JP2007316361A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which excels in developing property, transferability and storage stability, and does not cause toner fusion even in any environment. <P>SOLUTION: The toner contains: toner particles containing at least a binder resin, a magnetic material and a wax; and inorganic fine particles, wherein the binder resin contains at least a polyester unit and has an acid value (RAv) of 1-50 mgKOH/g, the wax has an acid value (WAv) of 1-30 mgKOH/g and satisfies an expression (1): 0≤¾(RAv-WAv)¾≤35, and with respect to peaks of carbon atoms, oxygen atoms and iron atoms measured by ESCA of the toner particles, an intensity ratio of the peak of the carbon atoms is ≥88.5%, and an intensity ratio of the peak of the oxygen atoms is ≤11.5%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a toner used for electrophotography, an image forming method for developing an electrostatic image, and a toner used for a toner jet.

  In recent years, devices using electrophotography have begun to be used in printers for output of computers, facsimiles, etc., in addition to copying machines for copying original documents. As a result, smaller, lighter, faster, and more reliable are being sought, and machines are becoming simpler in various ways. As a result, the performance required for the toner becomes higher, and if the improvement in the performance of the toner cannot be achieved, a better machine cannot be realized.

  Many techniques for incorporating a polyester resin having an acid value and a wax having an acid value into the toner have been disclosed. Patent Document 1 discloses a technique for defining an acid value ratio between a resin and a wax. Patent Document 2 discloses a technique used for a positively charged one-component nonmagnetic developer. Patent Document 3 discloses a technique using a mixture of a polyester resin and a styrene-acrylic resin and two types of waxes. Patent Document 4 discloses a technique using a Fischer-Tropsch wax having an acid value. Patent Documents 5 and 6 disclose techniques using polyethylene wax and acid value type polypropylene wax as wax. Patent Document 7 discloses a technique using a polyester resin having a specific molecular weight and a wax. Patent Document 8 discloses a non-magnetic one-component full-color toner using an acid value type polyolefin wax. Patent Document 9 discloses a technique using a hydrocarbon wax having an ester bond or an amide bond. Patent Document 10 discloses a technique using a thermoplastic polyester resin and a low acid value wax. Patent Document 11 discloses a technique using a high acid value wax and a low acid value wax. Patent Document 12 discloses a technique using ester wax and carnauba wax. Patent Document 13 discloses a technique using carboxylic acid-modified paraffin wax and alcohol-modified paraffin wax. Even if these techniques are used, it is difficult to provide the toner with sufficient developability in the electrophotographic technique in which high speed and high definition are progressing.

  A technique for measuring the toner surface composition using ESCA is also disclosed. Patent Document 14 discloses a technique for defining the existence ratio of polyolefin on the toner surface. Patent Documents 15 and 16 disclose techniques for controlling O / C on the toner surface. Patent Document 17 discloses a technique for defining the amount of wax having a polar group. Patent Document 18 discloses a technique that defines the area occupied by carbon and oxygen. These techniques have some effect on improving the developability of the toner, but have not yet achieved sufficient developability for the toner, and have sufficient performance for toner fusion to the photoreceptor. It is hard to say that toner is obtained.

Japanese Patent Laid-Open No. 3-168651 JP-A-8-82957 JP-A-8-106173 Japanese Patent Laid-Open No. 9-179342 Japanese Patent Laid-Open No. 10-246980 Japanese Patent Laid-Open No. 10-246982 Japanese Patent Laid-Open No. 11-153886 JP 2000-235280 A JP 2002-40712 A JP 2003-29445 A JP 2003-195554 A JP 2003-270837 A JP 2004-29160 A Japanese Patent No. 2742693 Japanese Patent Laid-Open No. 3-243156 Japanese Patent Laid-Open No. 5-273794 Japanese Patent Application Laid-Open No. H8-123071 JP 2004-157423 A

  An object of the present invention is to provide a toner that solves the above-mentioned problems of the prior art.

  An object of the present invention is to provide a toner having excellent developability as in the initial stage even in long-term use.

  An object of the present invention is to provide a toner having excellent developability in any environment.

  An object of the present invention is to provide a toner that does not cause fusion of a photosensitive drum.

  An object of the present invention is to provide a toner that does not generate a sleeve ghost.

  An object of the present invention is to provide a toner having excellent storage stability.

  An object of the present invention is to provide a toner having excellent transferability.

The present invention is a toner containing toner particles containing at least a binder resin, a magnetic material, wax, and inorganic fine particles,
The binder resin contains at least a polyester unit,
The binder resin has an acid value (RAv) of 1 to 50 mgKOH / g, and the wax has an acid value (WAv) of 1 to 30 mgKOH / g and satisfies the following formula (1):
0 ≦ | (RAv−WAv) | ≦ 35 (1)
Regarding the carbon atom, oxygen atom, and iron atom peaks measured by ESCA of the toner particles, the intensity ratio of the carbon atom peaks is 88.5% or more, and the intensity ratio of the oxygen atom peaks is 11.5% or less. It is related with the toner characterized by being.

  Even in high-speed development under severe conditions such as high temperature and high humidity and low temperature and low humidity, high developability is maintained over long-term use, sleeve ghosts and transfer defects do not occur, and image defects caused by toner fusion do not occur. Toner can be provided.

  As a result of intensive studies, the inventors of the present invention have controlled the acid values of the binder resin and wax used in the toner to appropriate values and controlled the ratio of the elements present on the toner particle surface, thereby developing the toner development characteristics. It was found that can be improved.

  The binder resin used in the toner of the present invention has an acid value (RAv) of 1 to 50 mgKOH / g, preferably 3 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. Characteristics can be provided, and the developability of the toner is improved. Since the binder resin has an acid value, the acid groups exposed on the toner surface enhance the charging performance of the toner, so that the chargeability of the toner is much higher than when it does not have an acid value. improves. By improving the charging property, the developing characteristics of the toner are also improved, and particularly the effect of increasing the image density is brought about. Further, the binder resin of the present invention is characterized by containing at least a polyester unit. The polyester unit has an ester bond, the ester group has high chargeability, and further has a suitable acid value as in the present invention, thereby imparting higher development characteristics to the toner. be able to.

  In the present invention, when the acid value (WAv) of the wax is 1 to 30 mgKOH / g, preferably 2 to 25 mgKOH / g, more preferably 3 to 20 mgKOH / g, the toner can have good charging characteristics. And improve the developability of the toner.

  In the present invention, the fact that the binder resin has an acid value and at the same time the wax has an acid value improves the charging characteristics of the toner and further improves the developability of the toner. The inventors have found.

  In the present invention, both the binder resin and the wax have an appropriate acid value, which brings about an effect that was not obtained when each was used alone. That is, the binder resin and the wax are hardly compatible with each other, and due to the uneven distribution of the wax in the toner, the chargeability of the toner may be deteriorated and the developability may be deteriorated. This is remarkable when a binder resin having a polyester unit is used. However, when the binder resin and the wax have an acid value as in the present invention, the respective acid groups have affinity, and the wax can be finely dispersed in the binder resin. It can be considered that the charging property can be provided and the developing property of the toner is improved.

  If the acid value of the binder resin is less than 1 mg KOH / g, it is considered that the compatibility with the wax becomes insufficient and the developability of the toner is deteriorated. When the acid value of the binder resin exceeds 50 mgKOH / g, it is considered that the moisture resistance of the toner is deteriorated and the developability in a high temperature and high humidity environment is deteriorated.

  If the acid value of the wax is less than 1 mg KOH / g, it is considered that the compatibility with the binder resin becomes insufficient and the developability of the toner is deteriorated. When the acid value of the wax exceeds 30 mgKOH / g, the wax is excessively compatible with the binder resin, and the plasticity of the wax with respect to the binder resin becomes too strong, thereby reducing the heat resistance and stress resistance of the toner. As a result, the storage stability of the toner is considered to deteriorate.

