JP2003302784A - Magnetic toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a magnetic toner having satisfactory low temperature fixing property and high temperature offset resistance, maintaining high developing property even in a severe environment and causing no sleeve ghost. <P>SOLUTION: The magnetic toner comprises at least a binder resin, magnetic iron oxide and two or more kinds of hydrocarbon wax. In the hydrocarbon wax, at least one kind of hydrocarbon wax (a) has 5 to 150 mgKOH/g hydroxyl value (HV) and 1 to 50 mgKOH/g ester value (EV), in the relation of HV>EV. At least one kind of hydrocarbon wax (b) is selected from polyolefin wax, Fischer-Tropsch wax and paraffin wax. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a magnetic toner used in electrophotography and an image forming method for visualizing an electrostatic charge image, and a magnetic toner used in a toner jet.

[0002]

2. Description of the Related Art In electrophotography and an image forming method for visualizing an electrostatic charge image, various methods and apparatuses have been developed for fixing a magnetic toner image on a sheet such as paper. A pressure-bonding heating method using a heat roller and a heat fixing method in which a heating member is brought into close contact with a heating member via a film have been proposed.

In the heating method using a heating roller or a film, a magnetic toner image surface of a sheet to be fixed is passed while being brought into contact with the surface of a heating roller or a film whose surface is formed of a material having releasability for magnetic toner. By doing so, fixing is performed. In this method, since the surface of the heat roller or the film comes into contact with the magnetic toner image on the sheet to be fixed, the thermal efficiency at the time of fusing the magnetic toner image on the sheet to be fixed is extremely good, and the fixing is performed quickly. And is very good in electrophotographic copiers or printers. However, in the above method, since the magnetic toner image is in contact with the surface of the heat roller or the film in a molten state, a part of the magnetic toner image adheres to and transfers to the fixing roller or the film surface, and is retransferred to the next sheet to be fixed. As a result, an offset phenomenon may occur and the sheet to be fixed may be soiled. It is one of the important conditions of the heat fixing method to prevent the magnetic toner from adhering to the heat fixing roller or the film surface.

Conventionally, for the purpose of preventing the magnetic toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material such as silicone rubber or fluorine resin which has excellent releasability from the magnetic toner, and the surface of the roller is offset. In order to prevent the above and prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having a good releasing property such as silicone oil. However, this method is extremely effective in preventing offset of the magnetic toner, but has a problem that the fixing device becomes complicated because an apparatus for supplying the offset preventing liquid is required. In addition, this is the opposite direction to downsizing and weight saving, and moreover, silicone oil or the like may evaporate due to heat and pollute the inside of the machine.

In view of the idea that instead of supplying a silicone oil supply device, the offset preventing liquid is supplied from the magnetic toner during heating, a release agent such as low molecular weight polyethylene or low molecular weight polypropylene is added to the magnetic toner particles. A method of adding is proposed. But,
If a large amount of such an additive is added in order to obtain a sufficient effect, filming on the photoconductor and contamination of the surface of the magnetic toner carrier such as the carrier or the developing sleeve may cause deterioration of the image.

Therefore, a small amount of releasing agent is added to the magnetic toner particles so as not to deteriorate the image, and a small amount of releasing oil is supplied or the offset magnetic toner is wound into a member such as a web. A cleaning device is also used together with the cleaning device. However, considering recent demands for size reduction, weight reduction, and high reliability, it is necessary and preferable to remove these auxiliary devices. Therefore, it is necessary to further improve the fixability and anti-offset property of the magnetic toner, and further improvement of the binder resin and the release agent of the magnetic toner is desired.

It is known to include a wax as a releasing agent in the toner particles. For example, Japanese Patent Publication Sho 52-3
304, Japanese Patent Publication No. 52-3305, Japanese Patent Publication No. 5
No. 7-52574.

These waxes are used to improve the offset resistance of the toner at low temperatures and high temperatures.
However, on the other hand, these properties are improved, but on the other hand, the blocking resistance is lowered and the developability is lowered.

Further, Japanese Patent Laid-Open No. 2000-267347 discloses a technique in which a wax having a polar group is contained in a toner. However, when such a wax is used in the toner, the developability of the toner is unsatisfactory. In some cases it was enough.

Further, Japanese Patent Laid-Open No. 63-113558,
JP-A-63-188158, JP-A2-1346
Japanese Patent Laid-Open No. 48-97162 and Japanese Patent Laid-Open No. 4-97162 disclose a technique of containing an alcohol component in toner particles. These alcohol components have been found to have the effect of improving the fixability of the magnetic toner at low temperatures and the anti-offset property at high temperatures, but they sometimes deteriorate the developability of the toner.

Japanese Unexamined Patent Publication (Kokai) No. 4-97163 discloses a toner containing a resin composition for a toner containing an aliphatic alcohol and a polyolefin wax, but it has some effect on the fixing property and offset resistance of the toner. Although obtained, the developability and storability of the toner may deteriorate.

Further, Japanese Patent Application Laid-Open No. 1-109359 discloses a technique of incorporating a low molecular weight polyolefin polyol in toner particles. Although such a wax has an effect on the fixing property and developing property of the toner, the blocking resistance and the offset resistance at high temperature may be insufficient.

Further, JP-A-4-184350, JP-A-4-194947 and JP-A-4-194948.
Japanese Unexamined Patent Publication (Kokai) Publication discloses a technique in which toner particles contain a partially esterified polyglycerin. Even by adding such a polyglycerin compound, sufficient fixing property and offset resistance have not yet been satisfied.

Further, Japanese Patent Application Laid-Open No. 4-194946 discloses a resin composition for toner which is prepared by blending a partially esterified product of polyglycerin and a polyolefin wax, but the fixing property and the offset resistance are to some extent. Although effective, it has not yet been able to provide the toner with sufficient fixability, releasability and sufficient developability.

[0015]

SUMMARY OF THE INVENTION An object of the present invention is to provide a magnetic toner that solves the above problems.

An object of the present invention is to provide a magnetic toner having improved low-temperature fixing property and anti-offset property and exhibiting good fixing performance.

An object of the present invention is to provide a magnetic toner that does not adhere to the fixing member even when used for a long period of time and has excellent image characteristics similar to those at the initial stage.

It is a further object of the present invention to provide a magnetic toner in which a hydrocarbon wax is uniformly dispersed in magnetic toner particles and has excellent image characteristics similar to those at the initial stage even when used for a long period of time. .

A further object of the present invention is to provide a magnetic toner which does not cause sleeve ghost even in a high speed developing system.

A further object of the present invention is to provide a magnetic toner which has both low temperature fixability and high durability of the magnetic toner even at a high process speed.

A further object of the present invention is to provide a magnetic toner excellent in long-term storage stability.

[0022]

The inventors of the present invention have conducted extensive studies on the composition of the magnetic toner in order to solve the above problems, and as a result, the magnetic toner contains at least two kinds of hydrocarbon wax. And at least one hydrocarbon wax (a) has a hydroxyl value (H _V ) of 5 to 150.
is a mgKOH / g, ester value (E _V) from 1 to 50
mgKOH / g, the relationship is H _V > E _V , and the at least one hydrocarbon wax (b) is a hydrocarbon wax selected from polyolefin wax, Fischer-Tropsch wax, and paraffin wax. It shows good fixability in a wide temperature range from low temperature to high temperature, and maintains high-temperature, high-humidity, low-temperature while maintaining charge stability of magnetic toner for a long time and charge uniformity when mixing magnetic toner. It has been found that a magnetic toner having a good developing property can be obtained even in a low humidity environment.

That is, the present invention is a magnetic toner containing at least a binder resin, a colorant and a hydrocarbon wax, wherein at least one hydrocarbon wax (a) is a hydroxyl group. value (H _V) is 5~150mgKOH / g, an ester value (E _V) is 1~50mgKOH / g, the relationship is H _V> E _V, at least one hydrocarbon wax (b ) Relates to a magnetic toner characterized by being a hydrocarbon wax selected from polyolefin wax, Fischer-Tropsch wax and paraffin wax.

[0024]

DETAILED DESCRIPTION OF THE INVENTION As a result of intensive studies, the present inventors have found that the hydroxyl value (H _V ) is 5 to 150 mgKOH / g (preferably 10 to 100 mgKOH / g, more preferably 20 to 10 mgKOH / g).
90mgKOH / g) and is, ester value (E _V) is 1
-50 mgKOH / g (preferably 1-30 mgKOH
/ G, more preferably 1 to 20 mgKOH / g, particularly preferably 1 to 15 mgKOH / g), and a hydrocarbon wax (b) selected from polyolefin wax, Fischer-Tropsch wax and paraffin wax. ) Is used as a magnetic toner, it exhibits good fixing performance in a wide temperature range from low temperature to high temperature, and exhibits good developability over long-term use even in high-temperature high-humidity and low-temperature low-humidity environments. It has been found that a magnetic toner can be obtained.

The hydrocarbon wax (a) used in the present invention preferably contains a hydrocarbon molecular chain having the following structure. At least a molecular chain having a structure of a secondary alcohol having a hydroxyl group on a secondary carbon represented by the following partial structural formula A and a molecular chain having an ester structure having an ester bond represented by the following partial structural formula B are defined as hydrocarbon wax molecules. What is contained therein, and one molecular chain may have both structures.

