JP2010107555A - Toner for developing electrostatic charge image, developer, image forming method, image forming apparatus and observation method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner for developing electrostatic charge image, having excellent low temperature fixability, having an enough fixing temperature width, favorable offset resistance, and capable of forming an image of high image quality; a developer, an image forming apparatus and an image forming method. <P>SOLUTION: In the toner for developing an electrostatic charge image at least including resin, a coloring agent and WAX, the HFIP (hexafluoro isopropanol) soluble component of the toner shows the following relationship: the molecular weight of 1≤Mw/Mn≤25 and 100,000 or more is 0.01-6.5%, wherein Mn is number average molecular weight, and Mw is weight average molecular weight. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner used as a developer for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, and the like, a developer, an image forming method using the developer, and an image formation. Relates to the device. More specifically, a toner for developing an electrostatic image used for a copying machine, a laser printer, a plain paper fax machine, or the like using a direct or indirect electrophotographic developing system, a developer containing the toner, and an image using the developer. The present invention relates to a forming method, an image forming apparatus, and a process cartridge. Further, the present invention relates to an image forming method, an image forming apparatus, and a process cartridge used for a full-color copying machine, a full-color laser printer, and a full-color plain paper fax machine using a direct or indirect electrophotographic multicolor developing system.

  In the developing process, a developer used in electrophotography, electrostatic recording, electrostatic printing, and the like is once attached to an image carrier such as a photoreceptor on which an electrostatic charge image is formed, and then transferred to a transfer process. After being transferred from the photoconductor to a transfer medium such as transfer paper, the toner is fixed on the paper surface in a fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer not requiring a carrier (magnetic toner, Non-magnetic toners are known.

  Conventionally, as dry toners used for electrophotography, electrostatic recording, electrostatic printing, etc., toner binders such as styrene resins and polyesters are melt-kneaded together with colorants and finely pulverized.

  In order to obtain high-quality and high-quality images, improvements have been made by reducing the particle diameter of the toner. However, the particle shape is indefinite in the production method by the usual kneading and pulverization methods, and classification is performed. Even after passing through the process, the ultrafine particles have a drawback that they have strong adhesive force and remain attached to the toner having the target particle size and cannot be classified. Inside the machine, such ultrafine particles are generated by agitation with the carrier in the developing unit, or when used as a one-component developer, due to contact stress between the developing roller and the toner supply roller, the layer thickness regulating blade, the friction charging blade, etc. Further, a phenomenon occurs in which image quality is deteriorated because it adheres to and adheres to machine parts and a fluidizing agent is embedded in the toner surface. Further, because of its shape, the fluidity as a powder is poor, a large amount of fluidizing agent is required, and the filling rate into the toner bottle is low, which is an obstacle to downsizing. Therefore, the current situation is that the merit of reducing the particle size is not utilized. In addition, the pulverization method has a limit on the particle size and cannot cope with further reduction in particle size.

  Further, in order to stabilize various characteristics such as toner chargeability, a means for sharpening the particle size distribution of the toner is used, but it is sufficient if the average particle size of the toner does not match the specific particle size distribution. The effect is not obtained. That is, it is not sufficient to define the general relationship between the average particle size and the particle size distribution, and there are specific particle size distributions and shapes corresponding to the average particle size of each toner.

  Furthermore, in order to produce a full-color image, the transfer process of a toner image formed from multicolor toner from a photoreceptor to a transfer medium or paper has become complicated, and transfer caused by an irregular shape such as pulverized toner Due to the poor nature, problems such as omission of the transferred image and a large amount of toner consumption have occurred.

  However, the spherical toner cannot be completely removed by a device (for example, a cleaning blade or a cleaning brush) for removing the toner remaining on the photosensitive member or the transfer medium, resulting in poor cleaning. In addition, the toner surface is exposed to the outside in all directions due to its spherical shape, and is easily exposed to contact with a charging member such as a carrier or a charging blade. There is a problem in durability such that the agent is easily embedded in the toner surface and the fluidity of the toner is directly reduced.

  Accordingly, there is an increasing demand for further improving transfer efficiency to reduce toner consumption to obtain a high-quality image with no missing images, or to reduce running costs. If the transfer efficiency is very good, there is no need for a cleaning unit for removing untransferred toner from the photoconductor or transfer medium, and there is an advantage that equipment can be reduced in size and cost and waste toner is eliminated. Because. Various spherical toner manufacturing methods have been devised to compensate for the disadvantages of such irregular shape effects.

  Spherical toner is generally manufactured by a chemical method. Among them, in the toner manufacturing method by suspension polymerization, only a spherical or nearly spherical toner can be manufactured, and irregularly when suspended in water. Due to shearing, ultra fine powder is likely to be generated, and the problems of cleaning properties and adhesion to carriers and machine parts have not been solved. On the other hand, in the toner manufacturing method by emulsion polymerization, it is possible to manufacture from an irregular shaped toner to a spherical shape, but it is necessary to adjust the shape by heating in the post-treatment, and in addition, aggregation in water and ultrafine powder that did not aggregate during association remain. The problem of carrier contamination and sticking to mechanical parts due to such fine particles has not been solved.

As a method for solving these problems, Patent Document 1 (Japanese Patent Laid-Open No. 7-152202) discusses a method involving volume shrinkage called a polymer dissolution suspension method.
In this method, a toner material is dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is emulsified and formed into droplets in an aqueous medium containing a dispersant, and then the volatile solvent is removed. At that time, although the volumetric shrinkage of the droplets occurs, when a solid fine particle dispersant that does not dissolve in an aqueous medium is selected as the dispersant, only amorphous particles can be obtained. When the solid content in the solvent was increased in order to increase productivity, the viscosity of the dispersed phase increased, and the resulting particles had a large particle size and a broad distribution. On the other hand, when the molecular weight of the resin used is reduced to lower the viscosity of the dispersed phase, the fixability (particularly hot offset resistance) must be sacrificed.

  On the other hand, in Patent Document 2 (Japanese Patent Application Laid-Open No. 11-149179), the resin used in the polymer dissolution suspension method has a low molecular weight to reduce the viscosity of the dispersed phase, to facilitate emulsification, and to carry out the polymerization reaction within the particles. To improve the fixability. However, the transferability and cleaning performance were not improved by adjusting the shape of the particles. In addition, since it is sheared irregularly when suspended in water, ultrafine powder is easily generated, and the problem of sticking to carriers and machine parts has not been solved.

  Also, these dry toners are developed and transferred onto paper or the like, and then fixed by heating and melting using a hot roll. At that time, if the temperature of the hot roll is too high, there is a problem that the toner is excessively melted and fused to the hot roll (hot offset). If the temperature of the hot roll is too low, the toner is not sufficiently melted and fixing is insufficient. Problem occurs.

  On the other hand, from the viewpoint of energy saving and downsizing of the apparatus, a toner having a higher hot offset generation temperature (hot offset resistance) and a lower fixing temperature (low temperature fixing property) is required. In addition, heat storage stability is required so that the toner is not blocked during storage and at ambient temperature in the apparatus. In particular, full-color copying machines and full-color printers require glossiness and color mixing of their images, so the toner must have a lower melt viscosity and a sharp-melt polyester toner binder is used. However, since such toner is likely to cause hot offset, conventionally, in a full-color device, silicone oil or the like is applied to a heat roll. However, the method of applying silicone oil to the hot roll requires an oil tank and an oil application device, and the device becomes complicated and large. Moreover, it causes deterioration of the heat roll and requires maintenance every certain period. Furthermore, the adhesion of oil to copy paper, OHP (overhead projector) film, etc. is unavoidable. In particular, OHP has a problem of deterioration of color tone due to the adhered oil.