In particular, in the present invention, the acid value (RAv) of the binder resin and the acid value (WAv) of the wax are
0 ≦ | (RAv−WAv) | ≦ 35 (1)
With this relationship, the compatibility between the binder resin and the wax becomes better.

  In the case of | (RAv−WAv) |> 35, the binder resin and the wax are phase-separated, and the charge distribution of the toner becomes non-uniform and sleeve ghost is generated.

  The toner particles of the present invention have a carbon atom peak intensity ratio of 88.5% or more, preferably 90.5% or more, more preferably 92 with respect to the carbon atom, oxygen atom, and iron atom peaks measured by ESCA. The oxygen atom peak intensity ratio is 11.5% or less, preferably 9.5% or less, more preferably 8.0% or less. In ESCA, the amount of the element on the outermost surface of the toner particle can be quantified, and the presence state of each raw material for toner on the outermost surface of the toner particle can be specified from the amount of element measured there. That is, the carbon atom measured by ESCA is a peak mainly derived from the wax component contained in the toner particles, and the oxygen atom measured by ESCA is mainly in the binder resin component contained in the toner particles. It is a peak derived from, and in the present invention, measuring the abundance of carbon atoms and oxygen atoms on the toner particle surface is synonymous with measuring the wax component and binder resin component on the toner particle surface. Conceivable. When the intensity ratio of the peak of carbon atoms is 88.5% or more and the intensity ratio of the peak of oxygen atoms is 11.5% or less, the binder resin and wax are present at the proper ratio on the toner particle surface. As a result, good development characteristics can be imparted to the toner. The wax present on the surface of the toner particles imparts a degree of lubricity to the toner. As a result, the fluidity of the toner is improved, and it is considered that the developability of the toner is improved by the toner being easily developed in the development process. If the ratio of the wax on the toner particle surface is reduced, the fluidity of the toner is lowered, so that it is considered that sufficient developability cannot be imparted to the toner.

  In the present invention, the binder resin and the wax have an appropriate acid value, and the peak intensity of each of carbon atoms and oxygen atoms on the surface of the toner particles measured by ESCA is defined, whereby the toner to the photosensitive drum is obtained. It has been found that fusion can be effectively prevented. That is, the binder resin and the wax of the present invention have an appropriate acid value, but the resin and wax having such an acid value are excellent in chargeability, but are static on a developing member such as a photosensitive drum. Electric adhesion is also strengthened. In particular, on the photosensitive drum, when the toner is transferred to a transfer sheet such as paper, physical pressure from a transfer member such as a transfer roller is also applied, and the toner and the photosensitive drum are rubbed to easily cause toner fusion. . At this time, the toner particles of the present invention have an appropriate amount of carbon atoms and oxygen atoms on the surface of the toner particles, in other words, an appropriate amount of wax and binder resin on the surface of the toner particles, and the toner has appropriate lubricity. Therefore, even when the toner adheres to the photosensitive drum with a strong electrostatic force during development and the toner is strongly rubbed against the photosensitive drum by a physical force from a transfer member such as a transfer roller, the toner slips on the photosensitive drum. It is thought that the toner fusion to the photosensitive drum can be reduced because it peels without being in close contact. At this time, the fact that the binder resin of the present invention has a polyester unit also works effectively, that is, the polyester unit is relatively hard, so that it deforms even if the toner is subjected to physical pressure on the photosensitive drum. Therefore, it is considered that this also serves to prevent the toner from fusing to the photosensitive drum.

  If the intensity ratio of the carbon atom peak is less than 88.5%, the ratio of the binder resin on the surface of the toner particles is large and the ratio of the wax is small, so that the fluidity of the toner is insufficient and the developability is lowered. . Further, the toner is fused to the photosensitive drum. When the intensity ratio of the oxygen atom peak exceeds 11.5%, the toner is likely to absorb moisture, and the developability in a high humidity environment decreases.

  In the present invention, for example, Quantum 2000 (ULVAC-PHI) is used for ESCA measurement. As a measurement principle, photoelectrons are generated by using an X-ray source, and energy based on an intrinsic scientific combination of substances is measured. As the X-ray, monochromatic Al—Kα is used, and measurement is performed under the conditions of a beam diameter of 50 μm and a pass energy of 46.95 eV.

  The toner particles of the present invention preferably have an iron atom peak intensity ratio of less than 1% as measured by ESCA, and can impart high chargeability to the toner. Since the toner particles of the present invention contain magnetic iron oxide, iron atoms are also present on the toner particle surfaces, but the peak intensity of iron atoms measured by ESCA is smaller than that of carbon atoms and oxygen atoms. In the toner particles of the present invention, it is preferable that the iron atom peak is present on the toner particle surface to such an extent that almost no iron atom peak is detected. However, when iron atoms, that is, magnetic substances are present on the surface of the toner particles such that the intensity ratio of the peak of iron atoms measured by ESCA exceeds 1%, the toner charge leaks through the iron atoms. And developability may be reduced.

  Further, in a solution obtained by dispersing 150 mg of the toner particles of the present invention in 5 ml of an aqueous surfactant solution and further adding 5 ml of 6 mol / l hydrochloric acid and extracting for 30 minutes, the absorbance at 340 nm absorption is 0.1 to 1.0. Preferably it is 0.1 or more and 0.9 or less, more preferably 0.1 or more and 0.8 or less. Absorption at 340 nm is mainly due to elution of iron. When the absorbance at 340 nm is 0.1 or more and 1.0 or less, it means that a small amount of iron, that is, a magnetic substance is present on the surface of the toner particles, and imparts proper chargeability to the toner. Can do. When the absorbance is less than 0.1, there is almost no magnetic substance on the surface of the toner particles, and the charge of the toner becomes too high, and the image density may be lowered by charging up. When the absorbance exceeds 1.0, the toner charge tends to leak, and the image density may decrease.

  As described above, in the present invention, it is preferable that a magnetic material is appropriately present on the surface of the toner particles, and as a result, good development characteristics can be provided to the toner.

  In the present invention, the absorbance at 340 nm is determined as follows.

  A dispersant prepared by adding 1.23 vol% of a surfactant, preferably an alkylbenzene sulfonate, to water from which impurities in the container have been removed in advance is prepared. 150 mg of toner particles are put in a sample bottle, and 5 ml of a dispersant is added to sufficiently disperse the sample. Subsequently, 5 ml of 6 mol / l hydrochloric acid is added and left for 30 minutes.

  The solution after being allowed to pass is passed through a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corp., Excro Disc 25CR manufactured by Gelman Science Japan Ltd., etc.). A sample for absorbance measurement.

The filtrate is measured with a spectrophotometer (for example, Shimadzu UV-3100PC). At this time, a mixed solution of 5 ml of the dispersant and 5 ml of 6 mol / l hydrochloric acid is put in a control cell.
Measurement conditions: scan speed (medium speed), slit width (0.5 nm), sampling pitch (2 nm), measurement range (600 to 250 nm)

  In the toner particles of the present invention, a large part of the toner particle surface is covered with a binder resin and wax, so that most of the magnetic material is buried and some of the toner particles are exposed on the surface. . If such a magnetic material is dissolved only with hydrochloric acid, it will be greatly affected by the hydrophobic binder resin and wax in the vicinity, and it cannot be adequately adjusted with hydrochloric acid alone. It is difficult to know the amount of magnetic material accurately. In order to accurately determine the surface magnetic substance amount of the toner of the present invention having such a surface state, it is effective to add a surfactant to hydrochloric acid.

