kneader is used in the step of previously dispersing the masterbatch resin, the release agent, and the colorant. Production method".
(31) Items (23) to (30), wherein the pigment of the magenta toner is a combination of pigments represented by CI Pigment Red 269 and CI Pigment Red 122 The manufacturing method of the full-color toner in any one of claim | items.
(32) “Manufacture of a full-color toner according to any one of (23) to (30) above, wherein the cyan toner pigment is a pigment represented by CI Pigment Blue 15” Method".
(33) The production of a full-color toner according to any one of (23) to (30) above, wherein the yellow toner pigment is a pigment represented by CI Pigment Yellow 185 Method".

  As will be well understood from the following detailed and specific description, according to the present invention, the oil phase of the toner material containing at least a binder resin and / or its precursor, a colorant and a release agent is used as an aqueous medium. In the full-color electrophotographic toner obtained by suspending and granulating in the masterbatch, the colorant is a masterbatch previously dispersed in the masterbatch resin, and the masterbatch resin has two or more types having different viscosities. The storage modulus G1 ′ at 90 ° C. of the resin R1 having the highest viscosity is 8.0 × 10E4 to 5.0 × 10E5, and the resin R2 having the lowest viscosity is stored at 90 ° C. Since the elastic modulus G2 ′ is from 2.0 × 10E4 to 7.0 × 10E4, the color reproducibility is good, there is no abnormal image such as scumming in long-term running, and the film has excellent low-temperature fixability. Color toner is extremely excellent effect demonstrated that the obtained.

Hereinafter, the present invention will be described in detail.
As described above, the toner of the present invention is a full color obtained by suspending and granulating an oil phase of a toner material containing at least a binder resin and / or its precursor, a colorant and a release agent in an aqueous medium. In an electrophotographic toner, the colorant is a master batch in which the colorant is previously dispersed in a master batch resin, and two or more resins having different viscosities are used as the master batch resin, and the resin having the highest viscosity is used. The storage elastic modulus G1 ′ at 90 ° C. of R1 is 8.0 × 10E4 to 5.0 × 10E5, and the storage elastic modulus G2 ′ at 90 ° C. of the resin R2 having the lowest viscosity is 2.0 × 10E4 to 7 This is a full-color toner that uses the CX method to explain that it is 0.0 × 10E4.
When two or more types having different viscosities are used as the master batch resin, it becomes easy to apply a shearing force during kneading by using a resin having a high viscosity, and the pigment dispersibility is improved. On the other hand, when a resin having a low viscosity is used, the resin is easily adsorbed to the pigment when melted at the time of kneading, and the effect of improving dispersibility is given. If the viscosity of the masterbatch resin is too high, the fixability and gloss will be adversely affected. Glossiness also affects color development and should not be lowered.

In the toner of the present invention, as described above, the storage elastic modulus G1 ′ at 90 ° C. of at least the resin R1 having the highest viscosity of the binder resin used in the masterbatch is 8.0 × 10E4 to 5.0 ×. The storage elastic modulus G2 ′ at 90 ° C. of the resin R2 having the lowest viscosity is 10E5 and is characterized by 2.0 × 10E4 to 7.0 × 10E4.
The storage modulus G1 ′ at 90 ° C. of the masterbatch resin R1 having a higher viscosity is set to 8.0 × 10E4 to 5.0 × 10E5. When the viscosity is lower than 8.0 × 10E4, sufficient shearing force is obtained. This is because if it exceeds 5.0 × 10E5, the fixing property and glossiness are adversely affected. Further, the storage elastic modulus G2 ′ at 90 ° C. of the resin R2 having a lower viscosity is set to 2.0 × 10E4 to 7.0 × 10E4. This is because the running stability is lowered, for example, the dispersibility is not sufficiently obtained because the force is reduced, and the viscosity of the toner is lowered and the carrier spent is generated in the long-term running. On the other hand, if it is larger than 7.0 × 10E4, since the viscosity of the resin is high, it is difficult for the pigment to penetrate into the pigment when the resin is melted. Therefore, sufficient pigment dispersibility cannot be obtained.