Further, a hydrocarbon wax molecule having a molecular chain having an acid group structure having a carboxyl group at a primary or secondary carbon represented by the following partial structural formulas C and D is also preferable. Further, it may have a molecular chain having a structure of a primary alcohol having a hydroxyl group on the primary carbon represented by the following partial structural formula E. One hydrocarbon chain may have any structure of the following partial structural formulas A, B, C, D and E.

[0027]

[Chemical 4]

Since the hydrocarbon wax (a) used in the present invention has an appropriate hydroxyl group in the molecule, the hydrocarbon wax (a) can be dispersed in fine particles in the binder resin. A moderate plasticizing effect is obtained, and the fixability is improved. Hydrocarbon wax (a) has a hydroxyl value of 5 m
If it is less than gKOH / g, the hydrocarbon wax (a) is not sufficiently finely dispersed, and the fixability of the magnetic toner is lowered. Further, the hydroxyl value of the hydrocarbon wax (a) is 150 mg.
When it is higher than KOH / g, the plasticizing effect of the hydrocarbon wax (a) becomes too large, and the blocking resistance of the magnetic toner deteriorates.

Further, since the ester group in the hydrocarbon wax (a) has a high affinity with the binder resin component of the magnetic toner, the hydrocarbon wax (a) should be uniformly present in the magnetic toner particles. Hydrocarbon wax (a)
The effect of can be effectively exhibited. When the ester value of the hydrocarbon wax (a) is less than 1 mgKOH / g, the effect of the hydrocarbon wax (a) on the fixability of the magnetic toner is reduced. Further, when the ester value of the hydrocarbon wax (a) is larger than 50 mgKOH / g, the affinity of the hydrocarbon wax (a) for the binder resin becomes too high, and the binder resin is apt to deteriorate.
The developability of the magnetic toner becomes poor after long-term use.

The hydrocarbon wax (b) used in the present invention is a hydrocarbon wax selected from polyethylene wax, Fischer-Tropsch wax, and paraffin wax, and has excellent releasability from the fixing member and resistance to magnetic toner. Improve the offset property. Hydrocarbon wax (b) has a hydroxyl value (Hv) of less than 5 mgKOH / g and an ester value (Ev) of less than 1 mgKOH / g, preferably a hydroxyl value of less than 1 mgKOH / g and an ester value of less than 1 mgKOH / g, Acid value (Av) is 1 mg
It is less than KOH / g. These hydrocarbon waxes (b) may be insufficiently dispersed in the magnetic toner and may deteriorate the developability of the magnetic toner. However, in the present invention, the hydrocarbon wax (a) is suitable for the magnetic toner. Since the hydrocarbon wax (a) has a high affinity with the hydrocarbon wax (b), the hydrocarbon wax (b) can also be finely dispersed, and the hydrocarbon wax (b) can be dispersed from the magnetic toner during fixing. The hydrocarbon wax (b) can be quickly exuded onto the surface of the magnetic toner, and good offset resistance can be imparted to the magnetic toner even in a high-speed fixing system. Further, since the hydrocarbon wax (a) has an excellent affinity with the binder resin and has a high plasticity, it may accelerate the deterioration of the magnetic toner, especially in a high temperature and high humidity environment for a long time. , The magnetic toner is likely to deteriorate due to stress in the toner developing device. However, in the present invention, the releasing action of the hydrocarbon wax (b) with the binder resin can suppress the excessive plasticizing action of the hydrocarbon wax (a),
The good developability of the magnetic toner can be maintained for a long period of time.

Further, in continuous development in a high-speed development system, it is particularly required that the magnetic toner regulated by the regulation blade is rapidly and uniformly charged on the developer carrier, so-called developing sleeve. As a result, a good image can always be provided even in a high-speed developing system, but if the magnetic toner is unevenly charged and the distribution of the charge amount varies, images with a large printing area are continuously developed. When the subsequent image is developed, the magnetic toner supplied onto the developing sleeve when developing the subsequent image is not sufficiently charged, and as a result, the image density of the subsequent image is reduced and a difference in density occurs on the image. A so-called ghost image may occur. When two or more kinds of waxes are used for the magnetic toner as in the present invention, the charge distribution of the magnetic toner becomes non-uniform and the ghost phenomenon is likely to occur, but in the present invention, the hydrocarbon wax (a) is used. Since the hydrocarbon wax (b) is excellent in mixing properties, the ghost phenomenon does not occur even in a high-speed developing system. In particular, since the hydrocarbon wax (a) of the present invention has an appropriate ester value, it promotes the uniform dispersion of the hydrocarbon wax (a) and the hydrocarbon wax (b) in the magnetic toner, and the ester Since the base keeps the charge amount of the magnetic toner at an appropriate value, the magnetic toner particles having a non-uniform charge amount are reduced, and the ghost phenomenon can be effectively suppressed.

The hydrocarbon wax (a) of the present invention has an acid value (A _V ) of 1 to 30 mgKOH / g (preferably 1 to 30 mgKOH / g).
15 mgKOH / g, more preferably 1-10 mgKO
H / g) is preferred. Since the hydrocarbon wax (a) has an acid group, the interfacial adhesion between the hydrocarbon wax (a) and other components constituting the magnetic toner increases, and the hydrocarbon wax (a) plasticizes the magnetic toner. And the fixing property of the magnetic toner is improved. When the acid value of the hydrocarbon wax (a) is less than 1 mgKOH / g, the interfacial adhesion with other components constituting the magnetic toner becomes small, and the hydrocarbon wax (a) is likely to be liberated, so that the hydrocarbon The action of the system wax (a) may not be sufficiently obtained. The hydrocarbon wax (a) has an acid value of 30 mg.
If it is higher than KOH / g, on the contrary, the interfacial adhesive force becomes too large, the plasticization of the magnetic toner is greatly promoted, and sufficient releasability may not be maintained.

Further, the hydrocarbon wax (a) of the present invention has a hydroxyl value of (H _V) and ester value (E _V) moderately, characterized in that and satisfy the following relationships. H _V ＞ E _V

Further, it is preferable that the relationship of H _V > 2E _V is satisfied. More preferably, H _V
/ A E _V = 2.5~20.

The hydrocarbon wax (a) in the present invention preferably has the acid value (A _V ) and the hydroxyl value (H _V ) satisfying the following relationships. H _V ＞ A _V

Furthermore, it is preferable to satisfy the relationship of H _V > 2A _V. More preferably, H _V
/ A A _V = 2.5~20.

Hydrocarbon wax (a) in the present invention
Since the hydroxyl groups of the above enhance the slipperiness of the magnetic toner, the releasability of the magnetic toner from the fixing member is enhanced. Further, the ester group of the hydrocarbon wax (a) has a high affinity with the binder resin, and the hydrocarbon wax (a) has a hydroxyl group at the same time, so that the hydrocarbon wax is uniformly distributed in the magnetic toner. Since the wax (a) is present, the slipperiness of the magnetic toner with the fixing member can be improved, and the adhesion of the magnetic toner to the fixing member can be reduced. At the same time, the releasing action of the hydrocarbon wax (b) also works effectively. If the ester value of the hydrocarbon wax (a) is equal to or higher than the hydroxyl value, the affinity between the hydrocarbon wax (a) and the binder resin becomes high, and the hydrocarbon wax (a) is less likely to exude to the surface of the magnetic toner. Therefore, the slidability of the hydrocarbon wax (a) with the fixing member and the releasability of the hydrocarbon wax (b) become difficult to work, and image stains easily occur due to adhesion of the magnetic toner to the fixing member. . Further, the ester group in the hydrocarbon wax (a) has a high affinity with the binder resin component, and the hydroxyl group has a high affinity with the sheet to be fixed such as paper, so that the effect of discharging the magnetic toner from the fixing member is obtained. Bring As a result, the releasability of the magnetic toner from the fixing member and the discharging property to the sheet to be fixed are improved, and the image stain caused by the accumulation of the magnetic toner on the fixing member can be reduced.

Further, since the acid group of the hydrocarbon wax (a) has a high adhesive strength with other components of the magnetic toner, the hydrocarbon wax (a) component and the hydrocarbon wax are adhered to the surface of the magnetic toner on the fixing member. (B) is retained. As a result, the effects of the hydrocarbon wax (a) and the hydrocarbon wax (b) work effectively at the interface between the magnetic toner and the fixing member. When the acid value of the hydrocarbon wax (a) is equal to or higher than the hydroxyl value, the slipperiness of the hydrocarbon wax (a) deteriorates, and image stains may occur due to the adhesion of the magnetic toner to the fixing member. . Further, since the hydrocarbon wax (a) has an acid group and an ester group at the same time, the hydrocarbon wax (a) and the hydrocarbon wax (b) have an appropriate dispersion diameter in the magnetic toner particles. The hydrocarbon wax (a) and the hydrocarbon wax (b) can effectively function. If either the acid group or the ester group is lacking, the dispersion diameter of the hydrocarbon wax (a) and the hydrocarbon wax (b) in the magnetic toner particles becomes non-uniform, and the hydrocarbon wax (a) and the hydrocarbon wax (a) are dispersed. The action of the hydrocarbon wax (b) may not work sufficiently.

Further, the hydrocarbon wax (a) used in the present invention is excellent in the releasing action and the plasticizing action when finely dispersed in the magnetic toner particles, and in the present invention, the hydrocarbon wax is used. Since the main chain of the wax system (a) has a carbon bond (that is, a long chain of a methylene group), the substituents of the acid group, the hydroxyl group, and the ester group easily function in the magnetic toner particles, effectively Fixability and releasability can be improved. When other elements are contained in the main chain of the hydrocarbon wax (a), for example, when an ether bond containing oxygen such as polyglycerin exists,
The action and effect of the hydrocarbon wax (a) are reduced, and further, the functions of the respective substituents, which are the features of the present invention, are hindered, and preferable fixability and releasability cannot be obtained.