  As a preferable method for producing toner particles in the present invention, for example, each raw material is premixed and then melt-kneaded, pulverized, classified, and the obtained particles are instantaneously blown with hot hot air on the surface of the toner particles, and immediately after that with cold air Examples thereof include a method for modifying the surface of the toner particles using an apparatus for cooling the toner particles. Modifying the surface of the toner particles by such a technique does not apply excessive heat to the toner particles, so that the surface modification of the toner particles can be performed while preventing deterioration of the raw material components. In addition, since the toner particles are instantaneously cooled, the toner particles do not excessively coalesce and do not vary greatly from the toner particle diameter before the surface modification. Easy to control.

  For the surface modification of the toner particles, for example, a surface modification apparatus as shown in FIG. 1 can be used. The toner particles 1 are supplied by the auto feeder 2 through the supply nozzle 3 to the inside 4 of the surface reforming apparatus in a fixed amount. Since the interior 4 of the surface modifying apparatus is sucked by the blower 8, the toner particles 1 introduced from the supply nozzle 3 are dispersed in the apparatus. The toner particles 1 dispersed in the machine are hot-air introduced from the hot-air inlet 5 and are instantaneously heated to be surface-modified. In the present invention, hot air is generated by a heater, but the apparatus is not particularly limited as long as it can generate hot air sufficient for surface modification of toner particles. The surface-modified toner particles 7 are instantaneously cooled by the cold air introduced from the cold air inlet 6. In the present invention, liquid nitrogen is used for the cold air, but the means is not particularly limited as long as the surface-modified toner particles 7 can be instantaneously cooled. The surface-modified toner particles 7 are sucked by the blower 9 and collected by the cyclone 8.

  The toner of the present invention has an average circularity of 0.935 or more, preferably 0.940 or more, more preferably 0.945 or more in a toner having a particle diameter of 3 μm or more and 400 μm or less. When the circularity of the toner is within the above range, the cohesiveness of the toner can be reduced and the transferability of the toner is improved. In particular, since the toner of the present invention uses a resin having an acid value and a wax, the toner aggregates through acid groups present on the toner surface, and the toner is packed on the photosensitive drum. Although separation of the toner from the photosensitive drum may be insufficient, in the present invention, since the circularity of the toner is within the above range, there is an effect of reducing the cohesiveness of the toner itself. It is considered that the toner is easily separated from the photosensitive drum and the toner transfer property is improved. If the average circularity of the toner is less than 0.935, the toner transferability may be insufficient.

<Measurement of average toner circularity>
The average circularity of the toner is measured using a flow type particle image measuring device “FPIA-2100 type” (manufactured by Sysmex Corporation), and is calculated using the following equation.
Circularity = (perimeter of a circle having the same area as the particle projection area) / (perimeter of the particle projection image)

  Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define. The measurement uses the perimeter of the particle image when image processing is performed at an image processing resolution of 512 × 512 (pixels of 0.3 μm × 0.3 μm).

  In the present invention, the circularity is an index indicating the degree of unevenness of the toner particles, and is 1.000 when the toner particles are completely spherical. The more complicated the surface shape, the smaller the circularity.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  In addition, “FPIA-2100”, which is a measuring apparatus used in the present invention, calculates the circularity of each particle, and then calculates the average circularity. 1.0 is divided into classes equally divided every 0.01, and the average circularity is calculated using the center value of the division points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser “Tetora 150 type” (manufactured by Nikka Ki Bios Co., Ltd.) is used, and dispersion treatment is performed for 2 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not be 40 degreeC or more. In order to suppress variation in circularity, the installation environment of the apparatus is controlled at 23 ° C. ± 0.5 ° C. so that the temperature inside the flow type particle image analyzer FPIA-2100 is 26 to 27 ° C. Preferably, autofocus is performed using 2 μm latex particles every 2 hours.

  To measure the circularity of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toners are measured. To do. After the measurement, using this data, data having an equivalent circle diameter of less than 2 μm is cut to determine the average circularity of the toner.

  Furthermore, “FPIA-2100”, which is a measuring apparatus used in the present invention, improves the magnification of the processed particle image as compared with “FPIA-1000” conventionally used for calculating the shape of the toner. Furthermore, the accuracy of toner shape measurement is improved by improving the processing resolution of the captured image (256 × 256 → 512 × 512), thereby achieving more reliable capture of fine particles. Therefore, when it is necessary to measure the shape more accurately as in the present invention, the FPIA 2100 that can obtain information on the shape more accurately is more useful.

  The composition of the polyester resin used in the present invention is as follows.

  Examples of the divalent alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and bisphenol represented by the formula (A) and derivatives thereof;

（式中Ｒはエチレンまたはプロピレン基であり、ｘ，ｙはそれぞれ０以上の整数であり、かつ、ｘ＋ｙの平均値は０〜１０である。）

(In the formula, R is an ethylene or propylene group, x and y are each an integer of 0 or more, and the average value of x + y is 0 to 10.)

  And diols represented by the formula (B);

ｘ’，ｙ’は０以上の整数であり、かつ、ｘ＋ｙの平均値は０〜１０である。）
が挙げられる。

x ′ and y ′ are integers of 0 or more, and the average value of x + y is 0 to 10. )
Is mentioned.

  Examples of the divalent acid component include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and phthalic anhydride or anhydrides thereof, lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid. Acids or anhydrides thereof, lower alkyl esters; alkenyl succinic acids or alkyl succinic acids such as n-dodecenyl succinic acid and n-dodecyl succinic acid, or anhydrides, lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, itaconic acid Dicarboxylic acids such as unsaturated dicarboxylic acids or anhydrides thereof, lower alkyl esters;

  Further, it is preferable to use a trivalent or higher alcohol component or a trivalent or higher acid component that acts as a crosslinking component alone or in combination.

  Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butane. Triol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, etc. Is mentioned.

  Examples of other dihydric alcohols include (1) ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, Alkylene glycols having 2 to 12 carbon atoms such as 1,5-pentanediol and 1,6-hexanediol; (2) alkylene glycols such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; -Terglycols; (3) C6-C30 alicyclic diols such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A; and (4) Bisphenols such as bisphenol A, bisphenol F, and bisphenol S; common To, and (5) above bisphenols alkylene oxide (EO, PO, butylene oxide, etc.) 2-8 mole adducts.

  Specific examples of other trivalent or higher alcohols include (1) sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1, 2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, etc. 20 aliphatic polyhydric alcohols; (2) aromatic polyhydric alcohols having 6 to 20 carbon atoms such as 1,3,5-trihydroxylmethylbenzene; and alkylene oxide adducts thereof.

  Examples of the trivalent or higher polyvalent carboxylic acid component in the present invention include pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, and 2,5,7-naphthalenetricarboxylic acid. Acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (Methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, emporic trimer acid, and their anhydrides, lower alkyl esters;

（式中Ｘは炭素数３以上の側鎖を１個以上有する炭素数５〜３０のアルキレン基又はアルケニレン基）
で表わされるテトラカルボン酸等、及びこれらの無水物、低級アルキルエステル等の多価カルボン酸類及びその誘導体が挙げられる。なかでも、１，２，４−ベンゼントリカルボン酸、１，２，５−ベンゼントリカルボン酸およびこれらの無水物、低級アルキルエステルが好ましい。

(Wherein X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having one or more side chains having 3 or more carbon atoms)
And polycarboxylic acids such as anhydrides and lower alkyl esters thereof and derivatives thereof. Of these, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, anhydrides thereof, and lower alkyl esters are preferable.

  The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol%, and the acid component is 60 to 40 mol%, preferably 55 to 45 mol%. Moreover, it is preferable that the polyvalent component more than trivalence is 5-60 mol% in all the components.

  The polyester resin is usually obtained by a generally known condensation polymerization. The polymerization reaction of the polyester resin is usually performed in the presence of a catalyst at a temperature of about 150 to 300 ° C., preferably about 170 to 280 ° C. The reaction can be carried out under normal pressure, reduced pressure, or increased pressure.