  In the toner of the present invention, the ratio R1 / R2 of the resin R1 having a higher viscosity and the resin R2 having a lower viscosity is preferably 50/50 to 10/90. When the ratio of R1 is greater than 50, the viscosity becomes too high, and the fixability and glossiness may be adversely affected. On the other hand, if the ratio of R1 is less than 10, the resin viscosity may be too low to provide sufficient shearing force during kneading, and pigment dispersibility may not be improved.

Further, the toner of the present invention comprises a first step of kneading the resin R2 having a lower viscosity and a colorant (typically, for example, a pigment) in the masterbatch production process, and then the obtained material. It is preferable to have a second stage of kneading the resin R1.
First, the masterbatch resin R2 having a low viscosity and the pigment are kneaded because the resin is heated and melted in the first step, wets the pigment surface, easily adsorbs to the pigment, and is then kneaded with R1 having a high viscosity. Thus, since strong shear is imparted, pigment dispersibility can be further improved.

  The toner of the present invention preferably uses a pigment dispersant in the masterbatch production process. By using the pigment dispersant, the pigment dispersibility is improved, and the toner is improved in chroma and a toner having good color developability can be obtained.

  In the toner of the present invention, the pigment dispersant used in the masterbatch production process is preferably an ester wax. The ester wax has a good affinity with the pigment, and also acts as a so-called external lubricant during melt kneading in the masterbatch processing, so that stronger shear is imparted, thereby improving the pigment dispersibility. be able to.

  In the toner of the present invention, the pigment dispersant used in the process for producing the masterbatch preferably has a melting point of 60 ° C to 80 ° C. The reason why the melting point of the dispersant is 60 degrees or more is that when it is less than 60 degrees, it may adversely affect the storage stability and spent property in two-component development when it is present in the toner. In addition, a dispersant is present between the processing machine and the raw material during melt-kneading, and the raw material slips down, so that sufficient dispersibility may not be obtained.

  In the toner of the present invention, it is preferable that the step of dispersing the masterbatch resin, the release agent, and the colorant in advance uses a presscake pigment after pigment washing as the colorant. When a press cake pigment is used, water is contained in the vicinity of the pigment, and water and the resin in the vicinity of the pigment are replaced during melt kneading, so that aggregation is suppressed and pigment dispersibility is improved.

  Furthermore, it is preferable that the toner of the present invention uses an open-type melt kneader in the step of melt-mixing the binder resin, the release agent, and the colorant in advance. The open-type melt kneader can efficiently dissipate heat generated by self-heating at the time of melt-kneading to the atmosphere, so that low-temperature kneading is possible, shear force is improved, and sufficient pigment dispersibility is obtained.

  In the toner of the present invention, the isoindoline pigment is C.I. I. Pig. It is preferable to use Y-185. Due to its skeleton, isoindoline pigments have excellent weather resistance among azo pigments and C.I. I. Pigment Yellow 185 shows a bright yellow color and has a strong coloring power. Moreover, since the transmissivity in the visible region on the long wavelength side of 500 to 700 nm is high, the secondary color developability is also good.

  The toner of the present invention is a C.I. I. Pig. B15: 3, the magenta toner pigment is C.I. I. Pig. R269 and C.I. I. Pig. A mixed system of R122 is preferable. Cyan pigment PIG. B-15: 3, as magenta pigment. I. Pig. R269 and C.I. I. Pig. The mixed system of R122 has a high coloring degree and color reproducibility as a toner pigment. Moreover, when color matching is taken into consideration, a higher color developability can be obtained by combining these pigments.

In the present invention, a polyester resin can be preferably used as the binder resin and / or its precursor. These can be pure polyesters, modified polyesters, and blended polyesters, but the masterbatch resin also has compatibility with the binder resin and the pigment (usually the pigment has a polar group or polar site) Polyester resin can be preferably used also from the viewpoint of dispersibility and the like.
From the viewpoint of pigment dispersibility, the polyester resin used in the present invention preferably contains a propylene oxide adduct of bisphenols in an amount of 50 mol% or more based on the diol component used when polymerizing the polyester resin. 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.