On the other hand, attempts have been made to control the molecular weight distribution of THF (tetrahydrofuran) solubles or the ratio of insolubles as means for controlling fixability. For example, Patent Document 3 (Japanese Patent No. 3413024), Patent In toners containing a large amount of crosslinking components, such as Document 4 (Japanese Patent No. 3397661) and Patent Document 5 (Japanese Patent Application Laid-Open No. 2002-351143), it is sufficient to control the upper and lower limits of fixing by simply controlling the amount of soluble THF (see FIG. It was not possible to satisfy the hot offset property, the cold offset property, the wrapping property, the friction strength after fixing, the gloss, or the toner stain on paper due to a slight offset, etc. Means for controlling the molecular weight distribution of soluble HFIP (Japanese Patent Laid-Open No. 2005-148719 of Patent Document 6) and the like have been studied, but further low-temperature fixability is required. , Not sufficient in order to obtain a high-quality toner having excellent low-temperature fixability and a wide fixing temperature range.
Hei 7-152202 JP-A-11-149179 Japanese Patent No. 3413024 No. 3397661 JP 2002-351143 A JP 2005-148719 A

  The present invention has been made in view of the above-described state of the art, and has excellent low-temperature fixability, a sufficient fixing temperature range, good offset resistance, and a static image capable of forming a high-quality image. An object is to provide a toner for developing a charge image, a developer, an image forming apparatus, and an image forming method.

The present invention is solved by the following (1) to (14).
(1) A toner for developing an electrostatic charge image, wherein the toner containing at least a resin, a colorant, and WAX exhibits the parameter value, and the HFIP (hexafluoroisopropanol) -soluble component of the toner has the following relationship: . The molecular weight of 1 ≦ Mw / Mn ≦ 25 and 100,000 or more is 0.01% to 6.5%. Here, Mn is a number average molecular weight, Mw is a weight average molecular weight,
(2) The electrostatic charge developing toner according to (1) above, wherein the toner has a glass transition point Tg of 40 to 65 ° C.
(3) The item (1) or the item (2) above, comprising at least a low molecular weight resin for ensuring low-temperature fixability and a high-crosslinking component for maintaining hot offset resistance The toner for developing an electrostatic image according to claim 1,
(4) The toner according to the first aspect, wherein the toner contains particles formed by an extension reaction and / or a crosslinking reaction in which oil droplets of an organic solvent in which a toner composition containing a prepolymer is dissolved are dispersed in an aqueous medium. The electrostatic image developing toner according to any one of (1) to (3),
(5) The electrostatic image developing toner according to any one of (1) to (4), wherein the toner comprises at least a polyester resin,
(6) The electrostatic image developing toner according to any one of (1) to (5), wherein the toner comprises at least a modified polyester resin.
(7) The volume average particle diameter Dv of the toner particles is 2 to 7 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.25 or less. ) To (6), the electrostatic image developing toner according to any one of
(8) The electrostatic image developing toner according to any one of (1) to (7), wherein the toner particles have an average circularity of 0.93 to 0.99.
(9) A two-component developer comprising at least a carrier comprising the toner according to any one of (1) to (8) and magnetic particles,
(10) In the image forming apparatus using toner, the electrostatic image developing toner according to any one of (1) to (8) above, without applying a certain amount of oil on the belt. An image forming apparatus comprising toner fixing means using the two-component developer according to item (9),
(11) The electrostatic image on the electrostatic image bearing member is developed with a developer for developing an electrostatic image to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image bearing member via a transfer material. In the image forming apparatus for electrostatically transferring an image to the transfer material, the developer is a two-component system comprising a carrier made of magnetic particles and the toner according to any one of (1) to (8). An image forming apparatus characterized by being a developer of
(12) The image forming apparatus according to (11), further comprising a process cartridge that integrally supports the latent image carrier and at least the developing unit and is detachable from the main body of the image forming apparatus.
(13) a developing unit, a heating element, and one or more heat transfer media heated by the heating element, and a pressure member that presses the recording medium against one of the heat transfer media, An image forming apparatus having fixing for heating and fixing a toner image on a recording medium, wherein the developing unit uses the toner according to any one of the items (1) to (8), An image forming apparatus including a toner fixing method in which at least one of the heat transfer medium is a belt-like heat transfer medium and used with or without applying a certain amount of oil on the belt;
(14) An image forming method used in the image forming apparatus according to any one of (10) to (13).

  In other words, since the power consumption during fixing accounts for the majority of copiers, environmental considerations are required to lower the temperature required for fixing and reduce the power used. In order to ensure low-temperature fixability, it is necessary to melt at a low temperature. However, if the toner is melted too much, the melted toner moves to the fixing roller side instead of onto the paper at the time of fixing. Therefore, it is also necessary to ensure hot offset resistance with a highly crosslinked component. According to another aspect, the present invention can be said to be for achieving both of these two points.

  The toner for developing an electrostatic charge image of the present invention is suitable for a low-temperature fixing system, but can provide a toner having a wide fixing upper limit temperature, a wide fixing temperature range, and a high-quality image. It becomes possible.

  Hereinafter, the present invention will be described in detail. Here, as for the toner, the manufacturing method and material of the developer used in the present invention, and the overall system relating to the electrophotographic process, known ones can be used if the conditions are satisfied.

(HFIP dissolved GPC)
In the present invention, the molecular weight distribution of the toner was measured by GPC (gel permeation chromatography) under the following conditions.
<Measurement conditions of HFIP dissolution GPC of toner>
1) Apparatus: HLC-3220 manufactured by Tosoh Corporation
2) Solvent; HFIP + 5 mM sodium trifluoroacetate 3) Column; TSK guardcolumn H _HR -H (S) 1 + TSKgel GMH _HR -M 3 4) Temperature: 40 ° C.
5) Flow rate: 0.2 ml / min
6) Sample: Measurement after filtration in a 0.45 μm filter after dissolution in a solvent. Concentration 0.15%, injection volume 10 μl
7) Detector; Detector (RI)

The molecular weight distribution is calculated using the molecular weight calibration curve prepared with the monodisperse polymethylmethacrylate standard sample when the molecular weight of the sample is calculated under the above conditions. In addition, it is more preferable to contain 5-20 mM sodium trifluoroacetate as a salt in the solvent in order to improve the dissolution / separation property. If it is less than 5 mM, the effect is not exhibited, which is not preferable. Moreover, when it contains exceeding 20 mM, it is unpreferable at a column damage or a soluble point.
The molecular weight distribution obtained here is such that the molecular weight component of 1 ≦ Mw / Mn ≦ 25 and 100,000 or more is 0.01% to 6.5% (Mn is the number average molecular weight and Mw is the weight average molecular weight). It is preferable for obtaining an upper limit, hot offset property and high image quality.

  As described above, Japanese Patent Application Laid-Open No. 2005-148719 of Patent Document 6 discloses controlling the molecular weight distribution of HFIP (hexafluoroisopropanol) soluble matter. Although there is no direct relationship with the present invention, the amount of “HFIP-insoluble component” is also mentioned at this time. However, although the resin solubility of HFIP is relatively high, it still has a very high molecular weight. In the molecular material, an HFIP insoluble component exists (a molecular weight of 10000000 or more is difficult to dissolve. Also, as shown in Comparative Example 3 described later, a styrene-acrylic resin does not dissolve in HFIP. In the case of the polyester resin mentioned as an example of such a resin, HFIP has a gel-like component remaining when the solvent is volatilized, so it is very difficult to measure the weight of the accurate insoluble component of the toner. However, according to the assumptions based on the experiences of the inventors, it is estimated that it is about 20% at most.) In the present invention, regarding the HFIP-dissolved component, not the HFIP-insoluble component, (a) the value of Mw / Mn is 1 to 25, and (b) the molecular weight of 100,000 or more is 0.01% to 6 .5% "is an indispensable requirement. However, conventionally, there is no one that satisfies both the requirement (a) and the requirement (b) at the same time.