  Examples of the catalyst include catalysts usually used for polyesterification, for example, metals such as tin, titanium, antimony, manganese, nickel, zinc, lead, iron, magnesium, calcium, germanium; and these metal-containing compounds (dibutyltin oxide, orthodibutyl). Titanate, tetrabutyl titanate, zinc acetate, lead acetate, cobalt acetate, sodium acetate, antimony trioxide, etc.).

  The binder resin used in the present invention has an acid value, but when the polyester unit has an acid value, the amount and type of the alcohol component and acid component as raw materials are adjusted, and further the reaction during the synthesis of the polyester unit. A polyester unit having a desired acid value can be obtained by adjusting the conditions (temperature, time, etc.).

  Other types of binder resins that can be used in the present invention include styrene resins, styrene copolymer resins, polyol resins, polyvinyl chloride resins, phenol resins, natural modified phenol resins, natural resin modified maleic resins, Examples thereof include acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, and petroleum resin.

  As a comonomer for the styrene monomer of the styrene copolymer, a styrene derivative such as vinyltoluene; acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, acrylic Acrylic acid ester such as phenyl acid; Methacrylic acid ester such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate; Maleic acid; Double such as butyl maleate, methyl maleate, dimethyl maleate Dicarboxylic acid ester having a bond; acrylamide, acrylonitrile, methacrylonitrile, butadiene; vinyl ester such as vinyl chloride, vinyl acetate, vinyl benzoate; ethylene, propylene, butylene Such ethylenic olefins, vinyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl propionate ether. These vinyl monomers are used alone or in combination of two or more.

  In order to give the acid value characteristic of the present invention to the binder resin other than the polyester unit, the types and amounts of the components used as raw materials are set appropriately, and the synthesis reaction conditions (temperature, time, etc.) are appropriately set. By changing, a binder resin having a desired acid value can be obtained.

  The binder resin used in the present invention has a glass transition temperature (Tg) of 45 to 80 ° C, preferably 50 to 70 ° C, from the viewpoint of storage stability. When Tg is lower than 45 ° C., it tends to cause toner deterioration under a high temperature atmosphere and offset during fixing. On the other hand, when Tg exceeds 80 ° C., fixability tends to be lowered.

The measuring method of Tg is performed according to ASTM D3418 using TA Instruments Q-1000. The DSC curve used in the present invention is a DSC curve measured when the temperature is raised at a rate of 10 ° C./min after raising and lowering the temperature once and taking a previous history. The definition is as follows.
・ Glass transition point (Tg)
The temperature at the intersection of the DSC curve and the line connecting the midpoints of the baseline before and after the change in specific heat appears in the DSC curve during temperature rise.

  In the present invention, the molecular weight distribution by GPC of the THF (tetrahydrofuran) soluble part of the binder resin is measured under the following conditions.

The column is stabilized in a 40 ° C. heat chamber. Tetrahydrofuran (THF) is allowed to flow through the column at this temperature as a solvent at a flow rate of 1 ml per minute, and about 100 μl of a sample THF solution is injected and measured. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 102 to 107 manufactured by Tosoh Corporation or Showa Denko is used, and at least about 10 standard polystyrene samples are suitably used. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko KK, TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ) manufactured by Tosoh Corporation , G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ), and TSK guard column.

  The sample is prepared as follows.

  Put the sample in THF, let stand for several hours, then shake well and mix well with THF (until the sample is no longer united), and let stand for more than 12 hours. At this time, the sample is left in THF for 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, Mysori Disc H-25-5 manufactured by Tosoh Corporation, Excro Disc 25CR manufactured by Gelman Science Japan Co., Ltd., etc.) can be used. A measurement sample for GPC is used. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The wax used in the present invention has a hydroxyl value (WOHv) of 20 to 100 mgKOH / g, preferably 20 to 90 mgKOH / g, more preferably 30 to 80 mgKOH / g. The ester value (WEv) is 1 to 50 mgKOH / g, preferably 2 to 40 mgKOH / g, more preferably 3 to 30 mgKOH / g, and the relationship between the hydroxyl value and the ester value is represented by the following formula. Is preferred.
WOHv> WEv

  Since the hydroxyl group and ester group in the wax have a strong affinity for the polyester unit contained in the binder resin used in the present invention, the wax is more easily dispersed in the toner. As a result, the dispersibility of the material in the toner becomes more uniform, the distribution of the charge amount of the toner becomes uniform, and fogging derived from improperly charged toner can be reduced. At this time, the hydroxyl value in the wax is preferably higher than the ester value. In other words, the ester group in the wax is easily combined with the polyester unit in the binder resin, the wax is finely dispersed in the binder resin, and the plastic effect of the wax with respect to the binder resin is too great, thereby preserving the toner. In the present invention, since the hydroxyl value in the wax is higher than the ester value, the hydroxyl value prevents excessive fine dispersion of the wax in the polyester unit. Will not worsen. When the hydroxyl value of the wax is less than 20 mgKOH / g or the ester value is less than 1 mgKOH / g, the dispersion of the wax in the toner may be insufficient and fogging may be deteriorated. When the hydroxyl value of the wax exceeds 100 mgKOH / g, or the ester value exceeds 50 mgKOH / g, the wax may be too finely dispersed in the toner to deteriorate the storage stability of the toner. Further, when the hydroxyl value of the wax is smaller than the ester value, the storage stability of the toner may be deteriorated.

  In order to give an acid value, a hydroxyl value, and an ester value to the wax in the present invention, a boric acid ester of the wax is generated from an aliphatic hydrocarbon wax, and the boric acid ester of the wax is hydrolyzed to obtain an acid value. It is preferable to adjust and adjust other functional groups. It is preferable to use this process to obtain a wax having desired characteristics because it is easy to control the conversion rate of the acid group, hydroxyl group and ester group of the wax.

  As the aliphatic hydrocarbon wax, for example, (A) a higher aliphatic unsaturated hydrocarbon having one or more double bonds obtained by an ethylene polymerization method or an olefination method by thermal decomposition of petroleum hydrocarbon, (B) An n-paraffin mixture obtained from a petroleum fraction, (C) a polyethylene wax obtained by an ethylene polymerization method, (D) one or more of higher aliphatic hydrocarbons obtained by a Fischer-Tropsch synthesis method are preferably used. .

  As an example of the production of the wax in the present invention, it can be obtained, for example, by subjecting an aliphatic hydrocarbon wax to liquid phase oxidation with a molecular oxygen-containing gas, preferably in the presence of boric acid and boric anhydride.

  In the present invention, the acid value, hydroxyl value, ester value, and saponification value of the wax are determined by the following methods. The basic operation conforms to J1S K 0070.

Acid value measurement / equipment and instrument Erlenmeyer flask (300ml)
Burette (25ml)
Water bath or hot plate / reagent 0.1 kmol / m ³ hydrochloric acid 0.1 kmol / m ³ potassium hydroxide ethanol solution (standard is 25 ml of 0.1 kmol / m ³ hydrochloric acid in an Erlenmeyer flask using all pipettes, phenolphthalein Add the solution, titrate with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and determine the factor from the amount required for neutralization.)
Phenolphthalein solution Solvent (diethyl ether and ethanol (99.5) mixed at a volume ratio of 1: 1 or 2: 1. These were added with a few drops of the phenolphthalein solution as an indicator immediately before use, and were added in an amount of 0.0. Neutralize with 1 kmol / m ³ potassium hydroxide ethanol solution.)
Measurement method (a) Weigh accurately 1 to 20 g of wax in an Erlenmeyer flask.
(B) Add 100 ml of solvent and a few drops of phenolphthalein solution as an indicator, and shake well until the wax is completely dissolved in a water bath.
(C) Titrate with a 0.1 kmol / m ³ potassium hydroxide ethanol solution, and the end point is when the light red color of the indicator lasts for 30 seconds.
・ Calculation A = 5.611 × B × f / S
However, A: Acid value (mgKOH / g)
B: 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration
Amount (ml)
f: Factor of 0.1 kmol / m ³ potassium hydroxide ethanol solution S: Mass of wax (g)
5.611: Formula weight of potassium hydroxide 56.11 × 1/10