Examples of the colorant for yellow toner of the present invention include C.I. I. Pigment yellow 1, C.I. I. Pigment yellow 5, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 15 or C.I. I. An azo pigment such as CI Pigment Yellow 17, or an inorganic pigment such as yellow iron oxide or ocher can be used.
Examples of the dye include C.I. I. Nitro dyes such as Agit Yellow 1 or C.I. I. Solvent Yellow 2, C.I. I. Solvent Yellow 6, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 15, C.I. I. Solvent Yellow 19 or C.I. I. Oil-soluble dyes such as Solvent Yellow 21 can be used. In particular, from the viewpoint of hue and color development, C.I. I. Pigment Yellow 185 is used.

  Further, as a colorant for cyan toner, as a pigment for cyan toner, C.I. I. Pigment blue-15, C.I. I. Pigment blue-16, C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 70 or the like can be used. I. A copper phthalocyanine pigment such as CI Pigment Blue-15 is selected from the viewpoint of color.

  Examples of the magenta toner pigment include C.I. I. Pigment red 49, C.I. I. Pigment red 57, C.I. I. Pigment red 81, C.I. I. Pigment red 122, C.I. I. Solvent Red 19, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Basic Red 10 or C.I. I. Disperse Red 15 or the like can be used.

Further, each color toner pigment may be used as a mixture. In particular, for magenta toner pigments, C.I. I. Pigment red 122 and C.I. I. A mixed system of CI Pigment Red 269 can be favorably used.
In addition, it is preferable that 2 types of ester wax, a pigment, and a surface treating agent are previously disperse | distributed to masterbatch resin, and the said pigment is put.

  Examples of the melt kneader include a uniaxial extrusion kneader, a biaxial extrusion kneader, a twin roll, and a triple roll. More preferably, a continuous open two-roll kneader is used for the purpose of improving the dispersibility of the surface treatment agent and the pigment. This kneading machine has the kneading force of the open roll kneading machine, in which a strong shearing force is applied over the entire kneading part, by making the roll gap on the kneaded product discharge side wider than the roll gap on the raw material charging side. By concentrating on the raw material charging part in the first half and mainly mixing by melting in the second half part, generation of heat of kneading itself can be suppressed, so that the kneading effect is increased. Two rolls arranged close to each other are heated rolls through which a heating medium is passed, and the other roll is a cooling roll through which a cooling medium is passed. Thus, the dispersibility of the release agent and the pigment is improved.

  Examples of the ester wax include fatty acid esters such as lauric acid ester, palmitic acid ester, stearic acid ester, linoleic acid ester, and montanic acid ester. The melting point of the pigment dispersant is preferably lower than the melting point of the binder resin, and preferably 60 ° C. or higher and 80 ° C. or lower, from the viewpoint of pigment dispersibility, chargeability under high temperature and high humidity, and storage stability. Therefore, stearic acid esters and montanic acid esters having a relatively high molecular weight are used.

In the present invention, besides the ester wax used in the masterbatch for the pigment dispersant, a wax may be preferably used as a release agent. The wax used in the present invention is natural wax such as beeswax derived from animals, whale wax, shellac wax, carnauba wax derived from plants, wood wax, rice bran wax (rice wax), candelilla wax, paraffin wax derived from petroleum, microcrystalline. There are wax, mineral-derived montan wax, ozokerite and the like, and synthetic waxes include Fischer-Tropsch wax, polyethylene wax, oil-based synthetic wax (ester, ketones, amide), hydrogenated wax and the like.
The type is not limited, but a hydrocarbon wax obtained by separating and refining a petroleum distillation distillation fraction from a viewpoint of releasability is preferably modified with a carboxylic acid or the like. This is because paraffin wax has a relatively low temperature and low viscosity, has a low penetration, and can be controlled easily by modifying the acid value.

  In the present invention, a charge control agent is preferably used. 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 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. When the content is less than 0.1% by mass, the charge controllability may not be obtained. When 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 binder resin (and / or its precursor) contained in the oil phase preferably has a weight average molecular weight of 1000 to 30000, 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.
Further, the acid value of the binder resin is preferably 5 to 30 mg KOH / g from the viewpoint of pigment dispersibility and environmental stability.

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, cellosolve (registered trademark), 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 the oil phase containing a toner material containing at least a binder resin and / or a precursor thereof 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.

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.
Examples of the site capable of reacting with the active hydrogen group-containing compound of the prepolymer include an isocyanate group, an epoxy group, a carboxyl group, and a functional group represented by the chemical structural formula -COCl. Among them, 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 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.