Hydrocarbon wax (a) in the present invention
Producing a borate ester of the hydrocarbon wax from an aliphatic hydrocarbon wax and hydrolyzing the borate ester of the hydrocarbon wax to produce a hydrocarbon wax (a) having a hydroxyl group. Is preferred. A series of steps for producing a hydrocarbon wax having a hydroxyl group from an aliphatic hydrocarbon wax is called alcohol conversion. It is preferable to obtain a hydrocarbon wax having desired properties by utilizing the step of alcohol conversion, since it is easy to control the conversion rate of the acid group, hydroxyl group and ester group of the hydrocarbon wax (a).

As the aliphatic hydrocarbon wax, the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 100 to 3000, preferably 200 to 2000, more preferably 250 to 1000 in terms of polyethylene. Saturated or unsaturated aliphatic hydrocarbons in the range of are preferably used.

In the present invention, a hydrocarbon wax (a)
The molecular weight distribution of is measured by gel permeation chromatography (GPC) under the following conditions.

(GPC measurement conditions) Device: HLC-8121 GPC / HT (manufactured by Tosoh Corporation) Column: TSKgel GMHHR-H HT 7.8
cmI. D × 30 cm 2 stations (manufactured by Tosoh Corporation) Detector: RI for high temperature Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.05% ionol added) Flow rate: 1.0 ml / min Sample: 0.1% sample Measurement is performed under the condition of 0.4 ml injection or more, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Further, it is calculated by performing polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

Examples of the aliphatic hydrocarbon wax include higher aliphatic unsaturated hydrocarbons having one or more double bonds obtained by an ethylene polymerization method or an olefination method by thermal decomposition of petroleum hydrocarbons, petroleum distillates. N-paraffin mixture obtained from the above, polyethylene hydrocarbon wax obtained by the ethylene polymerization method, and higher aliphatic hydrocarbon obtained by the Fischer-Tropsch synthesis method.
One kind or two or more kinds are preferably used.

Hydrocarbon wax (a) in the present invention
As a production example of, for example, an aliphatic hydrocarbon wax can be obtained by liquid phase oxidation with a molecular oxygen-containing gas, preferably in the presence of boric acid and boric anhydride.
The obtained hydrocarbon wax may be further purified by a press perspiration method, purified by using a solvent, hydrogenated, washed with sulfuric acid, and then treated with activated clay. A mixture of boric acid and boric anhydride can be used as the catalyst. The mixing ratio of boric acid and boric anhydride (boric acid / boric anhydride) is preferably in the range of 1 to 2, preferably 1.2 to 1.7 in terms of molar ratio. If the ratio of boric anhydride is less than the above range, the excessive amount of boric acid causes an aggregation phenomenon, which is not preferable. On the other hand, when the ratio of boric anhydride is higher than the above range, powdery substances derived from boric anhydride are recovered after the reaction, and excess boric anhydride does not contribute to the reaction, which is not economically preferable.

The amount of boric acid and boric anhydride to be used is 0.001 to 10 mol, especially 0.1 to 10 mol, based on 1 mol of the aliphatic hydrocarbon as a raw material, when the mixture is converted into the amount of boric acid. -1 mol is preferred.

Besides boric acid / boric anhydride, metaboric acid and pyroboric acid can also be used. In addition, examples of forming an ester with an alcohol include an oxygen acid of boron, an oxygen acid of phosphorus, and an oxygen acid of sulfur. Specific examples include boric acid, nitric acid, phosphoric acid, and sulfuric acid.

As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of those diluted with an inert gas can be used. The gas has an oxygen concentration of 1 to 3.
It is preferably 0% by volume, more preferably 3 to 20.
% By volume.

The liquid phase oxidation reaction is usually carried out in the molten state of the raw material aliphatic hydrocarbon without using a solvent. The reaction temperature is 120 to 280 ° C, preferably 150 to 250 ° C. The reaction time is preferably 1 to 15 hours.

It is preferable that boric acid and boric anhydride are premixed and added to the reaction system. Adding boric acid alone is not preferable because it causes a dehydration reaction of boric acid. The addition temperature of the mixed catalyst of boric acid and boric anhydride is 100 to 1
80 ° C. is preferable, preferably 110 to 160 ° C., 1
When the temperature is lower than 00 ° C, the catalytic ability of boric anhydride is reduced due to water remaining in the system, which is not preferable.

After completion of the reaction, water is added to the reaction mixture to hydrolyze and purify the borate ester of the hydrocarbon wax thus produced, whereby the hydrocarbon wax (a) having a desired functional group is obtained.

In the present invention, the acid value, hydroxyl value, ester value and saponification value of the hydrocarbon wax (a) are determined by the following methods. Basic operation is J1S K 0070
According to.

Acid value measurement / apparatus and equipment Erlenmeyer flask (300 ml) Burette (25 ml) Water bath or hot plate / reagent 0.1 kmol / m ³ hydrochloric acid 0.1 kmol / m ³ potassium hydroxide ethanol solution (standard: 25 ml of 1 kmol / m ³ hydrochloric acid was placed in an Erlenmeyer flask using a whole pipette, a phenolphthalein solution was added, and titration was performed with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and the factor was determined 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. A few drops of the phenolphthalein solution as an indicator were added immediately before use. .1kmol / m ³ is neutralized with potassium hydroxide solution in ethanol.) measurement method (a) a hydrocarbon wax (a) The precisely weighed in an Erlenmeyer flask ~20g. (B) 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator are added, and the mixture is thoroughly shaken on a water bath until the hydrocarbon wax is completely dissolved. (C) Titrate with 0.1 kmol / m ³ potassium hydroxide ethanol solution, and make the end point when light red color of the indicator continues for 30 seconds. Calculation A = 5.611 × B × f / S where A: acid value (mgKOH / g) B: amount of 0.1 kmol / m ³ potassium hydroxide ethanol solution used for titration (ml) f: 0. Factor S of 1 kmol / m ³ potassium hydroxide ethanol solution: mass of hydrocarbon wax (a) (g) 5.611: formula weight of potassium hydroxide 56.11 × 1/1
0

[0054]Measurement of hydroxyl value ・ Devices and equipment Measuring cylinder (100 ml) Whole volume pipette (5 ml) Flat bottom flask (200 ml) Glycerin bath ·reagent Acetylating reagent (25 g of acetic anhydride was added to the flask 100
Take up to ml and add pyridine to bring the total volume to 100 ml,
Shake well. ) Phenolphthalein solution 0.5 kmol / m³Potassium hydroxide ethanol solution ・ Measuring method (A) 0.5 to 6.0 g of a hydrocarbon wax, a flat bottom flask
Accurately weigh it and add 5 ml of the acetylating reagent to the pipette.
Add using (B) Place a small funnel in the mouth of the flask and set the temperature to 95-1.
Approximately 1 cm bottom is immersed in a glycerin bath at 00 ° C and heated
It The neck of the flask is heated by the heat of the glycerin bath and the temperature rises.
A cardboard disc with a round hole in it to prevent it from rolling
Cover the base of the neck of the flask. (C) After 1 hour, remove the flask from the glycerin bath,
After cooling, add 1 ml of water from the funnel and shake to shake acetic anhydride.
Disassemble. (D) Furthermore, in order to complete the decomposition, the flask should be closed again.
Heat in a lyserine bath for 10 minutes, allow to cool, then ethanol (9
5) Wash the funnel and flask walls with 5 ml. (E) Add a few drops of phenolphthalein solution as an indicator
Eh, 0.5 kmol / m ³Potassium hydroxide ethanol solution
When titrated with liquid and light red color of indicator continues for about 30 seconds
Is the end point. (F) Blank test does not include hydrocarbon wax (a)
(A) to (e) are performed. (G) If the sample is difficult to dissolve, add a small amount of pyridine.
Add or dissolve in xylene or toluene. ・ Calculation A = [{(B−C) × 28.05 × f} / S] + D However, A: hydroxyl value (mgKOH / g) B: 0.5 kmol / m used for blank test³Potassium hydroxide
Amount of ethanol solution (ml) C: 0.5 kmol / m used for titration³Potassium hydroxide
Amount of ethanol solution (ml) f: 0.5 kmol / m³Potassium hydroxide ethanol solution
Liquid factor S: Mass of hydrocarbon wax (g) D: Acid value 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

Measurement of Ester Value It is calculated by the following formula. (Ester value) = (Saponification value)-(Acid value)