Hydroxyl value measurement / equipment and instrument graduated cylinder (100ml)
Full pipette (5ml)
Flat bottom flask (200ml)
Glycerin bath / reagent Acetylation reagent (25 g of acetic anhydride is placed in a 100-ml flask, and pyridine is added to bring the total volume to 100 ml.)
Phenolphthalein solution 0.5 kmol / m3 potassium hydroxide ethanol solution / Measurement method (a) Wax is precisely weighed in a 0.5-6.0 g flat bottom flask, and 5 ml of acetylating reagent is added to this using a pipette.
(B) Place a small funnel on the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at a temperature of 95-100 ° C. and heat. In order to prevent the temperature of the neck of the flask from rising due to the heat of the glycerin bath, a cardboard disc with a round hole in it is put on the base of the neck of the flask.
(C) After 1 hour, the flask is removed from the glycerin bath, allowed to cool, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride.
(D) Further, in order to complete the decomposition, the flask is heated again in a glycerin bath for 10 minutes, and after cooling, the funnel and the wall of the flask are washed with 5 ml of ethanol (95).
(E) A few drops of phenolphthalein solution is added as an indicator, and titrated with 0.5 kmol / m3 potassium hydroxide ethanol solution, and the end point is when the indicator is light red for about 30 seconds.
(F) In the blank test, (a) to (e) are performed without adding wax.
(G) If the sample is difficult to dissolve, add a small amount of pyridine, or add xylene or toluene to dissolve.
Calculation A = [{(BC) × 28.05 × f} / S] + D
Where A: hydroxyl value (mgKOH / g)
B: 0.5 kmol / m ³ potassium hydroxide ethanol solution used for the blank test
Liquid volume (ml)
C: 0.5 kmol / m ³ potassium hydroxide ethanol solution used for titration
Amount (ml)
f: Factor of 0.5 kmol / m ³ potassium hydroxide ethanol solution S: Mass of wax (g)
D: Acid value 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

Measurement of ester value Calculated by the following formula.
(Ester value) = (Saponification value)-(Acid value)

Saponification value measurement device and instrument Erlenmeyer flask (200-300ml)
Air cooler (outer diameter 6-8mm, length 100cm glass tube or recirculating cooler, all of which can be connected to the mouth of the Erlenmeyer flask)
Water bath, sand bath or hot plate (can be adjusted to a temperature of about 80 ° C)
Burette (50ml)
Full pipette (25ml)
Reagent 0.5 kmol / m ³ hydrochloric acid 0.5 kmol / m ³ potassium hydroxide ethanol solution Phenolphthalein solution Measurement method (a) Wax 1.5-3.0 g is precisely weighed to the order of 1 mg in an Erlenmeyer flask.
(B) Add 25 ml of 0.5 kmol / m3 potassium hydroxide ethanol solution using a pipette.
(C) Attach an air cooler to the Erlenmeyer flask and allow it to react by gently heating on a water bath, sand bath or hot plate for 30 minutes with occasional shaking. When heating, the heating temperature is adjusted so that the circulating ethanol ring does not reach the top of the air cooler.
(D) Immediately after the reaction is completed, the inner wall is washed by spraying a small amount of water or a mixed solution of xylene: ethanol = 1: 3 from the top of the air cooler before the contents are hardened into agar. After that, remove the air cooler.
(E) Add 1 ml of phenolphthalein solution as an indicator and titrate with 0.5 kmol / m ³ hydrochloric acid, and when the light red color of the indicator does not appear for about 1 minute, the end point is set.
(F) In the blank test, (a) to (e) are performed without adding wax.
(G) If the sample is difficult to dissolve, dissolve it in advance using xylene or a xylene-ethanol mixed solvent.
Calculation A = {(BC) × 28.05 × f} / S
However, A: Saponification value (mgKOH / g)
B: Amount of 0.5 kmol / m ³ hydrochloric acid used for the blank test (ml)
C: Amount of 0.5 kmol / m ³ hydrochloric acid used for titration (ml)
f: Factor of 0.5 kmol / m ³ hydrochloric acid S: Mass of wax (g)
28.05: Formula weight of potassium hydroxide 56.11 × 1/2

  In the present invention, when measuring the acid value, hydroxyl value, ester value, and saponification value of the wax contained in the toner, the wax may be separated from the toner and then measured according to the above measurement method. good.

  Further, the wax in the present invention has a melting point of 50 to 130 ° C., preferably 60 to 125 ° C., more preferably 65 to 120 ° C., to give the toner good fixability, offset resistance and storage stability. It is preferable from the viewpoint. When the melting point of the wax is less than 50 ° C., the blocking resistance of the toner may be lowered. When the melting point exceeds 130 ° C., the fixing performance of the toner may be adversely affected.

  In the present invention, the melting point of the wax can be measured using a differential thermal analysis measuring device (DSC measuring device) and DSC-7 (manufactured by Perkin Elmer) under the following conditions.

Measuring method of wax melting point Measured according to ASTM D3418.
Sample: 0.5-2 mg, preferably 1 mg
Measurement method: Place the sample in an aluminum pan and use an empty aluminum pan as a reference.
Temperature curve: Temperature increase I (20 ° C. to 180 ° C., temperature increase rate 10 ° C./min)
Temperature drop I (180 ° C. to 10 ° C., temperature drop rate 10 ° C./min)
Temperature increase II (10 ° C to 180 ° C, temperature increase rate 10 ° C / min)

  The endothermic peak temperature measured at the temperature elevation II in the temperature curve is defined as the melting point.

  A preferable addition amount of the wax to the toner in the present invention is 0.2 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the binder resin. Used in a range.

  The toner of the present invention preferably contains a charge control agent.

  Examples of the toner that controls the negative charge include the following compounds.

  For example, organometallic complexes and chelate compounds are effective, and there are monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  Among these, an azo metal complex represented by the following general formula (1) is preferable.

  In particular, the central metal is preferably Fe, the substituent is preferably a halogen, an alkyl group or an anilide group, and the counter ion is preferably hydrogen, an alkali metal, ammonium or aliphatic ammonium. A mixture of complex salts having different counter ions is also preferably used.

  Alternatively, a basic organic acid metal complex represented by the following general formula (2) is also preferable as a charge control agent that imparts negative chargeability.

  In particular, Fe, Cr, Si, Zn or Al is preferred as the central metal, alkyl groups, anilide groups, aryl groups and halogens are preferred as substituents, and hydrogen, ammonium and aliphatic ammonium are preferred as counter ions.

  The following compounds are used to control the toner to be positively charged.

  Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts thereof. And lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide) Metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyl Such diorgano tin borate of Suzuboreto; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, triphenylmethane compounds and quaternary ammonium salts whose counter ions are not halogen are preferably used. Moreover, general formula (3)

［式中、Ｒ₁はＨ又はＣＨ₃を示し、Ｒ₂及びＲ₃は置換または未置換のアルキル基（好ましくはＣ₁〜Ｃ₄）を示す。］
で表わされるモノマーの単重合体：前述したスチレン、アクリル酸エステル、メタクリル酸エステルの如き重合性モノマーとの共重合体を正荷電性制御剤として用いることができる。この場合これらの荷電制御剤は、結着樹脂（の全部または一部）としての作用をも有する。

[Wherein R ₁ represents H or CH ₃ , and R ₂ and R ₃ represent a substituted or unsubstituted alkyl group (preferably C _{1 to} C ₄ ). ]
Monomers of monomers represented by: A copolymer with a polymerizable monomer such as styrene, acrylic acid ester or methacrylic acid ester described above can be used as a positive charge control agent. In this case, these charge control agents also have an action as a binder resin (all or a part thereof).