  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.

The toner of the present invention is used by externally adding an external additive to the base particles. As the external additive, organic fine particles such as PMMA and inorganic particles can be appropriately selected from known materials according to the purpose. Specific examples of the orientation particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. , Chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like. 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. These inorganic particles are used after surface treatment from the viewpoints of improvement in fluidity and blocking property, and preservation and water resistance. Specific examples of the surface treatment include a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent, silicone oil, and modified silicone oil. Can be mentioned.

Next, 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, a release agent, a charge control agent, and the polyester. It can be carried out by dissolving or dispersing a toner material such as a 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. 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, 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 long-term 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 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.

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 content of the carrier in the two-component developer is preferably 90 to 98% by mass, and more preferably 93 to 97% by mass.

  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.

Examples 1-13 Comparative Examples 1-4
[Synthesis Example 1; Synthesis of polyester resin for binder resin]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of a 2-mole adduct of bisphenol A, 84 parts of a 3-mole adduct of bisphenol A, 274 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and the polyester resin was synthesize | combined. The obtained polyester resin had an acid value of 20.2 mgKOH / g and a melting point of 95 ° C.

[Synthesis Example 2; Synthesis of polyester resin R1 (R1-1) for masterbatch]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 77 parts of 2-molar addition product of ethylene oxide of bisphenol A, 74 parts of 3-mole addition product of propion oxide of bisphenol A, 289 parts of terephthalic acid and 2 parts of dibutyltin oxide And allowed to react at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 6 hours, and polyester resin R1-1 was synthesize | combined. The obtained polyester resin R1-1 had an acid value of 15.3 mg KOH / g and a melting point of 108 ° C. The viscosity with a rheometer was 2.0 × 10E5.

[Synthesis Example 3; Synthesis of polyester resin R1 (R1-2) for masterbatch]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 82 parts of a 2-mole addition product of ethylene oxide of bisphenol A, 69 parts of a 3-mole addition product of propion oxide of bisphenol A, 294 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 10 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 6 hours, and polyester resin R1-2 was synthesize | combined. The obtained polyester resin R1-2 had an acid value of 15.8 mgKOH / g and a melting point of 118 ° C. The viscosity with a rheometer was 4.6 × 10E5.

[Synthesis Example 4; Synthesis of polyester resin R1 (R1-3) for masterbatch]
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 82 parts of a 2-mole addition product of ethylene oxide of bisphenol A, 69 parts of a 3-mole addition product of propion oxide of bisphenol A, 294 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 6 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 6 hours, and polyester resin R1-3 was synthesize | combined. The obtained polyester resin R1-3 had an acid value of 15.4 mgKOH / g and a melting point of 102 ° C. The viscosity with a rheometer was 8.3 × 10E4.

[Synthesis Example 5: Synthesis of polyester resin R2 (R2-1) for masterbatch]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of a 2-mole adduct of bisphenol A, 84 parts of a 3-mole adduct of bisphenol A, 274 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and polyester resin R2-1 was synthesize | combined. The obtained polyester resin R2-1 had an acid value of 14.8 mgKOH / g and a melting point of 88 ° C. The viscosity with a rheometer was 5.1 × 10E4.

[Synthesis Example 6; Synthesis of polyester resin R2 (R2-2) for masterbatch]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of a 2-mole adduct of bisphenol A, 84 parts of a 3-mole adduct of bisphenol A, 274 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 10 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and polyester resin R2-2 was synthesize | combined. The obtained polyester resin R2-2 had an acid value of 15.6 mgKOH / g and a melting point of 91 ° C. The viscosity with a rheometer was 6.6 × 10E4.

[Synthesis Example 7: Synthesis of polyester resin R2 (R2-3) for masterbatch]
Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 67 parts of a 2-mole adduct of bisphenol A, 84 parts of a 3-mole adduct of bisphenol A, 274 parts of terephthalic acid and 2 parts of dibutyltin oxide are added. And allowed to react at 230 ° C. for 6 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and polyester resin R2-3 was synthesize | combined. The obtained polyester resin R2-3 had an acid value of 14.3 mg KOH / g and a melting point of 81 ° C. The viscosity with a rheometer was 2.5 × 10E4.