Measurement of Saponification Value / Apparatus and Equipment Erlenmeyer Flask (200-300 ml) Air Cooler (Outer diameter 6-8 mm, 100 cm long glass tube or reflux condenser, both of which are rubbed on the Erlenmeyer flask mouth. Can be connected) Water bath, sand bath or hot plate (which can be adjusted to a temperature of about 80 ° C) Burette (50 ml) Total volume pipette (25 ml) -Reagent 0.5 kmol / m ³ Hydrochloric acid 0.5 kmol / m ³ Potassium hydroxide ethanol Solution Phenolphthalein solution-Measurement method (a) Hydrocarbon wax (a) 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 / m ³ potassium hydroxide ethanol solution using a pipette. (C) An Erlenmeyer flask is equipped with an air cooler and the contents are shaken occasionally for 30 minutes while gently heating in a water bath, sand bath or hot plate to react. When heating, the heating temperature is adjusted so that the circulating ethanol ring does not reach the upper end of the air cooler. (D) Immediately after the reaction is completed, the contents are cooled, and a small amount of water or a mixed solution of xylene: ethanol = 1: 3 is sprayed on the inner wall of the air cooler to wash the inner wall before the contents solidify into agar. After that, remove the air cooler. (E) Add 1 ml of a phenolphthalein solution as an indicator, and titrate with 0.5 kmol / m ³ hydrochloric acid. The end point is when the pale red color of the indicator disappears for about 1 minute. (F) In the blank test, (a) to (e) are performed without adding the hydrocarbon wax (a). (G) When the sample is difficult to dissolve, it is dissolved in advance using xylene or a xylene-ethanol mixed solvent. Calculation A = {(B−C) × 28.05 × f} / S where A: saponification value (mgKOH / g) B: amount of 0.5 kmol / m ³ hydrochloric acid used in blank test (m
l) C: amount of 0.5 kmol / m ³ hydrochloric acid used for titration (m
l) f: 0.5 kmol / m ³ Factor S of hydrochloric acid S: Mass of hydrocarbon wax (a) (g) 28.05: Formula weight of potassium hydroxide 56.11 × 1/2

When the acid value, hydroxyl value, ester value and saponification value of the hydrocarbon wax (a) contained in the magnetic toner of the present invention are measured, the hydrocarbon wax (a) is used as the magnetic toner. After collecting from, the measurement may be carried out according to the above measuring method.

The hydrocarbon wax (a) and the hydrocarbon wax (b) according to the present invention have a melting point of 65 to 5.
It is preferably 130 ° C., preferably 70 to 125 ° C., more preferably 75 to 120 ° C., further preferably 78 to 115 ° C. By using the hydrocarbon wax having a melting point in the above range for the magnetic toner, the effect of the hydrocarbon wax for plasticizing the magnetic toner can be further improved, and the fixability of the magnetic toner can be enhanced. Further, when the melting point of the hydrocarbon wax is within the above range, the hydrocarbon wax easily exudes from the magnetic toner when the fixing member is excessively heated, and the high temperature offset resistance of the magnetic toner is improved. You can If the melting point of the hydrocarbon wax is less than 65 ° C, the blocking resistance of the magnetic toner may decrease. Melting point 130
If the temperature exceeds ℃, the fixing performance of the magnetic toner may be adversely affected.

In the present invention, the melting point of the hydrocarbon wax is the differential thermal analysis measuring device (DSC measuring device), DSC2.
920 (manufactured by TA Instruments Japan),
It can be measured under the following conditions. Method for measuring melting point of hydrocarbon wax Measured according to ASTM D3418. Sample: 0.5-2 mg, preferably 1 mg Measurement method: Put 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 decrease I (180 ° C to 10 ° C, temperature decrease rate 10 ° C / min) Temperature increase II (10 ° C to 180 ° C, temperature increase rate 10 ° C / mi
n) The melting point is the endothermic peak temperature measured at the temperature rise II in the temperature curve.

The hydrocarbon wax (a) and the hydrocarbon wax (b) according to the present invention have a penetration at 25 ° C. of 15 or less (preferably 12 or less, more preferably 10 or less). It is preferable to enhance the charging performance of the magnetic toner and to obtain higher developability even in a high temperature and high humidity environment. If the penetration of the hydrocarbon wax at 25 ° C. is greater than 15, the blocking resistance of the magnetic toner may decrease. In the present invention, the penetration of the hydrocarbon wax is JIS K-2235-5.4.
Required by.

Hydrocarbon wax (a) in the present invention
The preferable addition amount of the hydrocarbon wax (b) to the magnetic toner is 0.1% with respect to 100 parts by mass of the binder resin.
It is used in the range of 2 to 20 parts by mass, preferably 0.5 to 15 parts by mass, more preferably 1 to 15 parts by mass.

Hydrocarbon wax (a) in the present invention
And the content ratio of the hydrocarbon wax (b) is such that when the content of the hydrocarbon wax (a) is 1, the content of the hydrocarbon wax is 0.05 to 20, preferably 0.07. It is preferably -15, more preferably 0.1-10. When the content ratio of the hydrocarbon wax (a) and the hydrocarbon wax (b) is out of the above range,
The fixability and offset resistance of the toner may be insufficient.

The hydrocarbon wax (a) and the hydrocarbon wax (b) according to the present invention have a temperature of 120 ° C.
Has a viscosity of 500 mPa · s or less, preferably 20
0 mPa · s or less, more preferably 100 mPa · s or less, or viscosity at a temperature of 135 ° C. is 400 mPa · s
-S or less, preferably 200 mPa-s or less, more preferably 100 mPa-s or less, or viscosity at a temperature of 150 ° C is 300 mPa-s or less, preferably 200.
It is preferably mPa · s or less, and more preferably 100 mPa · s or less, from the viewpoint of reducing the melt viscosity of the magnetic toner and achieving good fixability. Viscosity at 120 ° C is 500 mPa · s, or viscosity at temperature 135 ° C is 400 mPa · s, or temperature 150 ° C.
If the viscosity at 300 is more than 300 mPa · s, the fixability of the magnetic toner may be insufficient. In the present invention, the viscosity of the hydrocarbon wax is JIS K-6862.
-7.2.

The hydrocarbon wax (a) and the hydrocarbon wax (b) of the present invention have a softening point of 65.
˜140 ° C., preferably 70 to 130 ° C., and more preferably 75 to 120 ° C. is preferable from the viewpoint of obtaining good fixability, offset resistance, and blocking resistance of the magnetic toner. If the softening point of the hydrocarbon wax is lower than 65 ° C., the blocking resistance and offset resistance of the magnetic toner may deteriorate. If the softening point of the hydrocarbon wax exceeds 140 ° C., the fixability of the magnetic toner may become insufficient. In the present invention, the softening point of the hydrocarbon wax is determined according to JIS K-2207-6.4.

The hydrocarbon wax (b) of the present invention is a hydrocarbon wax selected from polyolefin wax, Fischer-Tropsch wax and paraffin wax. Among these, waxes preferably used are polyethylene wax, Fischer-Tropsch wax and paraffin wax.

As the polyolefin wax, polypropylene wax, polyethylene wax, ethylene-
Examples thereof include a propylene copolymer and an ethylene-butene copolymer, and among them, polyethylene wax is preferable.

The polyethylene wax preferably used is a low molecular weight polyethylene obtained by radical polymerization of ethylene under high pressure or by using a Ziegler catalyst or a metallocene catalyst, and a by-product at this time and a high molecular weight polyethylene which are thermally decomposed. It is a low molecular weight polyethylene obtained by the above.

Further, Fischer-Tropsch wax and paraffin wax are preferable. Among them, Fischer-Tropsch wax is particularly preferable and has a carbon number of several thousand,
Especially up to a thousand things are good.

From these waxes, the wax was fractionated according to its molecular weight by using a press sweating method, a solvent method, a vacuum distillation, a supercritical gas extraction method, fractional crystallization (for example, melted liquid crystal precipitation and crystal filtration). Wax is also preferably used in the present invention. For example, those having an arbitrary molecular weight distribution, such as those obtained by removing low molecular weight components, those obtained by extracting low molecular weight components, and those obtained by further removing low molecular weight components by these methods, can be used.

In the present invention, in addition to the hydrocarbon wax (a) and the hydrocarbon wax (b), known waxes generally used for magnetic toners such as those described in the description of the prior art are conventionally used. It may be used in combination with. For example, montan wax, microcrystalline wax, carnauba wax, polyolefin wax derivative and the like. Examples of the derivative include a block copolymer with a vinyl monomer and a graft modified product.

These optional waxes are based on the binder resin 10
0.2 to 20 parts by weight, preferably 0.
It is used in an amount of 5 to 15 parts by mass, more preferably 1 to 15 parts by mass.

The types of the binder resin used in the present invention include styrene resins, styrene copolymer resins, polyester resins, polyol resins, polyvinyl chloride resins, phenol resins, natural modified phenol resins and natural resin modified maleines. Examples thereof include acid resin, 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-based resin.

As a comonomer for the styrene monomer of the styrene type copolymer, a styrene derivative such as vinyltoluene; acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-acrylic acid acrylate Acrylic esters such as ethylhexyl and phenyl acrylate; Methacrylic acid esters such as methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate; maleic acid; butyl maleate, methyl maleate, dimethyl maleate A dicarboxylic acid ester having a double bond such as: acrylamide, acrylonitrile, methacrylonitrile, butadiene; a vinyl ester such as vinyl chloride, vinyl acetate, vinyl benzoate; ethylene, propylene Emissions, such as ethylene-based olefin butylene; 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 the present invention, a styrene-acrylic acid ester copolymer and a styrene-methacrylic acid copolymer are used as particularly preferable binder resins, whereby the hydrocarbon wax (a) and the hydrocarbon wax (b) are used. It is possible to obtain an appropriate dispersibility in the magnetic toner (1).

The binder resin or resin composition used in the present invention has a glass transition temperature (Tg) of 45 from the viewpoint of storability.
-80 degreeC, Preferably it is 50-70 degreeC. Tg is 45
If the temperature is lower than 0 ° C, it tends to cause deterioration of the magnetic toner in a high temperature atmosphere and offset during fixing. Also, Tg is 8
If the temperature exceeds 0 ° C, the fixability tends to decrease.