  In particular, a compound represented by the following general formula (4) is preferred as the positive charge control agent of the present invention.

  As a method for adding the charge control agent to the toner, there are a method of adding the toner inside the toner particles and a method of adding the toner outside the toner particles. The amount of use of these charge control agents is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin.

  The toner of the present invention contains a magnetic material. The magnetic material can also serve as a colorant. Magnetic materials used in the toner include iron oxides such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, Examples include alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

These magnetic materials preferably have a number average particle diameter of 0.05 to 1.0 μm, more preferably 0.1 to 0.5 μm. A magnetic substance having a BET specific surface area of ² to 40 m ² / g (more preferably 4 to 20 m ² / g) is preferably used. There is no restriction | limiting in particular in a shape, The thing of arbitrary shapes is used. As magnetic characteristics, a saturation magnetization is 10 to 200 Am ² / kg (more preferably 70 to 100 Am ² / kg) under a magnetic field of 795.8 kA / m, and a residual magnetization is 1 to 100 Am ² / kg (more preferably ² to 20 Am). ² / kg) and a coercive force of 1 to 30 kA / m (more preferably 2 to 15 kA / m) are preferably used. These magnetic materials are used in an amount of 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin. Preferably it is used at 40 to 150 parts by mass.

  The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope or the like with a digitizer or the like. The magnetic properties of the magnetic material can be measured under an external magnetic field of 795.8 kA / m using a “vibrating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.). The specific surface area can be calculated by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Auto Soap 1 (manufactured by Yuasa Ionics) according to the BET method and using the BET multipoint method.

  Other colorants that can be used in the toner of the present invention include any suitable pigment or dye. Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, Bengala, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient to maintain the optical density of the fixed image, and an addition amount of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass is good with respect to 100 parts by mass of the binder resin. . Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes. The addition amount of the dye is 0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  Inorganic particles are externally added to the toner particles of the present invention. The inorganic fine particles are preferably hydrophobic inorganic fine powders. For example, silica fine powder, titanium oxide fine powder, or a hydrophobized product thereof can be used. They are preferably used alone or in combination.

  Examples of the silica fine powder include both a dry process produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica, and wet silica produced from water glass or the like. Dry silica with fewer silanol groups on the surface and inside and no production residue is preferred.

  Further, the silica fine powder is preferably hydrophobized. The hydrophobizing treatment is applied by chemically treating with an organosilicon compound that reacts or physically adsorbs with silica fine powder. Preferable methods include a method in which a dry silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with a silane compound or with a silane compound and simultaneously with an organosilicon compound such as silicone oil.

  The silane compounds used for the hydrophobization treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethyl. Chlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane , Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldi Examples thereof include siloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the organosilicon compound include silicone oil. As a preferable silicone oil, one having a viscosity at 25 ° C. of about 30 to 1,000 mm ² / s is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, and fluorine modified silicone oil are preferred.

  Silicone oil treatment can be performed by directly mixing silica powder treated with a silane compound and silicone oil using a mixer such as a Henschel mixer, or spraying silicone oil onto the base silica. It may be by the method. Alternatively, the silicone oil may be dissolved or dispersed in an appropriate solvent, and then mixed with the base silica fine powder to remove the solvent.

  As a preferable hydrophobizing treatment of the silica fine powder, there is a method of preparing by treating with hexamethyldisilazane and then treating with silicone oil.

  As described above, it is preferable to treat the silica fine powder with the silane compound and then oil-treat it later, so that the degree of hydrophobicity can be effectively increased.

  The silica fine powder is preferably subjected to a hydrophobization treatment, and further, an oil treatment applied to the titanium oxide fine powder, similarly to the silica-based one.

  To the toner of the present invention, additives other than fine silica powder or fine titanium oxide powder may be externally added as necessary.

  Examples thereof include resin fine particles and inorganic fine particles that act as charging aids, conductivity imparting agents, fluidity imparting agents, anti-caking agents, mold release agents at the time of hot roll fixing, lubricants, and abrasives.

  The fine resin particles preferably have an average particle size of 0.03 to 1.0 μm. As the polymerizable monomer constituting the resin, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene derivatives; acrylic acid; methacrylic acid; methyl acrylate , Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acrylic acid esters such as: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, Lil, phenyl methacrylate, dimethylaminoethyl methacrylate, such as methacrylic acid esters of diethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, and the like monomers acrylamide.

  Examples of the polymerization method include suspension polymerization, emulsion polymerization, and soap-free polymerization. More preferably, particles obtained by soap-free polymerization are good.

  Other fine particles include lubricants such as poly (ethylene fluoride), zinc stearate and polyvinylidene fluoride (polyvinylidene fluoride is preferred); abrasives such as cerium oxide, silicon carbide and strontium titanate (especially strontium titanate). Fluidity-imparting agents such as titanium oxide and aluminum oxide (especially hydrophobic ones are preferred); anti-caking agents; and conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide. . Further, a small amount of white fine particles and black fine particles having a polarity opposite to that of the toner may be used as a developability improver.

  The resin fine particles, inorganic fine powder or hydrophobic inorganic fine powder mixed with the toner is preferably used in an amount of 0.01 to 5 parts by mass (preferably 0.01 to 3 parts by mass) with respect to 100 parts by mass of the toner.

  The toner of the present invention preferably exhibits a sufficient effect when the weight average particle diameter is 2.5 to 10.0 μm, preferably 4.0 to 9.0 μm, more preferably 5.0 to 8.0 μm. And preferred.

  The weight average particle diameter and particle size distribution of the toner are determined using a Coulter counter method. For example, a Coulter Multisizer (manufactured by Coulter Inc.) can be used. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 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 volume and number of toner particles of 2.00 μm or more are measured using the 100 μm aperture as the aperture by the measuring device. Volume distribution and number distribution are calculated. Then, the weight-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention is calculated. 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 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Use 13 channels less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm.

  The toner of the present invention can be used as a two-component developer in combination with a carrier. As the carrier for use in the two-component development method, a conventionally known carrier can be used. Specifically, particles having an average particle diameter of 20 to 300 μm formed of surface oxidized or unoxidized metal such as iron, nickel, cobalt, manganese, chromium, rare earth and their alloys or oxides are used as carrier particles. The

  The surface of the carrier particles is preferably coated with a substance such as styrene resin, acrylic resin, silicone resin, fluorine resin, or polyester resin.

  In order to produce the toner according to the present invention, the above-described toner constituent materials are sufficiently mixed by a ball mill or other mixer, and then kneaded well using a heat kneader such as a hot roll, a kneader or an extruder, and cooled. A method in which after the solidification and coarse pulverization, fine pulverization and classification, and then surface modification of the toner particles using a surface modification device is preferable. Furthermore, the toner according to the present invention can be produced by sufficiently mixing desired additives with a mixer such as a Henschel mixer, if necessary.

  For example, as a mixer, Henschel mixer (Mitsui Mining Co., Ltd.); Super mixer (Kawata Co., Ltd.); Ribocorn (Okawara Seisakusho Co., Ltd.); (Pacific Kiko Co., Ltd.); Ladige mixer (Matsubo Co., Ltd.), and KRC kneader (Kurimoto Iron Works Co.); Bus Co Kneader (Buss Co.); TEM type extruder (Manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikekai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Mining company); MS pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe Steel) It is below. As a pulverizer, a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd.); a cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); SK Jet Oh Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); Turbo Mill (manufactured by Turbo Industry Co., Ltd.); Super Rotor (manufactured by Nissin Engineering Co., Ltd.). Classifiers include: Classy, Micron Classifier, Spedick Classifier (manufactured by Seishin Enterprise); Turbo Classifier (manufactured by Nisshin Engineering); Micron Separator, Turbo Flex (ATP), TSP Separator (manufactured by Hosokawa Micron) Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industrial Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.). Ultrasonic (Made by Sakae Sangyo Co., Ltd.); Resona sieve, Gyroshifter (Deoksugaku Kojo Co., Ltd.); Vibrasonic system (Made by Dalton); Soniclean (Shinto) (Industry company); Turbo screener (Turbo industry company); Micro shifter (Ogino industry company); Circular vibration sieve, etc.