(Volume average particle diameter _{D v, D v / D n} ( volume average particle diameter / number average particle diameter ratio of))
The volume average particle diameter (D _v ) and number average particle diameter (D _n ) of the toner and the ratio (D ₄ / D _n ) were measured using a Coulter Multisizer II. The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably polyoxyethylene alkyl ether (nonionic surfactant)) is added as a dispersant to 100 to 150 ml of an electrolytic aqueous solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the volume average particle diameter (D _v ) and the number average particle diameter of the toner can be obtained. As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 .35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to less than 12.70 μm; 12.70 to less than 16.00 μm; 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

(Average circularity)
The average circularity can be measured using a flow type particle image analyzer FPIA-2100 manufactured by Sysmex Corporation. The measurement was adjusted to a 1% NaCl aqueous solution using primary sodium chloride and then passed through a 0.45 μm filter to 50 to 100 ml of a surfactant, preferably 0.1 to 5 ml of an alkylbenzene sulfonate as a dispersant. In addition, add 1-10 mg of sample. This is subjected to a dispersion process for 1 minute with an ultrasonic disperser and measured. For the measurement of the number of particles, a two-dimensional image area captured by a CCD camera and a diameter of a circle having the same area are calculated as an equivalent circle diameter. From the accuracy of the CCD pixel, a circle equivalent diameter of 0.6 μm or more is effective and particle measurement data is obtained.

(Glass transition point; Tg)
The glass transition point (Tg) was measured using a TG-DSC system TAS-100 manufactured by Rigaku Corporation. First, about 10 mg of a sample is placed in an aluminum sample container, which is placed on a holder unit and set in an electric furnace. Next, after heating from room temperature to 150 ° C. at a heating rate of 10 ° C./min, the sample is allowed to stand at 150 ° C. for 10 minutes, and then the sample is cooled to room temperature and left for 10 minutes. Further, the DSC measurement is performed by heating again to 150 ° C. at a heating rate of 10 ° C./min under a nitrogen atmosphere. Tg is calculated from the contact point between the tangent line and the base line of the endothermic curve near Tg, using the analysis system in the TAS-100 system.

  (A) Mw / Mn value of the HFIP-dissolved component in the present invention is 1 to 25, and (b) that satisfies both “100,000 or more molecular weight of 0.01% to 6.5%” simultaneously In order to achieve low temperature fixing, a low molecular weight substance and a high molecular weight substance are mixed to increase the amount of the low molecular weight substance. Etc.) to adjust the molecular weight. In adjusting the molecular weight, for example, a modified polyester resin can be preferably used.

The molecular weight component in the present invention is area%.
FIG. 4 is a graph showing the molecular weight distribution of a specific toner of the present invention described later. The horizontal axis indicates the logarithm of molecular weight M (−), and the vertical axis indicates the area (%). The molecular weight component of 0.01 to 6.5% indicates that the area of 100,000 or more corresponds to 0.01 to 6.5% of the total area in the figure.

(Modified polyester resin)
In the present invention, the following modified polyester resins can be used as the polyester resin. For example, a polyester prepolymer having an isocyanate group can be used. Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

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

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

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactams, etc. And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as the equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. When the number is less than 1 per molecule, the molecular weight of the modified polyester after crosslinking and / or elongation becomes low, and the hot offset resistance deteriorates.

(Crosslinking agent and extender)
In the present invention, amines can be used as a crosslinking agent and / or an extender. As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the block (B6) obtained by blocking the amino group of B1 to B5 include ketimine compounds and oxazoline compounds obtained from the amines of B1 to B5 and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the modified polyester after completion of the reaction can be adjusted by using a terminator for crosslinking and / or elongation. Examples of the terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. If [NCO] / [NHx] is greater than 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low and the hot offset resistance deteriorates.

(Unmodified polyester)
In the present invention, it is important not only to use the modified polyester (A) alone, but also to contain the unmodified polyester (C) as a toner binder component together with the (A). By using (C) in combination, the low-temperature fixability and the glossiness when used in a full-color apparatus are improved. Examples of (C) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (A), and preferred ones are also the same as (A). (C) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with, for example, a urethane bond. It is preferable that (A) and (C) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (A) and (C) preferably have similar compositions. When (A) is contained, the weight ratio of (A) to (C) is usually 5/95 to 75/25, preferably 10/90 to 25/75, more preferably 12/88 to 25/75, Especially preferably, it is 12 / 88-22 / 78. If the weight ratio of (A) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (C) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (C) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (C) is usually from 0.5 to 40, preferably from 5 to 35. By having an acid value, it tends to be negatively charged. Further, those having an acid value and a hydroxyl value exceeding these ranges are easily affected by the environment under high temperature and high humidity and low temperature and low humidity, and are liable to cause image deterioration.

In the present invention, the glass transition point (Tg) of the toner is 40 to 65 ° C. If it is less than 40 ° C., the heat-resistant storage stability of the toner deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the crosslinked and / or elongated polyester resin, the toner for developing an electrostatic charge image of the present invention exhibits good storage stability even when the glass transition point is low as compared with known polyester-based toners. As the storage elastic modulus of the toner, the temperature (TG ′) at which the measurement frequency is 20 Hz is 10000 dyne / cm ² is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the toner, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, from the viewpoint of achieving both low temperature fixability and hot offset resistance, TG ′ is preferably higher than Tη. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

(Coloring agent)
As the colorant of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), Permanent Yellow (NCG), Vulcan Fast Yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red , Fais red, parachlorol Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine B, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazolone , Polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, in Dunslen Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Lake Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used. The content of the colorant is usually 1 to 15% by weight, preferably 3 to 10% by weight, based on the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin. The binder resin to be kneaded together with the production of the master batch or the master batch includes polymers of styrene and substituted products thereof such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene, etc. in addition to the modified and unmodified polyester resins mentioned above. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α -Chloromethyl methacrylate copolymer, Tylene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-malein Styrene copolymers such as acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, poly Acrylic resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like can be mentioned, and these can be used alone or in combination.
This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet cake of a coloring agent, is a method of mixing and kneading an aqueous paste containing water of a coloring agent together with a resin and an organic solvent, transferring the coloring agent to the resin side, and removing moisture and organic solvent components. Can be used as it is, so that it is not necessary to dry and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

(Release agent)
Further, a wax may be contained together with the toner binder and the colorant. Known waxes can be used as the wax of the present invention. Examples include polyolefin waxes (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sasol wax, etc.); carbonyl group-containing waxes, etc. It is done. Of these, carbonyl group-containing waxes are preferred. Examples of the carbonyl group-containing wax include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. Polyoctanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenylamide, etc.); polyalkylamides (trimellitic acid tristearylamide, etc.) And dialkyl ketones (such as distearyl ketone). Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of the wax of the present invention is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinacridone Azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the toner production method including the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method, and is uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent, or fixed on the toner surface after preparation of toner particles. May be.

(External additive)
As an external additive for assisting fluidity, developability and chargeability of the colored particles obtained in the present invention, in addition to oxide fine particles, inorganic fine particles and hydrophobized inorganic fine particles are used in combination as external additives. It is more desirable that the primary particles subjected to the hydrophobization treatment contain at least one kind of inorganic fine particles having an average particle diameter of 1 to 100 nm, more preferably 5 nm to 70 nm. Further, it is more preferable that the hydrophobized primary particles contain at least one kind of inorganic fine particles having an average particle diameter of 20 nm or less and at least one kind of inorganic fine particles of 30 nm or more. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g.

  Any of them can be used as long as the conditions are satisfied. For example, silica fine particles, hydrophobic silica, fatty acid metal salts (such as zinc stearate and aluminum stearate), metal oxides (such as titania, alumina, tin oxide, and antimony oxide), fluoropolymers, and the like may be contained.

  Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H 1303 (above Hoechst), and R972, R974, RX200, RY200, R202, R805, and R812 (above Nippon Aerosil). Further, as titania fine particles, P-25 (Nippon Aerosil), STT-30, STT-65C-S (above Titanium Industry), TAF-140 (Fuji Titanium Industry), MT-150W, MT-500B, MT-600B MT-150A (taker). Particularly, the hydrophobized titanium oxide fine particles include T-805 (Nippon Aerosil), STT-30A, STT-65S-S (above Titanium Industry), TAF-500T, TAF-1500T (above Fuji Titanium Industry), MT -100S, MT-100T (above Taka), IT-S (Ishihara Sangyo), etc. In order to obtain hydrophobized oxide fine particles, silica fine particles, titania fine particles, and alumina fine particles, hydrophilic fine particles are treated with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. In addition, silicone oil-treated oxide fine particles and inorganic fine particles obtained by treating silicone oil with heat if necessary to treat it with inorganic fine particles are also suitable.