Examples of the method for polymerizing the binder resin of the present invention include a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) which is almost insoluble in water is dispersed in the aqueous phase as small particles with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and the phase in which the polymerization takes place (oil phase consisting of polymer and monomer)
And the aqueous phase are different, the termination reaction rate is low, and as a result, the polymerization rate is high and the polymerization degree is high. Furthermore, the fact that the polymerization process is relatively simple, and that the polymerization product is fine particles, it is easy to mix with a colorant and a charge control agent and other additives in the production of a magnetic toner. For this reason, there is an advantage as a method for producing a binder resin for magnetic toner.

However, the resulting polymer is liable to become impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. To avoid this inconvenience, suspension polymerization is convenient.

In suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is used with respect to 100 parts by mass of the aqueous solvent.
0 to 90 parts by mass) is preferable. As dispersants that can be used, polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like are used, and generally 0.05 to 1 part by mass relative to 100 parts by mass of the aqueous solvent. The polymerization temperature is suitably 50 to 95 ° C., but it is appropriately selected depending on the initiator used and the target polymer.

The binder resin used in the present invention is preferably produced by a polyfunctional polymerization initiator as exemplified below or in combination with a monofunctional polymerization initiator.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-
Butyl peroxy octane and various polymer oxides, a polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule, and diallyl peroxy dicarbonate, t-butyl peroxy A polyfunctional compound having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group in one molecule such as maleic acid, t-butylperoxyallyl carbonate and t-butylperoxyisopropyl fumarate. It is selected from the group of polymerizable polymerization initiators.

Of these, more preferred are 1,1
-Di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyase Rate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with monofunctional polymerization initiators in order to satisfy various performances required as a binder for magnetic toners. In particular, it is preferably used in combination with a polymerization initiator having a half-life of 10 hours, which is lower than the decomposition temperature for obtaining the half-life of 10 hours of the polyfunctional polymerization initiator.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
-Organic peroxides such as butyl peroxide; azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator, but in order to keep the efficiency of the polyfunctional polymerization initiator appropriate,
It is preferably added after the half-life indicated by the polyfunctional polymerization initiator has elapsed in the polymerization step.

From the viewpoint of efficiency, these polymerization initiators are preferably used in an amount of 0.05 to 2 parts by mass with respect to 100 parts by mass of the monomer.

The binder resin is also preferably crosslinked with a crosslinkable monomer.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4). -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
-Hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds in which the acrylate is replaced by methacrylate); diacrylate compounds linked by an alkyl chain containing an ether bond (for example, diethylene glycol diacrylate, triethylene glycol) Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and the above compounds in which acrylate is replaced with methacrylate); aromatic groups and ether bonds Chain-containing diacrylate compounds (eg, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane diacryle) DOO, polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propanediacrylate, and those in which the acrylates of the above compounds are replaced by methacrylates; and further polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)) ) Is mentioned. As the polyfunctional cross-linking agent, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, and acrylate of the above compounds are replaced with methacrylate. And so on; triallyl cyanurate, triallyl trimellitate; and the like.

These cross-linking agents are based on other monomer components 10
It is preferable to use 0.00001 to 1 part by mass, preferably 0.001 to 0.05 part by mass, relative to 0 part by mass.

Of these crosslinkable monomers, those which are preferably used from the viewpoints of the fixing property and anti-offset property of the magnetic toner include a chain containing an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. Included are diacrylate compounds that are tied.

As other synthetic methods, a bulk polymerization method or a solution polymerization method can be used. However, in the bulk polymerization method, although a low molecular weight polymer can be obtained by polymerizing at a high temperature to accelerate the termination reaction rate, there is a problem that the reaction is difficult to control. In that respect, the solution polymerization method makes it possible to easily obtain a polymer having a desired molecular weight under mild conditions by utilizing the difference in the chain transfer of radicals depending on the solvent and by adjusting the amount of the initiator and the reaction temperature. Is preferable because it can In particular, the solution polymerization method under a pressurized condition is also preferable in that the amount of the polymerization initiator used is minimized and the influence of the remaining polymerization initiator is minimized.

As a method for producing the binder resin composition, a solution blending method in which a high molecular weight polymer and a low molecular weight polymer are separately synthesized by a solution polymerization method, these are mixed in a solution state, and then the solvent is removed, , A dry blending method of melt-kneading with an extruder or the like, a low molecular weight polymer obtained by a solution polymerization method or the like is dissolved in a monomer constituting a high molecular weight polymer, suspension polymerization is performed, washing and drying are performed, A two-step polymerization method for obtaining a resin composition and the like can be mentioned. However, the dry blend method has some points to be improved in terms of uniform dispersion and compatibility. The two-step polymerization method has many advantages such as uniform dispersibility, but it is possible to increase the amount of low-molecular-weight components to higher than that of high-molecular weight compounds, and to synthesize high-molecular-weight polymers with high molecular weight. The solution blending method is most suitable because it has few problems that coalescence occurs as a by-product. Further, as a method for introducing a predetermined acid value into the low molecular weight polymer component,
Solution polymerization is preferable because the acid value can be easily set as compared with the polymerization method using an aqueous medium.

Examples of the composition of the polyester resin used as the binder resin in the present invention are shown below.

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

[0095]

[Chemical 5] (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.) The diols represented by the formula (B);

[0096]

[Chemical 6]

Examples of the divalent acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides, lower alkyl esters;
Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides or lower alkyl esters; alkenylsuccinic acids or alkylsuccinic acids such as n-dodecenylsuccinic acid, n-dodecylsuccinic acid or their anhydrides Or lower alkyl ester; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or its anhydride, or lower alkyl ester; and the like dicarboxylic acids and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component acting as a crosslinking component and a trivalent or higher valent acid component in combination.

The polyhydric alcohol component having 3 or more valences includes
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, 1,3,5-trihydroxybenzene and the like can be mentioned.

Examples of the trivalent or higher polycarboxylic acid component in the present invention include trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5.
-Benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-
Hexanetricarboxylic acid, 1,3-Sicarboxyl-2
-Methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, empol trimer acid, and their anhydrides, lower alkyl esters;

[0101]

[Chemical 7] (In the formula, X is an alkylene group or an alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms.), A tetracarboxylic acid represented by the formula, and their anhydrides or lower alkyl esters. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component is 40 to 60 mol
%, Preferably 45-55 mol%, and 6 as the acid component
It is preferably 0 to 40 mol%, and more preferably 55 to 45 mol%.

Moreover, it is preferable that the trivalent or higher polyvalent component accounts for 5 to 60 mol% of all components. The polyester resin is also usually obtained by commonly known polycondensation.

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

The following compounds may be mentioned as examples of controlling the magnetic toner to be negatively charged.

Organic metal complexes and chelate compounds are effective, for example, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid type metal complexes. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

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

[0108]

[Chemical 8]

Particularly, Fe or Cr is preferable as the central metal, halogen, an alkyl group or an anilide group is preferable as the substituent, and hydrogen, alkali metal, ammonium or aliphatic ammonium is preferable as the counter ion. Also, a mixture of complex salts having different counter ions is preferably used.

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

[0111]

[Chemical 9]

Particularly, as the central metal, Fe, Cr, Si,
Zn or Al is preferable, the substituent is an alkyl group,
Anilide group, aryl group and halogen are preferable, and counter ion is preferably hydrogen, ammonium and aliphatic ammonium.

The following compounds are available for controlling the magnetic toner to be positively charged.

Modifications with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate,
And their analogs, such as onium salts such as phosphonium salts, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, diorganotin oxide such as dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate. Diorgano tin borates such as; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. Also, the general formula (3)

[0115]

[Chemical 10]

Monopolymer of monomer represented by: A copolymer with a polymerizable monomer such as styrene, acrylic acid ester and methacrylic acid ester described above can be used as a positive charge control agent. In this case, these charge control agents also function as (all or part of) the binder resin.

Particularly, the compound represented by the following general formula (4) is preferable as the positive charge control agent of the present invention.

[0118]

[Chemical 11]

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

The magnetic toner of the present invention contains a magnetic material. The magnetic material can also serve as a coloring agent. Magnetic materials used in magnetic toners 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. , Beryllium, bismuth, cadmium,
Included are alloys with metals such as calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof.

The number average particle diameter of these magnetic materials is 0.05.
.About.1.0 .mu.m is preferable, and 0.1 to 0.5 .mu.m is more preferable. The magnetic material has a BET specific surface area of 2 to 40 m.
² / g (more preferably 4 to 20 m ² / g) is preferably used. The shape is not particularly limited, and any shape can be used. As magnetic characteristics, a magnetic field 795.
Saturation magnetization is 10-200 Am ² / kg under 8 kA / m
(More preferably 70-100 Am ² / kg), remanent magnetization is 1-100 Am ² / kg (more preferably 2-20).
Am ² / kg) and one having a coercive force of 1 to 30 kA / m (more preferably 2 to 15 kA / m) are preferably used. These magnetic materials are based on 100 parts by mass of the binder resin,
Used in 20 to 200 parts by mass. Preferably 40 to 1
Used in 50 parts by mass.

The number average diameter can be determined by measuring a photograph enlarged with a transmission electron microscope or the like with a digitizer or the like. The magnetic characteristics 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 Industry Co., Ltd.). The specific surface area can be calculated according to the BET method by using a specific surface area measuring device Auto Soap 1 (manufactured by Yuasa Ionics) to adsorb nitrogen gas on the sample surface and using the BET multipoint method.