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

[Binder resin production example]
(Polyester resin production example 1)
-27 parts by mass of terephthalic acid-2 parts by mass of trimellitic anhydride-Bisphenol derivative represented by formula (A) (R: propylene group x + y = 2.2)
60 parts by mass / bisphenol derivative represented by formula (A) (R: ethylene group x + y = 2)
11 parts by weight 0.36 parts by weight of dibutyltin oxide as a catalyst was added thereto, and condensation polymerization was carried out at 230 ° C. to produce a low molecular weight polyester resin A (Tg 59 ° C., weight average molecular weight Mw = 7300, acid value = 14.2 mgKOH / g). Got.

(Polyester resin production example 2)
-28 parts by mass of terephthalic acid-Bisphenol derivative represented by formula (A) (R: propylene group x + y = 2.2)
72 parts by mass Dibutyltin oxide 0.51 part by mass as a catalyst was added thereto, and condensation polymerization was carried out at 225 to 240 ° C. to obtain a low molecular weight polyester resin B (Tg 58 ° C., weight average molecular weight Mw = 9300, acid value = 3.6 mgKOH / g) was obtained.

(Polyester resin production example 3)
-35 parts by weight of terephthalic acid-1 part by weight of trimellitic anhydride-Bisphenol derivative represented by formula (A) (R: propylene group x + y = 2.2)
64 parts by weight Dibutyltin oxide 0.52 parts by weight as a catalyst was added thereto, and condensation polymerization was carried out at 220 ° C. to obtain a low molecular weight polyester resin C (Tg 59 ° C., weight average molecular weight Mw = 13600, acid value = 43.4 mgKOH / g). Got.

(Polyester resin production example 4)
-21 parts by mass of terephthalic acid-7 parts by mass of trimellitic anhydride-Bisphenol derivative represented by formula (A) (R: propylene group x + y = 2.2)
69 parts by mass-bisphenol derivative represented by the formula (A) (R: ethylene group x + y = 2)
3 parts by mass 0.43 parts by mass of dibutyltin oxide as a catalyst was added to these and subjected to condensation polymerization at 225 ° C. to obtain a high molecular weight polyester resin D (Tg 57 ° C., weight average molecular weight Mw = 24200, acid value = 23.3 mgKOH / g). Got.

(Polyester resin production example 5)
-10 parts by mass of terephthalic acid-3 parts by mass of trimellitic anhydride-Bisphenol derivative represented by formula (A) (R: propylene group x + y = 2.2)
67 parts by mass-bisphenol derivative represented by formula (A) (R: ethylene group x + y = 2)
20 parts by weight Dibutyltin oxide (0.48 parts by weight) was added to these as a catalyst and subjected to condensation polymerization at 220 to 235 ° C. to obtain a high molecular weight polyester resin E (Tg 60 ° C., weight average molecular weight Mw = 18000, acid value = 7.2 mgKOH / g) was obtained.

(Polyester resin production example 6)
-19 parts by mass of terephthalic acid-15 parts by mass of trimellitic anhydride-Bisphenol derivative represented by the formula (A) (R: propylene group x + y = 2.2)
66 parts by weight Dibutyltin oxide 0.50 parts by weight as a catalyst was added thereto, and condensation polymerization was carried out at 220 ° C. to obtain a high molecular weight polyester resin F (Tg 58 ° C., weight average molecular weight Mw = 101100, acid value = 62.2 mgKOH / g). Got.

[Production Example 1 of resin melt blend]
・ Low molecular weight polyester resin A 50 parts by mass High molecular weight polyester resin D 50 parts by weight The above materials are premixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) and rotated with a melt kneader PCM30 (Ikegai Iron Works Co., Ltd.) Blend blend 1 was obtained by melt blending under the conditions of several 200 rpm and kneading resin temperature of 100 ° C.

[Production Examples 2-5 and 7 of resin melt blend]
Blend resins 2 to 5 and 7 were obtained according to the polyester resins and blend ratios shown in Table 2 in the same manner as in blend resin 1 of Production Example 1 of resin melt blend.

樹脂６：スチレン−アクリル酸ブチル共重合体（Ｔｇ６０℃、重量平均分子量Ｍｗ＝２７００００、酸価０．１ｍｇＫＯＨ／ｇ）

Resin 6: Styrene-butyl acrylate copolymer (Tg 60 ° C., weight average molecular weight Mw = 270000, acid value 0.1 mgKOH / g)

  Table 3 shows the physical properties of the magnetic material (magnetite) used in the present invention.

[Example of wax synthesis]
Wax synthesis example 1:
1000 g of paraffin wax [number average molecular weight (Mn) 398] as a raw material was placed in a glass cylindrical reactor, and the temperature was raised to 140 ° C. while blowing a small amount of nitrogen gas (3.5 liters / minute). After 26.6 g of mixed catalyst of boric acid / boric anhydride = 1.44 (molar ratio) was added, reaction was performed at 180 ° C. for 2 hours while blowing air (20 liter / min) and nitrogen (15 liter / min). Went. After completion of the reaction, an equal amount of warm water (95 ° C.) is added to the reaction mixture, the reaction mixture is hydrolyzed, left to stand to separate the separated wax into the upper layer, and the separated wax is washed with water to obtain wax 1. It was. Hydrocarbon wax 1 had an acid value of 7.2 mgKOH / g, a hydroxyl value of 62.6 mgKOH / g, an ester value of 19.4 mgKOH / g, a melting point of 72 ° C. and Mn of 322. Table 4 shows the physical properties of Wax 1.

Wax synthesis example 2:
Wax 2 (Mn = 998) was obtained in the same manner as in Wax Synthesis Example 1 except that 1000 g of polyethylene wax (Mn = 1212) was used as a raw material and the synthesis conditions were changed. Table 4 shows the physical properties of Wax 2.

Wax synthesis example 3:
Wax 3 (Mn = 321) was obtained in the same manner as in Wax Synthesis Example 1 except that 1000 g of Fischer-Tropsch wax (Mn = 330) was used as a raw material and the synthesis conditions were changed. Table 4 shows the physical properties of Wax 3.

Wax synthesis example 4:
Wax 4 (Mn = 1302) was obtained in the same manner as in Wax Synthesis Example 1 except that 1000 g of polyethylene wax (Mn = 1563) was used as a raw material and the synthesis conditions were changed. Table 4 shows the physical properties of the wax 4.

Wax synthesis example 5:
A wax 5 (Mn = 276) was obtained in the same manner as in the wax synthesis example 1 except that 1000 g of paraffin wax (Mn = 282) was used as a raw material and the synthesis conditions were changed. Table 4 shows the physical properties of the wax 5.

Wax synthesis example 6:
Wax 6 (Mn = 2240) was obtained in the same manner as in Wax Synthesis Example 1 except that 1000 g of polyethylene wax (Mn = 2250) was used as a raw material and the synthesis conditions were changed. Table 4 shows the physical properties of the wax 6.

Wax synthesis example 7:
A wax 7 (Mn = 251) was obtained in the same manner as in the wax synthesis example 1 except that 1000 g of paraffin wax (Mn = 254) was used as a raw material and the synthesis conditions were changed. Table 4 shows the physical properties of Wax 7.