(Resin fine particles)
In the present invention, resin fine particles can be contained as required. The resin fine particles used have a glass transition point (Tg) of 40 to 100 ° C., a weight average molecular weight of 9000 to 200,000 is more preferable, and as described above, the glass transition point (Tg) is less than 40 ° C., and When the weight average molecular weight is less than 9,000, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the glass transition point (Tg) is 100 ° C. or higher and / or the weight average molecular weight is 200,000 or higher, the resin fine particles inhibit the adhesiveness to the fixing paper, and the minimum fixing temperature increases. More preferably, the residual ratio with respect to the toner particles is 0.5 to 5.0 wt%. When the residual ratio is less than 0.5 wt%, the storage stability of the toner is deteriorated, and blocking occurs during storage and in the developing machine. When the residual amount is 5.0 wt% or more, the resin fine particles are not present. The exudation of the wax is obstructed, the effect of releasing the wax is not obtained, and the occurrence of offset is observed. The residual rate of the resin fine particles can be measured by analyzing a substance caused by the resin fine particles, not by the toner particles, using a pyrolysis gas chromatograph mass spectrometer, and calculating from the peak area. The detector is preferably a mass spectrometer, but is not particularly limited. The resin fine particles may be any resin as long as it can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, polyamide resins, polyimides Examples thereof include resins, silicon-based resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

(Production method)
The toner binder can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off while reducing the pressure as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.

  The dry toner of the present invention can be produced by the following method, but is not limited thereto.

(Toner production method in aqueous medium)
The aqueous phase used in the present invention is used by adding resin fine particles in advance. The water used for the aqueous phase may be water alone, or a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohols (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like. Toner particles are obtained by reacting a dispersion made of a polyester prepolymer (A) having an isocyanate group dissolved or dispersed in an organic solvent in an aqueous phase with amines (B). As a method for stably forming a dispersion comprising a polyester prepolymer (A) in an aqueous phase, a composition of a toner raw material comprising a polyester prepolymer (A) dissolved or dispersed in an organic solvent in an aqueous phase is added. And a method of dispersing by shearing force. Polyester prepolymer (A) dissolved or dispersed in an organic solvent and other toner composition (hereinafter referred to as toner raw material), colorant masterbatch, release agent, charge control agent, unmodified The polyester resin or the like may be mixed when forming the dispersion in the aqueous phase, but after the toner raw material is mixed in advance and dissolved or dispersed in an organic solvent, the mixture is added to the aqueous phase and dispersed. Is more preferable. In the present invention, other toner raw materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in the aqueous phase. After the particles are formed, It may be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear type, a high-speed shear type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion of the polyester prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous phase used is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight, based on 100 parts of the toner composition containing the polyester prepolymer (A). If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor, and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters, alkylamine salts, amino acids as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in the aqueous phase Alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, quaternary ammonium such as alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, benzethonium chloride Nonionic surfactants such as salt-type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N- Dimethyl Amphoteric surfactants such as Nmo betaine and the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Examples of the anionic surfactant having a fluoroalkyl group preferably used include fluoroalkylcarboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6- C11) sodium oxy] -1-alkyl (C3-C4) sulfonate, sodium 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonate, fluoroalkyl (C11-C20) Carboxylic acid and metal salt, perfluoroalkyl carboxylic acid (C7 to C13) and metal salt thereof, perfluoroalkyl (C4 to C12) sulfonic acid and metal salt thereof, perfluorooctane sulfonic acid diethanolamide, N-propyl-N -(2 hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F150 (manufactured by Neos).

  In addition, as the cationic surfactant, an aliphatic quaternary ammonium salt such as an aliphatic primary, secondary or secondary amic acid, perfluoroalkyl (C 6 -C 10) sulfonamidopropyltrimethylammonium salt that has a right fluoroalkyl group, Benzalkonium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) ), MegaFuck F-150, F-824 (Dainippon Ink Co., Ltd.), Xtop EF-132 (Tochem Products Co., Ltd.), Footgent F-300 (Neos Co., Ltd.) and the like.

  Further, tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can be used as an inorganic compound dispersant which is hardly soluble in water.

  Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N- Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as acetic acid Pinyl, pinyl propionate, vinyl butyrate, etc., acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, nitrogen such as pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine Homopolymers or copolymers such as those having atoms or heterocycles thereof, polyoxyethylene, polyoxypropylene, polyoxyethylene Alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester, etc. Celluloses such as polyoxyethylene, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and the like can be used.

  In addition, when an acid such as calcium phosphate salt or an alkali-soluble material is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by an operation such as degradation with an enzyme.

  When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

The elongation and / or crosslinking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate. In order to remove the organic solvent from the obtained emulsified dispersion, a method can be employed in which the temperature of the entire system is gradually raised and the organic solvent in the droplets is completely evaporated and removed. Alternatively, it is also possible to spray the emulsified dispersion in a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and to evaporate and remove the aqueous dispersant together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient quality can be obtained with a short time treatment such as spray dryer, belt dryer, rotary kiln.
Further, as a method for removing the organic solvent, air can be blown away by a rotary evaporator or the like. Thereafter, rough separation is performed by centrifugal separation, the emulsified dispersion is washed in a washing tank, and the drying process is repeated in a hot air dryer, and the solvent is removed and dried to obtain a toner base. Thereafter, a ripening step is further performed, so that the hollow state inside the toner can be controlled, which is more preferable. It is preferably 30 to 55 ° C. (more preferably 40 to 50 ° C.), and more preferably aging for 5 to 36 hours (more preferably 10 to 24 hours).

When the particle size distribution at the time of emulsification dispersion is wide, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying, but it is preferable in the liquid to perform the classification operation. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
The dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
Mixing or giving mechanical impact force to the powder mixture after drying with different types of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles By immobilizing and fusing on the surface, it is possible to prevent detachment of foreign particles from the surface of the resulting composite particle.

Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) is modified to reduce the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.
Finally, an external additive such as inorganic fine particles and a toner are mixed with a Henschel mixer or the like, and coarse particles are removed with an ultrasonic sieve or the like to obtain a final toner.

(Carrier for two components)
When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier, and the content ratio of the carrier and the toner in the developer is 1 to 10 wt. Part is preferred. As the magnetic carrier, conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 to 200 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoro Propylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride And fluoro such as terpolymers of non-fluoride monomers including, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter is larger than 1 μm, it becomes difficult to control electric resistance.
The toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.

(Intermediate transfer member)
In the present invention, an intermediate transfer member can also be used. One embodiment of the intermediate transfer member of the transfer system will be described. FIG. 1 is a schematic configuration diagram of a copying machine according to the present embodiment. Around a photosensitive drum (hereinafter referred to as a photosensitive member) 10 as an image carrier, a charging roller 20 as a charging device, an exposure device 30, a cleaning device 60 having a cleaning blade, a static elimination lamp 70 as a static elimination device, and development. An apparatus 40 and an intermediate transfer member 50 as an intermediate transfer member are provided. The intermediate transfer member 50 is suspended by a plurality of suspension rollers 51 and is configured to run endlessly in the direction of the arrow by a driving unit such as a motor (not shown). A part of the suspension roller 51 also serves as a transfer bias roller for supplying a transfer bias to the intermediate transfer member, and a predetermined transfer bias voltage is applied from a power source (not shown). A cleaning device 90 having a cleaning blade for the intermediate transfer member 50 is also provided. Further, a transfer roller 80 is provided as a transfer means for transferring the developed image onto the transfer paper 100 as the final transfer material, facing the intermediate transfer member 50, and the transfer roller 80 is transferred by a power supply device (not shown). Supplied. Around the intermediate transfer member 50, a corona charger 52 as a charge applying unit is provided.