[Synthesis Example 8; Synthesis of Polyester Resin Containing Isocyanate Group]
(Synthesis of intermediate polyester)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 81 parts by mass of bisphenol A propylene oxide 2 mol adduct, 283 parts by mass of terephthalic acid, trimellitic anhydride 22 parts by mass of acid and 2 parts by mass of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Subsequently, it was made to react under reduced pressure of 10 mmHg-15 mmHg for 5 hours, and the intermediate polyester was synthesize | combined.
The resulting intermediate polyester has a number average molecular weight (Mn) of 2,100, a weight average molecular weight (Mw) of 9,500, a glass transition temperature (Tg) of 55 ° C., an acid value of 0.5, and a hydroxyl value of 51.

[Comparative Synthesis Example 1; Synthesis of polyester resin R1 (R1-4) for masterbatch]
85 parts of bisphenol A ethylene oxide 2-mole adduct, 65 parts of bisphenol A propion oxide 3-mole adduct, 294 parts of terephthalic acid and 2 parts of dibutyltin oxide are charged into a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe. And allowed to react at 230 ° C. for 10 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 8 hours, and polyester resin R1-2 was synthesize | combined. The obtained polyester resin R1-4 had an acid value of 14.8 mgKOH / g and a melting point of 120 ° C. The viscosity with a rheometer was 5.5 × 10E5.

[Comparative Synthesis Example 2; Synthesis of polyester resin R2 (R2-4) for masterbatch]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 60 parts of bisphenol A ethylene oxide 2 mol adduct, 89 parts of bisphenol A propion oxide 3 mol adduct, 274 parts terephthalic acid and 2 parts dibutyltin oxide are added. And allowed to react at 230 ° C. for 6 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and polyester resin R2-3 was synthesize | combined. The obtained polyester resin R2-3 had an acid value of 15.2 mg KOH / g and a melting point of 79 ° C. The viscosity with a rheometer was 1.5 × 10E4.

[Comparative Synthesis Example 3; Synthesis of polyester resin R2 (R2-5) for masterbatch]
70 parts of bisphenol A ethylene oxide 2-mole adduct, 81 parts of bisphenol A propion oxide 3-mole adduct, 274 parts of terephthalic acid and 2 parts of dibutyltin oxide are charged into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube. And allowed to react at 230 ° C. under normal pressure for 12 hours. Next, it was made to react under reduced pressure of 10-15 mmHg for 5 hours, and polyester resin R2-2 was synthesize | combined. The obtained polyester resin R2-2 had an acid value of 15.1 mg KOH / g and a melting point of 93 ° C. The viscosity with a rheometer was 7.4 × 10E4.

(Synthesis of isocyanate group-containing polyester resin (polymer having a site capable of reacting with an active hydrogen group-containing compound))
Next, 410 parts by mass of the intermediate polyester, 89 parts by mass of isophorone diisocyanate, and 500 parts by mass of ethyl acetate are charged in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Thus, a polyester resin containing an isocyanate group (a polymer having a site capable of reacting with an active hydrogen group-containing compound) was synthesized.
The free isocyanate content of the obtained polyester resin containing an isocyanate group was 1.53% by mass.

[Synthesis Example 9; Synthesis of ketimine compound (active hydrogen group-containing compound)]
In a reaction vessel equipped with a stir bar and a thermometer, 170 parts by mass of isophoronediamine and 75 parts by mass of methyl ethyl ketone were charged and reacted at 50 ° C. for 5 hours to synthesize a ketimine compound (active hydrogen group-containing compound).
The amine value of the obtained ketimine compound was 418.

(Viscoelasticity measurement)
The measurement was performed using a HAAKE rheostress RS6000. The measurement conditions are
Sensor; φ20mm parallel plate gap; 2mm
Frequency: 1Hz
Temperature increase rate: 2.5 ° C / min
Measurement temperature range: 70 ° C. to 180 ° C.
As a measuring method, 0.85 g of toner was weighed, dispersed on a sensor, left to melt sufficiently, and after melting, the sensor was lowered to perform measurement. The value of the storage elastic modulus G ′ at 90 ° C. was read and used as the viscoelastic value of the master batch resin.