[Preparation of Toner 1]
-Blend resin 1 100 parts by mass-Magnetic substance 1 95 parts by mass-Monoazo iron complex (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 2 parts by mass-Wax 1 4 parts by mass After premixing the above mixture with a Henschel mixer, 110 ° C Then, the mixture was melt-kneaded with a biaxial extruder heated to 1 and the cooled kneaded product was coarsely pulverized with a hammer mill to obtain a coarsely pulverized toner product. The obtained coarsely pulverized product was coated with a mechanical pulverizer turbo mill (manufactured by Turbo Kogyo Co., Ltd .; coated with chromium alloy plating containing chromium carbide on the rotor and stator surfaces (plating thickness 150 μm, surface hardness HV1050)). Then, the finely pulverized product and the finely pulverized product were classified and removed at the same time using a multi-division classifier (Elbow Jet Classifier manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect. The toner particles thus obtained had a weight average particle diameter (D ₄ ) measured by a Coulter counter method of 6.3 μm.

The raw toner particles were subjected to surface modification by the surface modification apparatus shown in FIG. The conditions for the surface modification were a raw material supply rate of 2 kg / hr, a hot air flow rate of 700 L / min, a discharge hot air temperature of 300 ° C., and the toner particles 1 obtained had a weight average particle diameter (D ₄ ) of 6.8 μm. It was. Table 5 shows the physical properties of Toner Particles 1.

  100 parts by mass of the toner particles and 1.35 parts by mass of hydrophobic silica fine powder treated with hexamethyldisilazane and then with dimethylsilicone oil were mixed with a Henschel mixer to prepare negatively charged toner 1. . Table 5 shows the physical properties of the negatively chargeable toner 1.

[Preparation of Toners 2 to 8]
Toners 2 to 8 were obtained in the same manner as in Toner 1 except that the binder resin, magnetic material and wax used were changed as shown in Table 5 and the surface modification conditions were changed as shown in Table 5. Table 5 shows the physical properties of Toner Particles 2-8 and Toner 2-8.

<Examples 1-5, Comparative Examples 1-3>
Next, the prepared toner was used for evaluation by the following method. The evaluation results are shown in Table 6.

  The following evaluation was performed using a laser beam printer Laser Jet 4300n manufactured by Hewlett-Packard Co., modified to 55 sheets / min.

(1) Image density, fog Under normal temperature and normal humidity (23 ° C, 60% RH), low temperature and low humidity (15 ° C, 10% RH), high temperature and high humidity (32.5 ° C, 80% RH) Under each environment, a printing test of 10,000 sheets was performed on plain paper for copying machines (A4 size: 75 g / m ² ) at a printing speed of 2 sheets / 10 seconds and a printing ratio of 5%, and left again for one day. An image forming test of 10,000 sheets, a total of 20,000 sheets, was performed while supplying toner. The results are shown in Table 6.

  For the image density, a “Macbeth reflection densitometer” (manufactured by Macbeth) was used to measure a relative density with respect to a printout image of a white background portion having an original density of 0.00.

  The fog was calculated from a comparison between the whiteness of the transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white.

(2) Transfer rate The transfer rate of the toner image from the photosensitive drum to the transfer paper at the endurance of 20000 sheets in a room temperature and humidity environment was determined by the following method.

The transfer rate of the toner image from the photosensitive drum to the transfer paper is determined by taking the toner image formed on the photosensitive drum with a transparent adhesive tape and measuring the image density using a Macbeth densitometer or a color reflection densitometer (for example, a color reflection density meter X). -RITE404A manufactured by X-RiteCo.) Next, the toner image is again formed on the photosensitive drum, the toner image is transferred to the transfer paper, the toner image on the transfer paper corresponding to the toner image collected on the photosensitive drum is collected with a transparent adhesive tape, and the like. The image density was measured. The transfer rate was calculated from the following formula.
Transfer rate (%) = (Image density of toner image collected from transfer paper) / (Image density of toner image collected from photoreceptor) × 100

(3) Fusion of toner to photoconductor The photoconductor and a solid black image after 20000 printing in a high temperature and high humidity environment were visually evaluated.
A: No toner fusion is observed on the photoreceptor.
B: The toner is slightly fused on the photoreceptor, but does not appear on the image.
C: An image omission of white dots is seen on a solid black image.
D: Shooting star-like image omission is seen from a white dot on a solid black image.

(4) Sleeve negative ghost Print out 20000 sheets of ordinary copier plain paper (75 g / m ² ) at low temperature and low humidity (15 ° C, 10% RH), and evaluate the sleeve negative ghost every 10,000 sheets. It was. For the image evaluation related to the ghost, a solid black band was output for one round of the sleeve, and then a halftone 3 image was output. A schematic diagram of the pattern is shown in FIG. In the evaluation method, the Macbeth density at the place where the black image is formed in the second round of the sleeve (black print portion 1) and the place where the black image is not formed (non-image portion 2) in one print image. The difference in reflection density measured by a reflectometer was calculated as follows. In the negative ghost 4, the image density of the black printed portion in the first round of the sleeve is generally lower than the image density of the non-image portion in the first round of the sleeve. This is a ghost phenomenon in which the shape of the pattern produced in the first round appears as it is. The density difference here was evaluated by measuring the reflection density difference.
Reflection density difference = reflection density (place where no image is formed) −reflection density (place where an image is formed)

The smaller the reflection density difference is, the better the level is without ghosting. As the overall evaluation of the ghost, the evaluation is made in four stages of A, B, C, and D, and the worst evaluation result in the evaluation for every 10,000 sheets is shown in Table 6.
Reflection density difference 0.00 or more and less than 0.02: A
0.02 or more and less than 0.04: B
0.04 or more and less than 0.06: C
0.06 or more: D

(5) Blocking resistance test:
About 10 g of toner was put in a 100 ml plastic cup and allowed to stand at 50 ° C. for 3 days, and then visually evaluated.
A: Aggregates are not seen.
B: Although an aggregate is seen, it collapses easily.
C: Although aggregates are seen, they collapse when shaken.
D: Aggregates can be grasped and do not collapse easily.

The schematic of the surface modification apparatus used for this invention is shown. It is explanatory drawing of the pattern for evaluating a sleeve ghost.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Toner particle 2 Auto-feeder 3 Supply nozzle 4 Inside surface modification apparatus 5 Hot air introduction port 6 Cold air introduction port 7 Surface-modified toner particle 8 Cyclone 9 Blower

Claims (7)

A toner containing at least a binder resin, a magnetic material, wax-containing toner particles, and inorganic fine particles,
The binder resin contains at least a polyester unit,
The binder resin has an acid value (RAv) of 1 to 50 mgKOH / g, and the wax has an acid value (WAv) of 1 to 30 mgKOH / g and satisfies the following formula (1):
0 ≦ | (RAv−WAv) | ≦ 35 (1)
Regarding the carbon atom, oxygen atom, and iron atom peaks measured by ESCA of the toner particles, the intensity ratio of the carbon atom peaks is 88.5% or more, and the intensity ratio of the oxygen atom peaks is 11.5% or less. Toner characterized by being.   The toner according to claim 1, wherein the wax has a hydroxyl value (WOHv) of 20 to 100 mgKOH / g.   The toner according to claim 1, wherein the wax has a melting point measured by DSC of 50 ° C. to 120 ° C. 3.   4. The toner according to claim 1, wherein an intensity ratio of iron atom peaks measured by ESCA of the toner particles is less than 1%. 5.   In a solution obtained by dispersing 150 mg of the toner particles in 5 ml of a surfactant aqueous solution and further adding 5 ml of 6 mol / l hydrochloric acid and extracting for 30 minutes, the absorbance at 340 nm is 0.1 to 1.0. The toner according to claim 1.   6. The average circularity of toner particles having an equivalent circle diameter of 3 μm or more and 400 μm or less measured by the toner flow-type particle image measuring apparatus is 0.935 or more. toner.   The toner according to claim 1, wherein the wax is a hydrocarbon wax obtained by converting an aliphatic hydrocarbon wax into an alcohol.

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