  The developing device 40 includes a developing belt 41 as a developer carrier, a black (hereinafter referred to as “Bk”) developing unit 45K, a yellow (hereinafter referred to as “Y”) developing unit 45Y, The developing unit 45M is hereinafter referred to as magenta and the cyan (hereinafter referred to as C) developing unit 45C. Further, the developing belt 41 is stretched between a plurality of belt rollers, and is configured to run endlessly in a direction indicated by an arrow by a driving unit such as a motor (not shown). Moves at approximately the same speed as 10.

  Since the configuration of each developing unit is common, the following description will be given only for the Bk developing unit 50Bk, and for the other developing units 50Y, 50M, and 50C, the portions corresponding to those in the Bk developing unit 50Bk in the figure are as follows. Y, M, and C are appended to the numbers given to those in the unit, and the description is omitted. The developing unit 50Bk is disposed so that a developing tank 42Bk containing a high-viscosity, high-concentration liquid developer containing toner particles and a carrier liquid component, and a lower part is immersed in the liquid developer in the developing tank 42Bk. And a coating roller 44Bk that thins the developer pumped from the pumping roller 43Bk and applies it to the developing belt 41. The application roller 44Bk has conductivity, and a predetermined bias is applied from a power source (not shown).

  In addition to the apparatus configuration as shown in FIG. 1, the apparatus configuration of the copying machine according to the present embodiment is an apparatus configuration in which development units 45 for each color are provided around the photoconductor 10 as shown in FIG. It may be.

  Next, the operation of the copying machine according to the present embodiment will be described. In FIG. 1, the photosensitive member 10 is uniformly charged by the charging roller 20 while being driven to rotate in the direction of the arrow, and then the reflected light from the original is imaged and projected by an optical system (not shown) by the exposure device 30 on the photosensitive member 10. An electrostatic latent image is formed on the surface. This electrostatic latent image is developed by the developing device 40 to form a toner image as a visible image. The developer thin layer on the developing belt 41 is peeled off from the belt 41 in a thin layer state by contact with the photosensitive member in the developing region, and moves to a portion where a latent image is formed on the photosensitive member 10. The toner image developed by the developing device 40 is transferred to the surface of the intermediate transfer member 50 at the contact portion (primary transfer region) between the photosensitive member 10 and the intermediate transfer member 50 moving at a constant speed (primary transfer). Transcription). When transferring three or four colors to be superimposed, this process is repeated for each color to form a color image on the intermediate transfer member 50.

  The corona charger 52 for applying an electric charge to the superimposed toner image on the intermediate transfer member is provided at a contact facing portion between the photosensitive member 10 and the intermediate transfer member 50 in the rotation direction of the intermediate transfer member 50. It is installed on the downstream side and on the upstream side of the contact facing portion between the intermediate transfer member 50 and the transfer paper 100. The corona charger 52 gives the toner image a true charge having the same polarity as the charge polarity of the toner particles forming the toner image, and is sufficient for good transfer to the transfer paper 100. Charge is applied to the toner image. The toner image is charged by the corona charger 52, and then transferred to the transfer paper 100 conveyed in the direction of the arrow from a paper supply unit (not shown) by a transfer bias from the transfer roller 80 (two). Next transfer). Thereafter, the transfer paper 100 onto which the toner image has been transferred is separated from the photoconductor 10 by a separation device (not shown), and after a fixing process is performed by a fixing device (not shown), the transfer paper 100 is discharged from the device. On the other hand, after the transfer, the untransferred toner is collected and removed by the cleaning device 60, and the residual charge is discharged by the discharging lamp 70 in preparation for the next charging.

As described above, the static friction coefficient of the intermediate transfer member is preferably 0.1 to 0.6, and more preferably 0.3 to 0.5. The volume resistance of the intermediate transfer member is preferably from several Ωcm to 10 ³ Ωcm. By setting the volume resistance to several Ωcm or more and 10 ³ Ωcm or less, the intermediate transfer member itself is prevented from being charged, and the charge imparted by the charge imparting means hardly remains on the intermediate transfer member. Transfer unevenness can be prevented. Further, it is possible to easily apply a transfer bias at the time of secondary transfer.

  The material of the intermediate transfer member is not particularly limited, and all known materials can be used. An example is shown below. (1) A material having a high Young's modulus (tensile modulus) is used as a single-layer belt. PC (polycarbonate), PVDF (polyvinylidene fluoride), PAT (polyalkylene terephthalate), PC (polycarbonate) / PAT ( Polyalkylene terephthalate) blend materials, ETFE (ethylene tetrafluoroethylene copolymer) / PC, ETFE / PAT, PC / PAT blend materials, carbon black dispersed thermosetting polyimide, and the like. These single-layer belts having a high Young's modulus have the advantage that the amount of deformation with respect to stress during image formation is small, and registration is not likely to occur particularly during color image formation. (2) A belt having a two- or three-layer structure in which a belt having a high Young's modulus is used as a base layer and a surface layer or an intermediate layer is provided on the outer periphery thereof. Therefore, the line image has a performance capable of preventing the line image from being lost. (3) Belts having a relatively low Young's modulus using rubber and elastomer, and these belts have an advantage that line images are hardly lost due to their softness. In addition, the width of the belt is made larger than that of the drive roll and the tension roll, and the elasticity of the belt ear protruding from the roll is used to prevent meandering, so that a low cost can be realized without the need for ribs or meandering prevention devices. .

  Conventionally, a fluorine-based resin, a polycarbonate resin, a polyimide resin, or the like has been used for the intermediate transfer belt, but in recent years, an elastic belt in which the entire belt layer or a part of the belt is used as an elastic member has been used. The transfer of a color image using a resin belt has the following problems. A color image is usually formed with four colored toners. On one color image, toner layers of 1 to 4 layers are formed. The toner layer receives pressure by passing through the primary transfer (transfer from the photoreceptor to the intermediate transfer belt) and the secondary transfer (transfer from the intermediate transfer belt to the sheet), and the cohesive force between the toners increases. When the cohesive force between the toners increases, the phenomenon of missing characters in the characters and missing edges in the solid portion image tends to occur. Since the resin belt has a high hardness and does not deform according to the toner layer, the toner layer is easily compressed, and the character dropout phenomenon is likely to occur. Recently, there is an increasing demand for forming full-color images on various papers, for example, Japanese paper, intentionally irregularities, and forming images on paper. However, a paper with poor smoothness is liable to generate toner and voids at the time of transfer, and transfer loss is likely to occur. When the transfer pressure at the secondary transfer portion is increased to improve the adhesion, the condensing power of the toner layer is increased, and the above-described character void is generated. The elastic belt is used for the following purposes. The elastic belt is deformed corresponding to the toner layer and the paper having poor smoothness at the transfer portion. In other words, since the elastic belt deforms following local irregularities, the paper does not have excessive flatness and has good adhesion without excessively increasing the transfer pressure on the toner layer. In contrast, a transfer image with excellent uniformity can be obtained.

  The elastic belt resin is polycarbonate, fluorine resin (ETFE, PVDF), polystyrene, chloropolystyrene, poly-α-methylstyrene, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer. Polymer, styrene-maleic acid copolymer, styrene-acrylic acid ester copolymer (styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-acrylic acid Octyl copolymer and styrene-phenyl acrylate copolymer), styrene-methacrylic acid ester copolymer (styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer) Coalesce etc.), styrene-α-chloroacryl Styrenic resin (monopolymer or copolymer containing styrene or styrene-substituted product), methyl methacrylate resin, butyl methacrylate resin, acrylic resin, such as methyl phosphate copolymer, styrene-acrylonitrile-acrylic acid ester copolymer Ethyl acid resin, butyl acrylate resin, modified acrylic resin (silicone modified acrylic resin, vinyl chloride resin modified acrylic resin, acrylic / urethane resin, etc.), vinyl chloride resin, styrene-vinyl acetate copolymer, vinyl chloride-vinyl acetate Polymer, rosin-modified maleic resin, phenol resin, epoxy resin, polyester resin, polyester polyurethane resin, polyethylene, polypropylene, polybutadiene, polyvinylidene chloride, ionomer resin, polyurethane resin, silicone resin, ketone resin, Len - ethyl acrylate copolymer, may be used xylene resin and polyvinyl butyral resin, polyamide resin, one kind or two kinds or more selected from the group consisting of modified polyphenylene oxide resin. However, it is natural that the material is not limited to the above materials.