(Measurement method of resin and wax 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, and specifically, the calculation is performed as follows.
Titrate with a pre-standardized N / 10 caustic potash to alcohol solution, and determine the acid value from the consumption of the alcohol potash solution by the following calculation.
Acid value = KOH (ml) x N x 56.1 / sample mass (where N is a factor of N / 10 KOH)

[Example 1]
Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) at the ratio shown in Table 2 (the wax is not used in this Example 1) with 50% of the pigment shown in Table 2 and the two types of polyester resins R1-1 and R2-1 synthesized above. Was mixed at 1000 rpm for 5 minutes, and then kneaded with an open roll kneader (manufactured by Mitsui Mining Co., Ltd.), and a 2 mm large pigment dispersion powder was prepared with a rotoplex grinder to obtain a master batch.

In a beaker, 10 parts of a polyester prepolymer, 75 parts of a polyester resin and 130 parts of ethyl acetate were stirred and dissolved. Next, 5 parts of paraffin wax and 20 parts of the above master batch were added, and the particle size was measured at a feeding speed of 1 kg / hour and a peripheral speed of the disk of 6 m / second using an ultra visco mill (manufactured by Imex). Three passes were performed under the condition of filling 80% by volume of 0.5 mm zirconia beads. Further, 2.7 parts of a ketimine compound was added and dissolved to prepare a toner material liquid.
Add 150 parts of an aqueous medium into a container, add 100 parts of toner material solution while stirring at 12,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), and mix for 10 minutes to prepare an emulsified slurry. did.
In a Kolben equipped with a stirrer and a thermometer, 100 parts of an emulsified slurry was charged, and the solvent was removed at 30 ° C. for 12 hours while stirring at a stirring peripheral speed of 20 m / min to obtain a dispersed slurry.
After filtering 100 parts of the dispersion slurry under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, followed by mixing at 12000 rpm for 10 minutes using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice. 20 parts of a 10 wt% aqueous sodium hydroxide solution was added to the obtained filter cake, mixed at 12000 rpm for 30 minutes using a TK homomixer, and then filtered under reduced pressure. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed at 12000 rpm for 10 minutes using a TK homomixer, and then filtered. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice. Further, 20 parts of 10 wt% hydrochloric acid was added to the obtained filter cake, and the mixture was mixed for 10 minutes at 12000 rpm using a TK homomixer, followed by filtration. To the obtained filter cake, 300 parts of ion-exchanged water was added, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a 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.
For 100 parts of the toner base particles obtained, 1.0 part of hydrophobic silica as an external additive and titanium oxide shown in Table 2 were mixed using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) for evaluation. A toner was prepared.

[Example 2]
A toner for evaluation was produced in the same manner as in Example 1 except that the high-viscosity resin R1-1 in Example 1 was replaced with the resin R1-3 and the low-viscosity resin R2-1 was replaced with R2-3. did.

Example 3
An evaluation toner was prepared in the same manner as in Example 1 except that the high-viscosity resin R1-1 in Example 1 was replaced with the resin R1-2 and the low-viscosity resin R2-1 was replaced with R2-3. .

Example 4
A toner for evaluation was produced in the same manner as in Example 1 except that the high-viscosity resin R1-1 in Example 1 was replaced with the resin R1-3 and the low-viscosity resin R2-1 was replaced with R2-2. .

Example 5
An evaluation toner was prepared in the same manner as in Example 1 except that the high-viscosity resin R1-1 in Example 1 was replaced with the resin R1-2 and the low-viscosity resin R2-1 was replaced with R2-2. .

Example 6
An evaluation toner was prepared in the same manner as in Example 1 except that the amount ratio of the high viscosity resin R1-1 and the low viscosity resin R2-1 in Example 1 was changed as shown in the table.

Example 7
An evaluation toner was prepared in the same manner as in Example 1 except that the high-viscosity resin R1-1 in Example 1 was replaced with the resin R1-3.

Example 8
An evaluation toner was prepared in the same manner as in Example 1 except that the low-viscosity resin R2-1 and the pigment in Example 1 were previously dispersed.

Example 9
Toner for evaluation in the same manner as in Example 1, except that 40% of R1-1 resin, 55% of R2-1 resin, and 5% of a pigment dispersant (ester wax) having a melting point of 63.6 ° C. were added. Was made.