Other colorants that can be used in the magnetic toner of the present invention include any appropriate pigments or dyes. As a pigment, carbon black, aniline black,
Acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, red iron oxide, phthalocyanine blue, indanthrene blue and the like can be mentioned. These are used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and the amount added is 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass, relative to 100 parts by mass of the binder resin. . Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes. The dye is 0.1 to 100 parts by mass of the binder resin.
The addition amount of 20 parts by mass, preferably 0.3 to 10 parts by mass is good.

Inorganic fine powder or hydrophobic inorganic fine powder is preferably externally added to the magnetic toner of the present invention. 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.

[0125] Examples of the silica fine powder include both dry silica produced by vapor phase oxidation of a silicon halogen compound and referred to as fumed silica, and wet silica produced from water glass and the like. Dry silica, which has few silanol groups on the surface and inside and has no production residue, is preferred.

Further, the silica fine powder is preferably hydrophobized. The hydrophobic treatment is applied by chemically treating with an organosilicon compound that reacts with or physically adsorbs on the silica fine powder. As a preferred method, there is a method of treating dry silica fine powder produced by vapor phase oxidation of a silicon halogen compound with a silane compound, or simultaneously treating with a silane compound and then treating with an organosilicon compound such as silicone oil.

As the silane compound used for the hydrophobic treatment, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane. , Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, Dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinylthene Tramethyldisiloxane, 1,
3-diphenyl tetramethyldisiloxane is mentioned.

Examples of the organic silicon compound include silicone oil. The preferred silicone oil has a viscosity of about 30 to 1,000 mm at 25 ° C.
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 preferable.

The silicone oil treatment may be carried out by directly mixing the silica fine powder treated with the silane compound and the silicone oil with a mixer such as a Henschel mixer, or by adding silica oil to the base silica. The method of injecting Alternatively, it may be produced by dissolving or dispersing silicone oil in an appropriate solvent, then mixing with silica fine powder of base and removing the solvent.

As a preferable hydrophobic treatment for the silica fine powder, there may be mentioned a method in which it is prepared by treating with dimethyldichlorosilane, then with hexamethyldisilazane, and then with silicone oil.

As described above, it is preferable to treat the silica fine powder with two or more silane compounds and then to treat with oil, since the degree of hydrophobicity can be effectively increased.

[0132] The fine silica powder obtained by subjecting the fine silica powder to a hydrophobizing treatment and further an oil treatment to the fine titanium oxide powder may also be used.
It is preferable as well as silica type.

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

For example, a charging auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent at the time of heat roll fixing,
Resin fine particles or inorganic fine particles that act as a lubricant or an abrasive.

The resin fine particles have an average particle size of 0.
It is preferably from 03 to 1.0 μm. As the polymerizable monomer constituting the resin, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene derivative; 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, stearyl 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. Particles obtained by soap-free polymerization are more preferable.

Other fine particles include lubricants such as polyethylene fluoride, zinc stearate and polyvinylidene fluoride (polyvinylidene fluoride is preferred); abrasives such as cerium oxide, silicon carbide and strontium titanate (among others). Strontium titanate is preferred); Flowability-imparting agents such as titanium oxide and aluminum oxide (particularly hydrophobic ones are preferred); Anti-caking agent; Conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide, tin oxide Is mentioned. Further, a small amount of white fine particles and black fine particles having a polarity opposite to that of the magnetic toner may be used as a developing property improver.

The resin fine particles or the inorganic fine powder or the hydrophobic inorganic fine powder mixed with the magnetic toner is the magnetic toner 10.
0.1 to 5 parts by mass (preferably 0.1 parts by mass)
~ 3 parts by mass) is preferably used.

The magnetic toner of the present invention preferably exhibits a sufficient effect when the weight average particle diameter is 2.5 to 10 μm, which is preferable.

The weight average particle size and particle size distribution of the magnetic toner are measured by the Coulter counter method, but for example, Coulter Multisizer (manufactured by Coulter Co.) can be used. The electrolyte is 1% using first-grade sodium chloride.
An aqueous NaCl solution is prepared. For example, ISOTON R-
II (Made by Coulter Scientific Japan)
Can be used. As a measuring method, the electrolytic aqueous solution 100 is used.
A surface active agent (preferably alkylbenzene sulfonate) as a dispersant is added in an amount of 0.1 to 5 ml in 150 ml, and a measurement sample is added in an amount of 2 to 20 mg. The electrolytic solution in which the sample is suspended is dispersed by an ultrasonic disperser for about 1 to 3 minutes, and 100 μm as an aperture is measured by the measuring device.
Using an aperture, the volume and number of magnetic toner particles of 2.00 μm or more are measured to calculate the volume distribution and number distribution. Then, the weight-based weight average particle diameter (D4) obtained from the volume distribution according to the present invention is calculated. As the channel, 2.00 to less than 2.52 μm; 2.52 to 3.
Less than 17 μm; 3.17 to less than 4.00 μm; 4.00
˜5.04 μm; 5.04˜6.35 μm;
6.35 to less than 8.00 μm; 8.00 to 10.08 μ
less than m; 10.08 to less than 12.70 μm; 12.70
˜16.00 μm; 16.00-20.20 μm; 20.20-25.40 μm; 25.40-3
Less than 2.00 μm; 13 channels of 32.00 to less than 40.30 μm are used.

The magnetic toner of the present invention can be used as a two-component developer in combination with a carrier. As the carrier used in the two-component developing method, conventionally known carriers can be used. Specifically, surface-oxidized or unoxidized iron, nickel, cobalt, manganese, chromium,
Particles formed from metals such as rare earths and their alloys or oxides with an average particle size of 20-300 μm are used as carrier particles.

The surface of the carrier particles is a styrene resin,
It is preferable that a substance such as an acrylic resin, a silicone resin, a fluorine resin, or a polyester resin is attached or coated.

To produce the magnetic toner of the present invention,
After thoroughly mixing the above-described magnetic toner constituent materials with a ball mill or other mixer, a heat roll, a kneader,
Knead well using a heat kneader such as an extruder,
After cooling and solidification, a method of obtaining a magnetic toner by mechanical pulverization / classification is preferable. Alternatively, a predetermined material is mixed with a monomer to form a binder resin to prepare an emulsified suspension, followed by polymerization. To obtain a magnetic toner, a method for producing a polymerized magnetic toner, a method for containing a core material or a shell material in a so-called microcapsule magnetic toner composed of a core material and a shell material, or both of them containing a predetermined material, in a binder resin solution A method of obtaining a magnetic toner by spray-drying after dispersing the constituent materials in can be applied. Further, if necessary, desired additives can be sufficiently mixed with a mixer such as a Henschel mixer to produce the magnetic toner according to the present invention.

For example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Co., Ltd.); a ribocon (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); The spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); the Ledige mixer (manufactured by Matsubo Co., Ltd.), and the kneaders include KRC kneader (manufactured by Kurimoto Iron Works Co., Ltd.); Mold extruder (made by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (made by Japan Steel Works); PCM kneader (made by Ikegai Iron Works Co., Ltd.); three-roll mill, mixing roll mill, kneader (made by Inoue Seisakusho); knee Decks (manufactured by Mitsui Mining Co., Ltd.); MS type pressure kneader, Nider Ruder (manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe) Tokorosha, Ltd.) and the like. As a crusher, a counter jet mill, a micron jet, an innomizer (manufactured by Hosokawa Micron Co.); an IDS type mill, a PJM jet crusher (manufactured by Nippon Pneumatic Mfg. Co.); a cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); Ulmax ( Nisso Engineering Co., Ltd.); SK Jet
O-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 Nisshin Engineering Co., Ltd.). As classifiers, class sealer, micron classifier, spedic classifier (manufactured by Seishin Enterprise Co., Ltd.); turbo classifier (manufactured by Nisshin Engineering Co., Ltd.); micron separator, turbo flex (ATP), TSP separator (manufactured by Hosokawa Micron Co., Ltd.) Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Mfg. Co., Ltd.); YM Microcut (manufactured by Yasukawa Shoji Co., Ltd.). As a sieving device used for sieving coarse particles, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonator Sieve, Gyro Shifter (manufactured by Tokuju Kosakusho); Vibrasonic System (manufactured by Dalton); Soniclean (new Toko Kogyo Co., Ltd.); Turbo Screener (Turbo Kogyo Co., Ltd.); Micro Shifter (Makino Sangyo Co., Ltd.);

[0145]

Although the basic structure and features of the present invention have been described above, the present invention will be specifically described based on the following examples. However, this does not limit the embodiments of the present invention in any way. The number of parts in the examples is part by mass.

Example of Synthesis of Hydrocarbon Wax (a) Example of Synthesis of Hydrocarbon Wax (a) 1: Fischer-Tropsch wax [number average molecular weight (Mn) as raw material]
721, average carbon number 49.4] 1000 g was put in a glass cylindrical reactor, and a small amount of nitrogen gas (3.5 liters /
(Min) While blowing, the temperature was raised to 140 ° C. Boric acid/
26.1 g of mixed catalyst of boric anhydride = 1.44 (molar ratio)
After adding (0.41 mol), air (20 liters /
Min) and nitrogen (15 l / min) while blowing 1
The reaction was carried out at 80 ° C for 2 hours. After completion of the reaction, an equal amount of warm water (95 ° C.) was added to the reaction mixture, the reaction mixture was hydrolyzed, and the mixture was allowed to stand to separate the hydrocarbon wax separated in the upper layer, and the separated hydrocarbon wax was washed with water. Thus, a hydrocarbon wax 1 was obtained. Hydroxyl wax 1 has a hydroxyl value of 50.2 mg KOH / g and an ester value of 12.6 mg
KOH / g, acid value 7.4 mg KOH / g, melting point 85
C., penetration was 6, viscosity was 13.2 mPa.s, softening point was 93.degree. C., and Mn was 617. In addition, the hydrocarbon wax 1 has the partial structural formulas (A), (B), (C),
Had (D). Table 1 shows the physical properties of the hydrocarbon wax 1.