  Elastic rubbers and elastomers include butyl rubber, fluorine rubber, acrylic rubber, EPDM, NBR, acrylonitrile-butadiene-styrene rubber natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene ter Polymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, hydrogenated nitrile Selected from the group consisting of rubber, thermoplastic elastomers (eg polystyrene, polyolefin, polyvinyl chloride, polyurethane, polyamide, polyurea, polyester, fluororesin) It is possible to use one kind or two or more kinds that. However, it is natural that the material is not limited to the above materials.

  There are no particular restrictions on the conductive agent for adjusting the resistance value. For example, carbon black, graphite, metal powder such as aluminum and nickel, tin oxide, titanium oxide, antimony oxide, indium oxide, potassium titanate, antimony oxide-tin oxide composite Conductive metal oxides such as oxides (ATO) and indium oxide-tin oxide composite oxides (ITO), and conductive metal oxides are coated with insulating fine particles such as barium sulfate, magnesium silicate and calcium carbonate But you can. Of course, the conductive agent is not limited thereto.

  The surface layer material and the surface layer are required to prevent contamination of the photoconductor by the elastic material, reduce the surface friction resistance to the transfer belt surface, reduce the adhesion of the toner, and improve the cleaning property and the secondary transfer property. . For example, materials that use one or more of polyurethane, polyester, epoxy resin, etc. to reduce surface energy and increase lubricity, such as powders of fluororesins, fluorine compounds, fluorocarbons, titanium dioxide, silicon carbide, etc. Can be used by dispersing one or more kinds of particles, particles or particles having different particle sizes, and by forming a fluorine-rich layer on the surface by heat treatment like a fluorine-based rubber material, the surface energy can be increased. It is also possible to use a smaller one.

  The method for manufacturing the belt is not limited. Centrifugal molding method in which material is poured into a rotating cylindrical mold to form a belt, spray coating method in which liquid paint is sprayed to form a film, dipping method in which a cylindrical mold is dipped in a solution of the material, and inner mold There is a casting method to be injected into the outer mold, a method in which a compound is wound around a cylindrical mold and vulcanization polishing is performed, but the invention is not limited to this, and a belt can be manufactured by combining a plurality of manufacturing methods. It is common.

As a method for preventing elongation as an elastic belt, there are a method of forming a rubber layer in a core resin layer with little elongation, a method of putting a material for preventing elongation into the core layer, and the like, but it is not particularly related to the production method.
Examples of materials constituting the core layer for preventing elongation include natural fibers such as cotton and silk, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, and polyurethanes. 1 or 2 types selected from the group consisting of fibers, polyacetal fibers, polyfluoroethylene fibers, phenol fibers and other synthetic fibers, carbon fibers, glass fibers, boron fibers and other inorganic fibers, iron fibers, copper fibers and other metal fibers By using the above, a woven fabric or a yarn can be obtained. Of course, the material is not limited to the above.
The yarn may be twisted in any manner, such as one or a plurality of filaments twisted, a single twisted yarn, various twisted yarns, a double yarn or the like. Further, for example, fibers of a material selected from the above material group may be blended. Of course, the yarn can be used after being subjected to an appropriate conductive treatment.
On the other hand, the woven fabric can be any woven fabric such as knitted fabric, and of course, a woven fabric that is interwoven can also be used, and naturally conductive treatment can be applied. The production method for providing the core layer is not particularly limited, for example, a method of providing a woven fabric woven in a cylindrical shape on a mold and the like, and providing a coating layer thereon, the woven fabric woven in a cylindrical shape is a liquid rubber And a method of providing a coating layer on one side or both sides of the core layer, and a method of winding a thread spirally around a mold at an arbitrary pitch and providing a coating layer thereon. The thickness of the elastic layer depends on the hardness of the elastic layer, but if it is too thick, the surface expands and contracts and cracks are likely to occur in the surface layer. In addition, it is not preferable that the thickness is too large (approximately 1 mm or more) because the amount of expansion and contraction becomes large and the spread of the image increases.

(Belt fixing system)
An example of the fixing device used in the image forming method of the present invention is shown in FIG. In FIG. 7, 2 is a fixing roller in which a metal (aluminum, iron, etc.) metal core is covered with an elastic body (silicon rubber, etc.), and 1 is a metallic (pipe made of aluminum, iron, copper, stainless steel, etc.) hollow cylinder It is a heating roller made of a cored bar and having a heating source 5 inside. Reference numeral 7 denotes a temperature sensor for measuring the surface temperature of the fixing belt 3 in contact with the heating roller 1 portion. A fixing belt 3 is stretched between the fixing roller 2 and the heating roller 1. The fixing belt 3 has a small heat capacity, and on a base (thickness of about 30 to 150 μm such as nickel or polyimide), a release layer (50 to 300 μm thick with silicon rubber, or 10 to 50 μm with fluorine resin). About a certain thickness, etc.). Reference numeral 4 denotes a pressure roller in which an elastic body is coated on a metal core, and the nip between the fixing belt 3 and the pressure roller 4 is pressed by pressing the fixing roller 2 from below through the fixing belt 3. Forming part. Moreover, the dimension of each member is set by various conditions required. These are only examples, and for example, it is possible to provide a heat source inside the fixing roller 2 or the pressure roller 4. In the present invention, a fixing device using a fixing belt in a configuration other than this example is also applied. Is done.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
Hereinafter, a part shows a weight part.

(Evaluation of two-component developer)
When evaluating an image with a two-component developer, a ferrite carrier having an average particle diameter of 35 μm coated with a silicone resin at an average thickness of 0.5 μm is used as follows, and toner 7 of each color is used with respect to 100 parts by weight of the carrier. A developer was prepared by uniformly mixing and charging parts by weight using a tumbler mixer of the type in which the container was rolled and stirred.

(Carrier production)
・ Core Mn ferrite particles (weight average diameter: 35 μm) 5000 parts ・ Coating material Toluene 450 parts ・ Silicone resin SR2400
(Toray Dow Corning Silicone, 50% non-volatile content) 450 parts Aminosilane SH6020
(Toray / Dow Corning / Silicone) 10 parts Carbon black 10 parts

  The coating material is dispersed with a stirrer for 10 minutes to prepare a coating solution, and the coating solution and the core material are coated in a fluidized bed while forming a swirling flow with a rotating bottom plate disk and stirring blades. The coating solution was applied on the core material. The obtained coated material was baked in an electric furnace at 250 ° C. for 2 hours to obtain the carrier.

<Example 1>
Synthesis of low molecular weight polyester In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 229 parts of ethylene glycol, 529 parts of adduct of bisphenol A propion oxide 3 mol, 104 parts of isophthalic acid + 104 parts of terephthalic acid, adipine 46 parts of acid and 2 parts of tin octylate were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize an unmodified polyester resin. . The obtained unmodified polyester resin had a number average molecular weight of 2,100, a weight average molecular weight of 6,400, a glass transition temperature of 41 ° C., and an acid value of 25 mgKOH / g.

Synthesis of masterbatch 1200 parts of water, 540 parts of carbon black Printex 35 (manufactured by Dexa; DBP oil absorption = 42 ml / 100 mg, pH = 9.5) and 1200 parts of unmodified polyester resin, Henschel mixer (manufactured by Mitsui Mining) And mixed. The resulting mixture was kneaded at 150 ° C. for 30 minutes using two rolls, then rolled and cooled, and pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare a master batch.

-Preparation of oil phase 378 parts of unmodified polyester resin, 110 parts of carnauba wax and 947 parts of ethyl acetate were charged into a reaction vessel equipped with a stir bar and a thermometer, and the temperature was raised to 80 ° C with stirring. After holding for 5 hours, it was cooled to 30 ° C. over 1 hour. Next, 500 parts of a master batch and 500 parts of ethyl acetate were charged into the reaction vessel and mixed for 1 hour to obtain a raw material solution. 1324 parts of the obtained raw material solution was transferred to a reaction vessel, and filled with 80% by volume of 0.5 mm zirconia beads using a bead mill Ultra Visco Mill (manufactured by Imex Co., Ltd.). Carnauba wax was dispersed by three passes under the condition of a speed of 6 m / sec to obtain a wax dispersion.