Example 10
Toner for evaluation in the same manner as in Example 1, except that 40% of R1-1 resin, 55% of R2-1 resin, and 5% of a pigment dispersant (ester wax) having a melting point of 76.2 ° C. were added. Was made.

Example 11
A toner for evaluation was produced in the same manner as in Example 1, except that wet cake was used as the pigment and flashing kneading was adopted.

Example 12
In Example 1, C.I. I. In place of Pigment Yellow 185, C.I. I. An evaluation toner was prepared in the same manner as in Example 1 except that CI Pigment Blue 15; 3 was used.

Example 13
In Example 1, C.I. I. In place of Pigment Yellow 185, C.I. I. Pigment red 269 and C.I. I. An evaluation toner was prepared in the same manner as in Example 1 except that CI Pigment Red 122 was used in combination.

[Comparative Example 1]
An evaluation toner was prepared in the same manner as in Example 1 except that the high viscosity resin R1-1 in Example 1 was replaced with the low viscosity resin R2-2.

[Comparative Example 2]
An evaluation toner was prepared in the same manner as in Example 1 except that the resin R1-1 in Example 1 was replaced with the resin R1-4.

[Comparative Example 3]
An evaluation toner was produced in the same manner as in Example 1 except that the resin R2-1 in Example 1 was replaced with the resin R2-4.

[Comparative Example 4]
An evaluation toner was prepared in the same manner as in Example 1 except that the resin R2-1 in Example 1 was replaced with the resin R2-5.

[Production of two-component developer]
5% by mass of the prepared toners of Examples 1 to 13 and Comparative Examples 1 to 4 and 95% by mass of a ferrite carrier having a volume average particle size of 40 μm were mixed to prepare a two-component developer of toners 1 to 21. .
About each obtained two-component developer, various characteristics were evaluated as follows. The results are shown in Table 3.

〔Evaluation method〕
(Soil dirt long-term running test)
The toner obtained above and 60 μm ferrite carrier were mixed with stirring at a toner concentration of 4% for 20 minutes to obtain a two-component developer. The two-component developer was subjected to a printing durability test for 10,000 sheets at a document density of 5% using a copying machine manufactured by Ricoh Co., Ltd. (Imagio Neo C355) in an environment of a temperature of 35 ° C. and a humidity of 80%. The image density of the formed first and 50,000-th non-image areas was measured by a reflection densitometer manufactured by Macbeth (modified so that three decimal places can be measured). Measure the density difference between the unused paper and the white area of the fixed image. If the density difference is less than 0.01, ◎, 0.01 to less than 0.02, ○, 0.02 to less than 0.03 Was judged as x for cases where Δ was 0.03 or more.

(Hue evaluation)
The developer prepared by the above charging evaluation was adjusted with our full-color copying machine (image Neo Neo C600) so that the amount of adhesion on the high-quality paper for color (type 6000 70W) was 0.4 mg / cm ^2. The sample was fixed at 170 ° C. with an external fixing machine modified so that the fixing temperature of the full color copying machine (Imagio Neo C600) can be freely set. Spectral reflection characteristics of this fixed sample were measured with a spectrophotometer (UV3100, manufactured by Shimadzu Corporation). At this time, the rise of the reflection region of the reflection characteristics, the reflectance and its wavelength, and the difference between absorption and reflection were confirmed, and the hue and saturation were confirmed. Those with good hue and saturation were marked with ◎, those with relatively good quality were marked with ◯, those with a little inferiority were marked with △, and those with bad hue were marked with ×.

(Fixing test)
The two-component developer obtained above was used to produce an unfixed image with an adhesion amount of 4.0 g / m ^{2 using} a copying machine manufactured by Ricoh Co. (Imagio Neo C355), and then a copying machine manufactured by Ricoh Co., Ltd. (Imagio Neo C355) Fixing device (oilless system) modified by using an external fixing machine that can freely set the roller temperature, fixing the paper feed at 120 mm / sec, and increasing the temperature from 100 ° C to 140 ° C in 5 ° C increments changed. At this time, the offset phenomenon in which the image was not fully melted and the image was retransferred to the non-image area was observed on the fixing roller and the paper, and the temperature at which the image was not retransferred was defined as the non-offset temperature. At this time, a non-offset temperature of less than 110 ° C. was marked with ◎, 110 ° C. or more and less than 120 ° C. with ○, 120 ° C. or more and less than 130 ° C. with Δ, and 130 ° C. or more with x.
Table 3 shows the evaluation results.