Hydrocarbon Wax (a) Synthesis Example 2: Polyethylene Wax (Mn = 851) 10 as Raw Material
Hydrocarbon wax (a) Hydrocarbon wax 2 was prepared in the same manner as in Synthesis Example 1 except that the synthesis conditions were changed.
(Mn = 734) was obtained. Table 1 shows the physical properties of the hydrocarbon wax 2.

Hydrocarbon Wax (a) Synthesis Example 3: Paraffin wax (Mn = 399) 100 as raw material
Hydrocarbon wax (a) Hydrocarbon wax 3 in the same manner as in Synthesis Example 1 except that 0 g was used and the synthesis conditions were changed.
(Mn = 325) was obtained. Table 1 shows the physical properties of the hydrocarbon wax 3.

Hydrocarbon Wax (a) Synthesis Example 4: Fischer-Tropsch wax (Mn = 4) as a raw material
46) A hydrocarbon wax 4 (Mn = 387) was obtained in the same manner as in the hydrocarbon wax synthesis example 1 except that 1000 g was used and the synthesis conditions were changed. Table 1 shows the physical properties of the hydrocarbon wax 4.

Hydrocarbon Wax (a) Synthesis Example 5: Polyethylene Wax (Mn = 1222) 1 as Raw Material
Hydrocarbon wax 5 (Mn = 100) was prepared in the same manner as in Wax Synthesis Example 1 except that 000 g was used and the synthesis conditions were changed.
1) was obtained. Table 1 shows the physical properties of the hydrocarbon wax 5.

Hydrocarbon Wax (a) Synthesis Example 6: Paraffin wax (Mn = 371) 100 as raw material
Hydrocarbon wax 6 (Mn = Mg) was used in the same manner as in Synthesis Example 1 of hydrocarbon wax except that 0 g was used and the synthesis conditions were changed.
311) was obtained. Table 1 shows the synthesis conditions and physical properties of the hydrocarbon wax 6.

Hydrocarbon Wax (a) Synthesis Example 7: Polyethylene Wax (Mn = 2054) 1 as Raw Material
Hydrocarbon Wax 7 (M) was prepared in the same manner as in Synthesis Example 1 of Hydrocarbon Wax except that the synthesis conditions were changed.
n = 1903) was obtained. Table 1 shows the synthesis conditions and physical properties of the hydrocarbon wax 7.

Hydrocarbon Wax (a) Synthesis Example 8: Paraffin wax (Mn = 327) 100 as raw material
Hydrocarbon wax 8 (Mn = Mg) was used in the same manner as in Synthesis Example 1 of hydrocarbon wax except that 0 g was used and the synthesis conditions were changed.
278) was obtained. Table 1 shows the physical properties of the hydrocarbon wax 8.

Hydrocarbon Wax (a) Synthesis Example 9: Paraffin Wax (Mn = 380) 100 as Raw Material
Hydrocarbon wax 9 (Mn = Mg) was used in the same manner as in Synthesis Example 1 of hydrocarbon wax except that 0 g was used and the synthesis conditions were changed.
315) was obtained. Table 1 shows the physical properties of the hydrocarbon wax 9.

Hydrocarbon Wax (a) Synthesis Example 10: Paraffin wax (Mn = 378) 10 as a raw material
Hydrocarbon Wax 10 (M) was prepared in the same manner as in Synthesis Example 1 of Hydrocarbon Wax except that the synthesis conditions were changed.
n = 312) was obtained. Table 1 shows the physical properties of the hydrocarbon wax 10.

Hydrocarbon wax (a) Synthesis example 11: α-olefin (Mn = 326) 1000 as a raw material
Hydrocarbon wax 11 (Mn = Mn) was used in the same manner as in Synthesis Example 1 of Hydrocarbon Wax except that the synthesis conditions were changed.
276) was obtained. Table 1 shows the physical properties of the hydrocarbon wax 11.
Shown in.

Further, Table 1 also shows the physical properties of the waxes 12 and 13 used in Comparative Examples 6 and 7 described later.

[0158]

[Table 1]

Hydrocarbon wax (b) used in the examples
The physical properties of are shown in Table 2.

[0160]

[Table 2]

Example 1 Styrene-acrylic acid ester copolymer 100 parts (peak molecular weight 12000, Tg 60 ° C.) Magnetic iron oxide 100 parts Monoazo iron complex 2 parts Hydrocarbon wax 1 7 parts Hydrocarbon wax 2 parts The mixture is melt-kneaded with a twin-screw extruder heated to 130 ° C., the cooled kneaded product is roughly crushed with a hammer mill, the coarsely crushed product is finely crushed with a jet mill, and the obtained finely pulverized powder is fixed wall. Classified powder was generated by classifying with a type wind power classifier. Further, the obtained classified powder is subjected to strict classification of ultrafine powder and coarse powder at the same time with a multi-division classifier utilizing the Coanda effect (Elbow Jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a weight average particle diameter (D ₄ ) A negatively chargeable magnetic toner of 6.8 μm was obtained.

100 parts of this magnetic toner and 1.2 parts of hydrophobic silica fine powder were mixed with a Henschel mixer to prepare a developer and evaluated. The evaluation results are shown in Table 3.

Example 2 Styrene-methacrylic acid ester copolymer 100 parts (peak molecular weight 15000, Tg 58 ° C.) Magnetic iron oxide 100 parts Monoazo iron complex 2 parts Hydrocarbon wax 1 5 parts Hydrocarbon wax 3 parts Above The mixture is melt-kneaded with a twin-screw extruder heated to 130 ° C., the cooled kneaded product is roughly crushed with a hammer mill, the coarsely crushed product is finely crushed with a jet mill, and the obtained finely pulverized powder is fixed wall. Classified powder was generated by classifying with a type wind power classifier. Further, the obtained classified powder is subjected to strict classification of ultrafine powder and coarse powder at the same time with a multi-division classifier utilizing the Coanda effect (Elbow Jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a weight average particle diameter (D ₄ ) A negatively chargeable magnetic toner of 6.8 μm was obtained.

100 parts of this magnetic toner and 1.2 parts of hydrophobic silica fine powder were mixed with a Henschel mixer to prepare a developer and evaluated. The evaluation results are shown in Table 3.

<Examples 3 and 4> Evaluations were made in the same manner as in Example 1 except that the wax used was changed to the wax shown in Table 3 and the addition amount was changed. The evaluation results are shown in Table 3.

Example 5 Polyester Resin 100 Parts (Peak Molecular Weight 7500, Tg 65 ° C.) Magnetic Iron Oxide 100 parts Monoazo Iron Complex 2 parts Hydrocarbon Wax 4 6 parts Hydrocarbon Wax 3 parts The above mixture was heated to 130 ° C. Melt and knead with a heated twin-screw extruder, then cool and knead the coarsely crushed product with a hammer mill, finely crush the coarsely crushed product with a jet mill, and classify the resulting finely pulverized powder with a fixed wall type air classifier. To produce classified powder. Further, the obtained classified powder is subjected to strict classification of ultrafine powder and coarse powder at the same time with a multi-division classifier utilizing the Coanda effect (Elbow Jet classifier manufactured by Nittetsu Mining Co., Ltd.) to obtain a weight average particle diameter (D ₄ ) A negatively chargeable magnetic toner of 6.8 μm was obtained.

100 parts of this magnetic toner and 1.2 parts of hydrophobic silica fine powder were mixed with a Henschel mixer to prepare a developer and evaluated. The evaluation results are shown in Table 3.

<Examples 6 to 8 and Comparative Examples 1 to 5> Evaluations were made in the same manner as in Example 1 except that the wax used was changed to the wax shown in Table 3 and the addition amount was changed. The evaluation results are shown in Table 3.

Comparative Example 6 The hydrocarbon wax (a) used was changed to 10 parts of the hydrocarbon wax 12 (polyglycerin distearate), and the hydrocarbon wax (b) was changed to 4 parts of Viscole 660P (Sanyo Kasei). Evaluation was performed in the same manner as in Example 1 except for the above. The evaluation results are shown in Table 3.

Comparative Example 7 The hydrocarbon wax (a) used was replaced with 20 parts of the hydrocarbon wax 13 (dottriancontanol), and the hydrocarbon wax (b) was replaced with 6 parts of the hydrocarbon wax. Evaluation was carried out in the same manner as in Example 1. The evaluation results are shown in Table 3.

The evaluation methods in Examples and Comparative Examples are shown below.

Image development test: The developer was put in a process cartridge, and L was manufactured by Hewlett-Packard.
under the high temperature and high humidity environment (32.
5 ℃, 80% RH, normal temperature and humidity environment (23 ℃, 60%
RH) and a low-temperature low-humidity environment (15 ° C., 10% RH), an image formation test of 30,000 sheets was continuously performed, and the obtained images were evaluated for the following items.

(1) Image Density 30,000 sheets of ordinary plain paper for copiers (75 g / m ² ) were printed out, and the image densities at the start and end were evaluated. The image density is "Macbeth reflection densitometer"
(Manufactured by Macbeth Co., Ltd.) was used to measure the relative density of a white background portion having a document density of 0.00 with respect to a printout image.