-Preparation of Toner Material Dispersion Next, 1324 parts of a 65 mass% ethyl acetate solution of an unmodified polyester resin was added to the wax dispersion. A layered inorganic mineral montmorillonite (Clayton APA Southern Clay modified at least partly with a quaternary ammonium salt having a benzyl group) was added to 200 parts of a dispersion obtained by one pass using Ultraviscomyl under the same conditions as above. 3 parts) (manufactured by Products) are added. K. The mixture was stirred for 30 minutes using a homodisper (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a toner material dispersion.

Synthesis of intermediate polyester In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 682 parts of bisphenol A ethylene oxide 2 mol adduct, 81 parts of bisphenol A propylene oxide 2 mol adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were charged and reacted at 230 ° C. for 8 hours under normal pressure. Next, it was made to react under reduced pressure of 10-15mHg for 5 hours, and the intermediate polyester resin was synthesize | combined. The obtained intermediate polyester resin had a number average molecular weight of 2100, a mass average molecular weight of 9,500, a glass transition temperature of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g.
Next, 410 parts of the intermediate polyester resin, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are charged into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Was synthesized. The free isocyanate content of the obtained prepolymer was 1.53% by mass.

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

・ Synthesis of organic fine particle dispersion In a reaction vessel equipped with a stir bar and a thermometer, 683 parts of water, reactive emulsifier (sodium salt of methacrylic acid ethylene oxide adduct) Eleminol RS-30 (Sanyo Chemical Industries, Ltd.) 11 parts), 83 parts of styrene, 83 parts of methacrylic acid, 110 parts of butyl acrylate and 1 part of ammonium persulfate were charged and stirred at 400 rpm for 15 minutes to obtain an emulsion. The emulsion was heated, heated to 75 ° C. and reacted for 5 hours. Next, 30 parts of a 1% by mass ammonium persulfate aqueous solution was added and aged at 75 ° C. for 5 hours to prepare a resin particle dispersion.

-Preparation of aqueous phase 990 parts of water, 83 parts of resin particle dispersion, 37 parts of 48.5% by weight aqueous solution of eleminol MON-7 (manufactured by Sanyo Chemical Industries) of sodium dodecyl diphenyl ether disulfonate, 135 parts of 1 mass% aqueous solution serogen BS-H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) and 90 parts of ethyl acetate were mixed and stirred to obtain an aqueous medium.

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

-Washing and drying After 100 parts by mass of the dispersion slurry was filtered under reduced pressure, 100 parts of ion-exchanged water was added to the filter cake, followed by mixing at 12000 rpm for 10 minutes using a TK homomixer, followed by filtration. To the obtained filter cake, 10% by mass hydrochloric acid was added to adjust the pH to 2.8, and the mixture was mixed for 10 minutes at 12,000 rpm using a TK homomixer, followed by filtration. Furthermore, 300 parts of ion-exchanged water was added to the obtained filter cake, mixed for 10 minutes at 12000 rpm using a TK homomixer, and then filtered twice to obtain a final filter cake. The obtained final filter cake was dried at 45 ° C. for 48 hours using a circulating dryer, and sieved with a mesh having a mesh size of 75 μm to obtain toner mother particles. To 100 parts of the prepared toner base particles, 1 part of hydrophobic treated silica was mixed with a Henschel mixer to obtain a toner.

<Example 2>
A toner was obtained in the same manner as in Example 1 except that the emulsification / solvent removal step was changed as follows.

-Emulsification / desolvation 867 parts of the oil phase mixed solution was added to 1200 parts of the aqueous medium, and mixed at 13000 rpm for 20 minutes using a TK homomixer to prepare a dispersion (emulsion slurry). Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 3 hours to obtain a dispersed slurry. A toner was obtained in the same manner as in Example 1 except that the emulsification / solvent removal step was changed as follows.

[Example 3]
A toner was obtained in the same manner as in Example 1 except that the emulsification / solvent removal step was changed as follows.

-Emulsification / desolvation 867 parts of the oil phase mixed solution was added to 1200 parts of the aqueous medium, and mixed at 13000 rpm for 20 minutes using a TK homomixer to prepare a dispersion (emulsion slurry). Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 40 ° C. for 12 hours to obtain a dispersed slurry.

[Example 4]
A toner was obtained in the same manner as in Example 1 except that the synthesis of the low molecular polyester and the emulsification / solvent removal step were changed as follows.

Synthesis of low molecular weight polyester In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propion oxide 3 mol adduct, 208 parts terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 5 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. under normal pressure for 1.5 hours to obtain an unmodified polyester resin. Synthesized. The obtained unmodified polyester resin had a number average molecular weight of 2400, a mass average molecular weight of 5,500, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

-Emulsification / desolvation 867 parts of the oil phase mixed solution was added to 1200 parts of the aqueous medium, and mixed at 13000 rpm for 20 minutes using a TK homomixer to prepare a dispersion (emulsion slurry). Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 3 hours to obtain a dispersed slurry.

<Comparative example 1>
A toner was obtained in the same manner as in Example 1 except that the synthesis of the low molecular weight polyester was changed.

-Synthesis of low molecular weight polyester In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propion oxide 3 mol adduct, 208 parts terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 8 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 2 hours under normal pressure to synthesize an unmodified polyester resin. .
The obtained unmodified polyester resin had a number average molecular weight of 2500, a mass average molecular weight of 6700, a glass transition temperature of 43 ° C., and an acid value of 25 mgKOH / g.

<Comparative example 2>
A toner was obtained in the same manner as in Example 1 except that the synthesis of the low molecular polyester and the emulsification / solvent removal step were changed as follows.

Synthesis of low molecular weight polyester In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 229 parts of bisphenol A ethylene oxide 2 mol adduct, 529 parts of bisphenol A propion oxide 3 mol adduct, 208 parts terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 10 hours under normal pressure. Next, after reacting under reduced pressure of 10 to 15 mmHg for 5 hours, 44 parts of trimellitic anhydride was added to the reaction vessel and reacted at 180 ° C. for 3 hours under normal pressure to synthesize an unmodified polyester resin. . The obtained unmodified polyester resin had a number average molecular weight of 7600, a mass average molecular weight of 12000, a glass transition temperature of 45 ° C., and an acid value of 25 mgKOH / g.

-Emulsification / desolvation 867 parts of the oil phase mixed solution was added to 1200 parts of the aqueous medium, and mixed at 13000 rpm for 20 minutes using a TK homomixer to prepare a dispersion (emulsion slurry). Next, the emulsified slurry was charged into a reaction vessel equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was performed at 45 ° C. for 3 hours to obtain a dispersed slurry.

<Comparative Example 3>
(First step)
-Preparation of dispersion (1)-
・ Styrene …… 370g
・ N-butyl acrylate 30g
・ Acrylic acid ... 8g
・ Dodecanethiol ・ ・ ・ ・ ・ ・ ・ ・ ・ 24g
・ Carbon tetrabromide ・ ・ ・ ・ ・ ・ ・ ・ ・ 4g
After mixing and dissolving the above, 6 g of nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 10 g of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 4 g of ammonium persulfate was dissolved, and after nitrogen substitution, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 8 hours. As a result, a dispersion (1) was prepared in which resin particles having an average particle size of 155 nm, a glass transition point of 60 ° C., and a weight average molecular weight (Mw) of 15,000 were dispersed.

-Preparation of dispersion (2)-
・ Styrene ... 280g
・ N-Butyl Acrylate ... 120g
・ Acrylic acid ... 8g
The above mixture was dissolved, and 6 g of a nonionic surfactant (Sanyo Kasei Co., Ltd .: Nonipol 400) and 12 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) were ionized. Dispersed in 550 g of exchange water, dispersed in a flask, emulsified, and slowly mixed for 10 minutes, charged with 50 g of ion exchange water in which 3 g of ammonium persulfate was dissolved, and after nitrogen replacement, While stirring in the flask, the contents were heated in an oil bath until the content reached 70 ° C., and emulsion polymerization was continued for 5 hours. The average particle size was 105 nm, the glass transition point was 51 ° C., and the weight average molecular weight (Mw) was 480. A dispersion liquid (2) was prepared by dispersing resin particles having a molecular weight of 1,000.