According to the above evaluation results, since Comparative Example 1 has a low viscosity of the master batch resin R1, the shearing force is low and sufficient pigment dispersibility cannot be obtained. In Comparative Example 2, since the viscosity of the masterbatch resin R1 is too high, the gloss is too low and the hue is poor, and the low-temperature fixability is deteriorated. In Comparative Example 3, since the resin viscosity of the master batch resin R2 is low, the shearing force is also low, and the pigment dispersibility is poor, so that the hue is bad. Also, the soiling in running evaluation is bad. In Comparative Example 4, since the viscosity of the master batch resin R2 is too high, the gloss is too low and the hue is poor, and the low-temperature fixability is deteriorated.
On the other hand, since Examples 1 to 13 were within the scope of the present invention, good results were obtained although there were differences in the degree.
Thus, according to the toner of the present invention, in a full-color electrophotographic toner obtained by suspending and granulating an oil phase comprising at least a binder resin, a colorant and a release agent in an aqueous medium. It has a masterbatch process in which the pigment is dispersed in the binder resin in advance, two or more kinds of resins having different viscosities are used as the masterbatch resin, and at least 90 ° C of the higher viscosity resin R1 of the masterbatch resin. The storage elastic modulus G1 ′ is 8.0 × 10E4 to 5.0 × 10E5, and the storage elastic modulus G2 ′ at 90 ° C. of the lower viscosity resin R2 is 2.0 × 10E4 to 7.0 × 10E4. For example, it can be seen that a full-color toner having good color reproducibility, no abnormal images such as background stains in long-term running, and excellent low-temperature fixability can be obtained.

Japanese Patent Laid-Open No. 7-077783 JP 2008-070466 A JP 2002-156790 A JP 2009-092864 A

Claims (10)

  In a full-color electrophotographic toner obtained by suspending and granulating an oil phase of a toner material containing at least a binder resin and / or its precursor, a colorant and a release agent in an aqueous medium, the colorant comprises: It is a masterbatch that is preliminarily dispersed in a masterbatch resin, and two or more types of resins having different viscosities are used as the masterbatch resin. It is 8.0 × 10E4 to 5.0 × 10E5, and the storage modulus G2 ′ at 90 ° C. of the resin R2 having the lowest viscosity is 2.0 × 10E4 to 7.0 × 10E4 Full color electrophotographic toner.   The full-color electrophotographic toner according to claim 1, wherein a ratio R1 / R2 of the resin R1 having the highest viscosity and the resin R2 having the lowest viscosity is 50/50 to 10/90.   The master batch is obtained by kneading the resin R2 having the lowest viscosity and a colorant, and then kneading the obtained material and the resin R1. Or 2. a toner for full-color electrophotography described in 2;   The full-color electrophotographic toner according to claim 1, wherein the master batch is made of a pigment dispersant.   The full color electrophotographic toner according to claim 4, wherein the melting point of the pigment dispersant is 60 ° C. to 80 ° C.   6. The master batch according to any one of claims 1 to 5, wherein a master batch resin, a release agent, and a press cake pigment after washing with a pigment as a colorant are preliminarily dispersed. The full color electrophotographic toner according to claim 1.   The full-color electron according to any one of claims 1 to 6, wherein the master batch is prepared by previously melting and mixing a binder resin, a release agent, and a colorant in an open-type melt kneader. Toner for photography.   The pigment of the magenta toner is C.I. I. Pigment red 269 and C.I. I. The full-color magenta toner according to any one of claims 1 to 7, wherein a pigment represented by pigment red 122 is used in combination.   The cyan toner pigment is C.I. I. The full-color cyan toner according to claim 1, which is a pigment represented by CI Pigment Blue 15.   The yellow toner pigment is C.I. I. The full-color yellow toner according to claim 1, which is a pigment represented by CI Pigment Yellow 185.