(2) Fog 30,000 sheets were printed out on ordinary plain paper for copiers (75 g / m ² ) in a low temperature and low humidity environment (15 ° C., 10% RH), and the fog at the end was evaluated. . Fog was calculated by comparing the whiteness of the transfer paper before printing measured with a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white.

(3) Evaluation of image black spots caused by adhesion of magnetic toner to fixing member 3000 under low temperature and low humidity environment (temperature 15 ° C., 10% RH)
The pressure roller and the image after printing 0 sheets were visually evaluated. A Black spot is not seen. B Magnetic toner adhered to the fixing roller, but did not appear on the image. 1 to 2 black spots are seen on the C image. D Three or more black spots are seen on the image.

(4) Sleeve negative ghost 30,000 sheets are printed out on ordinary plain paper for copiers (75 g / m ² ) under low temperature and low humidity (15 ° C., 10% RH), and a sleeve negative ghost is printed every 10,000 sheets. An evaluation was made. For the image evaluation of the ghost, a solid black band was output for one round of the sleeve, and then a halftone image was output. A schematic diagram of the pattern is shown in FIG. The evaluation method is
Of the printed image of one sheet, measured by a Macbeth densitometer at the second round of the sleeve, where the black image was formed at the first round (black print area) and where it was not (non-image area). The difference in reflection density was calculated as follows. In the negative ghost, in the image generally appearing on the second round of the sleeve, the image density of the black print portion on the first round of the sleeve is lower than the image density of the non-image portion on the first round of the sleeve. This is a ghost phenomenon in which the shape of the pattern produced on the first lap appears as it is. The density difference here was evaluated by measuring the reflection density difference. Reflection density difference = Reflection density (where image is not formed) -Reflection density (where image is formed)

The smaller the reflection density difference is, the less the ghost occurs and the better the level. A, B, as a comprehensive evaluation of the ghost
Table 4 shows the worst evaluation result among the evaluations for every 10,000 sheets, with the evaluation being divided into four stages of C and D.

[0178]

Low temperature fixability, high temperature offset resistance: The above developer is put in a process cartridge, and Hewlett-
Using LaserJet 9000n manufactured by Packard, the surface temperature of the heating roller of the heating and pressure roller fixing device was modified so that it could be changed from 120 to 250 ° C from the outside, and the set temperature was changed in 5 ° C increments at room temperature and normal humidity. The image sample was printed out under (23 ° C., 60% RH).

(5) Low-temperature fixability A fixed image is rubbed with a soft thin paper by applying a load of 4.9 kPa, and the reduction rate (%) of the image density before and after the rubbing is 10%.
The evaluation was carried out by setting the lowest temperature of not more than% as the lowest fixing temperature. Plain paper for copiers (9
0 g / m ² ) was used.

(6) High temperature offset resistance image A sample image having an area ratio of about 5% is printed out,
The degree of stain on the image was evaluated. The maximum temperature at which stains on the image did not occur was shown. As the test paper, plain paper for copiers (60 g / m ² ) in which offset easily occurs was used.

(7) Blocking resistance test: Approximately 10 g of the developer was put in a 100 ml poly cup, left at 50 ° C. for 3 days, and then visually evaluated. A Agglomerates are not seen. B Agglomerates can be seen, but easily disintegrate. C Agglomerates can be seen but collapse if shaken. D Agglomerates can be grabbed and do not collapse easily.

[0183]

[Table 3]

[0184]

As described above, according to the present invention, the low temperature fixability and the high temperature offset resistance are highly satisfied, and the high developability is maintained even in a severe environment such as high temperature and high humidity and low temperature and low humidity. It is possible to provide a magnetic toner that does not cause sleeve ghost, has excellent blocking resistance, and does not cause magnetic toner to adhere to the fixing member.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a pattern for evaluating a sleeve ghost.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kaori Hiratsuka             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Hirohide Tanikawa             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA01 AA02 AA06 CA04 CA08                       CA13 CA14 CB03 EA03 EA07                       EA10 FA06

Claims (32)

[Claims] 1. A magnetic toner containing at least a binder resin, magnetic iron oxide and two or more hydrocarbon waxes, wherein at least one hydrocarbon wax (a) is Hydroxyl value (H _V ) is 5 to 150
is a mgKOH / g, ester value (E _V) from 1 to 50
a mg KOH / g, the relationship is H _V> E _V, at least one hydrocarbon wax (b) is a polyolefin wax, Fischer-Tropsch waxes,
A magnetic toner comprising a hydrocarbon wax selected from paraffin wax. 2. The magnetic toner according to claim 1, wherein the hydrocarbon wax (a) has an acid value (A _V ) of 1 to 30 mgKOH / g. 3. The hydrocarbon wax (a) according to claim 2, wherein the relationship between the hydroxyl value (H _V ) and the acid value (A _V ) is H _V > A _V. Magnetic toner. 4. The hydrocarbon wax (a) has a melting point of 65 to 130 ° C. 3.
The magnetic toner according to any one of 1. 5. The hydrocarbon wax (a) is a hydrocarbon wax obtained by converting an aliphatic hydrocarbon wax into an alcohol, and the hydrocarbon wax is obtained in any one of claims 1 to 4. Magnetic toner. 6. A magnetic toner according to claim 1, wherein the ester value of the hydrocarbon wax (a) (E _V) is characterized in that it is a 1~30mgKOH / g. 7. The magnetic toner according to claim 2, wherein the hydrocarbon wax (a) has an acid value (A _V ) of 1 to 15 mgKOH / g. 8. The magnetic toner according to claim 1, wherein the hydrocarbon wax (a) has a hydroxyl value (H _V ) of 10 to 100 mgKOH / g. Wherein said hydrocarbon wax (a) has a hydroxyl value (H _V) is 20~90mgKOH / g, an ester value (E _V) is 1~20mgKOH / g, an acid value (A _V 6. The magnetic toner according to claim 2, wherein the amount is 1 to 10 mgKOH / g. 10. The hydrocarbon wax (a) is H
A magnetic toner according to any one of claims 1 to 9, characterized in that it satisfies the condition of _V> 2E _V. 11. The hydrocarbon wax (a) is H
The magnetic toner according to any one of claims 2 to 9, which satisfies the condition of _V 2> 2A _V. 12. The magnetic toner according to claim 4, wherein the hydrocarbon wax (a) has a melting point of 70 to 125 ° C. 13. The magnetic toner according to claim 4, wherein the hydrocarbon wax (a) has a melting point of 75 to 120 ° C. 14. The hydrocarbon wax (a) has a penetration of 15 or less.
3. The magnetic toner according to any one of 3 above. 15. The hydrocarbon wax (a) has a softening point of 65 to 140 ° C.
15. The magnetic toner according to any one of 1 to 14. 16. The hydrocarbon wax (a) has the following partial structural formulas (A) and (B): The composition according to claim 1, further comprising a component having
16. The magnetic toner according to any one of 1 to 15. 17. The hydrocarbon wax (a) has the following partial structural formulas (C) and (D): The composition according to claim 1, further comprising a component having
17. The magnetic toner according to any one of 1 to 16. 18. The hydrocarbon wax (a) has the following partial structural formula (E): The composition according to claim 1, further comprising a component having
18. The magnetic toner according to any one of 1 to 17. 19. The magnetic toner according to claim 1, wherein the hydrocarbon wax (b) has a melting point of 65 to 130 ° C. 20. The melting point of the hydrocarbon wax (b) is 70 to 125 ° C., wherein
The magnetic toner described in 1. 21. The melting point of the hydrocarbon wax (b) is 75 to 120 ° C.
The magnetic toner described in 1. 22. The hydrocarbon wax (b) has a penetration of 15 or less.
1. The magnetic toner according to any one of 1. 23. The hydrocarbon wax (b) has a softening point of 65 to 140 ° C.
23. The magnetic toner according to any one of 22 to 22. 24. The magnetic material according to any one of claims 1 to 23, wherein the hydrocarbon wax (b) is a hydrocarbon wax selected from polyethylene wax, Fischer-Tropsch wax and paraffin wax. toner. 25. The magnetic toner according to claim 24, wherein the hydrocarbon wax (b) is Fischer-Tropsch wax. 26. The binder resin has a glass transition temperature (T
The magnetic toner according to any one of claims 1 to 25, wherein g) is 45 to 80 ° C. 27. The magnetic toner according to claim 1, wherein the binder resin contains a styrene-acrylic acid ester copolymer. 28. The magnetic toner according to claim 1, wherein the binder resin contains a styrene-methacrylic acid ester copolymer. 29. The magnetic toner according to claim 1, wherein the binder resin contains a polyester resin. 30. The hydrocarbon wax (a) and the hydrocarbon wax (b) contain 0.2 to 20 parts by mass of each hydrocarbon wax with respect to 100 parts by mass of a binder resin. The magnetic toner according to any one of claims 1 to 29, wherein: 31. The hydrocarbon wax (a) and the hydrocarbon wax (b) contain 0.5 to 15 parts by mass of each hydrocarbon wax with respect to 100 parts by mass of a binder resin. 31. The magnetic toner according to claim 30, wherein. 32. When the content ratio of the hydrocarbon wax (a) and the hydrocarbon wax (b) is set to 1, the content of the hydrocarbon wax (a) is set to 1. 31. The magnetic toner according to claim 30, wherein the content of) is 0.05 to 20.