-Preparation of colorant dispersion (1)-
・ Carbon black ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 50g
(Cabot Corporation: Mogal L)
・ Nonionic surfactant ... 5g
(Sanyo Kasei Co., Ltd .: Nonipol 400)
・ Ion-exchanged water ... 200g
The above is mixed, dissolved, and dispersed for 10 minutes using a homogenizer (manufactured by IKA: Ultra Turrax T50) to disperse a colorant (carbon black) having an average particle size of 250 nm (carbon black) 1) was prepared.

-Preparation of release agent dispersion (1)-
・ Paraffin wax 50g
(Nippon Seiwa Co., Ltd .: HNP0190, melting point 85 ° C.)
・ Cationic surfactant 7g
(Manufactured by Kao Corporation: Sanizol B50)
・ Ion-exchanged water ... 200g
The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer to disperse a release agent having an average particle size of 550 nm. A release agent dispersion (1) was prepared.

-Preparation of aggregated particles-
・ Dispersion (1) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 120g
・ Dispersion (2) ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 80g
-Colorant dispersion (1) ... 30g
-Release agent dispersion (1) ... 40g
・ Cationic surfactant ... 1.5g
(Manufactured by Kao Corporation: Sanizol B50)
The above was mixed and dispersed in a round stainless steel flask using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then heated to 48 ° C. while stirring the inside of the flask in an oil bath for heating. After maintaining at 48 ° C. for 30 minutes, observation with an optical microscope confirmed that aggregated particles (volume: 95 cm ³ ) having an average particle diameter of about 5 μm were formed.

(Second step)
-Preparation of adhered particles-
To this, 60 g of the dispersion liquid (1) as the resin-containing fine particle dispersion liquid was gradually added. The volume of the resin particles contained in the dispersion liquid (1) is 25 cm ^3. And the temperature of the heating oil bath was raised to 50 degreeC, and was hold | maintained for 1 hour.

(Third step)
Thereafter, 3 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) was added here, and then the stainless steel flask was sealed, and stirring was continued using a magnetic seal up to 105 ° C. Heated and held for 3 hours. Then, after cooling, the reaction product was filtered, thoroughly washed with ion exchange water, and then dried to obtain a toner base. Thereafter, 100 parts of toner base particles were mixed with 1 part of hydrophobic silica and 1 part of hydrophobic titanium oxide using a Henschel mixer to obtain a toner. The physical properties of the obtained toner are shown in Table 1, and the evaluation results are shown in Table 2.

(Evaluation item)
1) Fixability (hot offset resistance, low temperature fixability)
A belt fixing method by remodeling Ricoh's imgio Neo 450, with a solid image and 1.0 ± 0.1mg / mm on a plain paper and cardboard transfer paper (type 6200 made by Ricoh and copy printing paper <135> made by NBS Ricoh) Fixing evaluation was performed with a toner adhesion amount of cm ² . The fixing test was conducted by changing the temperature of the fixing belt, and the upper limit temperature at which hot offset did not occur on plain paper was defined as the upper limit temperature for fixing. Further, the minimum fixing temperature was measured with a thick paper.
The lower limit fixing temperature was defined as the fixing lower limit temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more. The fixing lower limit temperature is ◎; 120 ° C. or less, ◯: 120-130 ° C., Δ: 140 ° C. or more, and the fixing upper limit temperature (hot offset) is ◎; 200 ° C. or more, ◯: 185-200, Δ: 160-185 ° C. X: 160 ° C. or lower.

2) High image quality (graininess, sharpness)
A photographic image was output in a single color using an evaluation machine in which Ricoh IPSiO Color 8100 was remodeled into an oil-less fixing system and tuned, and the degree of graininess and sharpness was visually evaluated. Evaluations were made from GOOD, ◎, ○, Δ, and ×.並 is equivalent to offset printing, ◯ is slightly worse than offset printing, Δ is much worse than offset printing, and × is very bad compared to conventional electrophotographic images.

  Table 1 is a list of toner characteristics.

  Table 2 is a list of evaluation results.

Schematic configuration diagram showing an example of an intermediate transfer system Schematic configuration diagram of a fixing device used in an image forming method Schematic configuration diagram of process cartridge Example of GPC measurement results using HFIP in the present invention

Explanation of symbols

[About Figure 1]
DESCRIPTION OF SYMBOLS 10 Photoconductor 20 Charging roller 30 Exposure apparatus 40 Developing apparatus 41 Developing belt 42 Developing tank 43 Pumping roller 44 Application roller 45 Developing unit 50 Intermediate transfer body 51 Suspension roller 52 Corona charger 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 100 Transfer paper [About Fig. 2]
DESCRIPTION OF SYMBOLS 1 Heating roller 2 Fixing roller 3 Fixing belt 4 Pressure roller 5 Heating source 7 Temperature sensor

Claims (14)

  What is claimed is: 1. A toner for developing an electrostatic charge image, comprising: a toner containing at least a resin, a colorant and WAX; wherein the HFIP (hexafluoroisopropanol) -soluble component of the toner exhibits the following relationship: The molecular weight of 1 ≦ Mw / Mn ≦ 25 and 100,000 or more is 0.01% to 6.5%. Here, Mn is a number average molecular weight, and Mw is a weight average molecular weight.   The electrostatic charge developing toner according to claim 1, wherein the toner has a glass transition point Tg of 40 to 65 ° C.   The electrostatic image developing toner according to claim 1, comprising at least a low molecular weight resin for securing low-temperature fixability and a highly crosslinked component for maintaining hot offset resistance.   4. The toner according to claim 1, wherein the toner contains particles formed by an extension reaction and / or a crosslinking reaction in which oil droplets of an organic solvent in which a toner composition containing a prepolymer is dissolved are dispersed in an aqueous medium. The toner for developing an electrostatic image according to any one of the above.   The electrostatic image developing toner according to claim 1, comprising at least a polyester resin.   The electrostatic image developing toner according to claim 1, comprising at least a modified polyester resin.   The volume average particle diameter Dv of the toner particles is 2 to 7 μm, and the ratio Dv / Dn of the volume average particle diameter Dv to the number average particle diameter Dn is 1.25 or less. The electrostatic image developing toner according to claim 1.   8. The electrostatic image developing toner according to claim 1, wherein the toner particles have an average circularity of 0.93 to 0.99.   A two-component developer comprising at least a carrier comprising the toner according to claim 1 and magnetic particles.   The toner for developing an electrostatic charge image according to any one of claims 1 to 8, or the two-component developer according to claim 9, wherein a predetermined amount of oil is not applied on the belt in an image forming apparatus using toner. An image forming apparatus including a toner fixing unit using a toner.   The electrostatic image on the electrostatic image bearing member is developed with a developer for developing an electrostatic image to form a toner image, and a transfer means is brought into contact with the surface of the electrostatic image bearing member via a transfer material so that the toner image is 9. An image forming apparatus for electrostatic transfer to a transfer material, wherein the developer is a carrier composed of magnetic particles and a two-component developer composed of toner according to claim 1. .   The image forming apparatus according to claim 11, further comprising a process cartridge that integrally supports the latent image carrier and at least the developing unit and is detachable from the image forming apparatus main body. A developing unit, a heating element, and one or more heat transfer media heated by the heating element, and a pressure member that presses the recording medium against one of the heat transfer media An image forming apparatus having fixing for heating and fixing the toner image, wherein the developing means uses the toner according to any one of claims 1 to 8, and at least one of the heat transfer media is a belt. An image forming apparatus including a toner fixing method which is a heat transfer medium and is used with or without applying a certain amount of oil on a belt.   An image forming method for use in the image forming apparatus according to claim 10.

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